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Chapter 104 - Guide to Chemicals

GENERAL PROFILE

The Guide to chemicals is designed to be a quick reference guide to approximately 2,000 chemicals which are of commercial interest. The chemicals have been divided into chemical “families” based on their chemical formulae. This division is somewhat arbitrary in that many chemicals can be classified into more than one family.

The reader who is searching for a particular chemical is advised to consult the chemical substances index in this volume to determine whether a chemical is covered and its location. The chemical substances index will also provide references to other chapters in the Encyclopaedia in which discussion of the chemical may also be found. The reader is referred to the chapters Metals: Chemical properties and toxicity and Minerals and agricultural chemicals for a systematic discussion of those elements and compounds and to the chapter, Using, storing and transporting chemicals for information on safe handling, usage, storage and transport of chemicals.

Each chemical family has a brief discussion of relevant toxicologic, epidemiologic or chemical safety information and four types of tables which summarize chemical, physical, safety and toxicologic data in a consistent format.

Because of page constraints, references for primary literature for the preparation of the textual materials are not provided here. The reader will be able to locate most primary data sources by referring to the Hazardous Substances Database (HSDB), produced by the US National Library of Medicine. In addition to the 3rd edition of this Encyclopaedia and the general scientific literature, the HSE Reviews published by the UK Health and Safety Executive served as a source of information. The Resources: Information and OSH chapter in this Encyclopaedia and the chapters mentioned above provide other general references.

The data on industrial uses of chemicals have been adapted from the 3rd edition of the Encyclopaedia and the HSDB. (For discussions of specific chemical industries, see the chapters Chemical processing, Oil and natural gas, Pharmaceutical industry and Rubber industry.)

Acknowledgements

This chapter is a collection of materials, some from articles in the 3rd edition of the Encyclopaedia of Occupational Health and Safety, which have been updated and consistently placed in tabular form.

The 4th edition contributors are:

Janet L. Collins

Linda S. Forst

David L. Hinkamp

Niels Koehncke

Kari Kurppa

Pia Markkanen

Debra Osinsky

Beth Donovan Reh

Jeanne Mager Stellman

Steven D. Stellman

Chemical structure diagrams which are given in the chemical identification tables were created using CS ChemDraw Pro® and obtained from the ChemFinder™ Web Server, courtesty of CambridgeSoft Corporation (www.camsoft.com).

The 3rd edition contributors are:

M. V. Aldyreva

Z. Aleksieva

D. D. Alexandrov

G. Armelli

Z. Bardodej

E. Bartalini

F. Bertolero

G. W. Boylen, Jr.

W. E. Broughton

E. Browning

G. T. Bryan

D. D. Bryson

S. Caccuri

B. Calesnick

N. Castellino

P. Catilina

A. Cavigneaux

W. B. Deichmann

D. DeRuggiero

P. Dervillee

E. Dervillee

J. Doignon

H. B. Elkins

M. Evrard

D. Fassett

A. T. Fenlon

L. D. Fernandez-Conradi

I. Fleig

V. Foá

A Forni

E. Fournier

I. D. Gadaskina

E. Gaffuri

J. C. Gage

P. J. Gehring

H. W. Gerarde

W. G. Goode

A. R. Gregory

P. Hadengue

H. I. Hardy

H. Heimann

E. V. Henson

A. Iannaccone

M. Ikeda

M. Inclan Cuesta

T. Inoue

N. G. Ivanov

W. H. Jones

F. Kaloyanova-Simeonova

B. D. Karpov

K. Knobloch

H. Kondo

E. J. Largent

J. Levèque

A. L. Linch

M. Lob

L. Magos

K. E. Malten

M. M. Manson

P. Manu

J. V. Marhold

D. Matheson

T. V. Mihajlova

A. Munn

S. Nomura

K. Norpoth

E. V. Olmstead

L. Parmeggiani

J. D. Paterson

F. L. M Pattison

M. Philbert

J. Piotrowski

J. Rantanen

D. W. Reed

G. Reggiani

C. F. Reinhardt

V. E. Rose

H. Rossmann

V. K. Rowe

N. I. Sadkovskaja

T. S. Scott

G. Smagghe

G. C. Smith

J. Sollenberg

M. J. Stasik

R. D. Stewart

W. G. Stocker

F. W. Sunderman, Jr.

O. N. Syrovadko

J. Teisinger

A. M. Thiess

A. A. Thomas

T. R. Torkelson

T. Toyama

D. C. Trainor

J. F. Treon

R. Truhaut

E. C. Vigliani

P. L. Viola

N. I. Volkova

M. Wassermann

D. Wassermann

N. K. Weaver

D. Winter

C. M. Woodbury

R. C. Woodcock

S. Yamaguchi

J. A. Zapp, Jr.

M. R. Zavon

J. B. Zuzik

Notes on the Tables

The four types of tables found in each family are:

1. Chemical identification

These tables list chemical names, synonyms, UN codes, CAS-numbers and chemical or structural formulae. An attempt has been made to use the same chemical name for each substance throughout the discussions in this Guide and this Encyclopaedia, to the extent possible. No attempt has been made, however, to use only the nomenclature system of the International Union of Pure and Applied Chemistry (IUPAC). Oftentimes the IUPAC name will be unfamiliar to those who work in a commercial setting and a less cumbersome and/or more familiar name is used. Thus the name which appears as the chemical name in the tables of each family is more often a “familiar” name than the IUPAC name. The list of synonyms given in these tables is not exhaustive but is a sample of some of the names which have been applied to the chemical. The CAS Registry Number (RN) is a numerical identifier used in each of the tables for consistent identification. The CAS number is unique and is applied to both chemicals and mixtures and is used universally and is in the format xxx-xx-x, which permits efficient database searching. The Chemical Abstracts Service is an entity within the American Chemical Society, a professional society of chemists headquartered in the United States.

2. Health Hazards

The data on short-term exposure, long-term exposure, routes of exposure and associated symptoms are adapted from the International Chemical Safety Cards (ICSC) series produced by the International Programme on Chemical Safety (IPCS), a cooperative programme of the World Health Organization (WHO), the International Labour Organization (ILO) and the United Nations Environment Programme (UNEP).

The abbreviations used are: CNS = central nervous system; CVS = cardiovascular system; GI = gastrointestinal system; PNS = peripheral nervous system; resp tract = respiratory tract.

The remaining data on target organs and routes of entry and their associated symptoms are taken from the NIOSH Pocket Guide to Chemical Hazards published by the US National Institute for Occupational Safety and Health (1994, NIOSH Publication No. 94-116).

The following abbreviations are used: abdom = abdominal; abnor = abnormal/abnormalities; album = albuminuria; anes = anesthesia; anor = anorexia; anos = anosmia (loss of the sense of smell); appre = apprehension; arrhy = arrhythmias; aspir = aspiration; asphy = asphyxia; BP = blood pressure; breath = breathing; bron = bronchitis; broncopneu = bronchopneumonia; bronspas = bronchospasm; BUN = blood urea nitrogen; [carc] = potential occupational carcinogen; card = cardiac; chol = cholinesterase; cirr = cirrhosis; CNS = central nervous system; conc = concentration; conf = confusion; conj = conjunctivitis; constip = constipation; convuls = convulsions; corn = corneal; CVS = cardiovascular system; cyan = cyanosis; decr = decreased; depress = depressant/depression; derm = dermatitis; diarr = diarrhea; dist = disturbance; dizz = dizziness; drow = drowsiness; dysfunc = dysfunction; dysp = dyspnea (breathing difficulty); emphy = emphysema; eosin = eosinophilia; epilep = epileptiform; epis = epistaxis (nosebleed); equi = equilibrium; eryt = erythema (skin redness); euph = euphoria; fail = failure; fasc = fasiculation; FEV = forced expiratory volume; fib = fibrosis; fibri = fibrillation; ftg = fatigue; func = function; GI = gastrointestinal; gidd = giddiness; halu = hallucinations; head = headache; hema = hematuria (blood in the urine); hemato = hematopoietic; hemog = hemoglobinuria; hemorr = hemorrhage; hyperpig = hyperpigmentation; hypox = hypoxemia (reduced oxygen in the blood); inco = incoordination; incr = increase(d); inebri = inebriation; inflamm = inflammation; inj = injury; insom = insomnia; irreg = irregularity/ irregularities; irrit = irritation; irrty = irritability; jaun = jaundice; kera = keratitis (inflammation of the cornea); lac = lacrimation (discharge of tears);lar = laryngeal; lass = 1assitude (weakness, exhaustion); leth = lethargy (drowsiness or indifference); leucyt = leukocytosis (increased blood leukocytes); leupen = leukopenia (reduced blood leukocytes); li-head = lightheadedness; liq = liquid; local = localized; low-wgt = weight loss; mal = malaise (vague feeling of discomfort); malnut = malnutrition; methemo = methemoglobinemia; monocy = monocytosis (increased blood monocytes); molt = molten; muc memb = mucous membrane; musc = muscle; narco = narcosis; nau = nausea; nec = necrosis; neph = nephritis; ner = nervousness; numb = numbness; opac = opacity; palp = palpitations; para = paralysis; pares = paresthesia; perf = perforation; peri neur = peripheral neuropathy; periorb = periorbital (situated around the eye); phar = pharyngeal; photo = phtophobia (abnormal visual intolerance to light); pneu = penumonia; pneuitis = pneumonitis; PNS = peripheral nervous system; polyneur = polyneuropathy; prot = proteinuria; pulm = pulmonary; RBC = red blood cell; repro = reproductive; resp = respiratory; restless = restlessness; retster = retrosternal (occurring behind the sternum); rhin = rhinorrhea (discharge of thin nasal mucus); salv = salivation; sens = sensitization; sez = seizure; short = shortness; sneez = sneezing; sol = solid; soln = solution; som = somnolence (sleepiness, unnatural drowsiness); subs = substernal (occurring beneath the sternum); sweat = sweating; swell = swelling; sys = system; tacar = tachycardia; tend = tenderness; terato = teratogenic; throb = throbbing; tight = tightness; trachbronch = tracheobronchitis; twitch=twitching; uncon = unconsciousness; vap = vapor; venfib = ventricular fibrillation; vert = vertigo (an illusion of movement); vesic = vesiculation; vis dist = visual disturbance; vomit = vomiting; weak = weakness; wheez=wheezing.

3. Physical and chemical hazards

The data on physical and chemical hazards are adapted from the International Chemical Safety Cards (ICSC) series produced by the International Programme on Chemical Safety (IPCS), a cooperative programme of the World Health Organization (WHO), the International Labour Organization (ILO) and the United Nations Environment Programme (UNEP).

The risk classification data are taken from Recommendations on the Transport of Dangerous Goods, 9th edition, developed by the United Nations Committee of Experts on the Transport of Dangerous Goods and published by the United Nations (9th edition, 1995).

The following codes are used: 1.5 = very insensitive substances which have a mass explosion hazard; 2.1 = flammable gas; 2.3 = toxic gas; 3 = flammable liquid; 4.1 = flammable solid; 4.2 = substance liable to spontaneous combustion; 4.3 = substance which in contact with water emits flammable gases; 5.1 = oxidizing substance; 6.1 = toxic; 7 = radioactive; 8 = corrosive substance.

The Recommendations are addressed to governments and international organizations concerned with the regulation of the transport of dangerous goods. They cover principles of classification and definition of classes, listing of the principal dangerous goods, general packing requirements, testing procedures, marking, labelling or placarding, and transport documents. Special recommendations address particular classes of goods. They do not apply to dangerous goods in bulk which, in most countries, are subject to special regulations. The following UN classes and divisions are frequently found in the chemical tables in this Guide to chemicals and in the chapter Metals: Chemical properties and toxicity:

Class 2—Gases

Division 2.3—Toxic gases: Gases which (a) are known to be so toxic or corrosive to humans as to pose a hazard to health or (b) are presumed to be toxic or corrosive to humans because they have an LC50 value equal to or less than 5,000 ml/m3 (ppm) when tested in accordance with 6.2.3. Gases meeting the above criteria owing to their corrosivity are to be classified as toxic with a subsidiary corrosive risk.

Class 4—Flammable solids; substances liable to spontaneous combustion; substances which in contact with water emit flammable gases

Division 4.2—Substances liable to spontaneous combustion: Substances which are liable to spontaneous heating under normal conditions encountered in transport, or to heating up in contact with air, and being then liable to catch fire.

Division 4.3—Substances which in contact with water emit flammable gases: Substances which, by interaction with water, are liable to become spontaneously flammable or to give off flammable gases in dangerous quantities.

Class 5—Oxidizing substances; organic peroxides

Division 5.1—Oxidizing substances: Substances which, while in themselves not necessarily combustible, may, generally by yielding oxygen, cause, or contribute to, the combustion of other material.

Class 6—Toxic and infectious substances

Division 6.1—Toxic substances: These are substances liable either to cause death or serious injury or to harm human health if swallowed or inhaled or by skin contact.

Class 8—Corrosive substances

These are substances which, by chemical action, will cause severe damage when in contact with living tissue, or, in the case of leakage, will materially damage, or even destroy, other goods or the means of transport; they may also cause other hazards.

UN Codes, identification numbers assigned to hazardous materials in transportation by the United Nations Committee of Experts on the Transport of Dangerous Goods, are used to readily identify hazardous materials in transportation emergencies. Those preceded by “NA” are associated with descriptions not recognized for international shipments, except to and from Canada.

4. Physical and chemical properties

Relative density is measured at 20 °C/4 °C, ambient and water temperature, respectively, unless otherwise specified.

The following abbreviations are found: bp = boiling point; mp = melting point; mw = molecular weight; sol = soluble; sl sol = slightly soluble; v sol = very soluble; misc = miscible; insol = insoluble; pvap = vapour pressure; inflam. limit = inflammability limit (vol-% in the air); ll = lower limit; ul = upper limit ; fl. p = flashpoint; cc = closed cup; oc = open cup; auto ig. p = auto ignition point

ACIDS, INORGANIC

David L. Hinkamp

An inorganic acid is a compound of hydrogen and one or more other element (with the exception of carbon) that dissociates or breaks down to produce hydrogen ions when dissolved in water or other solvents. The resultant solution has certain characteristics such as the ability to neutralize bases, turn litmus paper red and produce specific colour changes with certain other indicators. Inorganic acids are often termed mineral acids. The anhydrous form may be gaseous or solid.

An inorganic anhydride is an oxide of metalloid which can combine with water to form an inorganic acid. It can be produced by synthesis such as: S + O2 → SO2, which can be transformed into an acid by the addition of a water molecule (hydration); or by eliminating water from an acid, such as:

     2HMnO4 → Mn2O7 + H2O

Inorganic anhydrides share in general the biological properties of their acids, since hydration can readily occur in watery biological media.

Uses

Inorganic acids are used as chemical intermediates and catalysts in chemical reactions. They are found in a variety of industries, including metal- and woodworking, textile, dye-stuff, petroleum and photography. In metalworking they are often used as cleaning agents before welding, plating or painting. Sulphamic acid, sulphuric acid and hydrochloric acid are used in electroplating, and perchloric acid is used in metal plating.

Hydrochloric acid, sulphuric acid, perchloric acid and sulphamic acid are widely used in industry. Hydrochloric acid, or hydrogen chloride in aqueous solution, is used for industrial acidizing, for refining ores of tin and tantalum, for converting cornstarch to syrup, and removing scale from boilers and heat-exchange equipment. It is also a tanning agent in the leather industry. Sulphuric acid is used in parchment paper and in various processes including purification of petroleum, refining vegetable oil, carbonization of wool fabrics, extraction of uranium from pitchblende, and iron and steel pickling. Sulphuric acid and perchloric acid are used in the explosives industry. Sulphamic acid is a flame retardant in the wood and textile industries and a bleaching agent and bactericide in the pulp and paper industry. It is also used for chlorine stabilization in swimming pools.

Nitric acid is used in the manufacture of ammonium nitrate for fertilizer and explosives. In addition, it is used in organic synthesis, metallurgy, ore flotation, and for reprocessing spent nuclear fuel.

Hazards

The specific hazards of the industrially important inorganic acids will be found below; however, it should be noted that all these acids have certain dangerous properties in common. Solutions of inorganic acids are not flammable in themselves; however, when they come into contact with certain other chemical substances or combustible materials, a fire or explosion may result. These acids react with certain metals with the liberation of hydrogen, which is a highly flammable and explosive substance when mixed with air or oxygen. They may also act as oxidizing agents and, when in contact with organic or other oxidizable materials, may react destructively and violently.

Health effects. The inorganic acids are corrosive, especially in high concentrations; they will destroy body tissue and cause chemical burns when in contact with the skin and mucous membranes. In particular, the danger of eye accidents is pronounced. Inorganic acid vapours or mists are respiratory tract and mucous membrane irritants, although the degree of irritation depends to a large degree on the concentration; discolouration or erosion of the teeth may also occur in exposed workers. Repeated skin contact may lead to dermatitis. Accidental ingestion of concentrated inorganic acids will result in severe irritation of the throat and stomach, and destruction of the tissue of internal organs, perhaps with fatal outcome, when immediate remedial action is not taken. Certain inorganic acids may also act as systemic poisons.

Safety and Health Measures

Wherever possible, highly corrosive acids should be replaced by acids which present less hazard; it is essential to use only the minimum concentration necessary for the process. Wherever inorganic acids are used, appropriate measures should be instituted concerning storage, handling, waste disposal, ventilation, personal protection and first aid.

Storage. Avoid contact with other acids and combustible or oxidizable materials. Electrical installations should also be of the acid-resistant type.

Storage areas should be separated from other premises, well ventilated, sheltered from sunlight and sources of heat; they should have a cement floor and contain no substances with which an acid might react. Large stocks should be surrounded by kerbs or sills to retain the acid in the event of leakage, and provisions for neutralization should be made. A fire hydrant and a supply of self-contained respiratory protective equipment for emergency or rescue purposes should be provided outside the storage premises. Spillages should be dealt with immediately by hosing down; in the event of a large leakage, personnel should vacate the premises and then, having donned emergency equipment, return to neutralize the acid with water or calcined sand. Electrical equipment should be of the waterproof type and resistant to acid attack. Safety lighting is desirable.

Containers should be kept tightly closed and should be clearly labelled to indicate the contents. Decompression measures should be taken where necessary. Piping, couplings, gaskets and valves should all be made of material resistant to nitric acid. Glass or plastic containers should be adequately protected against impact; they should be kept off the floor to facilitate flushing in the event of leakage. Drums should be stored on cradles or racks and chocked in position. Gas cylinders of gaseous anhydrous acid should be stored upright with the cap in place. Empty and full containers should preferably be stored apart. Maintenance and good housekeeping are essential.

Handling. Wherever possible acids should be pumped through sealed systems to prevent all danger of contact. Wherever individual containers have to be transported or decanted, the appropriate equipment should be employed and only experienced persons allowed to undertake the work. Decanting should be done by means of special syphons, transfer pumps, or drum or carboy tilting cradles and so on. Cylinders of anhydrous acid gas require special discharge valves and connections.

Where acids are mixed with other chemicals or water, workers must be fully aware of any violent or dangerous reaction that may take place. For example, a concentrated acid should be slowly added to water, rather than vice versa, in order to avoid the generation of excessive heat and violent reactions which can cause splashes and skin or eye contact.

Ventilation. Where processes produce acid mists or vapours, such as in electroplating, exhaust ventilation should be installed.

Personal protection. Persons exposed to dangerous splashes of inorganic acids should be required to wear acid-resistant personal protective equipment including hand and arm protection, eye and face protection and aprons, overalls or coats. Provided safe working procedures are adopted, the use of respiratory protective equipment should not be necessary; however, it should be available for emergency use in the event of leakage or spillage.

When workers are required to enter a tank that has contained inorganic acids in order to carry out maintenance or repairs, the tanks should first be purged and all precautions for entry into enclosed spaces, as described elsewhere in the Encyclopaedia, should be taken.

Training. All workers required to handle acids should be instructed about their hazardous properties. Certain work activities, such as those involving enclosed spaces or handling of large quantities of acids, should always be done by two persons, one being ready to come to the other’s aid in case of need.

Sanitation. Personal hygiene is of utmost importance where there is contact with inorganic acids. Adequate washing and sanitary facilities should be provided and workers encouraged to wash thoroughly before meals and at the ends of shifts.

First aid. Essential treatment for inorganic acid contamination of skin or eyes is immediate and copious flushing with running water. Emergency showers and eyewash fountains, baths or bottles should be strategically located. Splashes in the eye should be treated with copious irrigation with water. Contaminated clothing should be removed and other appropriate emergency skin treatment procedures should be in place and personnel trained in their administration. Neutralization of the acid in the affected area with an alkaline solution such as 2 to 3% sodium bicarbonate, or 5% sodium carbonate and 5% sodium hyposulphite, or 10% triethanolamine is a standard procedure.

Persons who have inhaled acid mists should be removed immediately from the contaminated zone and prevented from making any effort. They should be put in the care of a physician immediately. In the event of accidental ingestion, the victim should be given a neutralizing substance, and gastric lavage should be carried out. In general, vomiting should not be induced since this may make the injury more widespread.

Medical supervision. Workers should receive pre-employment and periodic medical examinations. The pre-employment examination should be particularly directed at the detection of chronic respiratory, gastro-intestinal or nervous diseases and any eye and skin diseases. Periodic examinations should take place at frequent intervals and should include a check on the condition of the teeth.

Water pollution. This should be prevented by ensuring that wastewater containing spent acid is not emptied into watercourses or sewage systems until the pH (acidity) has been brought to a level that is between 5.5 and 8.5.

Hydrochloric acid

Anhydrous hydrogen chloride is not corrosive; however, aqueous solutions attack nearly all metals (mercury, silver, gold, platinum, tantalum and certain alloys are exceptions) with release of hydrogen. Hydrochloric acid reacts with sulphides to form chlorides and hydrogen sulphide. It is a very stable compound, but at high temperatures it decomposes into hydrogen and chlorine.

Hazards. The special hazards of hydrochloric acid are its corrosive action on skin and mucous membranes, the formation of hydrogen when it contacts certain metals and metallic hydrides, and its toxicity. Hydrochloric acid will produce burns of the skin and mucous membranes, the severity being determined by the concentration of the solution; this may lead to ulcerations followed by keloid and retactile scarring. Contact with the eyes may produce reduced vision or blindness. Burns on the face may produce serious and disfiguring scars. Frequent contact with aqueous solutions may lead to dermatitis.

The vapours have an irritant effect on the respiratory tract, causing laryngitis, glottal oedema, bronchitis, pulmonary oedema and death. Digestive diseases are frequent and are characterized by dental molecular necrosis in which the teeth lose their shine, turn yellow, become soft and pointed, and then break off.

Safety and health measures. In addition to the general measures described above, the acid should not be stored in the vicinity of flammable or oxidizing substances, such as nitric acid or chlorates, or near metals and metal hydrides which may be attacked by the acid with the formation of hydrogen. (The explosive limits of hydrogen are 4 to 75% by volume in air.) Electrical equipment should be flameproof and protected against the corrosive action of the vapours.

Nitric acid

Nitric acid is highly corrosive and attacks a large number of metals. Reactions between nitric acid and various organic materials are often highly exothermic and explosive, and reactions with metals may produce toxic gases. Nitric acid will cause skin burns, and the vapours are highly irritant to the skin and mucous membranes; inhalation of significant quantities will produce acute poisoning.

Fire and explosion. Nitric acid attacks most substances and all metals except the noble metals (gold, platinum, iridium, thorium, tantalum) and certain alloys. The rate of reaction varies depending on the metal and the concentration of the acid; the gases produced during the reaction include the nitrogen oxides, nitrogen and ammonia, which may have a toxic or asphyxiating effect. When in contact with sodium or potassium, the reaction is violent and dangerous, and nitrogen is released. However, in the case of certain metals, a protective oxide film is formed which prevents further attack. Nitric acid may react explosively with hydrogen sulphide. Nitrates obtained by the action of the acid on various bases are powerful oxidizing agents.

Even in dilute concentrations, nitric acid is a powerful oxidizing material. Solutions of a concentration higher than 45% may cause the spontaneous ignition of organic materials such as turpentine, wood, straw and so on.

Health hazards. Solutions of nitric acid are highly corrosive and will produce lesions of the skin, eyes and mucous membranes, the severity of which will depend on the duration of contact and the acid concentration; the lesions range from irritation to burns and localized necrosis following prolonged contact. Nitric acid mists are also corrosive to the skin, mucous membranes and dental enamel.

Nitric acid vapours will always contain a certain proportion of other gaseous nitrogen compounds (e.g., nitrogen oxides), depending on the concentration of the acid and the type of operation. Inhalation may produce acute poisoning and peracute poisoning. Peracute poisoning is rare and can be fatal. Acute poisoning generally comprises three phases: the first consists of irritation of the upper respiratory tract (burning in the throat, cough, feeling of suffocation) and of the eyes with tearing (lacrimation); the second phase is misleading, since pathological signs are absent for a period of up to several hours; in the third phase, the respiratory disorders reappear and may develop rapidly into acute pulmonary oedema, often with serious outcome.

Accidental ingestion will produce severe damage in the mouth, pharynx, oesophagus and stomach, and may have serious sequelae.

Safety and health measures. Depending on the quantities and concentrations involved, nitric acid should be stored in stainless steel, aluminium or glass containers. Glass carboys or winchesters should be protected by a metal envelope to provide resistance to impacts. However, nitric acid containing any fluorinated compounds should not be stored in glass. Organic materials such as wood, straw, sawdust and so on, should be kept away from operations involving nitric acid. When nitric acid is to be diluted with water, the acid should be poured into the water, and localized heating should be avoided.

Sulphuric acid

Sulphuric acid is a strong acid which, when heated to above 30 °C, gives off vapour and, above 200 °C, emits sulphur trioxide. When cold, it reacts with all metals including platinum; when hot, reactivity is intensified. Dilute sulphuric acid dissolves aluminium, chromium, cobalt, copper, iron, manganese, nickel and zinc, but not lead or mercury. It has a great affinity for water, absorbs atmospheric moisture, and abstracts water from organic materials, causing charring. It decomposes salts of all other acids except silicic acid.

Sulphuric acid is found in the native state in the vicinity of volcanoes, in particular in the volcanic gases.

Hazards. The action of sulphuric acid on the body is that of a powerful caustic and general toxic agent. Introduced into the body in liquid or vapour form, it causes intense irritation and chemical burns of the mucous membranes of the respiratory and digestive tract, the teeth, eyes and skin. On contact with the skin, sulphuric acid causes violent dehydration. It releases heat in sufficient quantities to produce burns that are similar to thermal burns and may be classified accordingly as first, second or third degree. The depth of the lesions depends on the concentration of the acid and the length of contact. Inhalation of vapours produces the following symptoms: nasal secretion, sneezing, a burning feeling in the throat and retrosternal region; these are followed by cough, respiratory distress, sometimes accompanied by spasm of the vocal cords, and a burning sensation in the eyes with lacrimation and conjunctival congestion. High concentrations may cause bloody nasal secretion and sputum, haematemesis, gastritis and so on. Dental lesions are common; they affect mainly the incisors and present as brown staining, enamel striation, caries and rapid and painless destruction of the tooth crown.

Occupational exposures to strong inorganic acid mists, such as sulphuric acid mists, have been classified by the International Agency for Research on Cancer (IARC) as being carcinogenic to humans.

Chemical burns are the injury most commonly encountered in sulphuric acid production workers. Concentrated solutions cause deep burns of mucous membranes and skin; initially the zone of contact with the acid is bleached and turns brown prior to the formation of a clearly defined ulcer on a light red background. These wounds are long in healing and may frequently cause extensive scarring that results in functional inhibition. If burning is sufficiently extensive, the outcome may prove fatal. Repeated skin contact with low concentrations of acid causes skin desiccation and ulceration of the hands, and panaris or chronic purulent inflammation around the nails. Splashes of acid in the eyes may have particularly serious consequences: deep corneal ulceration, kerato-conjunctivitis and palpebral lesions with severe sequelae.

The general toxic action of sulphuric acid causes alkaline depletion of the body (i.e., an acidosis which affects the nervous system and produces agitation, hesitant gait and generalized weakness).

Safety and health measures. The most effective measures are the total enclosure of processes and the mechanization of handling procedures to prevent all personal contact with sulphuric acid. Particular attention should be devoted to acid storage, handling and application procedures, the ventilation and lighting of workplaces, maintenance and good housekeeping, and personal protective equipment. In addition to the general precautions given above, sulphuric acid should not be stored in the vicinity of chromates, chlorates or similar substances in view of the fire and explosion hazard involved.

Fire and explosion. Sulphuric acid and oleum are not flammable per se. However, they react vigorously with numerous substances, especially organic materials, with the release of sufficient heat to produce a fire or explosion; in addition, the hydrogen released during reaction with metals may form an explosive mixture in air.

Catalysts. Where a vanadium catalyst is used in the contact process, workers should be protected against exposure to emissions of ammonium vanadate or vanadium pentoxide, which are employed on a diatomite or silica gel support.

Inorganic acids, tables

Table 104.1 Chemical identification

CHEMICAL

SYNONYMS / UN CODE

CAS-NUMBER

CHEMICAL FORMULA

BORIC ACID

Boracic acid; Orthoboric acid

10043-35-3

B(OH)3

CHLOROSULPHURIC ACID

Chlorosulphonic acid; Monochlorosulphuric acid; Sulphonic acid monochloride; Sulphuric chlorohydrin

UN1754

UN2240

7790-94-5

HClSO3

FLUOROSULPHURIC ACID

Fluorosulphonic acid; Fluosulphonic acid

UN1777

7789-21-1

HFSO3

HYDROCHLORIC ACID

Anhydrous hydrochloric acid; Chlorohydric acid; Hydrochloride; Hydrogen chloride

UN1050

UN1789

UN2186

7647-01-0

HCl

HYDROFLUOBORIC ACID

Borofluoric acid; Fluoboric acid; Hydrogen tetrafluoroborate; Tetrafluoroboric acid

UN1775

16872-11-0

HBF4

NITRIC ACID

Agua fortis; Azotic acid

UN2032

7697-37-2

HNO3

PERCHLORIC ACID

Perchloric acid

UN1802

UN1873

7601-90-3

HClO4

PHOSPHORIC ACID

Orthophosphoric acid

UN1805

7664-38-2

H3PO4

SILICIC ACID

Metasilicic acid; Precipitated silica; Silica gel

7699-41-4

SiH2O3

SULFAMIC ACID

Amidosulphonic acid; Amidosulphuric acid

UN2967

5329-14-6

NH2SO3 H

SULPHURIC ACID

Dihydrogen sulphate

UN1830

UN1832

7664-93-9

H2SO4

Table 104.2 Health hazards

Chemical Name

     Cas-Number

ICSC Short Term Exposure

ICSC Long Term Exposure

ICSC Routes Of Exposure and Symptoms

US NIOSH Target Organs Routes Of Entry

US NIOSH Symptoms

HYDROCHLORIC ACID

     7647-01-0

eyes; skin; resp tract; lungs

lungs; teeth

Inhalation: Corrosive, burning sensation, cough, laboured breathing, shortness of breath, sore throat, symptoms may be delayed

Skin: Corrosive, serious skin burns, pain

Eyes: Corrosive, pain, blurred vision, severe deep burns

resp sys; eyes; skin

inh, ing,(soln),con

Irrit nose, throat, larynx; cough, choking; derm; soln: eye, skin burns; liq: frostbite; in animals: lar spasm; pulm edema

NITRIC ACID

     7697-37-2

  

Inhalation: Corrosive, burning sensation, cough, laboured breathing, unconsciousness, symptoms may be delayed

Skin: Corrosive, serious skin burns, pain, yellow discolouration

Eyes: Corrosive, redness, pain, blurred vision, severe deep burns

Ingestion: Corrosive, abdominal pain, burning sensation, shock

eyes; resp sys; skin; teeth

inh, ing, con

Irrit eyes, skin, muc memb; delayed pulm edema, pneuitis, bron; dental erosion

PHOSPHORIC ACID

     7664-38-2

eyes; skin; resp tract; lungs

 

Inhalation: Burning sensation, cough, laboured breathing, shortness of breath, sore throat, unconsciousness

Skin: Redness, pain, blisters

Eyes: Redness, pain, blurred vision, severe deep burns

Ingestion: Abdominal cramps, burning sensation, confusion, laboured breathing sore throat, unconsciousness, weakness

resp sys; eyes; skin

inh, ing, con

Irrit eyes, skin, upper resp sys; eye, skin burns; derm

SULPHAMIC ACID

     5329-14-6

eyes; skin; resp tract; lungs

    

SULPHURIC ACID

     7664-93-9

eyes; skin; resp tract; lungs

 

Inhalation: Corrosive, burning sensation, cough, laboured breathing, sore throat

Skin: Corrosive, redness, serious skin burns, pain, severe deep burns

Ingestion: Corrosive, abdominal pain, burning sensation, vomiting, collapse

resp sys; eyes; skin; teeth

inh, ing, con

Irrit eyes, skin, nose, throat; pulm edema, bron; emphy; conj; stomatis; dental erosion; trachbronc; eye, skin burns; derm

Table 104.3 Physical & chemical hazards

For UN Class: 1.5 = very insensitive substances which have a mass explosion hazard; 2.1 = flammable gas; 2.3 = toxic gas; 3 = flammable liquid; 4.1 = flammable solid; 4.2 = substance liable to spontaneous combustion; 4.3 = substance which in contact with water emits flammable gases; 5.1 = oxidizing substance; 6.1 = toxic; 7 = radioactive; 8 = corrosive substance.

Chemical Name

CAS-Number

Physical

Chemical

UN Class Or Division / Subsidiary Risks

CHLOROSULPHURIC ACID

7790-94-5

 

 

8

FLUOROSULPHURIC ACID

7789-21-1

 

 

8

HYDROCHLORIC ACID

7647-01-0

The gas is heavier than air

The solution in water is a strong acid, it reacts violently with bases and is corrosive •Reacts violently with oxidants forming toxic gas (chlorine) •On contact with air it emits corrosive fumes (hydrochloric acid) •Attacks many metals forming combustible gas (HYDROGEN)

8

HYDROFLUOBORIC ACID

16872-11-0

 

 

8

NITRIC ACID

7697-37-2

 

The substance decomposes on warming producing nitrogen oxides •The substance is a strong oxidant and reacts violently with combustible and reducing materials, eg, turpentine, charcoal, alcohol •The substance is a strong acid, it reacts violently with bases and is corrosive to metals •Reacts very violently with organic chemicals (eg, acetone, acetic acid, acetic anhydride), causing fire and explosion hazard •Attacks some plastics

8

PERCHLORIC ACID

7601-90-3

 

 

5.1/ 8

PHOSPHORIC ACID

7664-38-2

 

The substance violently polymerizes under the influence of azo compounds, epoxides and other polymerizable compounds •On combustion, forms toxic fumes (phosphorous oxides) •The substance decomposes on contact with metals, alcohols, aldehydes, cyanides, ketones, phenols, esters, sulfides, halogenated organics producing toxic fumes •The substance is a medium strong acid •Attacks metals to liberate flammable hydrogen gas

8

SULPHAMIC ACID

5329-14-6

 

 

8

SULPHURIC ACID

7664-93-9

 

On combustion, forms toxic fumes (sulphur oxides) •The substance is a strong oxidant and reacts violently with combustible and reducing materials •The substance is a strong acid, it reacts violently with bases and is corrosive to most common metals forming a flammable/explosive gas (hydrogen) •Reacts violently with water and organic materials with evolution of heat •Upon heating, irritating or toxic fumes (or gases) (sulphur oxides) are formed

8

Table 104.4 Physical & chemical properties

Chemical Name

CAS-Number

Colour/Form

Boiling Point (°C)

Melting Point (°C)

Molecular Weight (g/mol)

Solubility In Water

Relative Density (water=1)

Relative Vapour Density  (air=1)

Vapour Pressure/ (Kpa)

Inflam. Limits

Flash Point (°C)

Auto Ignition Point (°C)

BORIC ACID

10043-35-3

colourless, transparent crystals or white granules or powder

300

169

61.84

1g/18ml

1.435  @15°C

 

 

 

 

 

CARBONIC ACID

2582-30-1

 

 

 

63.03

sol

 

 

 

 

 

 

CHLOROSULPHURIC ACID

7790-94-5

colourless or slightly yellow liquid

151-152  @755mmHg

-80

116.53

 

1.753

4.02

1mmHg  @32°C

 

 

 

FLUOROSULPHURIC ACID

7789-21-1

colourless liquid; reddish-brown colour with acetone

163

-89

100.07

 

1.726  @25°C/4°C

 

 

 

 

 

HYDROCHLORIC ACID

7647-01-0

colourless liquid

-85

-114

36.46

82.3g/100ml

1.05  @15°C/4°C

1.3

 

 

 

 

HYDROFLUOBORIC ACID

16872-11-0

colourless liquid

130

 

87.82

misc

1.84

 

 

 

 

 

NITRIC ACID

7697-37-2

transparent colourless or yellowish liquid

83

-42

63.01

sol

1.5027  @25°C/4°C

2-3

6.4

 

 

 

PERCHLORIC ACID

7601-90-3

colourless, oily liquid

19  @11mmHg

-112

100.47

misc

1.768  @22°C

 

 

 

 

 

PHOSPHORIC ACID

7664-38-2

unstable orthorhombic crystals or clear syrupy liquid; at 20 deg C, the 50 and 75% strengths are mobile liquids, the 85% is of a syrupy consistency, while the 100% acid is in the form of crystals; viscous, colourless, odorless liquid

213

42.4

98.00

v sol

 

3.4

4.0

 

 

 

SILICIC ACID

7699-41-4

jelly-like precipitate obtained when sodium silicate solution is acified during drying jelly is converted to a white amorphous powder.

 

 

 

 

 

 

 

 

 

 

SULPHAMIC ACID

5329-14-6

orthorhombic crystals; white crystalline solid

 

205

97.10

sol

2.15

 

 

 

 

 

SULPHURIC ACID

7664-93-9

clear, colourless, oily liquid when pure but brownish in hue when impure

290

10.4

98.08

sol

1.841

3.4

0.13

 

 

 

ACIDS AND ANHYDRIDES, ORGANIC

Organic acids and their derivatives cover a wide range of substances. They are used in nearly every type of chemical manufacture. Because of the variety in the chemical structure of the members of the organic acid group, several types of toxic effects may occur. These compounds have a primary irritant effect, the degree determined in part by acid dissociation and water solubility. Some may cause severe tissue damage similar to that seen with strong mineral acids. Sensitization may also occur, but is more common with the anhydrides than the acids.

For the purpose of this article, organic acids may be divided into saturated monocarboxylic and unsaturated monocarboxylic acids, aliphatic dicarboxylic acids, halogenated acetic acids, miscellaneous aliphatic monocarboxylic acids and aromatic carboxylic acids. Many carboxylic acids are of importance because of their use in food, beverages, drugs and a range of manufacturing processes. The following are among the most common: adipic acid, azelaic acid, fumaric acid, itaconic acid, maleic acid, malic acid, malonic acid, oxalic acid, pimelic acid, sebacic acid, succinic acid, tartaric acid and thiomalic acid.

The long-chain saturated monocarboxylic acids are the fatty acids and are in the main derived from natural sources. Synthetic fatty acids may also be manufactured by air oxidation of paraffins (aliphatic hydrocarbons) using metal catalysts. They are also produced by the oxidation of alcohols with caustic soda.

Uses

Organic acids are employed in the plastics, tanning, textile, paper, metal, pharmaceutical, food, beverage and cosmetics industries. Organic acids are also found in perfumes, herbicides, dyes, lubricants and cleaners.

Formic acid and acetic acid are the major industrial chemicals in the group of saturated monocarboxylic acids. Formic acid is primarily used in the textile and leather industries. It acts as a dye-exhausting agent for a number of natural and synthetic fibres and as a reducing agent in chrome dyeing. Formic acid is used as a deliming agent and a neutralizer in the leather industry, and as a coagulant for rubber latex. It also finds use in the manufacture of fumigants and insecticides. Acetic acid serves as a chemical intermediate, a deliming agent during leather tanning, a solvent, and an oil-well acidizer. In addition, it is an additive for various foods and glazes as well as a catalyst and a finishing agent in the dye-stuff and textile industries.

Weak concentrations of acetic acid (vinegar contains about 4 to 6%) are produced by aerobic fermentation (Acetobacter) of alcohol solutions. Acetic acid is one of the most widely used organic acids. It is employed in the production of cellulose acetate, vinyl acetate, inorganic acetates, organic acetates and acetic anhydride. Acetic acid itself is used in the dyeing industry, pharmaceutical industry, the canning and food preserving industry and pigment production.

Chloroacetic acid is used in the pharmaceutical, dye-stuffs and chemical industries as a chemical intermediate. Salicylic acid acts as another chemical intermediate used in the synthesis of aspirin and in the rubber and dye-stuffs industries. Benzoic acid, nonanoic acid, ascorbic acid and oleic acid (9-octadecenoic acid) are other useful compounds found in the food, beverage and pharmaceutical industries.

Palmitic acid and stearic acid have a wide application in soaps, cosmetics, detergents, lubricants, protective coatings and intermediate chemicals. Propionic acid is used in organic synthesis. It is also a mould inhibitor and a food preservative. Acrylic acid, methacrylic acid and crotonic acid are employed in the manufacture of resins and plasticizers in the paper, plastics and paint industries. In addition, acrylic acid is an ingredient in floor-polish formulations. Crotonic acid finds use in the manufacture of softening agents for synthetic rubber. Lactic acid, butyric acid and gallic acid are employed in the leather-tanning industry. Lactic acid is also used in adhesives, plastics and textiles. It serves as a food acidulant and as an agent in oil-well acidizing. Glycolic acid is used in the leather, textile, electroplating, adhesives and metal-cleaning industries.

The dicarboxylic acids (succinic acid, maleic acid, fumaric acid, adipic acid) and the tricarboxylic acid (citric acid) are useful in the food, beverage and pharmaceutical industries. Succinic acid is also used in the manufacture of lacquers and dyes. Maleic acid is used in the manufacture of synthetic resins and in organic syntheses. Maleic acid acts as a preservative for oils and fats; its salts are used in the dyeing of cotton, wool and silk. Fumaric acid is used in polyesters and alkyd resins, plastics surface coatings, food acidulants, inks and organic syntheses. The majority of adipic acid is utilized for nylon production, while smaller quantities are used in plasticizers, synthetic lubricants, polyurethanes and food acidulants.

Oxalic acid is a scouring agent in textile finishing, stripping and cleaning, and a component of household formulations for metal cleaning. It also finds use in the paper, photography and rubber industries. Oxalic acid is used in calico printing and dyeing, bleaching straw hats and leather, and cleaning wood. Aminoacetic acid is used as a buffering agent and in syntheses. Peracetic acid is used as a bleach, catalyst and oxidant.

Commercial naphthenic acid is usually a dark-coloured malodourous mixture of naphthenic acids. Naphthenic acids are derived from cycloparaffins in petroleum, probably by oxidation. Commercial acids are usually viscous liquid mixtures and may be separated as low- and high-boiling fractions. The molecular weights vary from 180 to 350. They are used principally in the preparation of paint dryers, where the metallic salts, such as lead, cobalt and manganese, act as oxidizing agents. Metallic naphthenic acids are used as catalysts in chemical processes. An industrial advantage is their solubility in oil.

Organic acid anhydrides

An anhydride is defined as an oxide which, when combined with water, gives an acid or a base. Acid anhydrides are derived from the removal of water from two molecules of the corresponding acid, such as:

     2HMnO4 → Mn2O7 + H2O

Industrially, the most important anhydrides are acetic and phthalic. Acetic anhydride is used in the plastics, explosives, perfume, food, textile and pharmaceutical industries, and as a chemical intermediate. Phthalic anhydride serves as a plasticizer in vinyl chloride polymerization. It is also used for the production of saturated and unsaturated polyester resins, benzoic acid, pesticides, and certain essences and perfumes. Phthalic anhydride is employed in the production of phthalocyanine dyes and alkyd resins used in paints and lacquers. Maleic anhydride has a significant number of applications as well.

Propionic anhydride is used in the manufacture of perfumes, alkyd resins, drugs and dyes, while maleic anhydride, trimellitic anhydride and acetic anhydride find use in the plastics industry. Trimellitic anhyide (TMA) is also utilized in the dye-stuff, printing and automotove upholstery industries. It is used as a curing agent for epoxy and other resins, in vinyl plasticizers, paints, coatings, dyes, pigments and a wide variety of other manufactured products. Some of these products find applications in high-temperature plastics, wire insulation and gaskets.

Hazards

Monocarboxylic acids

The low-molecular-weight monocarboxylic acids are primary irritants and produce severe damage to tissues. Strict precautions are necessary in handling; suitable protective equipment should be available and any skin or eye splashes irrigated with copious amounts of water. The most important acids of this group are acetic acid and formic acid.

The long-chain saturated monocarboxylic acids (the fatty acids) are non-irritant and of a very low order of toxicity. They appear to pose few problems in industrial use.

Unsaturated monocarboxylic acids are highly reactive substances and are recognized as severe irritants of the skin, eye and respiratory tract in concentrated solution. Hazards appear to be related to acute rather than cumulative exposures.

The majority of these acids appear to present minimal hazard from low-level chronic exposure, and many are normally present in human metabolic processes. Primary irritant effects are present with a number of these acids, however, particularly in concentrated solutions or as dusts. Sensitization is rare. As the materials are all solids at room temperature, contact is usually in the form of dust or crystals.

Acetic acid. Acetic acid vapour may form explosive mixtures with air and constitute a fire hazard either directly or by the release of hydrogen. Glacial acetic acid or acetic acid in concentrated form are primary skin irritants and will produce erythema (reddening), chemical burns and blisters. In cases of accidental ingestion, severe ulceronecrotic lesions of the upper digestive tract have been observed with bloody vomiting, diarrhoea, shock and haemoglobinuria followed by urinary disorders (anuria and uraemia).

The vapours have an irritant action on exposed mucous membranes, particularly the conjunctivae, rhinopharynx and upper respiratory tract. Acute bronchopneumonia developed in a woman who was made to inhale acetic acid vapours following a fainting attack.

Workers exposed for a number of years to concentrations of up to 200 ppm have been found to suffer from palpebral oedema with hypertrophy of the lymph nodes, conjunctival hyperaemia, chronic pharyngitis, chronic catarrhal bronchitis and, in some cases, asthmatic bronchitis and traces of erosion on the vestibular surface of the teeth (incisors and canines).

The extent of acclimatization is remarkable; however, such acclimatization does not mean that toxic effects will not also occur. Following repeated exposure, for example, workers may complain of digestive disorders with pyrosis and constipation. The skin on the palms of the hands is subject to the greatest exposure and becomes dry, cracked and hyperkeratotic, and any small cuts and abrasions are slow to heal.

Formic acid. The principal hazard is that of severe primary damage to the skin, eye or mucosal surface. Sensitization is rare, but may occur in a person previously sensitized to formaldehyde. Accidental injury in humans is the same as for other relatively strong acids. No delayed or chronic effects have been noted. Formic acid is a flammable liquid, and its vapour forms flammable and explosive mixtures with air.

Propionic acid in solution has corrosive properties towards several metals. It is irritant to eye, respiratory system and skin. The same precautions recommended for exposure to formic acid are applicable, taking into account the lower flashpoint of propionic acid.

Maleic acid is a strong acid and produces marked irritation of the skin and mucous membranes. Severe effects, particularly in the eye, can result from concentrations as low as 5%. There are no reports of cumulative toxic effects in humans. The hazard in industry is of primary irritation of exposed surfaces, and this should be averted where necessary by the provision of appropriate personal protective equipment, generally in the form of impermeable gloves or gauntlets.

Fumaric acid is a relatively weak acid and has a low solubility in water. It is a normal metabolite and is less toxic orally than tartaric acid. It is a mild irritant of skin and mucous membranes, and no problems of industrial handling are known.

Adipic acid is non-irritant and of very low toxicity when ingested.

Halogenated acetic acids

The halogenated acetic acids are highly reactive. They include chloroacetic acid, dichloroacetic acid (DCA), trichloroacetic acid (TCA), bromoacetic acid, iodoacetic acid, fluoroacetic acid and trifluoroacetic acid (TFA).

The halogenated acetic acids cause severe damage to the skin and mucous membranes and, when ingested, may interfere with essential enzyme systems in the body. Strict precautions are necessary for their handling. They should be prepared and used in enclosed plant, the openings in which should be limited to the necessities of manipulation. Exhaust ventilation should be applied to the enclosure to ensure that fumes or dust do not escape through the limited openings. Personal protective equipment should be worn by persons engaged in the operations, and eye protective equipment and respiratory protective equipment should be available for use when necessary.

Fluoroacetic acid. Di- and trifluoroacetic acids have a lower level of toxicity than monofluoroacetic acid (fluoroacetic acid). Monofluoroacetic acid and its compounds are stable, highly toxic and insidious. At least four biological plants in South Africa and Australia owe their toxicity to this acid (Dichapetalum cymosum, Acacia georginae, Palicourea marcgravii), and recently more than 30 species of Gastrolobium and Oxylobrium in Western Australia have been found to contain various amounts of fluoroacetate.

The biological mechanism responsible for the symptoms of fluoroacetate poisoning involves the “lethal synthesis” of fluorocitric acid, which in turn blocks the tricarboxylic acid cycle by inhibiting the enzyme aconitase. The resultant deprivation of energy by stopping of the Krebs cycle is followed by cellular dysfunction and death. It is impossible to be specific about the toxic dose of fluoroacetic acid for humans; a likely range lies between 2 and 10 mg/kg; but several related fluoroacetates are even more toxic than this. A drop or two of the poison by inhalation, ingestion and absorption through skin cuts and abrasion or undamaged skin can be fatal.

From a study of hospital case histories, it is apparent that the major toxic effects of fluoroacetates in humans involve the central nervous system and cardiovascular system. Severe epileptiform convulsions alternate with coma and depression; death may result from asphyxia during a convulsion or from respiratory failure. The most prominent features, however, are cardiac irregularities, notably ventricular fibrillation and sudden cardiac arrest. These symptoms (which are indistinguishable from those frequently encountered clinically) are usually preceded by an initial latent period of up to 6 h characterized by nausea, vomiting, excessive salivation, numbness, tingling sensations, epigastric pain and mental apprehension; other signs and symptoms which may develop subsequently include muscular twitching, low blood pressure and blurred vision.

Chloroacetic acid. This material is a highly reactive chemical and should be handled with care. Gloves, goggles, rubber boots and impervious overalls are mandatory when workers are in contact with concentrated solutions.

Other acids

Glycolic acid is stronger than acetic acid and produces very severe chemical burns of the skin and eyes. No cumulative effects are known, and it is believed to be metabolized to glycine. Strict precautions are necessary for its handling. These are similar to those required for acetic acid. Concentrated solutions can cause burns of the skin and eye. No cumulative effects are known. Personal protective equipment should be worn by persons handling concentrated solutions of this acid.

Sorbic acid is used as a fungicide in foods. It is a primary irritant of the skin, and individuals may develop sensitivities to it. For these reasons contact with the skin should be avoided.

Salicylic acid is a strong irritant when in contact with skin or mucous membranes. Strict precautions are necessary for plant operatives.

Anhydrides

Acid anhydrides have higher boiling points than the corresponding acids. Their physiological effects generally resemble those of the corresponding acids, but they are more potent eye irritants in the vapour phase, and may produce chronic conjunctivitis. They are slowly hydrolyzed on contact with body tissues and may occasionally cause sensitization. Adequate ventilation should be provided and suitable personal protective equipment should be worn. In certain circumstances, particularly those associated with maintenance work, suitable eye protection equipment and respiratory protective equipment are necessary.

There have been reports of conjunctivitis, bloody nasal excreta, atrophy of the nasal mucosa, hoarseness, cough and bronchitis in workers employed in the production of phthalic acid and anhydride. It has been recognized that phthalic anhydride causes bronchial asthma, and skin sensitization has been reported following prolonged exposure to phthalic anhydride; the lesion is usually an allergic dermatitis. A specific IgE to phthalic anhydride has also been identified.

Phthalic anhydride is flammable and constitutes a moderate fire hazard. Its toxicity is comparatively low in relation to other industrial acid anhydrides, but it acts as a skin, eye and upper respiratory tract irritant. Since phthalic anhydride has no effect on dry skin, but burns wet skin, it is probable that the actual irritant is phthalic acid, which is formed on contact with water.

Phthalic anhydride must be stored in a cool, well-ventilated place away from open flames and oxidizing substances. Good local and general ventilation are required where it is handled. In many processes phthalic anhydride is used not as flakes but as a liquid. When so used, it is brought to the plant in tanks and directly pumped into the pipe system, preventing contact as well as contamination of the air with dust. This has led to the complete disappearance of manifestations of irritations among the workers in such plants. However, vapours liberated from liquid phthalic anhydride are as irritating as the flakes; care must, therefore, be taken to avoid any leakage from the pipe system. In case of spillage or contact with the skin, the latter should be washed immediately and repeatedly with water.

Workers who are handling phthalic derivatives must be under medical supervision. Special attention should be paid to asthma-like symptoms and skin sensitization. If any such symptoms are noticed, the worker should be moved to another job. Skin contact is to be avoided under all circumstances. Suitable clothing, such as rubber hand protection, is recommended. Pre-employment examinations are necessary to ensure that persons with bronchial asthma, eczema or other allergic diseases are not exposed to phthalic anhydride.

Acetic anhydride. When exposed to heat, acetic anhydride can emit toxic fumes, and its vapours can explode in the presence of flame. It can react violently with strong acids and oxidizers such as sulphuric acid, nitric acid, hydrochloric acid, permanganates, chromium trioxide and hydrogen peroxide, as well as with soda.

Acetic anhydride is a strong irritant and has corrosive properties on contact with eyes, usually with delayed action; contact is followed by lacrimation, photophobia, conjunctivitis and corneal oedema. Inhalation can cause nasopharyngeal and upper respiratory tract irritation, with burning sensations, cough and dyspnoea; prolonged exposure may lead to pulmonary oedema. Ingestion causes pain, nausea and vomiting. Dermatitis can result from prolonged skin exposure.

When contacts are possible, protective clothing and goggles are recommended and eyewash and shower facilities should be available. Chemical cartridge respirators are appropriate for protection against concentrations up to 250 ppm; supplied air respirators with a full eyepiece are recommended for concentrations of 1,000 ppm; self-contained breathing apparatus is necessary in case of fire.

Butyric anhydride is manufactured by catalytic hydrogenation of crotonic acid. Butyric anhydride and propionic anhydride present hazards similar to those of the acetic anhydride.

Maleic anhydride can produce severe eye and skin burns. These may be produced either by solution of maleic anhydride or by flakes of the material in the manufacturing process coming into contact with moist skin. Skin sensitization has occurred. Strict precautions should be taken to prevent contact of the solution with skin or eyes. Suitable goggles and other protective clothing must be worn by plant operatives; ready access to eye irrigation solution bottles is essential. When suspended in air in a finely divided condition, maleic anhydride is capable of forming explosive mixtures with the air. Condensers in which the sublimed material settles in the form of fine crystals should be situated in a safe position outside an occupied room.

Trimellitic anhydride has been reported to have caused pulmonary oedema in workers after severe acute exposure, and airways sensitization after exposure periods of weeks to years, with rhinitis and/or asthma. Several incidents involving the occupational effects of exposure to TMA have been reported. Multiple inhalation exposures to an epoxy resin containing TMA being sprayed on heated pipes was reported to have caused pulmonary oedema in two workers. Exposure levels were not reported but there was no report of upper respiratory tract irritation while the exposures were being experienced, indicating that a hypersensitive reaction might have been involved.

In another report, 14 workers involved in the synthesis of TMA were observed to have respiratory symptoms resulting from sensitization to TMA. In this study three separate responses were noted. The first, rhinitis and/or asthma, developed over an exposure duration of weeks to years. Once sensitized, exposed workers exhibited symptoms immediately after exposure to TMA, which ceased when the exposure was stopped. A second response, also involving sensitization, produced delayed symptoms (cough, wheezing and laboured breathing) 4 to 8 hours after exposure had ceased. The third syndrome was an irritant effect following initial high exposures.

One study of adverse health effects, which also involved measurements of air concentrations of TMA, was conducted by the US National Institute for Occupational Safety and Health (NIOSH). Thirteen workers involved in the manufacture of an epoxy paint had complaints of eye, skin, nose and throat irritation, shortness of breath, wheezing, coughing, heartburn, nausea and headache. Occupational airborne exposure levels averaged 1.5 mg/m3 TMA (range from “none detected” to 4.0 mg/m3) during processing operations and 2.8 mg/m3 TMA (range from “none detected” to 7.5 mg/m3) during decontamination procedures.

Experimental studies with rats have demonstrated intra-alveolar haemorrhage with subacute exposures to TMA at 0.08 mg/m3. The vapour pressure at 20 °C (4 × 10-6 mm Hg) corresponds to a concentration slightly more than 0.04 mg/m3.

Oxalic acid and its derivatives. Oxalic acid is a strong acid which, in solid form or in concentrated solutions, can cause burns of the skin, eyes or mucous membranes; oxalic acid concentrations as low as 5 to 10% are irritating if exposure is prolonged. Human fatalities have been recorded following ingestion of as little as 5 g of oxalic acid. The symptoms appear rapidly and are marked by a shock-like state, collapse and convulsive seizures. Such cases may show marked renal damage with precipitation of calcium oxalate in the renal tubules. The convulsive seizures are thought to be the result of hypocalcaemia. Chronic skin exposure to solutions of oxalic acid or potassium oxalate have been reported to have caused a localized pain and cyanosis in the fingers or even gangrenous changes. This is apparently due to a localized absorption of the oxalic acid and a resultant arteritis. Chronic systemic injury from inhalation of oxalic acid dust appears to be very rare, although the literature describes the case of a man who had been exposed to hot oxalic acid vapours (probably containing an aerosol of oxalic acid) with generalized symptoms of weight loss and chronic inflammation of the upper respiratory tract. Because of the strongly acid nature of the dust of oxalic acid, exposure must be carefully controlled and work area concentrations held within acceptable health limits.

Diethyl oxalate is slightly soluble in water; miscible in all proportions in many organic solvents; a colourless, unstable, oily liquid. It is produced by esterification of ethyl alcohol and oxalic acid. It is used, as are other liquid oxalate esters, as a solvent for many natural and synthetic resins.

The symptoms in rats following ingestion of large quantities of diethyl oxalate are those of respiratory disturbances and muscle twitchings. Large quantities of oxalate deposits were found in the renal tubules of a rat after an oral dose of 400 mg/kg. It has been reported that workers exposed to 0.76 mg/l of diethyl oxalate over a period of several months developed complaints of weakness, headache and nausea together with some slight alterations in the blood count. Because of the very low vapour pressure of this substance at room temperature, the reported air concentrations may have been in error. There was also some use of diamyl acetate and diethyl carbonate in this operation.

Safety and Health Measures

All acids should be stored away from all sources of ignition and oxidizing substances. Storage areas should be well ventilated to prevent the accumulation of dangerous concentrations. Containers should be of stainless steel or glass. In the event of leakage or spillage, acetic acid should be neutralized by application of alkaline solutions. Eyewash fountains and emergency showers should be installed for dealing with cases of skin or eye contact. Marking and labelling of containers is essential; for all forms of transport, acetic acid is classified as a dangerous substance.

To prevent damage to the respiratory system and mucous membranes, the atmospheric concentration of organic acids and anhydrides with high vapour pressure should be kept below maximum permissible levels using standard industrial hygiene practices such as local exhaust ventilation and general ventilation, backed up by periodic determination of atmospheric acetic acid concentrations. Detection and analysis, in the absence of other acid vapours, is by means of bubbling in an alkaline solution and determination of residual alkali; in the presence of other acids, fractional distillation used to be necessary; however, a gas chromatographic method is now available for determination in air or water. Dust exposures should be minimized as well.

Persons working with the pure acid or concentrated solutions should wear protective clothing, eye and face protection, hand and arm protection and respiratory protective equipment. Adequate sanitary facilities should be provided and good personal hygiene encouraged.

Organic acids and anhydrides tables

Table 104.5 Chemical identification

CHEMICAL

synonyms

un code

CAS-number

CHEMICAL FORMULA

ACETIC ACID

Ethanoic acid; Ethylic acid; Methanecarboxylic acid

UN2789

UN2790

64-19-7

ACETIC ANHYDRIDE

Acetanhydride; Acetic oxide; Acetyl anhydride; Acetyl ether; Acetyl oxide; Ethanoic anhydrate

UN1715

108-24-7

ACETYLSALICYLIC ACID

Acetosalic acid; o-Acetoxybenzoic acid; 2-Acetoxybenzoic acid; Salicylic acid, acetate; Aspirin

50-78-2

ACRYLIC ACID

Ethylenecarboxylic acid; Propene acid; Propenoic acid

UN2218

79-10-7

ADIPIC ACID

Adipinic acid; 1,4-Butanedicarboxylic acid; Hexanedioic acid; 1,6-Hexanedioic acid

124-04-9

L-ASCORBIC ACID

3-Keto-l-gulofuranolactone; L-3-Ketothreohexuronic acid lactone; Vitamin C

50-81-7

BENZOIC ACID

Benzenecarboxylic acid; Benzeneformic acid; Benzenemethanoic acid; Benzoate; Phenyl carboxylic acid; Phenylformic acid

65-85-0

BUTYRIC ACID

Butanic acid; Butanoic acid; n-Butyric acid; Butyric acid; Ethylacetic acid; 1-Propanecarboxylic acid; Propylformic acid

UN2820

107-92-6

n-CAPROIC ACID

Butylacetic acid; Capronic acid; n-Hexanoic acid; N-Hexoic acid; Pentanecarboxylic acid; Pentiformic acid; Pentylformic acid

UN2829

142-62-1

CHLORENDIC ACID

1,4,5,6,7,7-Hexachloro-5-norbornene-2,3-dicarboxylic acid; Hexachloro-endo-Methylenetetrahydrophthalic acid

115-28-6

CHLOROACETIC ACID

Monochloroacetic acid; Monochloroethanoic acid

UN1750

UN1751

79-11-8

o-CHLOROBENZOIC ACID

2-CBA; 2-Chlorobenzoic acid

118-91-2

m-CHLOROBENZOIC ACID

3-Chlorobenzoic acid

535-80-8

p-CHLOROBENZOIC ACID

p-Carboxychlorobenzene; 4-Chlorobenzoic acid; Chlorodracylic acid

74-11-3

2-CHLOROPROPIONIC ACID

α-Chloropropionic acid

UN2511

598-78-7

4-CHLORO-o-TOLOXYACETIC ACID

4-Chloro-o-cresoxyacetic acid; (4-Chloro-2-methylphenoxy)acetic acid;

94-74-6

CITRIC ACID

Citro; 2-hydroxy-1,2,3-Propanetricarboxylic acid; β-Hydroxytricarballylic acid

77-92-9

CITRIC ACID HYDRATE

1,2,3-Propanetricarboxylic acid, 2-Hydroxy-, monohydrate

5949-29-1

CROTONIC ACID

α-Butenoic acid; β-Methylacrylic acid; 3-Methylacrylic acid

UN2823

3724-65-0

DICHLORACETIC ACID

Bichloracetic acid; 2,2-Dichloroacetic acid; Dichloroethanoic acid

UN1764

79-43-6

2,4-DICHLORPHENOXYACETIC ACID

2,4-D; Dichlorophenoxyacetic acid

94-75-7

2-ETHYLHEXOIC ACID

Butylethylacetic acid; α-Ethylcaproic acid; 2-Ethylhexanoic acid;

149-57-5

FLUOROACETIC ACID

Pymonic acid; Fluoroacetate; Fluoroethanoic acid; Monofluoroacetate; Monofluoroacetic acid

UN2642

144-49-0

FORMIC ACID

Aminic acid; Formylic acid; Hydrogen carboxylic acid; Methanoic acid

UN1779

64-18-6

FUMARIC ACID

trans-Butenedioic acid; trans-1,2-Ethylenedicarboxylic acid; 1,2-Ethylenedicarboxylic acid

110-17-8

GALLIC ACID

3,4,5-Trihydroxybenzoic acid

149-91-7

GLYCOLIC ACID

Hydroxyacetic acid; Hydroxyethanoic acid

79-14-1

HEPTANOIC ACID

n-Heptoic acid; Heptylic acid; 1-Hexanecarboxylic acid; Oenanthic acid; Oenanthylic acid

111-14-8

ISOBUTYRIC ACID

Dimethylacetic acid; Isopropylformic acid; 2-Methylpropanoic acid; 2-Methylpropionic acid

UN2529

79-31-2

ISOPHTHALIC ACID

Benzene-1,3-dicarboxylic acid; m-Benzenedicarboxylic acid; m-Phthalic acid

121-91-5

LAURIC ACID

Dodecanoic acid; Dodecoic acid; Duodecylic acid; Laurostearic acid; 1-Undecanecarboxylic acid

143-07-7

MALEIC ACID

cis-Butenedioic acid; cis-1,2-Ethylenedicarboxylic acid; 1,2-Ethylenedicarboxylic acid; Maleinic acid; Malenic acid; Toxilic acid

110-16-7

MALEIC ANHYDRIDE

cis-Butenedioic anhydride; 2,5-Furandione; Maleic acid anhydride; Toxilic anhydride

UN2215

108-31-6

MALONIC ACID

Carboxyacetic acid; Dicarboxymethane; Methanedicarboxylic acid; Propanedioic acid

141-82-2

MANDELIC ACID

α-Hydroxyphenylacetic acid; α-Hydroxy-α-toluic acid; Paramandelic acid; Phenylglycolic acid; Phenylhydroxyacetic acid

90-64-2

METHACRYLIC ACID

Methacrylic acid; 2-Methylpropenoic acid

UN2531

79-41-4

NONANOIC ACID

n-Nonylic acid; 1-Octanecarboxylic acid; Pelargonic acid

112-05-0

9-OCTADECENOIC ACID

cis-9-Octadecenoic acid; 9,10-Octadecenoic acid; Oleic acid; Oleinic acid

112-80-1

OXALIC ACID

Ethanedioic acid; Ethanedionic acid

144-62-7

PALMITIC ACID

Cetylic acid; Hexadecanoic acid; n-hexadecoic acid; Hexadecylic acid; 1-Pentadecanecarboxylic acid

57-10-3

PHTHALIC ACID

Benzene-1,2-dicarboxylic acid; o-benzenedicarboxylic acid; 1,2-Benzenedicarboxylic acid; o-Dicarboxybenzene; o-Phthalic acid

88-99-3

PHTHALIC ANHYDRIDE

1,2-Benzenedicarboxylic acid anhydride; 1,3-Dioxophthalan; 1,3-Isobenzofurandione; Phthalandione; 1,3-Phthalandione; Phthalic acid anhydride

UN2214

85-44-9

PIVALIC ACID

2,2-Dimethylpropanoic acid; &alpha,α-Dimethylpropionic acid; 2,2-Dimethylpropionic acid; Neopentanoic acid; tert-Pentanoic acid; Propanoic acid; Trimethylacetic acid

75-98-9

PROPIONIC ACID

Carboxyethane; Ethanecarboxylic acid; Ethylformic acid; Metacetonic acid; Methyl acetic acid; Propanoic acid

UN1848

79-09-4

PROPIONIC ANHYDRIDE

Methylacetic anhydride; Propanoic anhydride; Propionic acid anhydride; Propionyl oxide

UN2496

123-62-6

p-tert-BUTYL BENZOIC ACID

p-TBBA

98-73-7

p-TOLUENESULPHONIC ACID

p-Methylbenzenesulfonic acid; 4-Methylbenzenesulfonic acid; p-Methylphenylsulfonic acid; Toluenesulfonic acid; 4-Toluenesulfonic acid

104-15-4

SALICYLIC ACID

o-Hydroxybenzoic acid; 2-Hydroxybenzoic acid; Orthohydroxybenzoic acid

69-72-7

STEARIC ACID

Cetylacetic acid; 1-Heptadecanecarboxylic acid; Octadecanoic acid

57-11-4

SUCCINIC ACID

butanedioic acid; 1,2-Ethanedicarboxylic acid; Ethylenesuccinic acid

110-15-6

SULPHANILIC-ACID

p-Aminobenzenesulphonic acid; 4-Aminobenzenesulphonic acid; p-Aminophenylsulphonic acid; Aniline-p-sulphonic acid; Aniline-4-sulphonic acid

121-57-3

TARTARIC ACID

2,3-Dihydrosuccinic acid; 2,3-Dihydroxybutanedioic acid; Threaric acid

87-69-4

TEREPHTHALIC ACID

p-Benzenedicarboxylic acid; 1,4-Benzenedicarboxylic acid

100-21-0

TRICHLORACETIC ACID

TCA

UN1839

UN2564

76-03-9

TRICHLOROPHENOXYACETIC ACID

2,4,5-T

93-76-5

TRIFLUOROACETIC ACID

Perfluoroacetic acid; Trifluoroethanoic acid; TFA

UN2699

76-05-1

TRIMELLIC ACID ANHYDRIDE

4-Carboxyphthalic anhydride; 1,3-Dioxo-5-Phthalancarboxylic acid; 5-Phthalanacarboxylic acid; 1,2,4-Benzenetricarboxylic anhydride

552-30-7

VALERIC ACID

Butanecarboxylic acid; 1-Butanecarboxylic acid; Pentanoic acid; Propylacetic acid

109-52-4

Table 104.6 Health hazards

CHEMICAL NAME

     CAS-NUMBER

ICSC SHORT-TERM EXPOSURE

ICSC LONG-TERM EXPOSURE

ICSC ROUTES OF EXPOSURE AND SYMPTOMS

US NIOSH TARGET ORGANS & ROUTES OF ENTRY

US NIOSH SYMPTOMS

ACETIC ACID

     64-19-7

eyes; skin; resp tract; lungs

skin

Inhalation: sore throat, cough, shortness of breath, laboured breathing, symptoms may be delayed

Skin: redness, serious skin burns, pain

Eyes: pain, redness, blurred vision, severe deep burns

Ingestion: abdominal pain, burning sensation, diarrhoea, sore throat, vomiting

Resp sys; skin; eyes; teeth

Inh; con

Irrit eyes, nose, throat; eye, skin burns; derm; conj; cough; CNS depres; delayed pulm edema; in animals: kidney, repro, terato effects

ACETIC ANHYDRIDE

     108-24-7

eyes; skin; resp tract

skin

Inhalation: corrosive, cough, laboured breathing, shortness of breath, sore throat, symptoms may be delayed

Skin: corrosive, redness, pain, blisters

Eyes: corrosive, redness, pain, severe deep burns

Ingestion: corrosive, abdominal pain, sore throat, collapse

Resp sys; skin; eyes

Inh; con

Conj, lac, corn edema, opac, photo; nasal, phar irrit; cough, dysp, bron; skin burns, vesic, sens derm

ACETYLSALICYLIC ACID

     50-78-2

eyes; skin; resp tract

liver; kidneys; bladder; GI tract; CVS; CNS; resp tract

Inhalation: cough, dullness

Skin: redness

Eyes: redness

Eyes; skin; resp sys; blood; liver; kidney

Inh; ing; con

Irrit eyes, skin, upper resp sys; incr blood clotting time; nau, vomit; liver, kidney inj

ACRYLIC ACID

     79-10-7

eyes; skin; resp tract; lungs

 

Inhalation: burning sensation, cough, nasal discharge, laboured breathing, sore throat

Skin: may be absorbed, redness, pain, blisters

Eyes: redness, pain, loss of vision, severe deep burns

Ingestion: severe burns to lips, mouth and throat, abdominal cramps, diarrhoea, unconsciousness, shock

Eyes, skin, resp sys

Inh; abs; ing; con

Irrit eyes, skin, resp sys; eye, skin burns; skin sens; in animals: lung, liver, kidney inj

ADIPIC ACID

     124-04-9

eyes; skin; resp tract

skin

Inhalation: cough, laboured breathing, sore throat

Skin: redness

Eyes: redness, pain

 

 

L-ASCORBIC ACID

     50-81-7

eyes; resp tract

 

Inhalation: cough

Eyes: redness

Ingestion: only in case of large amount ingested: diarrhoea, vomiting

 

 

BENZOIC ACID

     65-85-0

eyes; skin; resp tract

skin

Inhalation: cough, irritant

Skin: redness, irritant

Eyes: redness, irritant, pain

Ingestion: abdominal pain, nausea, vomiting

 

 

n-CAPROIC ACID

     142-62-1

eyes; skin; resp tract

skin

Inhalation: cough, sore throat

Skin: may be absorbed, redness, burning sensation, pain

Eyes: redness, pain, blurred vision

Ingestion: abdominal pain, nausea, sore throat, vomiting

 

 

CHLOROACETIC ACID

     79-11-8

 

 

Inhalation: corrosive, burning sensation, cough, laboured breathing, sore throat, symptoms may be delayed

Skin: corrosive, may be absorbed, redness, pain, blisters

Eyes: redness, pain, severe deep burns

Ingestion: abdominal cramps, burning sensation, collapse

 

 

CITRIC ACID

     77-92-9

eyes; skin; resp tract

 

Inhalation: burning sensation, cough, laboured breathing

Skin: redness

Eyes: redness, pain

Ingestion: cough

 

 

CITRIC ACID HYDRATE

     5949-29-1

eyes; resp tract

 

Inhalation: cough, sore throat

Skin: redness

Eyes: redness, pain

Ingestion: sore throat, mild burning sensation

 

 

CROTONIC ACID

     3724-65-0

eyes; skin; resp tract; lungs

skin

Inhalation: burning sensation, cough, headache, nausea, shortness of breath, sore throat, symptoms may be delayed

Skin: skin burns, burning sensation, pain

Eyes: pain, blurred vision, severe deep burns

Ingestion: pain, burning sensation, diarrhoea, sore throat, vomiting

 

 

DICHLOROACETIC ACID

     79-43-6

eyes; skin; resp tract; lungs

 

Inhalation: burning sensation, cough, laboured breathing, unconsciousness, symptoms may be delayed

Skin: redness, pain, blisters

Eyes: redness, pain, severe deep burns

Ingestion: abdominal cramps, burning sensation, sore throat, unconsciousness, vomiting, weakness

 

 

2,4-DICHLOROPHENOXYACETIC ACID

     94-75-7

eyes; skin; resp tract

 

Inhalation: headache, nausea, weakness

Skin: redness

Eyes: redness

Ingestion: abdominal pain, burning sensation, diarrhoea, headache, nausea, unconsciousness, vomiting, weakness

Skin; CNS; liver; kidneys

Inh; abs; ing; con

Weak, stupor, hyporeflexia, musc twitch; convuls; derm; in animals: liver, kidney inj

ETHANEDIOIC ACID, DIHYDRATE

     6153-56-6

eyes; skin; resp tract; lungs; kidneys

kidneys

Inhalation: cough, shortness of breath, sore throat

Skin: may be absorbed, dry skin, redness, skin burns, pain, blisters

Eyes: redness, pain, severe deep burns

Ingestion: abdominal cramps, sore throat, vomiting, weakness, convulsions

 

 

2-ETHYLHEXANOIC ACID

     149-57-5

eyes; skin; resp tract

liver

Skin: redness

Eyes: redness, pain

 

 

FLUOROACETIC ACID

     144-49-0

eyes; skin; resp tract; CVS; CNS; kidneys

 

 

 

 

FORMIC ACID

     64-18-6

eyes; skin; resp tract; lungs

skin

Inhalation: burning sensation, cough, laboured breathing, shortness of breath, symptoms may be delayed

Skin: redness, serious skin burns, pain

Eyes: redness, pain, blurred vision, severe deep burns

Ingestion: abdominal pain, burning sensation, diarrhoea, sore throat, vomiting

Eyes; skin; resp sys

Inh; ing; con

Irrit eyes, skin, throat; skin burns; derm; lac; rhin; cough, dysp; nau

LACTIC ACID

     598-82-3

eyes; skin; resp tract

 

Inhalation: cough, shortness of breath, sore throat, symptoms may be delayed

Skin: redness, skin burns, pain

Eyes: redness, pain, severe deep burns

Ingestion: abdominal pain, burning sensation, nausea, sore throat, vomiting

 

 

MALEIC ACID

     110-16-7

eyes; skin; resp tract

skin; kidneys

Inhalation: cough, laboured breathing

Skin: redness, skin burns, severe irritant

Eyes: redness, pain, blurred vision

Ingestion: burning sensation, see inhalation ,

 

 

MALEIC ANHYDRIDE

     108-31-6

eyes; skin; resp tract

skin

Inhalation: cough, headache, laboured breathing, nausea, shortness of breath, vomiting

Skin: redness, skin burns

Eyes: redness, pain, lacrymation, severe deep burns

Ingestion: abdominal pain

Eyes; skin; resp sys

Inh; ing; con

Irrit nose, upper resp sys; conj; photo, double vision; bronchial asthma; derm

METHACRYLIC ACID

     79-41-4

eyes; skin; mucous membranes; resp tract; lungs

 

Inhalation: burning sensation, cough, laboured breathing

Skin: redness, skin burns, pain, blisters

Eyes: redness, pain, loss of vision, severe deep burns

Ingestion: abdominal cramps, abdominal pain, burning sensation, weakness

Eyes; skin; resp sys

Inh; abs; ing; con

Irrit eyes, skin, muc memb; eye, skin burns

2-METHYL-4-CHLOROPHENOACETIC ACID

     94-74-6

eyes; skin; resp tract

birth defects

Inhalation: headache, nausea

Skin: redness

Eyes: redness

Ingestion: abdominal pain, nausea, unconsciousness, vomiting, weakness

 

 

OXALIC ACID

     144-62-7

eyes; skin; resp tract; lungs; kidneys

skin; kidneys

Inhalation: burning sensation, cough, laboured breathing, sore throat, symptoms may be delayed

Skin: redness, skin burns, pain, blisters

Eyes: redness, pain, blurred vision, loss of vision, severe deep burns

Ingestion: burning sensation, drowsiness, sore throat, vomiting, shock, low back pain

Resp sys; skin; kidneys; eyes

Inh; ing; con

Irrit eyes, skin, muc memb; eye burns; local pain, cyan; shock, collapse, convuls; kidney damage

PALMITIC ACID

     57-10-3

eyes; skin; resp tract; lungs

skin

Eyes: redness

 

 

PHTHALIC ANHYDRIDE

     85-44-9

eyes; skin; resp tract

skin; lungs

 

Resp sys; eyes; skin; liver; kidneys

Inh; ing; con

Irrit eyes, skin, upper resp sys; conj; nasal ulcer bleeding; bron, bronchial asthma; derm; in animals: liver, kidney damage

PHTHALIC ACID

     88-99-3

eyes; skin; resp tract

 

Inhalation: cough

Skin: redness

Eyes: redness, pain

 

 

PROPIONIC ACID

     79-09-4

eyes; skin; resp tract

 

Inhalation: cough, laboured breathing, sore throat

Skin: skin burns, pain, blisters

Eyes: redness, pain, blurred vision, severe deep burns

Ingestion: abdominal pain, nausea, sore throat, vomiting,

Eyes; skin; resp sys

Inh; abs; ing; con

Irrit eyes, skin, nose, throat; blurred vision, com burns; skin burns; abdom pain, nau, vomit

PROPIONIC ANHYDRIDE

     123-62-6

eyes; skin; resp tract; lungs

 

Inhalation: burning sensation, cough, laboured breathing, sore throat, symptoms may be delayed

Skin: redness, skin burns

Eyes: redness, severe deep burns

Ingestion: sore throat, burns

 

 

SALICYLIC ACID

     69-72-7

eyes; skin; resp tract; CNS

skin

Inhalation: cough, sore throat

Skin: may be absorbed, redness, pain

Eyes: redness, pain, blurred vision

Ingestion: nausea, vomiting, ear ringing

 

 

STEARIC ACID

     57-11-4

eyes

lungs

Inhalation: cough, laboured breathing

Eyes: redness, pain

Ingestion: constipation

 

 

SULPHANILIC ACID

     121-57-3

eyes; skin; resp tract; blood

skin; lungs

Inhalation: blue lips or finger nails, blue skin, cough, dizziness, headache, laboured breathing, sore throat

Skin: redness

Eyes: redness

Ingestion: blue lips or fingernails, blue skin, dizziness, headache, laboured breathing

 

 

TEREPHTHALIC ACID

     100-21-0

eyes; skin

 

Inhalation: cough, irritant

Skin: redness, mild irritant

Eyes: redness, irritant

 

 

p-TOLUENESULPHONIC ACID

     104-15-4

eyes; skin; resp tract; lungs

 

Inhalation: burning sensation, cough, laboured breathing

Skin: redness, pain, blisters

Eyes: redness, pain, blurred vision

Ingestion: burning sensation, sore throat

 

 

2,4,5-TRICHLOROPHENOXYACETIC ACID

     93-76-5

eyes; skin; resp tract

 

 

Skin; liver; GI tract

Inh; ing; con

In animals: ataxia; skin irrit, acne-like rash, liver damage

TRIMELLITIC ANHYDRIDE

     552-30-7

eyes; skin; resp tract; lungs; blood

 

Inhalation: cough, dizziness, wheezing, chills

Skin: redness

Eyes: redness, pain

Eyes; skin; resp sys abs

Irrit eyes, skin; nose; resp sys; pulm edema, resp sens; rhinitis, asthma, cough, wheez, dysp, mal, fever, musc aches, sneez

VALERIC ACID

     109-52-4

eyes; skin; resp tract; lungs; CNS

 

 

 

 

Table 104.7 Physical & chemical hazards

For UN Class: 1.5 = very insensitive substances which have a mass explosion hazard; 2.1 = flammable gas; 2.3 = toxic gas; 3 = flammable liquid; 4.1 = flammable solid; 4.2 = substance liable to spontaneous combustion; 4.3 = substance which in contact with water emits flammable gases; 5.1 = oxidizing substance; 6.1 = toxic; 7 = radioactive; 8 = corrosive substance.

CHEMICAL NAME

CAS-NUMBER

PHYSICAL

CHEMICAL

UN CLASS OR DIVISION /  SUBSIDIARY RISKS

ACETIC ACID

64-19-7

 

The substance is a medium strong acid •Reacts violently with oxidants such as chromium trioxide and potassium permanganate •Reacts violently with strong bases •Attacks many metals forming combustible gas

8

ACETIC ANHYDRIDE

108-24-7

 

The substance decomposes on heating producing toxic fumes and gases including acetic acid •Reacts violently with boiling water, steam, strong oxidants, alcohols, amines, strong bases, and many other compounds •Attacks many metals in presence of water •The liquid is very corrosive, especially in presence of water or moisture

8/ 3

ACETYLSALICYLIC ACID

50-78-2

Dust explosion possible if in powder or granular form, mixed with air

The substance decomposes on contact with hot water or when dissolved in solutions of alkali hydroxides and carbonates •Upon heating, toxic fumes are formed •Reacts with strong oxidants, strong acids, strong bases

 

ACRYLIC ACID

79-10-7

The vapour is heavier than air •Vapour forms explosive mixture with air

The substance polymerizes readily due to heating, under the influence of light, oxygen, oxidizing agents such as peroxides or other activators (acid, iron salts), with fire or explosion hazard •Upon heating, toxic fumes are formed •The substance is a medium strong acid •Reacts violently with oxidants causing fire and explosion hazard •Reacts violently with strong bases and amines •Attacks many metals, including nickel and copper

8/ 3

ADIPIC ACID

124-04-9

Dust explosion possible if in powder or granular form, mixed with air •If dry, it can be charged electrostatically by swirling, pneumatic transport, pouring, etc.

The substance decomposes on heating producing volatile acidic vapours of valeric acid and other substances •The substance is a weak acid •Reacts with oxidizing materials

 

L-ASCORBIC ACID

50-81-7

 

The solution in water is a medium strong acid •Attacks many metals in presence of water

 

BENZOIC ACID

65-85-0

Dust explosion possible if in powder or granular form, mixed with air

The solution in water is a weak acid •Reacts with oxidants

 

BUTYRIC ACID

107-92-6

 

 

8

n-CAPROIC ACID

142-62-1

 

May explode on heating •On combustion, forms toxic/irritant gases •The substance is a medium strong acid •Reacts violently with oxidants (for instance chromium trioxide) causing fire and explosion hazard •Reacts vigorously with bases causing heat and pressure rise hazard •Attacks many metals forming combustible gas

8

CHLOROACETIC ACID

79-11-8

 

The substance decomposes on heating producing toxic and corrosive gases (hydrogen chloride, phosgene) •The solution in water is a strong acid, it reacts violently with bases and is corrosive

6.1/ 8

CITRIC ACID

77-92-9

Dust explosion possible if in powder or granular form, mixed with air

Reacts with oxidants, reductants, bases

 

CITRIC ACID HYDRATE

5949-29-1

 

The solution in water is a medium strong acid •Reacts violently with metal nitrates •Reacts with strong bases and oxidants •The substance will corrode copper, zinc, aluminium, and their alloys

 

CROTONIC ACID

3724-65-0

 

The substance may polymerize under the influence of UV-light or moisture •The solution in water is a weak acid •Reacts violently with bases, oxidants, reducing agents, causing fire and explosion hazard

8

DICHLOROACETIC ACID

79-43-6

 

The substance decomposes on heating producing toxic and corrosive fumes (phosgene, hydrogen chloride) •The substance is a medium strong acid •Attacks many metals forming flammable hydrogen gas •Attacks rubber

8

2,4-DICHLOROPHENOXY ACETIC ACID

94-75-7

 

The substance decomposes on heating producing hydrogen chloride and phosgene •The substance is a weak acid •Reacts with strong oxidants causing fire and explosion hazard

 

ETHANEDIOIC ACID, DIHYDRATE

6153-56-6

 

The substance decomposes on rapid heating above about 150°C producing toxic gas •The solution in water is a medium strong acid which reacts violently with strong bases •Reacts violently with oxidants causing fire and explosion hazard •Reacts with silver, forming explosive products

 

2-ETHYL HEXANOIC ACID

149-57-5

As a result of flow, agitation, etc, electrostatic charges can be generated •Vapour mixes readily with air

The substance is a strong reducing agent and reacts with oxidants •Reacts with strong oxidants

 

FLUOROACETIC ACID

144-49-0

 

 

6.1

FORMIC ACID

64-18-6

 

The substance decomposes on heating producing carbon monoxide •The substance is a medium strong acid •Reacts violently with oxidants •Reacts violently with strong bases causing fire and explosion hazard •Attacks many metals in presence of water •Attacks many plastics

8

ISOBUTYRIC ACID

79-31-2

 

 

3/ 8

LACTIC ACID

 598-82-3

 

The substance is a medium strong acid •Attacks many metals in presence of water

 

MALEIC ACID

110-16-7

 

On combustion, forms irritating smoke (maleic anhydride) •The substance decomposes on heating and on burning producing highly irritating fumes (maleic anhydride) •The solution in water is a medium strong acid

 

MALEIC ANHYDRIDE

108-31-6

 

The solution in water is a strong acid, it reacts violently with bases and is corrosive •Reacts with strong oxidants

8

METHACRYLIC ACID

79-41-4

 

The substance polymerizes easily due to heating or under the presence of light, oxygen, oxidizing agents such as peroxides, or in the presence of traces of hydrochloric acid, with fire or explosion hazard •The substance decomposes on heating producing acrid fumes •The substance is a strong reducing agent and reacts with oxidants •The substance is a medium strong acid •Attacks metals

8

2-METHYL-4-CHLOROPHENOACETIC ACID

94-74-6

 

The substance decomposes on heating producing toxic and corrosive fumes including hydrogen chloride •The substance is a weak acid

 

OXALIC ACID

144-62-7

 

On contact with hot surfaces or flames this substance decomposes forming formic acid and carbon monoxide •The substance is a strong reducing agent and reacts with oxidants •The solution in water is a medium strong acid •Reacts violently with strong oxidants causing fire and explosion hazard •Reacts with some silver compounds to form explosive silver oxalate

 

PALMITIC ACID

57-10-3

 

On heating forms carbon oxides •The substance is a weak acid •Reacts with bases, oxidants, and reducing agents

 

PHTALIC ANHYDRIDE

85-44-9

 

 

8

PHTHALIC ACID

88-99-3

 

The solution in water is a medium strong acid

 

PROPIONIC ACID

79-09-4

 

The substance is a medium strong acid •Reacts with oxidants •Attacks many metals in presence of water

8

PROPIONIC ANHYDRIDE

123-62-6

The vapour is heavier than air

On combustion, forms toxic gases •Reacts with oxidants, bases and water

8

SALICYLIC ACID

69-72-7

Dust explosion possible if in powder or granular form, mixed with air

The substance decomposes on heating producing phenol vapours •The substance is a medium strong acid •Reacts violently with strong bases and strong oxidants

 

STEARIC ACID

57-11-4

 

The substance decomposes on heating producing carbon oxides •The substance is a weak acid •Reacts with bases, oxidants and reducing agents

 

SULPHANILIC ACID

121-57-3

 

On combustion, forms toxic gases of carbon, nitrogen and sulphur oxides •The substance decomposes on heating •Reacts with oxidants

 

TEREPHTHALIC ACID

100-21-0

Dust explosion possible if in powder or granular form, mixed with air

Reacts violently with strong oxidants

 

p-TOLUENESULFONIC ACID

104-15-4

 

The substance decomposes on burning producing carbon oxides and sulphur oxides •The substance is a strong acid, it reacts violently with bases and is corrosive •Attacks many metals forming extremely flammable gas

 

2,4,5-TRICHLOROPHENOXYACETIC ACID

93-76-5

 

 

6.1

TRIFLUOROACETIC ACID

76-05-1

 

 

8

TRIMELLITIC ANHYDRIDE

552-30-7

Dust explosion possible if in powder or granular form, mixed with air •If dry, it can be charged electrostatically by swirling, pneumatic transport, pouring, etc

Reacts violently with oxidants •Reacts slowly with water to form trimellitic acid

 

Table 104.8 Physical & chemical properties

CHEMICAL NAME

CAS-NUMBER

COLOUR/FORM

BOILING POINT (°C)

MELTING POINT (°C)

MOLECULAR WEIGHT

SOLUBILITY IN WATER

RELATIVE DENSITY (WATER=1)

RELATIVE VAPOUR DENSITY (AIR=1)

VAPOUR PRESSURE/ (KPA)

INFLAM. LIMITS

FLASH POINT (°C)

AUTO IGNITION POINT (°C)

ACETIC ACID

64-19-7

rhombic crystals (<16.6°C melting point); colourless liquid (16.6°C melting point)

118

16.6

60.05

misc

1.0492

2.1

1.6

4 ll 16 ul

39 cc

426

ACETIC ANHYDRIDE

108-24-7

colourless, very mobile, strongly refractive liquid

139

-73

102.10

v sol

1.080  @15°C

3.5

0.5

2.9 ll 10.3 ul

49 cc

316

ACETYLSALICYLIC ACID

50-78-2

monoclinic tablets or needle-like crystals

 

135

180.15

sl sol

1.40

 

2.52 x  10-5 mmHg  @25°C

 

 

 

ACRYLIC ACID

79-10-7

colourless liquid

141

14

72.06

misc

1.0511

2.5

0.413

2.9 ll 8 ul

54 oc

360

ADIPIC ACID

124-04-9

monoclinic prisms from ethyl acetate, water, or acetone and petroleum ether; fine white crystals or powder

337.5

152

146.14

sl sol

1.360  @25°C/4°C

5.04

0.010  @18.5°C

10 ll 15mg/l ul

196 cc

422

L-ASCORBIC ACID

50-81-7

crystals (usually plates, sometimes needles, monoclinic system); white to slightly yellow crystals or powder

 

190-192

176.12

v sol

1.65  @25°C

 

 

 

 

 

BENZOIC ACID

65-85-0

monoclinic tablets, plates, leaflets; white scales or needle crystals

249.2

122.4

122.13

0.29g/100ml  @20°C

1.2659  @15°C/4°C

4.21

0.133  @96°C

 

121 cc

570

BUTYRIC ACID

107-92-6

oily liquid; colourless liquid

165.5

-7.9

88.10

misc

0.9577

3.0

0.43mmHg

2.0 ll 10.0 ul

72 cc

443

BUTYRYL CHLORIDE

141-75-3

colourless liquid

101-102

-89

106.55

slowly with decomposition

1.0263  @20.6°C/4°C

 

 

 

< 21

 

n-CAPROIC ACID

142-62-1

oily liquid

205.8

-3.4

116.16

insol

0.929

4.01

0.024

1.3 ll 9.3 ul

102 oc

380

CHLORENDIC ACID

115-28-6

crystalline solid

 

 

388.84

 

 

 

 

 

 

 

CHLOROACETIC ACID

79-11-8

monoclinic prisms; colourless or white crystals; colourless to light-brownish crystals

189

(alpha) 63 ; (beta) 55-56 ; (gamma) 50

94.50

v sol

1.6

3.26

0.13  @43°C

8.0 ll ? ul

126

>500

o-CHLOROBENZOIC ACID

118-91-2

monoclinic prisms from water

sublimes

142

156.6

sol

1.544

 

6.6x 10-4 mmHg  @25°C

 

 

 

m-CHLOROBENZOIC ACID

535-80-8

crystals; prisms from water

sublimes

158

156.6

v sol

1.496  @25°C/4°C

 

8.475x 10-5 mmHg  @25°C

 

 

 

p-CHLOROBENZOIC ACID

74-11-3

triclinic prisms from alcohol and ether; nearly white coarse powder

 

243

156.6

insol

 

 

1.85x 10-3 mmHg  @25°C

 

 

 

2-CHLOROPROPIONIC ACID

598-78-7

crystals

186

-12.1

108.53

misc

1.2585

 

 

 

 

 

CITRIC ACID

77-92-9

crystals/monoclinic holohedra/crystallize from hot concentrated aq soln; colourless, translucent crystals or white,granular to fine crystalline powder/ rhombic crystals from water with 1 mol of water of crystallization

decomp

153

192.12

v sol

1.665

 

 

0.28 ll 2.29 ul

 

 

CITRIC ACID HYDRATE

5949-29-1

crystals

decomp

100

 

sol

1.5

 

 

0.28 ll 2.29 ul

 

1010

CROTONIC ACID

3724-65-0

monoclinic needles or prisms (from water or petroleum ether); colourless needle-like crystals; white crystalline solid

185

71.5-71.7

86.09

v sol

1.018  @15°C/4°C; 0.964  @80°C/4°C

2.97

0.024

 

88

396

DICHLOROACETIC ACID

79-43-6

colourless liquid

194

9.7

128.94

misc

1.56

4.45

0.019

 

 

 

2,4-DICHLOROPHENOXYACETIC ACID

94-75-7

white to yellow crystalline powder; yellow colour is phenolic impurities; colourless powder; white

160  @0.4mmHg

138

221.04

insol

1.6

7.6

0.053  @160°C

 

88 oc

 

2,4-DICHLOROPHENOXYPROPIONIC ACID

120-36-5

colourless crystalline solid; white to tan, crystalline solid

 

117.5-118.1

235.07

 

1.42

 

 

 

 

 

ETHANEDIOIC ACID, DIHYDRATE

6153-56-6

colourless crystals

sublimes

102

 

10g/100ml

1.7

3.1

 

 

 

 

2-ETHYLHEXANOIC ACID

149-57-5

colourless liquid

228

- 59

144.2

sol

0.9031  @25°C/4°C

5.0

0.004

0.8 ll 6.0 ul

118 oc

310

FLUOROACETIC ACID

144-49-0

needles; colourless crystals

165

35.2

78.04

sol

1.3693  @36°C

 

1.9mmHg  @25°C

 

 

 

FORMIC ACID

64-18-6

colourless liquid

101

8.4

46.00

misc

1.22

1.6

4.4

14 ll 34 ul

69

480-520

FUMARIC ACID

110-17-8

needles, monoclinic prisms or leaflets from water; colourless crystals; white crystalline powder

165 sublimes  @1.7mmHg

300-302

116.07

sl sol

1.635

 

 

 

 

 

GALLIC ACID

149-91-7

prisms from water; needles from absolute methanol or chloroform

 

253

170.1

sl sol

1.694  @6°C/4°C

 

 

 

 

 

GLYCOLIC ACID

79-14-1

colourless crystals; rhombic needles from water; leaves from ethanol

100

80

76.05

sol

 

 

 

 

 

 

HEPTANOIC ACID

111-14-8

clear oily liquid

223.01

-7.5

130.2

sl sol

0.92

 

 

 

 

 

ISOBUTYRIC ACID

79-31-2

colourless liquid

152-155

-47

88.1

v sol

0.950

3.0

1mmHg  @14.7°C

 

 

 

ISOPHTHALIC ACID

121-91-5

needles

sublimes

347

166.13

sl sol

 

 

 

 

 

 

LACTIC ACID

598-82-3

colourless liquid or colourless crystals

 

16.8-18

90.08

v sol

 

 

 

 

>74

 

LAURIC ACID

143-07-7

colourless solid; white, crystalline powder

298.9

44.2

200.3

insol

0.883

 

1mmHg  @121.0°C

 

 

 

MALEIC ACID

110-16-7

monoclinic prisms from water; white crystals from water, alcohol & benzene; colourless crystals

135

138-139

116.07

788g/l  @25°C

1.590

4.0

 

 

 

 

MALEIC ANHYDRIDE

108-31-6

orthorhombic needles from chloroform; commercial grades in fused form, as briquettes; colourless needles or white lumps or pellets; needles from chloroform or ether

202.0

52.8

98.06

sol

1.48

3.4

0.025  @25°C

1.4 ll 7.1 ul

102

475

MALONIC ACID

141-82-2

white crystals

decomp

132- 134

104.06

sol

1.63

 

 

 

 

 

METHACRYLIC ACID

79-41-4

liquid or colourless crystals; colourless liquid

163

16

86.09

sol

1.0153

2.97

0.13  @25°C

 

77 oc

 

2-METHYL-4-CHLOROPHENOACETIC ACID

94-74-6

light brown solid; plates from benzene or toluene; white crystalline solid (pure compd); colourless crystalline solid (pure)

 

120

200.6

sl sol

1.56  @25°C/15.5°C

6.9

0.0002 Pa

 

 

 

METHACRYLIC ACID, 2-DIMETHYLAMINOETHYL

2867-47-2

liquid

62-65

-30

157.22

sol

0.933  @25°C/5°C

5.4

 

 

739 oc

 

NONANOIC ACID

112-05-0

colourless, oily liquid at ordinary temp; crystallizes when cooled; yellowish oil

255

12.5

158.23

insol

0.9057

 

 

 

 

 

OLEIC ACID

112-80-1

colourless or nearly colourless liquid (above 5-7°C); yellowish, oily liquid; water-white liquid

286  @100mmHg

16.3

282.45

insol

0.895  @25°C

 

 

 

 

363

OXALIC ACID

144-62-7

anhyd oxalic acid, crystallized fromglacial acetic acid is orthorhombic, crystals being pyramidal or elongated octahedra; transparent, colourless crystals or white powder

157

189.5

90.04

sol

1.900  @17°C /4°C

 

 

 

 

 

PALMITIC ACID

57-10-3

white crystalline scales; needles from alcohol

351  @15mmHg

63-64

256.5

insol

0.853  @62°C/4°C

 

0.133  @154°C

 

 

 

PHTHALIC ACID

88-99-3

crystals; plates from water

decomp

210-211

166.13

sl sol

1.59

5.73

 

 

168 oc

 

PHTHALIC ANHYDRIDE

85-44-9

white, lustrous needles; colourless or pale yellow solid flakes; colourless needles; monoclinic or rhombic prisms; white needles from alcohol and benzene

295

130.8

148.11

sl sol

1.527

5.1

0.27 Pa

1.7 ll 10.4. ul

 

570

PIVALIC ACID

75-98-9

coloured crystals

164

35.5

102.13

sl sol

0.905  @50°C

 

 

 

 

 

PROPIONIC ANHYDRIDE

123-62-6

colourless liquid

167

-45

130.2

decomposes

1.01

4.5

100

1.3 ll 9.5 ul

63

285

PROPIONIC ACID

79-09-4

colourless liquid; oily liquid

141

-20.8

74.09

misc

0.9930

2.56

0.386

2.9 ll 14.8 ul

544

955

SALICYLIC ACID

69-72-7

white, fine, needle-like crystals, or fluffy, white crystalline powder; needles in water; monoclinic prisms in alcohol

211

158

138.12

sl sol

1.443

4.8

0.114

1.1 ll ? ul

157

540

STEARIC ACID

57-11-4

monoclinic leaf from alcohol; white or slightly yellow, crystal masses or powder

360  @15mmHg

69

284.50

insol

0.9408

9.80

1mmHg  @173.7°C

 

196

395

SUCCINIC ACID

110-15-6

white minute monoclinic prisms; triclinic or monoclinic prisms

235

188

118.09

sl sol

1.572  @25°C/4°C

 

 

 

 

 

SULPHANILIC ACID

121-57-3

rhombic plates or monoclinic crystals from water

 

288

173.2

sl sol

1.485  @25°C/4°C

 

 

 

 

 

TARTARIC ACID

87-69-4

 

 

169

150.08

 

 

 

 

 

 

 

TEREPHTHALIC ACID

100-21-0

needles; white crystals or powder

402

 

166.13

insol

1.51

 

< 0.001

 

260

496

p-tert BUTYLBENZOIC ACID

98-73-7

needles from dilute alcohol

 

164.5-165.5

178.2

insol

 

 

 

 

 

 

p-TOLUENESULPHONIC ACID

104-15-4

monoclinic leaflets or prisms; colourless crystals

140

106-107

172.2

v sol

1.24

 

 

 

184 cc

 

TRICHLOROACETIC ACID

76-03-9

crystals; colourless; white solid

197.55

58

163.40

v sol

1.62  @25 C/4°C

 

1mmHg  @51.0°C

 

 

 

2,4,5-TRICHLOROPHENOXYACETIC ACID

93-76-5

white solid; light tan solid

decomp

153

255.5

insol

1.80

 

< 0.01 mPa

 

 

 

TRIFLUOROACETIC ACID

76-05-1

colourless, fuming liquid

73

-15.2

114.02

sol

1.5351  @25°C

 

 

 

 

 

TRIMELLITIC ANHYDRIDE

552-30-7

crystals; colourless solid

240-245

161-163.5

192.13

reacts

 

6.6

<0.01  @25°C

1 ll 7 ul

 

 

VALERIC ACID

109-52-4

colourless liquid

186-187

-34.5

102.15

sol

0.939

3.5

0.020

 

96 oc

400

ALCOHOLS

Alcohols are a class of organic compounds formed from hydrocarbons by the substitution of one or more hydroxyl groups for an equal number of hydrogen atoms; the term is extended to various substitution products which are neutral in reaction and which contain one or more of the alcohol groups.

Uses

Alcohols are used as chemical intermediates and solvents in the textile, dye-stuff, chemical, detergent, perfume, food, beverage, cosmetics, and paint and varnish industries. Some compounds are also used in denaturing alcohol, cleaning products, quick-drying oils and inks, antifreeze, and as frothing agents in ore flotation.

n-Propanol is a solvent found in lacquers, cosmetics, dental lotions, printing inks, contact lenses and brake fluids. It is also an antiseptic, a synthetic flavouring agent for non-alcoholic beverages and food, a chemical intermediate and a disinfectant. Isopropanol is another important industrial solvent, which is used in antifreeze, quick-drying oils and inks, denaturing alcohol and perfumes. It is used as an antiseptic and a substitute for ethyl alcohol in cosmetics (i.e., skin lotions, hair tonics and rubbing alcohol), but cannot be used for pharmaceuticals taken internally. Isopropanol is an ingredient in liquid soaps, window cleaners, a synthetic flavouring additive for non-alcoholic beverages and food, and a chemical intermediate.

n-Butanol is employed as a solvent for paints, lacquers and varnishes, natural and synthetic resins, gums, vegetable oils, dyes and alkaloids. It is used as an intermediate in the manufacture of pharmaceuticals and chemicals, and employed in industries producing artificial leather, textiles, safety glass, rubber cement, shellac, raincoats, photographic films and perfumes. sec-Butanol is also used as a solvent and chemical intermediate, and is found in hydraulic brake fluids, industrial cleaning compounds, polishes, paint removers, ore-flotation agents, fruit essences, perfumes, dye-stuffs, and as a chemical intermediate.

Isobutanol, a solvent for surface coatings and adhesives, is employed in lacquers, paint strippers, perfumes, cleaners and hydraulic fluid. tert-Butanol is used for the removal of water from products, as a solvent in the manufacture of drugs, perfumes and flavours, and as a chemical intermediate. It is also a component of industrial cleaning compounds, a denaturant for ethanol, and an octane booster in gasoline. The amyl alcohols are frothing agents in ore flotation. Numerous alcohols, including methylamyl alcohol, 2-ethylbutanol, 2-ethylhexanol, cyclohexanol, 2-octanol and methylcyclohexanol, are used in the manufacture of lacquers. In addition to their numerous uses as solvents, cyclohexanol and methylcyclohexanol are useful in the textile industry. Cyclohexanol is employed in finishing textiles, leather processing, and as a homogenizer for soaps and synthetic detergent emulsions. Methylcyclohexanol is a component in soap-based spot removers and a blending agent for special textile soaps and detergents. Benzyl alcohol is used in the preparation of perfumes, pharmaceuticals, cosmetics, dye-stuffs, inks and benzyl esters. It also serves as a lacquer solvent, a plasticizer, and as a degreasing agent in rug cleaners. 2-Chloroethanol finds use as a cleaning agent and as a solvent for cellulose ethers.

Ethanol is the raw material for numerous products, including acetaldehyde, ethyl ether and chloroethane. It is an antifreeze agent, food additive and yeast growth medium, and it is used in the manufacture of surface coatings and gasohol. The production of butadiene from ethyl alcohol has been of great importance to the plastics and synthetic rubber industries. Ethyl alcohol is capable of dissolving a wide range of substances, and for this reason it is used as a solvent in the manufacture of drugs, plastics, lacquers, polishes, plasticizers, perfumes, cosmetics, rubber accelerators and so on.

Methanol is a solvent for inks, dyes, resins and adhesives, and is used in the manufacture of photographic film, plastics, textile soaps, wood stains, coated fabrics, unshatterable glass and waterproofing formulations. It is a starting material in the manufacture of many chemical products as well as an ingredient of paint and varnish removers, dewaxing preparations, embalming fluids and antifreeze mixtures.

Pentanol is used in the manufacture of lacquers, paints, varnishes, paint removers, rubber, plastics, explosives, hydraulic fluids, shoe cement, perfumes, chemicals, pharmaceuticals, and in the extraction of fats. Mixtures of the alcohols perform well for many of the solvent uses, but for chemical syntheses or more selective extractions, a pure product is often required.

Next to allyl chloride, allyl alcohol is the most important of the allyl compounds in industry. It is useful in the manufacture of pharmaceuticals and in general chemical syntheses, but the largest single use of allyl alcohol is in the production of various allyl esters, of which the most important are diallyl phthalate and diallyl isophthalate, which serve as monomers and repolymers.

Health Hazards

Methanol

Among the synthetic processes by which methyl alcohol is produced is the Fischer-Tropsch reaction between carbon monoxide and hydrogen, from which it is obtained as one of the by-products. It can also be produced by the direct oxidation of hydrocarbons and by a two-step hydrogenation process in which carbon monoxide is hydrogenated to methyl formate, which in turn is hydrogenated to methyl alcohol. The most important synthesis, however, is the modern, medium-pressure, catalytic hydrogenation of carbon monoxide or carbon dioxide at pressures of 100 to 600 kgf/cm2 and temperatures of 250 to 400 °C.

Methyl alcohol has toxic properties under acute and chronic exposure. Injury has occurred amongst alcoholics from ingestion of the liquid, and to process workers from inhalation of the vapour. Animal experiments have established that methyl alcohol can penetrate the skin in sufficient quantity to cause fatal intoxication.

In cases of severe poisoning, most commonly following ingestion, methyl alcohol has a specific effect on the optic nerve, causing blindness as a result of optic nerve degeneration accompanied by degenerative changes of the ganglion cells of the retina and circulatory disturbances in the choroid. Amblyopia is commonly bilateral and may occur within a few hours of ingestion, whilst total blindness usually requires a week. The pupils are dilated, the sclera is congested, there is pallor of the optic disc with central scotoma; breathing and cardiovascular function are depressed; in fatal cases the patient is unconscious but coma may be preceded by delirium.

The consequences of industrial exposure to methyl alcohol vapour may vary considerably among individual workers. Under varying conditions of severity and duration of exposure, indications of intoxication include irritation of the mucous membranes, headache, ringing in the ears, vertigo, insomnia, nystagmus, dilated pupils, clouded vision, nausea, vomiting, colic and constipation. There may be skin injuries arising from the irritant and solvent action of methyl alcohol and from the harmful effects of stains and resins dissolved in it, and these are most likely to be located on the hands, wrists and forearms. In general, however, these harmful effects have been caused by prolonged exposures to concentrations very much in excess of limits recommended by authorities on methyl alcohol vapour poisoning.

Chronic combined exposure to methanol and carbon monoxide has been reported as a causative factor of cerebral atherosclerosis.

The poisonous action of methyl alcohol is attributed to its metabolic oxidation into formic acid or formaldehyde (which have a specific dangerous effect on the nervous system), and possibly to a severe acidosis. This oxidation process may be inhibited by ethyl alcohol.

Ethanol

The conventional industrial hazard is exposure to the vapour in the vicinity of a process in which ethyl alcohol is used. Prolonged exposure to concentrations above 5,000 ppm causes irritation of the eye and nose, headache, drowsiness, fatigue and narcosis. Ethyl alcohol is quite rapidly oxidized in the body to carbon dioxide and water. Unoxidized alcohol is excreted in the urine and expired in air, with the result that the cumulative effect is virtually negligible. Its effect on the skin is similar to that of all fat solvents and, in the absence of precautions, dermatitis may result from contact.

Recently another potential hazard in human exposure to synthetic ethanol was suspected because the product was found to be carcinogenic in mice treated at high doses. Subsequently, epidemiological analyses have revealed an excess incidence of laryngeal cancer (on average five times greater than expected) associated with a strong acid ethanol unit. Diethyl sulphate would appear to be the causative agent, although alkyl sultones and other potential carcinogens were also involved.

Ethyl alcohol is a flammable liquid, and its vapour forms flammable and explosive mixtures with air at normal temperature. An aqueous mixture containing 30% alcohol can produce a flammable mixture of vapour and air at 29 °C. One containing only 5% alcohol can produce a flammable mixture at 62 °C.

While ingestion is not a likely consequence of the use of industrial alcohol, it is a possibility in the case of an addict. The danger of such illicit consumption depends upon the concentration of ethanol, which above 70% is likely to produce oesophageal and gastric injuries, and upon the presence of denaturants. These are added to make the spirit unpalatable when it is obtained free of tax for non-potable purposes. Many of these denaturants (e.g., methyl alcohol, benzene, pyridine bases, methylisobutylketone and kerosene, acetone, gasoline, diethylphthalate and so on) are more harmful to a drinker than the ethyl alcohol itself. It is important therefore to ensure that there is no illicit drinking of the industrial spirit.

n-Propanol

Ill effects from the industrial usage of n-propanol have not been reported. In animals it is moderately toxic via inhalation, oral and dermal routes. It is an irritant of the mucous membranes and a depressant of the central nervous system. After inhalation, slight irritation of the respiratory tract and ataxia may occur. It is slightly more toxic than isopropyl alcohol, but it appears to produce the same biological effects. There is evidence of one fatal case after ingestion of 400 ml of n-propanol. The pathomorphological changes were mainly brain oedema and lung oedema, which have also been often observed in ethyl alcohol poisoning. n-Propanol is flammable and a moderate fire hazard.

Other compounds

Isopropanol in animals is slightly toxic via dermal and moderately toxic via oral and intraperitoneal routes. No case of industrial poisoning has been reported. An excess of sinus cancers and laryngeal cancers has been found among workers producing isopropyl alcohol. This could be due to the by-product, isopropyl oil. Clinical experience shows that isopropyl alcohol is more toxic than ethanol but less toxic than methanol. Isopropanol is metabolized to acetone, which can reach high concentrations in the body and is in turn metabolized and excreted by the kidneys and lungs. In humans, concentrations of 400 ppm produce mild irritation of the eyes, nose and throat.

The clinical course of isopropanol poisoning is similar to that of ethanol intoxication. The ingestion of up to 20 ml diluted with water has caused only a sensation of heat and slight lowering of the blood pressure. However, in two fatal cases of acute exposure, within a few hours after ingestion respiratory arrest and deep coma were observed and also hypotension, which is regarded as a bad prognostic sign, was also observed. Isopropanol is a flammable liquid and a dangerous fire hazard.

n-Butanol is potentially more toxic than any of its lower homologues, but the practical hazards associated with its industrial production and use at ordinary temperature are substantially reduced by its lower volatility. High vapour concentrations produce narcosis and death in animals. Exposure of human beings to the vapour may induce irritation of the mucous membranes. The reported levels at which irritation occurs are conflicting and vary between 50 and 200 ppm. Transient mild oedema of the conjunctiva of the eye and a slightly reduced erythrocyte count may occur above 200 ppm. Contact of the liquid with skin may result in irritation, dermatitis and absorption. It is slightly toxic when ingested. It is also a dangerous fire hazard.

The response of animals to sec-butanol vapours is similar to that to n-butanol, but it is more narcotic and lethal. It is a flammable liquid and a dangerous fire hazard.

At high concentrations the action of isobutanol vapour, like the other alcohols, is primarily narcotic. It is irritating to the human eye above 100 ppm. Contact of the liquid with the skin may result in erythema. It is slightly toxic when ingested. This liquid is flammable and a dangerous fire hazard.

Although tert-butanol vapour is more narcotic to mice than that of n- or isobutanol, few industrial ill effects have as yet been reported, other than occasional slight irritation of the skin. It is slightly toxic when ingested. In addition, it is flammable and a dangerous fire hazard.

Although headache and conjunctival irritation may result from prolonged exposure to cyclohexanol vapour, no serious industrial hazard exists. Irritation to the eyes, nose and throat of human subjects results at 100 ppm. Prolonged contact of the liquid with the skin results in irritation, and the liquid is slowly absorbed through the skin. It is slightly toxic when ingested. Cyclohexanol is excreted in the urine, conjugated with glucuronic acid. The liquid is flammable and a moderate fire hazard.

Headaches and irritation of the eye and upper respiratory tract may result from prolonged exposure to the vapour of methylcyclohexanol. Prolonged contact of the liquid with the skin results in irritation, and the liquid is slowly absorbed through the skin. It is slightly toxic when ingested. Methylcyclohexanol, conjugated with glucuronic acid, is excreted in urine. It is a moderate fire hazard.

Other than temporary headache, vertigo, nausea, diarrhoea and loss of weight during exposure to a high vapour concentration resulting from a mixture containing benzyl alcohol, benzene and ester solvents, no industrial illness is known from benzyl alcohol. It is slightly irritating to the skin and produces a mild lacrimating effect. The liquid is flammable and a moderate fire hazard.

Allyl alcohol is a flammable and irritant liquid. It causes irritation in contact with the skin, and absorption through the skin gives rise to deep pain in the region where absorption has occurred in addition to systemic injury. Severe burns may be caused by the liquid if it enters the eye. The vapour does not possess serious narcotic properties, but it has an irritant effect on the mucous membranes and the respiratory system when it is inhaled as an atmospheric contaminant. Its presence in a factory atmosphere has given rise to lacrimation, pain in the eye and blurred vision (necrosis of the cornea, haematuria and nephritis).

Amyl alcohols

Pentyl alcohols exist in several isomeric forms, and of the eight possible structural isomers, three also have optical active forms. Of the structural forms, four are primary alcohols—1-pentanol (amyl alcohol), 2-methyl-1-butanol, isopentyl alcohol (3-methyl-1-butanol, isoamyl alcohol) and neopentyl alcohol (2,2-dimethyl-1-propanol); three are secondary alcohols—2-pentanol, 3-pentanol and 3-methyl-2-butanol; and the final one is a tertiary alcohol—tert-pentyl alcohol (2-methyl-2-butanol).

Pentyl alcohol is irritating to the mucous membranes of the eyes, nose and throat at or somewhat above 100 ppm. Although it is absorbed by the gastrointestinal tract and the lungs, and through the skin, the incidence of industrial illness is quite low. Mucous membrane irritation occurs readily from the crude product because of the volatile extraneous materials present. The complaints from systemic illness include headache, dizziness, nausea, vomiting, diarrhoea, delirium and narcosis. Since pentyl alcohol is frequently used as the impure technical material and in conjunction with other solvents, distinctive symptoms and findings cannot be ascribed to the alcohol with any certainty. The ease with which the alcohols are metabolized is in the decreasing order of primary, secondary and tertiary; more tertiary is excreted unchanged than the others. Although toxicity varies with the chemical configuration, as a general estimation it can be said that a mixture of pentyl alcohols is about ten times as toxic as ethyl alcohol. This is reflected in the recommended exposure limits of the two alcohols—100 ppm and 1,000 ppm, respectively. The fire hazard from the amyl alcohols is not particularly great.

Alcohols tables

Table 104.9 Chemical identification

CHEMICAL

SYNONYMS

UN CODE

CAS-NUMBER

CHEMICAL FORMULA

ALLYL ALCOHOL

Allylic alcohol; 2-Propene-1-ol; Propenol; Propenyl alcohol

UN1098

107-18-6

BENZYL ALCOHOL

Benzenecarbinol; Benzenemethanol; Phenolcarbinol; Phenylmethanol

100-51-6

BUTYL ALCOHOL

n-Butanol; 1-Butyl alcohol; Butyl hydroxide; 1-Hydroxybutane; Propylcarbinol; Propylmethanol

71-36-3

sec-BUTYL ALCOHOL

2-Butanol; 2-Hydroxybutane; Methylethylcarbinol; 1-Methyl-1-propanol

78-92-2

tert-BUTYL ALCOHOL

tert-Butanol; 1,1-Dimethylethanol; 2-Methyl-2-propanol; Trimethylcarbinol

75-65-0

CYCLOHEXANOL

Cyclohexyl alcohol; Hexahydrophenol; Hexalin; Hydralin; Naxol

108-93-0

2-CHLOROETHANOL

Ethylene chlorohydrin; δ-Chloroethanol; β-Chloroethyl alcohol; 2-Chloroethyl alcohol

UN1135

107-07-3

1,3-DICHLORO-2-PROPANOL

Dichlorohydrin; α-Dichlorohydrin; 1,3-Dichloropropanol-2; sym-Glycerol dichlorohydrin

UN2750

96-23-1

2,2-DIMETHYL-1-BUTANOL

2,2,-Dimethylbutanol

1185-33-7

2,6-DIMETHYL-4-HEPTANOL

Diisobutyl carbinol; sec-Nonyl alcohol

108-82-7

ETHANOL

Ethyl alcohol; Ethyl hydrate; Ethyl hydroxide; Spirt

UN1170

UN1986

UN1987

64-17-5

2-ETHYLBUTYL ALCOHOL

2-Ethylbutanol; 2-Ethylbutanol-1; 2-Ethyl-1-butanol; 2-Ethylbutyl alcohol; sec-Hexyl alcohol; 3-Methylolpentane; sec-Pentylcarbinol; 3-Pentylcarbinol; Pseudohexyl alcohol;

 UN2275

97-95-0

2-ETHYL-1-HEXANOL

Ethylhexanol; 2-Ethylhexanol; 2-Ethylhexyl alcohol

104-76-7

HEPTANOL

1-Heptanol; Heptyl-alcohol ; 1-Hydroxyheptane

111-70-6

2-HEPTANOL

Amyl methyl carbinol; Heptanol-2; 2-Hydroxyheptane; Methyl amyl carbinol

543-49-7

HEXANOL

1-Hexanol; Hexyl-alcohol; Amylcarbinol; 1-Hydroxyhexane; Pentylcarbinol

111-27-3

ISOAMYL ALCOHOL

Isobutylcarbinol; Isopentanol; Isopentyl alcohol; 3-Methyl butanol; 3-Methyl-1-butanol

123-51-3

ISOBUTYL ALCOHOL

Isobutanol; 1-hydroxymethylpropane; Isopropylcarbinol; 2-Methyl propanol

UN1212

78-83-1

ISODECYL ALCOHOL

Isodecanol

25339-17-7

ISOOCTYL ALCOHOL

Isooctanol

26952-21-6

ISOPROPYL ALCOHOL

Dimethylcarbinol; 2-Hydroxypropane; Isopropanol; n-Propan-2-ol

UN1219

67-63-0

METHANOL

Methyl alcohol; Methyl hydrate; Methyl hydroxide; Monohydroxymethane

UN1230

67-56-1

2-METHYL-1-BUTANOL

D,L-sec-Butyl carbinol; 2-Methyl-1-butanol

137-32-6

METHYLCYCLOHEXANOL

Hexahydrocresol; Hexahydromethylphenol; Methylcyclohexanol

UN2617

25639-42-3

o-METHYL CYCLOHEXANOL

 

583-59-5

m-METHYLCYCLOHEXANOL

 

591-23-1

2-METHYL-4-PENTANOL

Isobutylmethylcarbinol; Isobutylmethylmethanol; MAOH; Methyl amyl alcohol

UN2053

108-11-2

NONANOL

n-Nonyl-alcohol; Octyl carbinol

143-08-8

OCTANOL

Octyl alcohol; Heptyl carbinol; 1-Hydroxyoctane

111-87-5

2-OCTANOL

Capryl alcohol

123-96-6

OLEYL ALCOHOL

Oleol; cis-9-Octadecen-1-ol ; Olive alcohol

143-28-2

1-PENTANOL

Amyl alcohol; n-Butylcarbinol; Pentyl-alcohol

71-41-0

3-PENTANOL

 

584-02-1

tert-PENTYL ALCOHOL

tert-Amyl alcohol; Dimethylethylcarbinol; Ethyl dimethyl carbinol; 2-Methyl-2-Butanol; 3-Methylbutan-3-ol; tert-Pentanol

75-85-4

PHENYLETHANOL

Benzyl carbinol; 2-Phenethyl alcohol; 2-Phenylethanol; Phenylethyl alcohol

60-12-8

PROPANOL

Ethyl carbinol; 1-Hydroxypropane; Propyl-alcohol; Propylic alcohol

UN1274

71-23-8

PROPARGYL ALCOHOL

Ethynylcarbinol; Methanol, Ethyny-1; 1-Propyne-3-ol; 2-Propynyl alcohol

107-19-7

TETRAHYDROFURFURYL ALCOHOL

Tetrahydro-2-furancarbinol ; Tetrahydro-2-furanmethanol ; Tetrahydro-2-furylmethanol; THFA

97-99-4

TRIDECANOL

Tridecyl alcohol

112-70-9

Table 104.10 Health hazards

Chemical Name

     CAS-Number

ICSC Short-Term Exposure

ICSC Long-Term Exposure

Routes of Exposure and Symptoms

US NIOSH Target Organs & Routes of Entry

US NIOSH Symptoms

ALLYL ALCOHOL

     107-18-6

eyes; skin; resp tract; muscles; liver; kidneys

 

Inhalation: headache, nausea, vomiting

Skin: may be absorbed, aching, pain, blisters

Eyes: redness, pain, blurred vision, temporary loss of vision, severe deep burns, sensitivity to light

Ingestion: abdominal pain, unconsciousness

Eyes; skin; resp sys

Inh, abs, ing, con

Eye irrit, tissue damage; irrit upper resp sys, skin; pulm edema

BENZYL ALCOHOL

     100-51-6

eyes; skin; resp tract; CNS

skin

Inhalation: cough, sore throat

Skin: redness

Eyes: redness

Ingestion: abdominal pain, diarrhoea, drowsiness, nausea, vomiting

 

 

BUTYL ALCOHOL

     71-36-3

 

 

 

Skin; eyes; resp sys; CNS

Inh, abs, ing, con

Irrit eyes, nose, throat; head, verti, drow; corn inflamm, blurred vision, lac, photo; derm; possible auditory nerve damage, hearing loss; CNS depres

sec-BUTYL ALCOHOL

     78-92-2

 

 

 

Eyes; skin, resp sys; CNS

Inh, ing, con

Irrit eyes, skin, throat, nose; narco

tert-BUTYL ALCOHOL

     75-65-0

 

 

 

Eyes; skin, resp sys, CNS

Inh, ing, con

Irrit eyes, skin, nose, throat; head; skin flush, burns

2-CHLOROETHANOL

     107-07-3

eyes; respiratory tract; CNS;  cardiovascular system; kidneys; liver; may result in death

 

Inhalation: Mucous membranes, nausea

Skin: Vomiting, vertigo, incoordination

Ingestion: Numbness, visual distortion, headache

Resp sys; liver; kidneys; CNS; skin; CVS; eyes

Inh, abs, ing, con

Irrit muc memb; nau, vomit; verti, inco; numb; vis dist; head; thirst; delirium; low BP; collapse, shock, coma; liver, kidney damage

CYCLOHEXANOL

     108-93-0

eyes; skin; resp tract; CNS

skin

 

Eyes; resp sys; skin

Inh, abs, ing, con

Irrit eyes, skin, nose, throat; skin; narco

ETHANOL

     64-17-5

eyes; skin; resp tract; CNS

skin; CNS; liver; blood

Inhalation: cough, drowsiness, headache, fatigue

Skin: dry skin

Eyes: redness, irritant pain, irritant burning

Ingestion: burning sensation, confusion, dizziness, headache, unconsciousness

Eyes; skin; resp sys; CNS; liver; blood; repro sys

Inh, ing, con

Irrit eyes, skin, nose; head, drow, ftg, narco; cough; liver damage; anemia; repro, terato effects

2-ETHYL-1-HEXANOL

     104-76-7

eyes; skin

 

Inhalation: dizziness, headache, nausea, weakness

Skin: may be absorbed, redness

Eyes: redness, pain

 

 

HEPTANOL

     111-70-6

eyes; skin; resp tract

liver; kidneys; birth defects

 

 

 

HEXANOL

     626-93-7

eyes; skin; resp tract; CNS

skin; CNS

Inhalation: cough, headache, sore throat

Skin: may be absorbed, redness

Eyes: redness, pain

Ingestion: abdominal pain, dizziness, drowsiness, headache, nausea

 

 

ISOAMYL ALCOHOL

     123-51-3

eyes; resp tract; CNS

skin

Inhalation: cough, dizziness, drowsiness, headache, nausea, sore throat

Skin: dry skin

Eyes: redness, pain

Ingestion: abdominal pain, unconsciousness

Eyes; skin; resp sys; CNS

Inh, ing, con

Irrit eyes, skin, nose, throat; head, dizz; cough, dysp, nau, vomit, diarr; skin cracking; in animals: narco

sec-ISOAMYL ALCOHOL

     528-75-4

 

 

 

Eyes; skin; resp sys; CNS

Inh, ing, con

Irrit eyes, skin, nose, throat; head, dizz; cough, dysp, nau, vomit, diarr; skin cracking; in animals: narco

ISOBUTYL ALCOHOL

     78-83-1

eyes; resp tract; CNS

skin

 

Eyes; skin; resp sys; CNS

Inh, ing, con

Irrit eyes, throat, head, drow; skin cracking; in animals: narco

ISODECYL ALCOHOL

     25339-17-7

eyes; skin; resp tract; CNS

skin

Inhalation: dizziness, dullness, headache, nausea

Skin: redness

Eyes: redness, pain

Ingestion: diarrhoea, nausea, vomiting

 

 

ISOOCTYL ALCOHOL

     26952-21-6

eyes; skin; resp tract; CNS

skin

Inhalation: dizziness, dullness, headache, nausea

Skin: may be absorbed, redness, skin burns

Eyes: redness, pain

Ingestion: diarrhoea, nausea, vomiting

Eyes; skin; resp sys; CNS; CVS

Inh, abs, ing, con

Irrit eyes, skin, nose throat; eye, skin burns

ISOPROPYL ALCOHOL

     67-63-0

eyes; skin; resp tract; CNS

skin

Inhalation: cough, dizziness, drowsiness, headache, nausea, sore throat, vomiting

Skin: redness

Eyes: redness, pain, blurred vision

Ingestion: dizziness, drowsiness, nausea, sore throat, vomiting

Eyes; skin; resp sys; CNS

Inh, ing, con

Irrit eyes, nose, throat; drow, dizz, head; dry cracking skin; in animals: narco

METHANOL

     67-56-1

eyes; skin; resp tract; CNS

CNS

Inhalation: cough, dizziness, headache, nausea

Skin: may be absorbed, dry skin, redness

Eyes: redness, pain

Ingestion: abdominal pain, shortness of breath, unconsciousness, vomiting

Eyes; skin, resp sys; CNS; GI tract

Inh, abs, ing, con

Irrit eyes, skin, upper resp sys; head, dizz, verti, li-head, nau, vomit; vis dist, optic nerve damage (blindness); derm

3-METHOXY 1-BUTANOL

     2517-43-3

eyes; skin; resp tract; lungs

skin

Inhalation: cough, headache, symptoms may be delayed

Skin: dry skin, burning sensation

Eyes: redness

Ingestion: abdominal pain, dullness, nausea, vomiting

 

 

2-METHYL-1-BUTANOL

     137-32-6

eyes; skin; resp tract; CNS

skin

Inhalation: cough, dizziness, drowsiness, sore throat

Skin: dry skin, redness

Eyes: redness, pain, blurred vision

 

 

METHYLCYCLOHEXANOL

     25639-42-3

eyes; upper resp tract

skin; CNS

Inhalation: cough, headache

Skin: dry skin, redness

Eyes: redness

Resp sys; skin; eyes; liver; kidneys; CNS

Inh, abs, ing, con

Irrit eyes, skin, upper resp sys; head; in animals: narco; liver, kidney damage

o-METHYLCYCLOHEXANOL

     583-59-5

eyes; upper resp tract

skin; CNS

Inhalation: cough, headache

Skin: dry skin, redness

Eyes: redness

 

 

m-METHYLCYCLOHEXANOL

     591-23-1

 

skin

Inhalation: cough, headache

Skin: dry skin, redness

Eyes: redness

 

 

2-METHYL-4-PENTANOL

     108-11-2

eyes; skin; resp tract; lungs; CNS; liver; kidneys

skin; CNS; liver; kidneys

Inhalation: confusion, drowsiness, headache, nausea, sore throat, unconsciousness

Skin: may be absorbed, redness, burning sensation

Eyes: redness, pain

Ingestion: abdominal pain

Eyes; skin; CNS

Inh, abs, ing, con

Irrit eyes, skin; head, drow; derm; in animals: narco

1-PENTANOL

     71-41-0

eyes; skin; resp tract; CNS

skin

Inhalation: cough, dizziness, headache, nausea

Skin: redness

Eyes: redness, pain, possible corneal damage

Ingestion: cough, dizziness, headache, nausea, vomiting

 

 

3-PENTANOL

     584-02-1

eyes; skin; resp tract; CNS

skin

Inhalation: cough, dizziness, headache, nausea, sore throat, vomiting

Skin: may be absorbed, redness

Eyes: redness, pain, blurred vision

Ingestion: abdominal pain, diarrhoea, nausea, vomiting

 

 

2-PHENYLETHANOL

     60-12-8

eyes; resp tract

CNS

Inhalation: cough

Eyes: redness

 

 

PROPANOL

     71-23-8

eyes; skin; resp tract; CNS

skin

Inhalation: cough, dizziness, drowsiness, headache, nausea, sore throat, vomiting

Skin: redness

Eyes: redness, pain, blurred vision

Ingestion: dizziness, drowsiness, nausea, sore throat, vomiting

Skin; eyes; resp sys; GI tract; CNS

Inh, abs, ing, con

Irrit eyes, nose, throat; dry cracking skin; drow, head; ataxia, GI pain; abdom cramps, nau, vomit, diarr; in animals: narco

PROPARGYL ALCOHOL

     107-19-7

eyes; skin; resp tract; liver; kidneys; blood

 

Inhalation: burning sensation

Skin: may be absorbed, redness

Eyes: pain, severe deep burns

Skin; resp sys; CNS; liver; kidneys

Inh, abs, ing, con

irrit skin, muc memb; CNS depres; in animals: liver, kidney damage

TETRAHYDROFURFURYL ALCOHOL

     97-99-4

 

 

Inhalation: sore throat, cough, headache, nausea, dizziness, drowsiness, unconsciousness

Skin: redness, irritation, pain

Eyes: redness, irritation, pain

Ingestion: abdominal pain

 

 

3,5,5-TRIMETHYL-1-HEXANOL

     3452-97-9

eyes; skin; resp tract

liver; kidneys

Inhalation: cough, headache, sore throat

Skin: may be absorbed, roughness, burning sensation

Eyes: redness, pain

Ingestion: headache, nausea, vomiting

 

 

Table 104.11 Physical & chemical hazards

For UN Class: 1.5 = very insensitive substances which have a mass explosion hazard; 2.1 = flammable gas; 2.3 = toxic gas; 3 = flammable liquid; 4.1 = flammable solid; 4.2 = substance liable to spontaneous combustion; 4.3 = substance which in contact with water emits flammable gases; 5.1 = oxidizing substance; 6.1 = toxic; 7 = radioactive; 8 = corrosive substance.

Chemical Name

CAS-Number

Physical

Chemical

UN Class or Division / Subsidiary Risks

ALLYL ALCOHOL

107-18-6

The vapour is heavier than air and may travel along the ground; distant ignition possible

On combustion, forms carbon monoxide •Upon heating, toxic fumes are formed •Reacts with carbon tetrachloride, nitric acid, chlorosulphonic acid causing fire and explosion hazard

6.1/ 3

BENZYL ALCOHOL

100-51-6

 

Reacts violently with strong oxidants and acids •Attacks many plastics •Can attack iron, aluminium upon heating •Slow oxidation in the presence of air

 

BUTYL ALCOHOL

71-36-3

 

 

3

sec-BUTYL ALCOHOL

78-92-2

 

 

3

tert-BUTYL ALCOHOL

75-65-0

 

 

3

2-CHLOROETHANOL

107-07-3

 

 

6.1/3

ETHANOL

64-17-5

The vapour mixes well with air, explosive mixtures are easily formed

On combustion, forms toxic gases •Reacts slowly with calcium hypochlorite, silver oxide and ammonia, causing fire and explosion hazard •Reacts violently with strong oxidants such as nitric acid, silver nitrate, mercuric nitrate or magnesium perchlorate, causing fire and explosion hazard

3

2-ETHYL-1-HEXANOL

104-76-7

 

Reacts vigorously with oxidizing materials

 

HEXANOL

111-27-3

 

 

3

ISOAMYL ALCOHOL

123-51-3

Vapour mixes readily with air

Reacts with strong oxidants

 

ISOBUTYL ALCOHOL

78-83-1

 

 

3

ISODECYL ALCOHOL

25339-17-7

 

The substance decomposes on heating producing acrid smoke and fumes •Reacts with strong oxidants

 

ISOOCTYL ALCOHOL

26952-21-6

 

The substance decomposes on heating producing acrid smoke and fumes •Reacts with strong oxidants (analogy with isodecyl alcohol)

 

ISOPROPYL ALCOHOL

67-63-0

The vapour mixes well with air, explosive mixtures are easily formed

Reacts with strong oxidants

3

METHANOL

67-56-1

The vapour mixes well with air, explosive mixtures are easily formed

Reacts violently with oxidants causing fire and explosion hazard

3/ 6.1

3-METHOXY-1-BUTANOL

2517-43-3

 

Reacts with oxidants

 

2-METHYL-4-PENTANOL

108-11-2

The vapour is heavier than air and may travel along the ground; distant ignition possible

Reacts with oxidants •Reacts violently with alkali metals causing fire and explosion hazard

3

METHYLCYCLOHEXANOL

25639-42-3

 

On combustion, forms toxic gases

3

o-METHYLCYCLOHEXANOL

583-59-5

 

 

3

m-METHYLCYCLOHEXANOL

591-23-1

 

 

3

1-PENTANOL

71-41-0

The vapour mixes well with air, explosive mixtures are easily formed

Reacts violently with oxidants

3

3-PENTANOL

584-02-1

The vapour is heavier than air and may travel along the ground; distant ignition possible

Reacts with strong oxidants

3

2-PHENYLETHANOL

60-12-8

 

Reacts with strong oxidants, strong acids

 

PROPANOL

71-23-8

The vapour mixes well with air, explosive mixtures are easily formed

Reacts with strong oxidants (perchlorates, nitrates)

3

PROPARGYL ALCOHOL

107-19-7

The vapour is heavier than air

Reacts violently with oxidants •Attacks many plastics •On contact with heavy metals, poorly soluble salts may be formed, which may explode on heating

 

TETRAHYDROFURFURYL ALCOHOL

97-99-4

 

The substance can presumably form explosive peroxides •The substance decomposes on heating producing acrid smoke and fume •Reacts violently with strong oxidants, several n-chloro- and n-bromoimides causing fire and explosion hazard •Attacks many resins and organic materials

 

3,5,5-TRIMETHYL 1-HEXANOL

3452-97-9

The vapour is heavier than air

May explode on heating •Reacts with strong oxidants, inorganic acids, aldehydes, alkenoxides, acid anhydrides •Reacts with rubber, PVC

 

Table 104.12 Physical & chemical properties

Chemical Name

CAS-Number

Colour/Form

Boiling Point (°C)

Melting Point (°C)

Molecular Weight

Solubility in Water

Relative Density (water=1)

Relative Vapour Density (air=1)

Vapour Pressure/ (Kpa)

Inflam. Limits

Flash Point (°C)

Auto Ignition Point (°C)

ALLYL ALCOHOL

107-18-6

mobile liquid; colourless liquid

97

-129

58.08

misc

0.8540

2.00

2.5

2.5 ll 18.0 ul

21 cc

443

BENZYL ALCOHOL

100-51-6

water-white liquid

205

-15.2

108.13

sol

1.04535

3.72

0.02  @25°C

1.3 ll 13 ul

93 cc

436

BUTYL ALCOHOL

71-36-3

liquid

117.2

-89.5

74.12

sol

0.8098

2.6

5.5mmHg

1.4 ll 11.2 ul

37 cc

 

sec-BUTYL ALCOHOL

78-92-2

colourless liquid

99.5

-115

74.12

15.4g/100g

0.8063

2.6

23.9mmHg  @30°C

1.7 ll 9.85  @100°C ul

24 cc

406

tert-BUTYL ALCOHOL

75-65-0

a colourless liquid, which forms rhombic crystals; rhombic prisms or plates

82.4

25.4

74.12

misc

0.7887

2.55

42.0mmHg  @25°C

2.35  @25°C ll 8  @55°C ul

 

 

2-CHLOROETHANOL

107-07-3

colourless glycerine-like liquid

128-130 °C  @ 760 mm Hg

-67.5 °C

80.52

sol

1.197  @ 20 °C/4 °C

2.78

4.9 mm Hg  @ 20°C

4.9% ll 15.9% ul

60 °C cc

425 °C

CYCLOHEXANOL

108-93-0

colourless needles or viscous liquid; hygroscopic crystals

161

25.1

100.2

sol

0.9624

3.5

80mmHg  @25°C

 

 

 

1,3-DICHLORO-2-PROPANOL

96-23-1

colourless slightly viscous liquid

174.3

-4

128.99

v sol

1.3506  @17°C/4°C

4.4

7mmHg

 

 

 

2,6-DIMETHYL-4-HEPTANOL

108-82-7

colourless liquid

176-177

<-65

144.3

insol

0.8114

4.97

0.21mmHg

 

 

 

2,2-DIMETHYL-1-BUTANOL

1185-33-7

 

136.5

<-15

102.17

sl sol

0.8283

 

 

 

 

 

2,4-DIMETHYL-3-PENTANOL

600-36-2

 

138.7

0

116.2

sl sol

0.8288

 

 

 

 

 

ETHANOL

64-17-5

clear, colourless, very mobile liquid

78.5

-114

46.07

misc

0.789

1.59

40mmHg  @19°C

3.3 ll 19 ul

13 cc

363

2-ETHYLBUTYL ALCOHOL

97-95-0

colourless liquid

146.27 °C  @ 760 mm Hg

less than -15 °C

102.18

slightly sol

0.8326  @ 20 °C/4 °C

 

0.9 mm Hg  @ 20 °C

 

 

 

2-ETHYL-1-HEXANOL

104-76-7

colourless liquid

184.6

-76

130.22

insol

0.8344

4.5

0.020

0.88 ll 9.7 ul

81 cc

231

HEPTANOL

111-70-6

colourless liquid

176

-34.6

116.2

sl sol

0.8219

 

 

 

71

 

HEXANOL

111-27-3

colourless liquid

157

-51.6

102.17

sl sol

0.8136

3.5

1mmHg  @24.4°C

 

 

 

2-HEXANOL

626-93-7

liquid

136

-23

102.18

 

0.81

 

 

 

41 cc

 

ISOAMYL ALCOHOL

123-51-3

oily, clear liquid

131.0

-117

88.1

moderate 2g/100ml  @14°C

0.8092

3.04

0.32

1.2 ll 9  @100°C ul

45

350

sec-ISOAMYL ALCOHOL

528-75-4

colourless liquid

113

-117

 

 

0.819

 

 

 

394

 

ISOBUTYL ALCOHOL

78-83-1

colourless liquid

107

-108

74.1

sl sol

0.8

2.56

1.2

1.7 ll 10.9 ul

27

441

ISODECYL ALCOHOL

25339-17-7

colourless liquid

220

7

158.32

insol

0.841

5.5

0.13  @70°C

0.8 ll ? ul

104 oc

285

ISOOCTYL ALCOHOL

26952-21-6

colourless liquid

83-91

<-76

130.3

640mg/l  @25°C

0.832

4.5

0.05

0.9 ll 5.7 ul

82 oc

277

ISOPROPYL ALCOHOL

67-63-0

liquid

83

-90

60.09

misc

0.79

2.1

4.4

2 ll 12 ul

117

455

METHANOL

67-56-1

colourless liquid

64.7

-98

32.04

misc

0.7914

1.11

12.3

6 ll 35.6 ul

12 cc

385

2-METHOXYPROPAN-1-OL

1589-47-5

 

130

 

90.12

 

0.938

 

 

 

 

 

3-METHOXY 1-BUTANOL

2517-43-3

liquid

160

-85

104.14

misc

0.92

3.59

0.12

1.9 ll ? ul

74

335

2-METHYL-1-BUTANOL

137-32-6

colourless liquid

128

<-70

88.17

sl sol

0.816

3.0

0.42

1.4 ll 9.0 ul

50 oc

385

METHYLCYCLOHEXANOL

25639-42-3

colourless liquid; viscous liquid

155-180

-50

114.1

3-4%

0.924  @15°C/15

3.94

0.2  @30°C

 

68 cc

296

o-METHYLCYCLOHEXANOL

583-59-5

liquid

163-166

-9.5

114.2

insol

0.93

3.9

 

 

58 cc

296

m-METHYLCYCLOHEXANOL

591-23-1

liquid

163

 

114.2

 

0.92

 

 

 

62 cc

295

2-METHYL-4-PENTANOL

108-11-2

colourless liquid

131.6

-60

102.2

sl sol

0.8075

3.5

2.8mmHg

1.0 ll 5.5 ul

41

 

NONANOL

143-08-8

colourless to yellowish liquid

215

-5

144.3

insol

0.8279

 

 

 

 

 

OCTANOL

111-87-5

colourless liquid

195

-16

130.22

insol

0.827

4.5

7.94x 10-2 mm Hg  @25°C

 

 

 

2-OCTANOL

123-96-6

colourless

 

 

130.22

1120mg/l  @25°C

 

4.5

2.42x 10-1 mmHg  @25°C

 

 

 

OLEYL ALCOHOL

143-28-2

oily liquid, usually pale yellow; clear, viscous liquid

333

13-19

268.5

insol

0.8489

 

9.3x 10-5 mmHg  @25°C

 

 

 

1-PENTANOL

71-41-0

colourless liquid

137.5

-79

88.15

insol

0.814

3.0

0.13

1.2 ll 10.0  @100°C ul

33 cc

300

3-PENTANOL

584-02-1

colourless liquid

116

-8

 

4.1g/100ml

0.82

3.04

930 Pa

1.2 ll 8.0 ul

40 cc

360

tert-PENTYL ALCOHOL

75-85-4

colourless liquid

102

-8.8

88.1

sol

0.8059  @25°C/4°C

 

 

 

67 cc

819

1-PHENYLETHANOL

98-84-1

 

 

 

122.17

 

 

 

 

 

 

 

2-PHENYLETHANOL

60-12-8

colourless, viscous liquid

218.2

-27

122.16

sl sol

1.0202

4.21

0.133  @58°C

 

102

 

PROPANOL

71-23-8

clear, colourless liquid

97.2

-127

60.09

misc

0.8053

2.1

20.8mm Hg  @25°C

2.29 ll 13.7 ul

23 cc

412

PROPARGYL ALCOHOL

107-19-7

light to straw coloured liquid; colourless liquid

114-115

-51.8

56.1

sol

0.9715

1.93

1.54

3.4 ll 70 ul

33 oc

 

TETRAHYDROFURFURYL ALCOHOL

97-99-4

colourless liquid

178

<-80

102.1

misc

1.054

3.5g/l

0.306

1.5 ll 9.7 ul

75 oc

282

TRIDECANOL

112-70-9

crystals

152  @14mmHg

32.5

200.4

insol

0.8223  @31°C/4°C

 

 

 

121 oc

 

3,5,5-TRIMETHYL-1-HEXANOL

3452-97-9

liquid

194

-70

144.25

0.05g/100ml

0.824

5.0

0.030

 

76

 

ALDEHYDES AND KETALS

Aldehydes are members of a class of organic chemical compounds represented by the general structural formula R-CHO. R may be hydrogen or a hydrocarbon radical—substituted or unsubstituted. The important reactions of aldehydes include oxidation (whereby carboxylic acids are formed), reduction (with the formation of alcohol), aldol condensation (when two molecules of an aldehyde react in the presence of a catalyst to produce a hydroxy aldehyde), and the Cannizzaro reaction (with the formation of an alcohol and the sodium salt of an acid). Ketals, or acetals, as they are also called, are diesters of aldehyde or ketone hydrates. They are produced by reactions of aldehydes with alcohols.

Uses

Because of their high chemical reactivity, aldehydes are important intermediates for the manufacture of resins, plasticizers, solvents and dyes. They are used in the textile, food, rubber, plastics, leather, chemical and health care industries. The aromatic aldehydes and the higher aliphatic aldehydes are used in the manufacture of perfumes and essences.

Acetaldehyde is primarily used to manufacture acetic acid, but it is also used in the manufacture of ethyl acetate, peracetic acid, pyridine derivatives, perfumes, dyes, plastics and synthetic rubber. Acetaldehyde is utilized for silvering mirrors, hardening gelatin fibers, and as an alcohol denaturant and a synthetic flavoring agent. Paraldehyde, a trimer of acetaldehyde, is used in the dyestuff and leather industries and as a hypnotic agent in medicine. Industrially it has been used as a solvent, rubber activator and antioxidant. Metaldehyde is used as a fuel in portable cooking stoves and for slug control in gardening. Glycidaldehyde has been used as a cross-linking agent for wool finishing, for oil tanning, and for fat liquoring of leather and surgical sutures. Propionaldehyde is utilized in the manufacture of polyvinyl and other plastics and in the synthesis of rubber chemicals. It also functions as a disinfectant and as a preservative. Acrolein is used as a starting material for the manufacture of many organic compounds, including plastics, perfumes, acrylates, textile finishes, synthetic fibres and pharmaceuticals. It has been used in military poison gas mixtures and as a liquid fuel, an aquatic herbicide and biocide, and a tissue-fixative in histology.

Formaldehyde has an extremely wide range of uses related to both its solvent and germicidal properties. It is used in plastics production (e.g., urea-formaldehyde, phenol-form-aldehyde, melamine-formaldehyde resins). It is also used in the photography industry, in dyeing, in the rubber, artificial silk and explosives industries, tanning, precious metal recovery and in sewage treatment. Formaldehyde is a powerful antiseptic, germicide, fungicide and preservative used to disinfect inanimate objects, improve fastness of dyes on fabrics, and preserve and coat rubber latex. It is also a chemical intermediate, an embalming agent and a fixative of histological specimens. Paraformaldehyde is the most common commercial polymer obtained from formaldehyde and consists of a mixture of products with different degrees of polymerization. It is used in fungicides, disinfectants, bactericides and in the manufacture of adhesives.

Butyraldehyde is used in organic synthesis, mainly in the manufacture of rubber accelerators, and as a synthetic flavoring agent in foods. Isobutyraldehyde is an intermediate for rubber antioxidants and accelerators. It is used in the synthesis of amino acids and in the manufacture of perfumes, flavorings, plasticizers and gasoline additives. Crotonaldehyde is used in the manufacture of n-butyl alcohol and crotonic acid and in the preparation of surface active agents, pesticides and chemotherapeutic agents. It is a solvent for polyvinyl chloride and acts as a shortstopper in vinyl chloride polymerization. Crotonaldehyde is used in the preparation of rubber accelerators, the purification of lubricating oils, leather tanning, and as a warning agent for fuel gases and for locating breaks and leaks in pipes.

Glutaraldehhyde is an important sterilizing agent effective against all microorganisms, including viruses and spores. It is used as a chemical disinfectant for cold sterilization of equipment and instruments in the health care industry and as a tanning agent in the leather industry. It is also a component of embalming fluid and a tissue fixative. p-Dioxane is a solvent in pulping of wood and as a wetting and dispersing agent in textile processing, dye-baths, stain and printing compositions. It is used in cleaning and detergent preparations, adhesives, cosmetics, fumigants, lacquers, paints, varnishes, and paint and varnish removers.

Ketals are used in industry as solvents, plasticizers, and intermediates. They are capable of hardening natural adhesives like glue or casein. Methylal is used in ointments, perfumes, special purpose fuel, and as a solvent for adhesives and coatings. Dichloroethyl formal is used as a solvent and as an intermediate for polysulphide synthetic rubber.

Safety Precautions

Many aldehydes are volatile, flammable liquids which, at normal room temperatures, form vapours in explosive concentrations. Fire and explosion precautions, as described elsewhere in this chapter, must be most rigorous in the case of the lower members of the aldehyde family, and safeguards with respect to irritant properties must also be most extensive for the lower members and for those with an unsaturated or substituted chain.

Contact with aldehydes should be minimized by attention to plant design and handling procedure. Spillages should be avoided where possible and, where they occur, adequate water and drainage facilities should be available. For those chemicals labelled as known or suspected carcinogens, routine precautions for carcinogens, described elsewhere in this chapter, must be applied. Many of these chemicals are potent eye irritants and approved chemical eye and face protection should be mandatory in the plant area. For maintenance work, plastic face shields should also be worn. Where conditions require, suitable protective clothing, aprons, hand protection and impervious foot protection should be provided. Water showers and eye irrigation systems should be available in the plant area and, as with all protective equipment, operators must be fully trained in their use and maintenance.

Health Hazards

Most of the aldehydes and ketals are capable of causing primary irritation of the skin, eyes and respiratory system—a tendency which is most pronounced in the lower members of a series, in members that are unsaturated in the aliphatic chain, and in the halogen-substituted members. The aldehydes can have an anaesthetic effect, but the irritant properties of some of them may force a worker to limit exposure prior to having sufficient exposure to suffer anaesthetic effects. The irritating effect on the mucous membranes may be related to the ciliostatic effect where the hairlike cilia that line the respiratory tract and provide essential clearance functions are disabled. The degree of toxicity varies greatly in this family. Some of the members of the aromatic aldehydes and certain aliphatic aldehydes are rapidly metabolized and are not associated with adverse effects and thus have been found to be safe for use in foods and as flavourings. However, other members of the family are known or suspected carcinogens and due caution must be exercised in all situations in which contact may be possible. Some are chemical mutagens and several are allergens. Other toxic effects include the ability to produce an hypnotic effect. More detailed data on specific family members are included in the text which follows and in the accompanying tables.

Acetaldehyde is a mucous membrane irritant and also has general narcotic action of the central nervous system. Low concentrations cause irritation of the eyes, nose and upper respiratory passages, as well as bronchial catarrh. Extended contact can damage the corneal epithelium. High concentrations cause headache, stupor, bronchitis and pulmonary oedema. Ingestion causes nausea, vomiting, diarrhoea, narcosis and respiratory failure; death may result from damage to kidneys and fatty degeneration of the liver and heart muscle. Acetaldehyde is produced in the blood as a metabolite of ethyl alcohol, and will give rise to facial flushing, palpitations and other disagreeable symptoms. This effect is enhanced by the drug disulphiram (Antabuse), and by exposure to the industrial chemicals cyanamide and dimethylformamide.

In addition to its acute effects, acetaldehyde is a Group 2B carcinogen, that is, it has been classified as possibly carcinogenic to humans and a carcinogen in animals by the International Agency for Research on Cancer (IARC). Acetaldehyde induces chromosomal aberrations and sister-chromatid exchange in a variety of test systems.

Repeated exposure to the vapours of acetaldehyde causes dermatitis and conjunctivitis. In chronic intoxication, the symptoms resemble those of chronic alcoholism, such as loss of weight, anaemia, delirium, hallucinations of sight and hearing, loss of intelligence and psychic disturbances.

Acrolein is a common atmospheric pollutant which is produced in the exhaust fumes of internal combustion engines, which contain many and varied aldehydes. Acrolein concentration is increased when diesel oil or fuel oil is used. In addition acrolein is found in tobacco smoke in considerable quantities, not only in the particulate phase of the smoke, but also, and even more, in the gaseous phase. Accompanied by other aldehydes (acetaldehyde, propionaldehyde, formaldehyde, etc.) it reaches such a concentration (50 to 150 ppm) that it seems to be among the most dangerous aldehydes in tobacco smoke. Thus acrolein represents a possible occupational and environmental hazard.

Acrolein is toxic and very irritating, and its high vapour pressure may result in the rapid formation of hazardous atmospheric concentrations. Vapours are capable of causing injury to the respiratory tract, and the eyes can be injured by both liquid and vapours. Skin contact may produce severe burns. Acrolein has excellent warning properties and severe irritation occurs at concentrations less than those expected to be acutely hazardous (its powerful lacrimatory effect in very low concentrations in the atmosphere (1 mg/m3) compels people to run away from the polluted place in search of protective devices). Consequently, exposure is most likely to result from leakage or spillage from pipes or vessels. Serious chronic effects, such as cancer, however, may not be completely avoided.

Inhalation presents the most serious hazard. It causes irritation of nose and throat, tightness of the chest and shortness of breath, nausea and vomiting. The bronchopulmonary effect is very severe; even if the victim recovers from acute exposure, there will be permanent radiological and functional damage. Animal experiments indicate that acrolein has a vesicant action, destroying respiratory tract mucous membranes to such an extent that respiratory function is fully inhibited within 2 to 8 days. Repeated skin contact may cause dermatitis, and skin sensitization has been observed.

The discovery of the mutagenic properties of acrolein is not recent. Rapaport pointed it out as long ago as 1948 in Drosophila. Research has been carried out to establish whether cancer of the lung, whose connection with the abuse of tobacco is unquestionable, can be traced to the presence of acrolein in the smoke, and whether certain forms of cancer of the digestive system that are found to have a link with the absorption of burnt cooking oil are due to the acrolein contained in the burnt oil. Recent studies have shown that acrolein is mutagenic for certain cells (Drosophila, Salmonella, algae such as Dunaliella bioculata) but not for others (yeasts such as Saccharomices cerevisiae). Where acrolein is mutagenic for a cell, ultrastructural changes can be identified in the nucleus which are reminiscent of those caused by x rays in algae. It also produces various effects on the synthesis of DNA by acting on certain enzymes.

Acrolein is very effective in inhibiting the activity of the cilia of the bronchial cells that help to keep the bronchial tree clear. This, added to its action favouring inflammation, implies a good probability that acrolein can cause chronic bronchial lesions.

Chloroacetaldehyde has very irritant properties not only with regard to mucous membranes (it is dangerous to the eyes even in the vapour phase and can cause irreversible damage), but also to the skin. It can cause burnlike injuries on contact at 40% solution, and an appreciable irritation at 0.1% solution on prolonged or repeated contact. Prevention should be based on the avoidance of any contact and the control of atmospheric concentration.

Chloral hydrate is mainly excreted in humans first as trichloroethanol and then, as time progresses, as trichloroacetic acid, which may reach up to half the dose in repeated exposure. On severe acute exposure chloral hydrate acts like a narcotic and impairs the respiratory centre.

Crotonaldehyde is a strongly irritant substance and a definite corneal burn hazard, resembling acrolein in toxicity. Some instances of sensitization in workers have been reported and some assays for mutagenicity have produced positive results.

In addition to the fact that p-dioxane is a dangerous fire hazard, it has also been classified by IARC as a Group 2B carcinogen, that is, an established animal carcinogen and possible human carcinogen. Inhalation studies in animals have demonstrated that p-dioxane vapour can cause narcosis, lung, liver and kidney damage, irritation of the mucous membrane, congestion and oedema of the lungs, behavioural changes and elevated blood counts. Large doses of p-dioxane administered in drinking water have led to the development of tumours in rats and guinea pigs. Animal experiments have also demonstrated that dioxane is rapidly absorbed through the skin producing signs of incoordination, narcosis, erythema as well as liver and kidney injury.

Experimental studies with humans have also shown eye, nose, and throat irritation at concentrations of 200 to 300 ppm. An odour threshold as low as 3 ppm has been reported, although another study resulted in an odour threshold of 170 ppm. Both animal and human studies have demonstrated that dioxane is metabolized to β-hydroxyethoxyacetic acid. An investigation in 1934 of the deaths of five men working in an artificial silk plant suggested that the signs and symptoms of dioxane poisoning included nausea and vomiting followed by diminished and finally absence of urine output. Necropsy findings included enlarged pale livers, swollen haemorrhagic kidneys and oedematous lungs and brains.

It should be noted that unlike many of the other aldehydes, the irritant warning properties of p-dioxane are considered poor.

Formaldehyde and its polymeric derivative paraformaldehyde. Formaldehyde polymerizes readily in both liquid and solid state to form the mixture of chemicals known as paraformaldehyde. This polymerization process is delayed by the presence of water and, consequently, commercial formaldehyde preparations (known as formalin or formol) are aqueous solutions containing 37 to 50% formaldehyde by weight; 10 to 15% methyl alcohol is also added to these aqueous solutions as a polymerization inhibitor. Formaldehyde is toxic by ingestion and inhalation and it may also cause skin lesions. It is metabolized into formic acid. The toxicity of polymerized formaldehyde is potentially similar to that of the monomer since heating produces depolymerization.

Exposure to formaldehyde is associated with both acute and chronic effects. Formaldehyde is a proven animal carcinogen and has been classed as a 1B probable human carcinogen by IARC. Consequently, when working with formaldehyde, appropriate precautions for carcinogens must be taken.

Exposure to low atmospheric concentrations of formaldehyde causes irritation, especially of the eyes and respiratory tract. Due to the solubility of formaldehyde in water, the irritant effect is limited to the initial section of the respiratory tract. A concentration of 2 to 3 ppm causes slight formication of the eyes, nose and pharynx; at 4 to 5 ppm, discomfort rapidly increases; 10 ppm is tolerated with difficulty even briefly; between 10 and 20 ppm, there is severe difficulty in breathing, burning of the eyes, nose and trachea, intense lacrimation and severe cough. Exposure to 50 to 100 ppm produces a feeling of restricted chest, headache, palpitations and, in extreme cases, death due to oedema or spasm of the glottis. Eye burns can also be produced.

Formaldehyde reacts readily with tissue proteins and promotes allergic reactions, including contact dermatitis, which has also arisen from contact with formaldehyde-treated clothing. Asthmatic symptoms may occur due to allergic sensitivity to formaldehyde, even at very low concentrations. Kidney injury may occur in excessive and repeated exposure. There have been reports of both inflammatory and allergic dermatitis, including nail dystrophy due to direct contact with solutions, solids or resins containing free formaldehyde. Inflammation follows even after short-term contact with large quantities of formaldehyde. Once sensitized, the allergic response may follow contact with only very small quantities.

Formaldehyde reacts with hydrogen chloride, and it was reported that such reaction in humid air could yield a non-negligible amount of bis(chloromethyl) ether, BCME, a dangerous carcinogen. Further investigations have shown that at ambient temperature and humidity, even at very high concentrations, formaldehyde and hydrogen chloride do not form bis-(chloromethyl) ether at the detection limit of 0.1 ppb. However, the US National Institute for Occupational Safety and Health (NIOSH) has recommended that formaldehyde be treated as a potential occupational carcinogen because it has shown mutagenic activity in several test systems and has induced nasal cancer in rats and mice, particularly in the presence of hydrochloric acid vapours.

Glutaraldehyde is a relatively weak allergen which can cause allergic contact dermatitis and the combination of irritant and allergen properties are suggestive of the possibility of respiratory system allergies as well. It is a relatively strong irritant to the skin and the eyes.

Glycidaldehyde is a highly reactive chemical which has been classified by IARC as a group 2B possible human carcinogen and established animal carcinogen. Thus precautions appropriate for the handling of carcinogens must be exercised with this chemical.

Metaldehyde, if ingested, may cause nausea, severe vomiting, abdominal pain, muscular rigidity, convulsions, coma and death from respiratory failure. Ingestion of paraldehyde ordinarily induces sleep without depression of respiration, although deaths occasionally occur from respiratory and circulatory failure after high doses or more. Methylal can produce liver and kidney impairment and acts as a lung irritant on acute exposure.

Aldehydes and ketals tables

Table 104.13 Chemical identification

CHEMICAL

SYNONYMS

UN CODE

CAS-NUMBER

CHEMICAL FORMULA

ACETAL

1,1-Diethoxyethane; Diethyl acetal; Ethylidene diethyl ether

UN1088

105-57-7

ACETALDEHYDE

Acetic aldehyde; Acetylaldehyde; Ethanal; Ethyl aldehyde

UN1089

75-07-0

ACROLEIN

Allyl aldehyde; Ethylene aldehyde; Propenal; 2-Propenal

UN1062

107-02-8

BENZALDEHYDE

Benzene carbaldehyde; Benzenecarbonal; Benzoic aldehyde; Phenylmethanal

100-52-7

BUTYLALDEHYDE

Butanal; Butyral; n-Butyraldehyde; Butyric aldehyde

UN1129

123-72-8

CHLOROACETALDEHYDE

2-Chloroacetaldehyde; 2-Chloroethanal

UN2232

107-20-0

o-CHLOROBENZALDEHYDE

2-Chlorobenzaldehyde; o-Chlorobenzenecarboxaldehyde

89-98-5

CINNAMIC ALDEHYDE

Cinnamal; Phenylacrolein; 3-Phenylacrylaldehyde; 3-Phenyl-2-propenal

14371-10-9

CROTONALDEHYDE

2-Butenal; Crotonic aldehyde; β-methylacrolein

UN1143

4170-30-3

DICHLOROETHYL FORMAL

Bis(2-chloroethoxy)-methane; Bis(β-chloroethyl)formal; Bis(2-chloroethyl)formal; Dichloroethyl formal; Di-2-chloroethyl formal; Ethane, 1,1'-(Methylenebis(oxy))bis(2-chloro-; formaldehyde bis-(β-chloroethyl) acetal

111-91-1

2,2-DIMETHYL-1,3-DIOXOLANE-4-METHANOL

2,2-Dimethyl-5-hydroxymethyl-1,3-dioxolane; 2,2-Dimethyl-4-oxymethyl-1,3-dioxolane; Glycerolacetone; 4-Hydroxymethyl-2,2-dimethyl-1,3-dioxolane; Isopropylidene glycerol

100-79-8

DIMETHYLACETAL

1,1-Dimethoxyethane; Dimethyl aldehyde; Ethylidene dimethyl ether; Methyl formyl

UN2377

534-15-6

p-DIOXANE

1,4-Diethylene dioxide; Diethylene dioxide; Diethylene ether; Dioxane; 1,4-Dioxane

UN1165

123-91-1

2-ETHYLHEXANAL

Butyl ethyl acetaldehyde; Ethylbutylacetaldehyde; Ethylhexaldehyde; 2-Ethylhexaldehyde

123-05-7

FORMALDEHYDE

Methanal; Methyl aldehyde; Methylene glycol; Methylene oxide

UN1198

UN2206

50-00-0

GLUTARALDEHYDE

Glutaral; Glutardialdehyde; Glutaric dialdehyde; 1,5-Pentanedial; 1,5-Pentanedione

111-30-8

GLYCIDALDEHYDE

2,3-Epoxypropanal; 2,3-Epoxypropionaldehyde; Glycidal; Propionaldehyde

UN2622

765-34-4

3-HYDROXYBUTYRALDEHYDE

Acetaldol; Aldol; 3-Butanolal; Oxybutanal

UN2839

107-89-1

ISOBUTYLALDEHYDE

Isobutanal; Isobutyral; Isopropyl formaldehyde; Methyl propanal

UN2045

78-84-2

METALDEHYDE

Metacetaldehyde; 2,4,6,8-Tetramethyl-1,3,5,7-tetroxocane

UN1332

108-62-3

METHYLAL

Dimethoxymethane; Dimethyl formal; Formaldehyde dimethylacetal; Methylal; Methylene dimethyl ether

UN1234

109-87-5

4-MORPHOLINECARBOXALDEHYDE

N-Formylmorpholine; 4-Formylmorpholine

4394-85-8

PARAFORMALDEHYDE

Paraform; Triformol; Trioxymethylene

UN2213

30525-89-4

PARALDEHYDE

Paracetaldehyde; Paral; 2,4,6-Trimethyl-1,3,5-trioxane

UN1264

123-63-7

PROPIONALDEHYDE

Methylacetaldehyde; Propaldehyde; Propanal; Propionic aldehyde; Propyl aldehyde

UN1275

123-38-6

SAFROLE

5-Allyl-1,3-benzodioxole; Allyldioxybenzene methylene ether; 1-Allyl-3,4-methylenedioxybenzene; 4-Allyl-1,2-methylenedioxybenzene

94-59-7

3,5,5-TRIMETHYLHEXANAL

tert-Butylisopentanal; Isononylaldehyde

5435-64-3

TRIOXANE

Triformol; sym-Trioxane; 1,3,5-Trioxane; Trioxymethylene

110-88-3

VALERALDEHYDE

Amyl aldehyde; Butyl formal; Pentanal; Valeric aldehyde; Valeral

UN2058

110-62-3

Table 104.14 Health hazards

Chemical Name

     CAS-Number

ICSC Short-Term Exposure

ICSC Long-Term Exposure

ICSC Routes of Exposure and Symptoms

US NIOSH Target Organs & Routes of Entry

US NIOSH Symptoms

ACETALDEHYDE

     75-07-0

eyes; skin; GItract; resp tract; lungs; CNS

skin; lungs; CNS; liver

Inhalation: cough, drowsiness, shortness of breath, unconsciousness, symptoms may be delayed

Skin: redness, burning sensation, pain

Eyes: redness, pain, blurred vision

Ingestion: burning sensation, diarrhoea, dizziness, nausea, vomiting

Eyes; skin; resp sys; kidneys; CNS; repro sys (in animals: nasal cancer)

Inh, ing, con

Irrit eyes, nose, throat; eye, skin burns; derm; conj; cough; CNS depres; delayed pulm edema; in animals: kidney, repro, terato effects; (carc)

ACROLEIN

     107-02-8

eyes; skin; resp tract; lungs

 

Inhalation: corrosive, burning sensation, cough, laboured breathing, shortness of breath, sore throat, symptoms may be delayed

Skin: corrosive, redness, serious skin burns, pain, blisters

Eyes: corrosive, redness, pain, severe deep burns

Ingestion: abdominal cramps, burning sensation, collapse

Heart; eyes; skin; resp sys

Inh, ing, con

Irrit eyes, skin, muc memb; decr pulm func; delayed pulm edema; chronic resp disease

BENZALDEHYDE

     100-52-7

eyes; skin; resp tract; lungs

skin

Inhalation: respiratory paralysis, shortness of breath, burning sensation of eye and nose mucosa, cough, dizziness

Skin: may be adsorbed, redness, loss of sensation contact dermatitis

Eyes: redness, pain

Ingestion: burning sensation, sensation, confusion,dizziness, drowsiness, headache, shortness of breath, unconsciousness, vomiting, convulsions

 

 

BUTYLALDEHYDE

     123-72-8

eyes; skin; resp tract; lungs

 

Inhalation: burning sensation, cough, sore throat

Skin: redness

Eyes: redness, pain

Ingestion: burning sensation

 

 

CHLORAL HYDRATE

     302-17-0

eyes; skin; resp tract; CNS; kidneys; liver; CVS

 

Inhalation: Confusion, drowsiness, nausea, unconsciousness.

Skin: Redness

Eyes: Redness

Ingestion: Abdominal pain, vomiting

 

 

o-CHOROBENZALDEHYDE

     89-98-5

eyes; skin; liver; kidneys

skin

Inhalation: burning sensation, cough, sore throat

Skin: may be absorbed, redness, burning sensation, pain

Eyes: redness, pain

Ingestion: abdominal cramps, burning sensation

 

 

2,2-DIMETHYL-1,3-DIOXOLANE- 4-METHANOL

     100-79-8

eyes; CNS

 

Inhalation: cough, sore throat

Eyes: redness

Ingestion: weakness

 

 

p-DIOXANE

     123-91-1

eyes; resp tract; CNS; liver; kidneys

skin

Inhalation: headache, nausea, cough, sore throat, abdominal pain, dizziness, drowsiness, vomiting, unconsciousness

Skin: may be absorbed, redness

Eyes: redness, irritant, pain

Liver; kidneys; skin; eyes; resp sys (in animals: lung, liver & nasal cavity tumors)

Inh, abs, ing, con

Irrit eyes, skin, nose, throat; drow, head, nau, vomit; liver damage; kidney failure; (carc)

ETHYL HEXALDEHYDE

     123-05-7

eyes; skin; resp tract

skin

Inhalation: burning sensation, cough, vomiting

Skin: may be absorbed, redness

Eyes: redness, pain

Ingestion: abdominal pain, nausea, vomiting

 

 

FORMALDEHYDE

     50-00-0

eyes; skin; resp tract; lungs

skin

Inhalation: burning sensation inthe nose and throat, cough, headache, laboured breathing, nausea, shortness of breath

Skin: redness

Eyes: effects will be delayed, redness, pain, blurred vision, severe deep burns

Resp sys; eyes; skin [nasal cancer]

Inh, con

Irrit eyes, nose, throat, resp sys; lac; cough; bron spasm; (carc)

GLUTARALDEHYDE

     111-30-8

eyes; skin; resp tract

skin; resp tract

 

Eyes; skin; resp sys

Inh, abs, ing, con

Irrit eyes, skin, resp sys; derm, sens skin; cough, asthma; nau, vomit

METHYLAL

     109-87-5

eyes; skin; resp tract

skin

Inhalation: cough, dizziness, drowsiness, headache, sore throat, unconsciousness

Skin: may be absorbed, dry skin, defats the skin, redness, pain

Eyes: redness, pain

Ingestion: abdominal pain, nausea, vomiting

Eyes; skin; resp sys; CNS

Inh, ing, con

Irrit eyes, skin, upper resp sys; anes

PARAFORMALDEHYDE

     30525-89-4

eyes; skin; resp tract

skin

Inhalation: cough, sore throat

Skin: redness

Eyes: redness

 

 

PROPANAL

     123-38-6

 

 

Inhalation: burning sensation, cough, laboured breathing, sore throat

Skin: redness

Eyes: redness, pain

Ingestion: burning sensation

Eyes; skin; resp sys; lungs

 

Table 104.15 Physical & chemical hazards

For UN Class: 1.5 = very insensitive substances which have a mass explosion hazard; 2.1 = flammable gas; 2.3 = toxic gas; 3 = flammable liquid; 4.1 = flammable solid; 4.2 = substance liable to spontaneous combustion; 4.3 = substance which in contact with water emits flammable gases; 5.1 = oxidizing substance; 6.1 = toxic; 7 = radioactive; 8 = corrosive substance

Chemical Name

CAS-Number

Physical

Chemical

Un Class/Div /  Subsidiary Risks

ACETAL

105-57-7

 

 

3

ACETALDEHYDE

75-07-0

The vapour is heavier than air and may travel along the ground; distant ignition possible

The substance can form explosive peroxides in contact with air •The substance may polymerize under the influence of acids, alkaline materials, such as sodium hydroxide, in the presence of trace metals (iron) with fire or explosion hazard •The substance is a strong reducing agent and reacts violently with oxidants •Reacts violently with various organic substances, halogens, sulfuric acid and amines, causing fire and explosion hazard

3

ACROLEIN

107-02-8

The vapour is heavier than air and may travel along the ground; distant ignition possible

The substance can form explosive peroxides •The substance may polymerize with fire and explosion hazard •Upon heating, toxic fumes are formed •Reacts with alkalis, acids, amines, sulfur dioxide, thiourea, metal salts and oxidants causing fire and explosion hazard

6.1/ 3

BUTYLALDEHYDE

123-72-8

The vapour is heavier than air, and may travel along the ground; distant ignition possible

The substance may polymerize due to heating, under the influence of acids or alkalis •On combustion, forms toxic gases •Reacts with oxidants •Reacts violently with strong acids and bases

3

CHLORAL

75-87-6

 

 

6.1

CHLOROACETALDEHYDE

107-20-0

The vapour is heavier than air

Upon heating, toxic fumes are formed •Reacts with water to form a hydrate with the evolution of some heat •Reacts with oxidants and acids, causing explosion hazard •The anhydrous substance can polymerize on standing

6.1

o-CHOROBENZALDEHYDE

89-98-5

 

The substance decomposes on heating, producing toxic and corrosive fumes including hydrogen chloride •Acts with iron, strong bases, strong oxidants, strong reducing agents and moisture

 

CROTONALDEHYDE

4170-30-3

 

 

6.1/ 3

2,2-DIMETHYL-1,3-DIOXOLANE-4-METHANOL

100-79-8

 

Reacts with oxidants

 

p-DIOXANE

123-91-1

The vapour is heavier than air and may travel along the ground; distant ignition possible •As a result of flow, agitation, etc, electrostatic charges can be generated

The substance can form explosive peroxides •Reacts vigorously with strong oxidants and concentrated strong acids •Reacts explosively with some catalysts (eg, Raney-nickel above 210°C) •Attacks many plastics

3

2-ETHYL HEXALDEHYDE

123-05-7

The vapour is heavier than air

The substance can form explosive peroxides on long-lasting contact with oxygen or air •The substance polymerize on contact with sodium hydroxide, ammonia, butyl- and dibutylamine, inorganic acids •Reacts with oxidants

3

FORMALDEHYDE

50-00-0

 

 

3/ 8

GLYCIDALDEHYDE

765-34-4

 

 

3/ 6.1

GLUTARALDEHYDE

111-30-8

 

Produces acrid smoke and fumes (carbon monoxide, carbon dioxide)

 

3-HYDROXYBUTYRALDEHYDE

107-89-1

 

 

6.1

ISOBUTYRALDEHYDE

78-84-2

 

 

3

METHYLAL

109-87-5

The vapour is heavier than air and may travel along the ground; distant ignition possible

The substance can presumably form explosive peroxides •May explode on heating and on burning producing carbon dioxide and/or carbon monoxide •Reacts vigorously with strong oxidants causing fire and explosion hazard

3

PARAFORMALDEHYDE

30525-89-4

Dust explosion possible if in powder or granular form, mixed with air

The substance decomposes on heating producing formaldehyde •Reacts with oxidants •Reacts with strong acids and strong bases producing formaldehyde

4.1

PARALDEHYDE

123-63-7

 

 

3

PHENYL CHLOROFORMATE

1885-14-9

 

 

6.1/ 8

PROPANAL

123-38-6

The vapour is heavier than air and may travel along the ground; distant ignition possible

The substance may polymerize due to heating and under the influence of acids and caustics •On combustion, forms toxic gases (carbon oxides) and combustible gas •Reacts violently with oxidants, acids and bases

3

VALERALDEHYDE

110-62-3

 

 

 

Table 104.16 Physical & chemical properties

Chemical Name

CAS-Number

Colour/Form

Boiling Point (°C)

Melting Point (°C)

Molecular Weight

Solubility in Water

Relative Density (water=1)

Relative Vapour Density (air=1)

Vapour Pressure/ (Kpa)

Inflam. Limits

Flash Point (°C)

Auto Ignition Point (°C)

ACETAL

105-57-7

colourless liquid

102.2

-100

118.17

sol

0.83

4.08

20mmHg

1.6 ll 10.4 ul

-21 cc

230

ACETALDEHYDE

75-07-0

colourless liquid; colourless gas

21

-123

44.05

misc

0.788  @16°C/4°C

1.52

99

4 ll 57 ul

-39

185

ACROLEIN

107-02-8

colourless or yellowish liquid

53

-88

56.06

v sol

0.84

1.94

29

2.8 ll 31 ul

-26 cc

234

BENZALDEHYDE

100-52-7

colourless liquid

179

-26

106.12

sl sol

1.050  @15°C/4°C

3.66

1mmHg  @26°C

 

63 cc

179

BUTYLALDEHYDE

123-72-8

colourless liquid; water-white liquid

74.8

-99

72.10

sol

0.8

2.5

12.2

1.9 ll 12.5 ul

-667 cc

230

CHLOROACETALDEHYDE

107-20-0

clear, colourless liquid

85.5

-16.3

78.50

misc

1.19

2.7

13.3

 

877 cc

88

CHLORAL

75-87-6

oily liq

97.8 ° C  @ 760 mm Hg

-57.5

147.40

sol

1.5121  @ 20 ° C/4 ° C

5.1

35 mm Hg  @ 20 ° C

 

 

 

CHLORAL HYDRATE

302-17-0

transparent, colorless crystals; large monoclinic plates; colorless or white crystals

96.3 ° C  @ 764 mm Hg (decomp)

57 ° C

165.42

14.3 g/ml water at 40 ° C

1.908  @ 20 ° C/4 ° C

 

 

 

 

 

o-CHOROBENZALDEHYDE

89-98-5

colourless to yellowish liquid

211.9

12.4

140.6

sl sol

1.2483

 

0.04

 

90 cc

385

CINNAMMICALDEHYDE

104-55-2

yellowish oily liquid;greenish-yellow liquid

253

-7.5

132.15

700ml

1.048-1.052  @25°C/ 25°C

4.6

1mmHg  @76°C

 

120

 

CROTONALDEHYDE

4170-30-3

water-white to straw-coloured liquid

104.0

-76.5

70.09

18.1g/100g

0.853

2.41

19mmHg

2.1 ll 15.5 ul

13 oc

232.2

DICHLOROETHYL FORMAL

111-91-1

colorless liquid

218.1

-32.8

173.05

81,000 mg/l  @ 25 ° C

1.2339  @ 20 ° C/20 ° C

6.0

0.1 mm Hg  @ 20 ° C

 

110 ° C

 

2,2-DIMETHYL-1,3-DIOXOLANE-4-METHANOL

100-79-8

colourless liquid

188-189

-26.4

132.2

misc

1.064

4.6

 

 

80 cc

 

DIMETHYLACETAL

534-15-6

colourless liquid; mobile liquid

64.5

-113

90.1

sol

0.85015

3.1

61mmHg

 

 

 

p-DIOXANE

123-91-1

colourless liquid

101.0

11.8

88.10

misc

1.0337

3.03

4.1

2.0 ll 22 ul

12

180

ETHYLHEXALDEHYDE

123-05-7

colourless liquid

163

-76

128.22

insol

0.8540

4.4

0.2

0.85  @93°C, ll 7.2  @135°C ul

50-52

190-210

FORMALDEHYDE

50-00-0

clear, water-white, very slightly acid,gas or liquid.; formaldehyde solution is a clear, colourless or nearly colourless liquid .

-19.5

-92

30.03

sol

0.8

1.08

 

7.0 ll 73 ul

flammable gas

300

GLUTARALDEHYDE

111-30-8

colourless liquid

187-189

-14

100.13

sol

0.72

3.4

17mmHg

 

 

 

GLYCIDALDEHYDE

765-34-4

colourless liquid

112-113

-62

72.1

misc

1.1403

2.58

27mmHg  @t 25°C

 

 

 

3-HYDROXYBUTYRALDEHYDE

107-89-1

clear, white to yellow syrupy liquid; colourless thick liquid

83

 

88.10

misc

1.103

3.00

21mmHg

 

 

 

ISOBUTYLALDEHYDE

78-84-2

transparent, colourless liquid

64.5

-65.9

72.10

sol

0.7938

2.48

173mmHg  @25°C

1.6 ll 10.6 ul

 

196

METALDEHYDE

 108-62-3

 

110

47

176.21

 

 

 

 

 

 

 

METHYLAL

109-87-5

colourless, clear liquid

42

-105

76.09

sol

0.8593

2.6

44

1.6 ll 17.6 ul

-18 oc

237

4-MORPHOLINECARBOXYALDEHYDE

4394-85-8

 

236.5

 

115.13

 

 

 

 

 

 

 

PARAFORMALDEHYDE

30525-89-4

white crystalline powder; white, amorphous powder

 

155-170

variable polymer

sl sol

1.46  @15°C (solid)

 

< 0.2  @25°C

7.0 ll 73.0 ul

71 cc

300

PARALDEHYDE

123-63-7

colourless, transparent liquid

124

12.6

132.16

sl sol

0.9943

4.5

25.3mmHg

1.3 ll ? ul

 

 

PROPANAL

123-38-6

colourless liquid

49

-81

58.08

sol

0.8071  @25°C

2.0

31.3

2.6 ll 16.1 ul

-30

207

SAFROLE

94-59-7

colourless or pale yellow oil; monoclinic crystals

234.5

11.2

162.18

insol

1.1

 

1mmHg  @63.8°C

 

97

 

TRIOXANE

110-88-3

crystalline solid; rhombic needles from ether; white

114.5

64

90.08

v sol

1.17  @65°C

 

 

 

45

 

VALERALDEHYDE

110-62-3

colourless liquid

103

-91.5

86.13

sl sol

0.8095

3.0

50mmHg  @25°C

 

 

 

ALKALINE MATERIALS

David L. Hinkamp

This article discusses ammonia, sodium, potassium, calcium and lithium, and their compounds. With the exception of ammonia, these are the most common alkali and alkaline earth metals.

Uses

Ammonia is an important source of various nitrogen-containing compounds. An enormous quantity of ammonia is used in the production of ammonium sulphate and ammonium nitrate, which are used as fertilizers. Ammonia is further used for oxidation into nitric acid, for the production of synthetic urea and soda, and for the preparation of water solutions used in chemical and pharmaceutical industries. It is employed in the explosives industry, in medicine and in agriculture. In refrigeration, ammonia is used to lower temperatures below the freezing point and for the manufacture of synthetic ice.

Ammonium hydroxide is employed in the textile, rubber, pharmaceutical, ceramics, photography, detergent and food industries. It is also used in extracting such metals as copper, nickel and molybdenum from their ores. Ammonium hydroxide is useful for removing stains and bleaching. It is a household cleansing agent as well as a solvent for casein in the pulp and paper industry. Diammonium phosphate is used for fireproofing textiles, paper and wood products. It is found in fertilizers and in flux for soldering metals. Ammonium chloride is used in flux for coating sheet iron with zinc, in safety explosives, medicine, and in cement for iron pipes. In addition, it is utilized in tinning, dyeing, electroplating and tanning.

Calcium is the fifth most abundant element and the third most abundant metal; it is widespread in nature as calcium carbonate (limestone and marble), calcium sulphate (gypsum), calcium fluoride (fluorspar) and calcium phosphate (apatite). Calcium minerals are quarried or mined; the metallic calcium is obtained by the electrolysis of molten calcium chloride or fluoride. Metallic calcium is used in the production of uranium and thorium and in the electronics industry. It serves as a deoxidizer for copper, beryllium and steel, and as a hardener for lead bearings. In addition, calcium is an industrial catalyst for polyester fibres.

Calcium chloride is obtained as a waste product in the Solvay ammonia-soda process. It is used as a pavement de-icer, a refrigerant, and as a drying agent in air-conditioning systems. Calcium chloride is utilized in the production of barium chloride, metallic calcium and various dyes. It is also used to prevent dust formation during road construction, to accelerate concrete curing times, and to inhibit spontaneous combustion of coal in coal mines. Calcium nitrate is used in agriculture as a fertilizer and in match manufacture as an oxidizing agent. It is also found in the explosives and pyrotechnics industries. Calcium sulphite is used as a reducing agent in the production of cellulose. Calcium carbide is used for the industrial production of acetylene and in the manufacture of calcium cyanamide. It is employed in the pyrotechnics industry and in acetylene generators for acetylene lamps. Calcium carbide is also used for oxyacetylene welding and cutting.

Lime is a general term for the products of calcined limestone—for example, calcium oxide and calcium hydroxide. Calcium oxide is used as a refractory material, as a flux in steelmaking, a binding agent in the building industry and as the raw material for chlorinated lime bleaching powder. It is employed in the pulp and paper, sugar refining, agriculture and leather tanning industries. Calcium hydroxide is used in building and civil engineering for mortars, plasters and cements. It is used for soil treatment, dehairing hides and fireproofing. Calcium hydroxide also finds use in lubricants and in the pulp and paper industry.

Lithium is used as a “getter” in vacuum tubes, a constituent of solder and brazing alloys, a coolant or heat exchanger in reactors, and as a catalyst in the manufacture of synthetic rubber and lubricants. It finds use in the manufacture of catalysts for polyolefin plastics and in the metal and ceramics industries. Lithium is also used in special glasses and in fuels for aircraft and missiles. Lithium chloride is used in the manufacture of mineral waters and for soldering aluminium. It is employed in the pyrotechnics industry and in medicine as an antidepressant. Lithium carbonate is utilized in the production of glazes on ceramic and electrical porcelain and for the coating of arc-welding electrodes. It is found in luminescent paints, varnishes and dyes. Lithium carbonate is also used in medicine as a mood-stabilizing drug and antidepressant. Lithium hydride is a source of hydrogen and a nuclear shielding material.

Potassium is used in the synthesis of inorganic potassium compounds. It is found in agriculture as a component of fertilizers. Potassium is also employed in sodium-potassium alloy for heat transfer in nuclear reactor systems and in high-reading thermometers.

Potassium hydroxide is used for the manufacture of liquid soap, for absorbing carbon dioxide, mercerizing cotton, and for the production of other potassium compounds. It finds use in electroplating, in lithography and as a mordant for wood. Potassium hydroxide is also used in paint and varnish removers and in printing inks.

Other potassium compounds include potassium bromate, potassium chlorate, potassium nitrate, potassium perchlorate and potassium permanganate. They are used in the pyrotechnics, food and explosives industries, and they serve as oxidizing agents. Potassium chlorate is a component of match tips, a bleaching agent and a dyeing agent for furs, cotton and wool. It is also used in the dye-stuffs and pulp and paper industries. Potassium chlorate is used in the manufacture of explosives, matches, pyrotechnics and dyes.

Potassium bromate is a dough conditioner, a food additive, an oxidizing agent and a permanent wave compound. Potassium nitrate is used in fireworks, fluxes, gunpowder and in the glass, match, tobacco and ceramics industries. It is also used for pickling meats and for impregnating candle wicks. Potassium nitrate acts as a fertilizer in agriculture and as an oxidizer in solid rocket propellants. Potassium perchlorate is used in the explosives, pyrotechnics and photography industries. It serves as an inflating agent in automobile safety air bags. Potassium permanganate is used as an oxidizing agent, a disinfectant and a bleaching agent in the leather, metal and textile industries. It is also employed in metal cleaning, separation and purification in mining. In addition, potassium permanganate is a tanning agent in the leather industry.

Sodium is used in the manufacture of sodium compounds and in organic syntheses. It serves as a reducing agent for metals and as a coolant in nuclear reactors. Sodium is also found in sodium lamps and in electric power cable. Sodium chlorate is an oxidizing agent in the dye-stuffs industry and an oxidizing and bleaching agent in the pulp and paper industry. It is used for dyeing and printing fabrics, tanning and finishing leather, and uranium processing. It is also employed as an herbicide and a rocket fuel oxidant. Sodium chlorate finds additional uses in the explosives, match and pharmaceutical industries.

Sodium hydroxide is used in the rayon, mercerized cotton, soap, paper, explosives, dye-stuffs and chemical industries. It is also used in metal cleaning, electrolytic extraction of zinc, tin plating, laundering and bleaching. Trisodium phosphate finds use in photographic developers, in detergent mixtures and in the paper industry. It it used for clarifying sugar, removing boiler scale, softening water, laundering, and for tanning leather. Trisodium phosphate is also a water-treatment agent and an emulsifier in processed cheese. Disodium phosphate is used in fertilizers, pharmaceuticals, ceramics and detergents. It is used for weighting silk, dyeing and printing in the textile industry, and for fireproofing wood and paper. Disodium phosphate is also a food additive and a tanning agent. Sodium hypochlorite is a household and laundry bleaching agent, and a bleaching agent in the paper, pulp and textile industries. It is employed as a disinfectant for glass, ceramics and water as well as a sanitizer in swimming pools. Sodium chloride is used for metalworking, curing hides, highway de-icing, and preserving food. It also finds use in the photography, chemical, ceramic and soap industries, and in nuclear reactors.

The salts of carbonic acid (H2CO3), or carbonates, are widespread in nature as minerals. They are used in the construction, glass, ceramics, agriculture and chemical industries. Ammonium bicarbonate is used in the plastics, ceramics, dye-stuffs and textile industries. It finds use as a blowing agent for foam rubber and as a leavening agent in the production of baked goods. Ammonium bicarbonate is also used in fertilizers and in fire extinguishers. Calcium carbonate is used primarily as a pigment and is employed in the paint, rubber, plastics, paper, cosmetics, match and pencil industries. Calcium carbonate also finds use in the manufacture of Portland cement, foods, polishes, ceramics, inks and insecticides. Sodium carbonate is widely used in the manufacture of glass, caustic soda, sodium bicarbonate, aluminium, detergents, salts and paints. It is utilized for the desulphurization of pig iron and for the purification of petroleum. Sodium bicarbonate is used in the confectionery, pharmaceutical, non-alcoholic beverage, leather and rubber industries, and for the manufacture of fire extinguishers and mineral waters. Potassium carbonate is widely used in potash fertilizers and in the textile industry for dyeing wool. It also finds use in the glass, soap and pharmaceutical industries.

Alkalis

Alkalis are caustic substances which dissolve in water to form a solution with a pH substantially higher than 7. These include ammonia; ammonium hydroxide; calcium hydroxide and oxide; potassium; potassium hydroxide and carbonate; sodium; sodium carbonate, hydroxide, peroxide and silicates; and trisodium phosphate.

Health hazards

In general, the alkalis, whether in solid form or concentrated liquid solution, are more destructive to tissues than most acids. The free caustic dusts, mists and sprays may cause irritation of the eyes and respiratory tract, and lesions of the nasal septum. Strong alkalis combine with tissue to form albuminates, and with natural fats to form soaps. They gelatinize tissue to form soluble compounds which may result in deep and painful destruction. Potassium and sodium hydroxide are the most active materials in this group. Even dilute solutions of the stronger alkalis tend to soften the epidermis and emulsify or dissolve the skin fats. First exposures to atmospheres slightly contaminated with alkalis may be irritating, but this irritation soon becomes less noticeable. Workers often work in such atmospheres without showing any effect, while this exposure will cause coughing and painful throat and nasal irritation in unaccustomed persons. The greatest hazard associated with these materials is the splashing or splattering of particles or solutions of the stronger alkalis into the eyes.

Potassium hydroxide and sodium hydroxide. These compounds are very dangerous to the eyes, both in liquid and solid form. As strong alkalis, they destroy tissues and cause severe chemical burns. Inhalation of dusts or mists of these materials can cause serious injury to the entire respiratory tract, and ingestion can severely injure the digestive system. Even though they are not flammable and will not support combustion, much heat is evolved when the solid material is dissolved in water. Therefore, cold water must be used for this purpose; otherwise the solution may boil and splatter corrosive liquid over a wide area.

Carbonates and bicarbonates. The principal carbonates are: calcium carbonate (CaCO3), magnesite (MgCO3), soda ash (NaCO3), sodium bicarbonate (NaHCO3) and potash (K2CO3). The normal carbonates (with the anion CO3) and the acid or bicarbonates (with the anion HCO3) are the most important compounds. All bicarbonates are water-soluble; of the normal carbonates only the salts of alkaline metals are soluble. Anhydrous carbonates decompose when being heated before reaching the melting point. Carbonate solutions give rise to alkaline reactions because of the considerable hydrolysis involved. The bicarbonates are converted to normal carbonates by heating:

     2 NaHCO3 = Na2CO3 + H2O + CO2

The normal carbonates are decomposed by strong acids (H2SO4, HCl) and set free CO2.

The sodium carbonates occur in the following forms: soda ash—anhydrous sodium carbonate (Na2CO3); crystallized soda— sodium bicarbonate (NaHCO3); and sodium carbonate decahydrate (Na2CO3·10 H2O).

Alkaline carbonates may cause harmful irritation of the skin, the conjunctivae and the upper airways during various industrial operations (handling and storage, processing). Workers who load and unload bagged carbonates may present cherry-sized necrotic skin portions on their arms and shoulders. Rather deep ulcerated pitting is sometimes observed after the black-brown scabs have fallen off. Prolonged contact with soda solutions may cause eczema, dermatitis and ulceration.

Calcium and compounds. Calcium is a well-known essential constituent of the human body, and its metabolism, alone or in association with phosphorus, has been widely studied with special reference to the musculoskeletal system and cellular membranes. Several conditions may lead to calcium losses such as immobilization, gastrointestinal disturbances, low temperature, weightlessness in space flights and so on. The absorption of calcium from the work environment by inhalation of calcium compounds dust does not increase significantly the calcium daily intake from vegetables and other food (usually 0.5 g). On the other hand, metallic calcium has alkaline properties, and it reacts with moisture, causing eye and skin burns. Exposed to air it may present an explosion hazard.

Calcium carbide. Calcium carbide exerts a pronounced irritant effect due to the formation of calcium hydroxide upon reaction with moist air or sweat. Dry carbide in contact with skin may cause dermatitis. Contact with moist skin and mucous membranes leads to ulceration and scarring. Calcium carbide is particularly hazardous to the eyes. A peculiar type of melanoderma with strong hyperpigmentation and numerous telangiectases is often observed. Burns caused by hot calcium carbide are common. The tissues are generally damaged in depths of 1 to 5 mm; the burns evolve very slowly, are difficult to treat, and often require excision. Injured workers may resume work only after the burnt skin surface is completely scarred. Persons exposed to calcium carbide frequently suffer from cheilitis characterized by dryness, swelling and hyperaemia of the lips, intense desquamation, and deep radial fissures; erosive lesions with a tendency to suppuration can be observed in the mouth angles. Workers with a long professional history often suffer from nail lesions—that is, occupational onychia and paronychia. Eye lesions with pronounced hyperaemia of the lids and conjunctiva, often accompanied by mucopurulent secretions, are also observed. In heavy cases the sensitivity of the conjunctiva and cornea is strongly reduced. While the keratitis and keratoconjunctivitis evolve first without symptoms, they may later degenerate into corneal opacities.

In calcium carbide production, impurities may produce additional hazards. Calcium carbide contaminated with calcium phosphate or calcium arsenate may, when moistened, give off phosphine or arsine, both of which are extremely toxic. Calcium carbide itself, when exposed to damp air, gives off acetylene, which is a moderate anaesthetic and asphyxiant, and a considerable fire and explosion hazard.

Calcium chloride has a powerful irritant action on the skin and mucous membranes, and cases have been reported, amongst workers packing dry calcium chloride, of irritation accompanied by erythema and peeling of facial skin, lacrimation, eye discharge, burning sensation and pain in the nasal cavities, occasional nose bleeding and tickling in the throat. Cases of perforation of the nasal septum have also been reported.

Calcium nitrate has an irritating and cauterizing action on skin and mucous membranes. It is a powerful oxidizing agent and presents a dangerous fire and explosion hazard.

Calcium sulphite. Cases of occupational calcium sulphite poisoning do not appear to have been reported. Accidental ingestion of a few grams may produce repeated vomiting, violent diarrhoea, circulatory disorders and methaemoglobinaemia.

Ammonia

Ammonia is present in small amounts in the air, water, earth, and particularly in decomposing organic matter. It is the product of normal human, animal and plant metabolism. Muscular effort and excitement of the nervous system result in the formation of an increased amount of ammonia, an accumulation of which in the tissues would result in poisoning. Endogenous formation of ammonia increases also in the course of many diseases. Through vital processes it is combined and excreted from the organism, mainly via urine and sweat, in the form of ammonium sulphate and urea. Ammonia is also of primary importance in the nitrogen metabolism of plants.

Ammonia is lightly reactive, easily undergoing oxidation, substitution (of hydrogen atoms) and additional reactions. It burns in air or in hydrogen to form nitrogen. An example of substitution would be the formation of amides of alkaline and alkaline-earth metals. As a result of addition it forms ammoniates (e.g., CaCl2·8NH3, AgCl3NH3) and other compounds. When ammonia dissolves in water, it forms ammonium hydroxide (NH4OH), which is a weak base and dissociates as follows:

     NH4OH → NH4+ + OH-

The radical NH4+ does not exist in free form since it decomposes into ammonia and hydrogen when an attempt is made to isolate it.

Ammonia poisoning may occur in the production of ammonia and in the manufacture of nitric acid, ammonium nitrate and sulphate, liquid fertilizers (ammoniates), urea and soda, in refrigeration, synthetic ice factories, cotton printing mills, fibre dyeing, electroplating processes, organic synthesis, heat treatment of metals (nitriding), chemical laboratories, and in a number of other processes. It is formed and emitted into the air during the processing of guano, in the purification of refuse, in sugar refineries and tanneries, and it is present in unpurified acetylene.

Industrial poisoning is usually acute, while chronic poisoning, although possible, is less common. The irritant effect of ammonia is felt especially in the upper respiratory tract, and in large concentrations it affects the central nervous system, causing spasms. Irritation of the upper respiratory tract occurs at concentrations of above 100 mg/m3, while the maximum tolerable concentration in 1 hour is between 210 and 350 mg/m3. Splashes of ammonia water into the eyes are particularly dangerous. The rapid penetration of ammonia into the ocular tissue may result in perforation of the cornea and even in death of the eyeball. Particular health hazards exist in each section of an ammonia plant. In the sections where the gas is generated, converted (oxidation of CO to CO2), compressed and purified, the main problem is the emission of carbon monoxide and hydrogen sulphide. Considerable quantities of ammonia may escape during its synthesis. Escaping ammonia in the atmosphere may reach explosive limits.

Chlorates and perchlorates

Chlorates and perchlorates are the salts of chloric acid (HClO3) and perchloric acid (HClO4 ). They are strong supporters of combustion, and their main hazard is associated with this property. The potassium and sodium salts are typical of the group and are those most commonly used in industry.

Fire and explosion hazards. Chlorates are powerful oxidizing agents, and the main dangers are those of fire and explosion. They are not themselves explosive but they form flammable or explosive mixtures with organic matter, sulphur, sulphides, powdered metals and ammonium compounds. Cloth, leather, wood and paper are extremely flammable when impregnated by these chlorates.

Perchlorates are also very strong oxidizing agents. Heavy metal salts of perchloric acid are explosive.

Health hazards. Chlorates are harmful if absorbed by ingestion or by inhalation of the dust, which can provoke sore throat, coughing, methaemoglobinaemia with bluish skin, dizziness and faintness, and anaemia. In case of large absorption of sodium chlorate an increased sodium content in the serum will be seen.

Perchlorates may enter the body either by inhalation as dust or by ingestion. They are irritant to skin, eyes and mucous membranes. They cause haemolytic anaemia with methaemoglobinaemia, Heinz bodies in the red cells, and liver and kidney injuries.

Alkaline materials tables

Table 104.17 Chemical identification

CHEMICAL

SYNONYMS

UN CODE

CAS-NUMBER

CHEMICAL FORMULA

AMMONIA

Ammonia anhydrous

UN1005

7664-41-7

NH3

AMMONIUM BICARBONATE

Ammonium carbonate; Ammonium hydrogen carbonate; Carbonic acid, monoammonium salt; Monoammonium carbonate

1066-33-7

(NH4)2 CO3

AMMONIUM CHLORIDE

Salmiac

12125-02-9

NH4Cl

AMMONIUM FLUORIDE

Ammonium fluoride

UN2505

12125-01-8

NH4F

AMMONIUM HYDROXIDE

UN2073

UN2672

1336-21-6

NH4OH

AMMONIUM NITRATE

Nitric acid, ammonium salt

UN0222

UN1942

UN2426

6484-52-2

HNO3NH3

CALCIUM

Calcicat

UN1401

7440-70-2

Ca

CALCIUM BROMATE

 

10102-75-7

CaBrO3

CALCIUM CARBIDE

Acetylenogen; Calcium acetylide; Calcium dicarbide

UN1402

75-20-7

CaC2

CALCIUM CARBONATE

Domolite; Limestone; Marble; Portland stone

1317-65-3

CaCO3

CALCIUM CHLORATE

Chloric acid, calcium salt

UN1452

UN2429

10137-74-3

CaCl2O6

CALCIUM CHLORIDE

 

10043-52-4

CaCl2

CALCIUM HYDRIDE

 

7789-78-8

CaH

CALCIUM HYDROXIDE

Calcium dihydroxide; Calcium hydrate; Hydrated lime

1305-62-0

Ca(OH)2

CALCIUM NITRATE

Calcium dinitrate; Calcium nitrate; Calcium saltpeter

UN1454

10124-37-5

N2-O6Ca

CALCIUM NITRITE

 

13780-06-8

Ca(NO2)2

CALCIUM OXIDE

Burnt lime; Calcia; Desical p; Lime; Lime, burned

UN1910

1305-78-8

CaO

CARBONIC ACID, CALCIUM SALT

Calcium carbonate (1:1); Calcium monocarbonate

471-34-1

CaCO3

LITHIUM CARBONATE

Carbonic acid, dilithium salt; Carbonic acid lithium salt; Dilithium carbonate

554-13-2

Li2CO3

LITHIUM CHLORIDE

 

7447-41-8

LiCl

LITHIUM HYDRIDE

UN1414

UN2805

7580-67-8

LiH

LITHIUM HYDROXIDE

UN2679

UN2680

1310-65-2

LiOH

LITHIUM HYDROXIDE MONOHYDRATE

 

1310-66-3

LiOH.H2O

SODIUM TRIPOLYPHOSPHATE

Pentasodium triphosphate; Triphosphoric acid, pentasodium salt; Pentasodium tripolyphosphate; Sodium phosphate

7758-29-4

Na5P3O10

PERCHLORIC ACID, POTASSIUM SALT

Potassium hyperchloride; Potassium perchlorate

UN1489

7778-74-7

KO4Cl

PERCHLORIC ACID, SODIUM SALT

Sodium perchlorate

UN1502

7601-89-0

NaO4 Cl

POTASSIUM

UN1420

UN2257

7440-09-7

K

POTASSIUM BROMATE

UN1484

7758-01-2

KBrO3

POTASSIUM BROMIDE

Bromide salt of potassium; Tripotassium tribromide

7758-02-3

KBr

POTASSIUM CARBONATE

Carbonic acid, dipotassium salt; K-gran; Pearl ash; Potash

584-08-7

K2H2CO3

POTASSIUM CHLORATE

Potassium chlorate

UN1485

UN2427

3811-04-9

KO3Cl

POTASSIUM FLUORIDE

UN1812

7789-23-3

KF

POTASSIUM HYDROXIDE

Caustic potash; Potassium hydrate

UN1813

UN1814

1310-58-3

KOH

POTASSIUM IODATE

Iodic acid, potassium salt

7758-05-6

KIO3

POTASSIUM IODIDE

Knollide; Potide

7681-11-0

KI

POTASSIUM NITRATE

Nitric acid, potassium salt; Saltpeter

UN1486

7757-79-1

KNO3

POTASSIUM NITRITE

Nitrous acid, potassium salt

UN1488

7758-09-0

KNO2

POTASSIUM OXIDE

 

12136-45-7

KO

POTASSIUM PERIODATE

 

7790-21-8

KIO

SODIUM

UN1428

7440-23-5

Na

SODIUM BICARBONATE

Baking soda; Monosodium carbonate; Sodium acid carbonate; Sodium hydrogen carbonate

144-55-8

NaHCO3

SODIUM BROMATE

Bromic acid, sodium salt

UN1494

7789-38-0

NaBrO3

SODIUM CARBONATE

Crystol carbonate; Disodium carbonate; Soda ash; Solvay soda; Trona

497-19-8

Na2CO3

SODIUM CHLORATE

Chloric acid, sodium salt ; Soda chlorate

UN1495

UN2428

7775-09-9

NaO3Cl

SODIUM CHLORIDE

Common salt; Sea salt; Table salt

7647-14-5

NaCl

SODIUM CHLORITE

UN1496

UN1908

7758-19-2

NaHO2Cl

SODIUM ETHYLATE

Sodium ethoxide; Ethanol, sodium salt;

141-52-6

NaOC2H5

SODIUM HYPOCHLORITE

Hypochlorous acid, sodium salt;

UN1791

7681-52-9

NaOCl

SODIUM HYDROXIDE

Caustic soda; Sodium hydrate; White caustic

UN1823

UN1824

1310-73-2

NaOH

SODIUM IODIDE

Sodium iodine; Sodium monoiodide

7681-82-5

NaI

LITHIUM

UN1415

7439-93-2

Li

SODIUM METHYLATE

Sodium methoxide; Methanol, sodium salt

UN1431

UN1289

124-41-4

NaOCH3

SODIUM MONOHYDROGEN PHOSPHATE

Disodium hydrogen phosphate; Disodium orthophosphate; Disodium phosphate; Disodium phosphoric acid; Sodium hydrogen phosphate

7558-79-4

Na2HPO4

SODIUM NITRATE

Nitric acid, sodium salt; Sodium saltpeter

UN1498

7631-99-4

NaNO3

SODIUM NITRITE

Nitrous acid, sodium salt

UN1500

7632-00-0

NaNO2

SODIUM PEROXIDE

Disodium dioxide; Disodium peroxide; Sodium dioxide; Sodium oxide (Na2O2)

UN1504

1313-60-6

Na2O2

SODIUM PHOSPHATE

Tribasic sodium phosphate; Trisodium orthophosphate; Trisodium phosphate

7601-54-9

Na3PO4

TETRAMETHYLAMMONIUM CHLORIDE

Methanaminium, N,N,N-trimethyl-, chloride; N,N,N-Trimethylmethanaminium chloride

75-57-0

N(CH3)4Cl

Table 104.18 Health hazards

Chemical Name

     CAS-Number

ICSC Short Term Exposure

ICSC Long Term Exposure

ICSC Routes of Exposure and Symptoms

US NIOSH Target Organs & Routes of Entry

US NIOSH Symptoms

AMMONIA

     7664-41-7

eyes; skin; resp tract; lungs

 

Inhalation: burning sensation, cough, laboured breathing, symptoms may have delayed effects

Skin: On contact with liquid: frostbite

Eyes: severe deep burns

Eyes; skin; resp sys

Inh, abs, ing (soln), con (soln/liq)

Irrit eyes, nose, throat; dysp, bronspas, chest pain; pulm edema; pink frothy sputum; skin burns, vesic; liq: frostbite

AMMONIUM CHLORIDE

     12125-02-9

eyes; skin; resp tract

 

Inhalation: cough

Skin: redness

Eyes: redness

Ingestion: nausea, sore throat, vomiting

Eyes, skin, resp sys

Inh, con

Irrit eyes, skin, resp sys; cough, dysp, pulm sens

CALCIUM CARBIDE

     75-20-7

eyes; skin; resp tract; lungs

 

Inhalation: cough, laboured breathing, shortness of breath, sore throat

Skin: redness, skin burns, pain

Eyes: redness, pain, blurred vision, severe deep burns

Ingestion: abdominal cramps, burning sensation

 

 

CALCIUM HYDROXIDE

     1305-62-0

skin; resp tract; eyes

skin

Inhalation: burning sensation, cough

Skin: redness, roughness, burning sensation

Eyes: redness, pain, blurred vision

Ingestion: abdominal cramps, burning sensation, vomiting, weakness

Eyes, skin, resp sys

Inh, ing, con

Irrit eyes, skin, upper resp sys; eye, skin burns; skin vesic; cough, bron, pneu

CALCIUM OXIDE

     1305-78-8

eyes; skin; resp tract; lungs

skin

Inhalation: burning sensation, cough, shortness of breath

Skin: redness, skin burns, burning sensation, pain

Eyes: redness, pain, blurred vision

Ingestion: abdominal cramps, abdominal pain, burning sensation, diarrhoea, vomiting, collapse

Resp sys; skin; eyes

Inh, ing, con

Irrit eyes, skin, upper resp sys; ulcer, perf nasal septum; pneu; derm

CARBONIC ACID, CALCIUM SALT

     471-34-1

eyes; resp tract

 

Inhalation: cough

Skin: dry skin

Eyes: redness

 

 

CHLORIC ACID, SODIUM SALT

     7775-09-9

eyes; skin; resp tract; blood ;kidneys

skin

Inhalation: cough, sore throat

Skin: redness

Eyes: redness, pain

Ingestion: abdominal pain, blue lips or fingernails, blue skin, diarrhoea, nausea, shortness of breath, unconsciousness, vomiting

 

 

LITHIUM

     7439-93-2

eyes; skin; resp tract; lungs

 

Inhalation: burning sensation, cough, laboured breathing, shortness of breath

Skin: redness, pain, blisters

Eyes: redness, pain, severe deep burns

Ingestion: abdominal cramps, abdominal pain, burning sensation, nausea, shock or collapse, vomiting, weakness

 

 

LITHIUM CARBONATE

     554-13-2

eyes; skin; resp tract; CNS; CVS; GI tract

skin; CNS; CVS; stomach; kidneys; genes

Inhalation: burning sensation, cough, sore throat

Skin: redness

Eyes: redness, pain

Ingestion: abdominal cramps, abdominal pain, confusion, diarrhoea, drowsiness, nausea, vomiting

 

 

LITHIUM CHLORIDE

     7447-41-8

eyes; skin; resp tract

skin; CNS; kidneys; genes

Inhalation: burning sensation, cough, sore throat

Skin: redness, pain

Eyes: redness, pain, blurred vision

 

 

LITHIUM HYDRIDE

     7580-67-8

eyes; skin; resp tract; lungs

 

Inhalation: cough, nausea, vomiting, tremors, twitching, confusion, blurred vision, laboured breathing, symptoms may be delayed

Skin: redness, skin burns

Eyes: redness, severe deep burns

Ingestion: dizziness, nausea, vomiting, diarrhoea

Eyes; skin; resp sys; CNS

Inh, ing, con

Irrit eyes, skin; eye, skin burns; mouth, esophagus burns (if ingested); nau; musc twitches; mental conf; blurred vision

LITHIUM HYDROXIDE

     1310-65-2

 

 

Inhalation: burning sensation, cough, laboured breathing, shortness of breath

Skin: redness, pain, blisters

Eyes: redness, pain, severe deep burns

Ingestion: abdominal cramps, burning sensation, nausea, shock or collapse, vomiting, weakness

 

 

LITHIUM HYDROXIDE MONOHYDRATE

     1310-66-3

 

 

Inhalation: burning sensation, cough, laboured breathing, shortness of breath

Skin: redness, pain, blisters

Eyes: redness, pain, severe deep burns

Ingestion: abdominal cramps, burning sensation, nausea, vomiting, weakness

 

 

PERCHLORIC ACID, POTASSIUM SALT

     7778-74-7

eyes; skin; resp tract

blood

Inhalation: cough, sore throat

Skin: redness

Eyes: redness, pain

 

 

POTASSIUM CHLORATE

     3811-04-9

mucous membranes; upper resp tract; blood; liver; kidneys; CNS

skin

Inhalation: blue lips or finger nails, anemia, haemolytic haemorrhage, nausea, shortness of breath, unconsciousness, vomiting, symptoms may be delayed

Skin: redness, burning sensation

Eyes: redness, pain

Ingestion: abdominal cramps, abdominal pain, blue lips or fingernails, blue skin, diarrhoea, headache, nausea, shortness of breath, sore throat, unconsciousness, vomiting, anuria, collapse, seizure

 

 

POTASSIUM HYDROXIDE

     1310-58-3

eyes; skin; resp tract; lungs

skin

Inhalation: corrosive, burning sensation, cough, laboured breathing

Skin: corrosive, redness, serious skin burns, pain

Eyes: corrosive, redness, pain, blurred vision, severe deep burns

Ingestion: corrosive, abdominal pain, burning sensation, diarrhoea, vomiting, collapse

Eyes; skin; resp sys

Inh, ing, con

Irrit eyes, skin, resp sys; cough, sneez; eye, skin burns; vomit, diarr

POTASSIUM NITRITE

     7758-09-0

eyes; skin; resp tract; blood; CVS

 

Inhalation: blue lips or finger nails, blue skin, cough, dizziness, headache, laboured breathing, sore throat, unconsciousness

Skin: redness, pain

Eyes: redness, pain

Ingestion: blue lips or finger nails, blue skin, cough, dizziness, headache, laboured breathing, sore throat, unconsciousness, vomiting, rapid pulse

 

 

POTASSIUM OXIDE

     12136-45-7

eyes; skin; resp tract; lungs

 

Inhalation: burning sensation, cough, shortness of breath

Skin: skin burns, pain, blisters

Eyes: redness, pain, severe deep burns

Ingestion: burning sensation, shock, abdominal cramps

 

 

SODIUM HYDROXIDE

     1310-73-2

eyes; skin; resp tract; lungs

skin

Inhalation: corrosive, burning sensation, cough, laboured breathing

Skin: corrosive, redness, serious skin burns, pain

Eyes: corrosive, redness,pain, blurred vision, severe deep burns

Ingestion: corrosive, severe pain, abdominal pain, burning sensation, diarrhoea, vomiting, collapse

Eyes; skin; resp sys

Inh, ing, con

Irrit eyes, skin, muc memb; pneuitis; eye, skin burns; temporary loss of hair

SODIUM METHYLATE

     124-41-4

eyes; skin; resp tract; lungs

 

Inhalation: burning sensation, cough, laboured breathing

Skin: redness, pain, blisters

Eyes: pain, severe deep burns

Ingestion: burning sensation, abdominal pain, shock

 

 

SODIUM NITRITE

     7632-00-0

eyes; skin; resp tract; blood; CNS; kidneys

 

Inhalation: blue lips or finger nails, blue skin, cough, dizziness, headache, laboured breathing, sore throat, unconsciousness

Skin: redness, pain

Eyes: redness, pain, may be adsorbed

Ingestion: abdominal pain, blue lips or finger nails, blue skin, diarrhoea, dizziness, headache, laboured breathing, unconsciousness

 

 

Table 104.19 Physical & chemical hazards

For UN Class: 1.5 = very insensitive substances which have a mass explosion hazard; 2.1 = flammable gas; 2.3 = toxic gas; 3 = flammable liquid; 4.1 = flammable solid; 4.2 = substance liable to spontaneous combustion; 4.3 = substance which in contact with water emits flammable gases; 5.1 = oxidizing substance; 6.1 = toxic; 7 = radioactive; 8 = corrosive substance.

Chemical Name

CAS-Number

Physical

Chemical

UN Class or Division / Subsidiary Risks

AMMONIA

7664-41-7

The gas is lighter than air •It is difficult to ignite •Spilled liquid has very low temperature and evaporates quickly

Shock-sensitive compounds are formed with mercury, silver and gold oxides •The substance is a strong base, it reacts violently with acid and is corrosive to eg, aluminum and zinc •Reacts violently with strong oxidants, halogens and interhalogens •Attacks copper, aluminum, zinc, and their alloys •Dissolves in water evolving heat

2.3/ 8

AMMONIUM CHLORIDE

12125-02-9

 

The substance decomposes on heating or on burning, producing toxic and irritating fumes (nitrogen oxides, ammonia and hydrogen chloride) •The solution in water is a weak acid •Reacts violently with ammonium nitrate and potassium chlorate causing fire and explosion hazard •Reacts with highly concentrated acids to form hydrogen chloride and with strong bases to form ammonia •Reacts with silver salts to form compounds that are sensitive to mechanical shock •Attacks copper and its compounds

 

AMMONIUM FLUORIDE

12125-01-8

 

 

6.1

AMMONIUM HYDROXIDE

1336-21-6

 

 

8

AMMONIUM NITRATE

6484-52-2

 

Heating may cause violent combustion or explosion •The substance decomposes on heating or on burning producing toxic fumes (nitrogen oxides) •The substance is a strong oxidant and reacts with combustible and reducing materials

5.1

CALCIUM

7440-70-2

 

 

4.3

CALCIUM CARBIDE

75-20-7

 

The substance decomposes violently on contact with water producing acetylene gas, causing fire and explosion hazard

4.3

CALCIUM CHLORATE

10137-74-3

 

 

5.1

CALCIUM HYDRIDE

7789-78-8

 

 

4.3

CALCIUM HYDROXIDE

1305-62-0

 

The substance decomposes on heating producing calcium oxide •The substance is a medium strong base

8

CALCIUM NITRATE

10124-37-5

 

 

5.1

CALCIUM OXIDE

1305-78-8

 

The solution in water is a medium strong base •Reacts violently with strong acids, water, chlorine or boron trifluoride •Reacts with water generating sufficient heat to ignite combustible materials

8

CARBONIC ACID, CALCIUM SALT

471-34-1

 

The substance decomposes on heating to high temperature producing carbon dioxide •Reacts with acids causing carbon dioxide release

 

CHLORIC ACID, SODIUM SALT

7775-09-9

 

Heating may cause violent combustion or explosion •The substance decomposes on heating above 300°C or on burning producing oxygen, which increases fire hazard, and toxic fumes (chlorine) •The substance is a strong oxidant and reacts violently with combustible and reducing materials, causing fire and explosion hazard •Reacts with strong acids giving off carbon dioxide •Reacts with organic contaminants to form shock-sensitive mixtures •Attacks zinc and steel

5.1

LITHIUM

7439-93-2

 

Heating may cause violent combustion or explosion •The substance may spontaneously ignite on contact with air when finely dispersed •Reacts violently with strong oxidants, acids and many compounds (hydrocarbons, halogens and halons) causing fire and explosion hazard •Reacts violently with water, forming highly flammable hydrogen gas and corrosive fumes of lithium hydroxide

4.3

LITHIUM CARBONATE

554-13-2

 

The substance decomposes on heating producing carbon monoxide and carbon dioxide •The solution in water is a strong base, it reacts violently with acid and is corrosive to aluminium and zinc •violently with strong acid (HCl)Reacts violently with fluorine •Attacks aluminum and zinc

 

LITHIUM CHLORIDE

7447-41-8

 

The solution in water is corrosive to metals

 

LITHIUM HYDRIDE

7580-67-8

Dust explosion possible if in powder or granular form, mixed with air

The substance may spontaneously ignite on contact with air •The substance decomposes exothermically on heating to about 500°C or in contact with moisture or acids, producing flammable gas •Reacts violently with strong oxidants •Reacts with water to form lithium hydroxide which is very caustic, and flammable hydrogen gas •Reacts with lower alcohols, carboxylic acids, chlorine and ammonia at 400°C to liberate hydrogen gas •Lithium hydride powder and liquid oxygen are detonable explosives

4.3

LITHIUM HYDROXIDE

1310-65-2

 

The solution in water is a strong base, it reacts violently with acid and is corrosive to aluminium and zinc

 

LITHIUM HYDROXIDE MONOHYDRATE

1310-66-3

 

The solution in water is a strong base, it reacts violently with acid and is corrosive to aluminium and zinc

8

PERCHLORIC ACID, POTASSIUM SALT

7778-74-7

 

The substance decomposes on heating producing toxic fumes (chlorine, chloroxides) •Reacts violently with metal powders, combustible, organic or other oxidizable materials causing fire and explosion hazard •When heated to decomposition toxic fumes of chloride, potassium- and chloroxide are formed

 

POTASSIUM

7440-09-7

 

 

4.3

POTASSIUM BROMATE

7758-01-2

 

 

5.1

POTASSIUM CHLORATE

3811-04-9

 

The substance decomposes on warming, on heating, on burning, on contact with organic substances, combustible agents, metal powders, sulfuric acid, ammonium containing substances, alcohols, producing chlorine dioxide, chlorine and oxygen, causing fire and explosion hazard •Upon heating, toxic fumes are formed •The substance is a strong oxidant and reacts violently with combustible and reducing materials •The substance is a strong reducing agent and reacts with oxidants

5.1

POTASSIUM FLUORIDE

7789-23-3

 

 

6.1

POTASSIUM HYDROXIDE

1310-58-3

 

The substance is a strong base, it reacts violently with acid and is corrosive in moist air toward metals such as zinc, aluminum, tin and lead forming a combustible/explosive gas (hydrogen) •Rapidly absorbs carbon dioxide and water from air •Contact with moisture or water will generate heat

8

POTASSIUM NITRATE

7757-79-1

 

The substance decomposes on heating or on burning producing nitrogen oxides, oxygen, which increases fire hazard •The substance is a strong oxidant and reacts with combustible and reducing materials

5.1

POTASSIUM NITRITE

7758-09-0

 

May explode on heating above 530°C •The substance decomposes on contact with even weak acids producing toxic fumes (nitrogen oxides) •The substance is a strong oxidant and reacts with combustible and reducing materials causing fire and explosion hazard

5.1

POTASSIUM OXIDE

12136-45-7

 

The substance decomposes on contact with water producing potassium hydroxide •The solution in water is a strong base, it reacts violently with acid and is corrosive •Attacks many metals in presence of water

 

SODIUM

7440-23-5

 

 

4.3

SODIUM BROMATE

7789-38-0

 

 

5.1

SODIUM CARBONATE

497-19-8

 

 

 

SODIUM CHLORITE

7758-19-2

 

 

5.1

SODIUM HYDROXIDE

1310-73-2

 

The substance is a strong base, it reacts violently with acid and is corrosive in moist air to metals like zinc, aluminum, tin and lead forming a combustible/explosive gas (hydrogen) •Attacks some forms of plastics, rubber or coatings •Rapidly absorbs carbon dioxide and water from air •Contact with moisture or water may generate heat

8

SODIUM HYPOCHLORITE

7681-52-9

 

 

8

SODIUM METHYLATE

124-41-4

Dust explosion possible if in powder or granular form, mixed with air

Heating may cause violent combustion or explosion •The substance decomposes on contact with water producing methanol, which increases fire hazard •The substance is a strong reducing agent and reacts violently with oxidants •The substance is a strong base, it reacts violently with acid and is corrosive •Attacks many metals in presence of water

4.2/ 8

SODIUM NITRATE

7631-99-4

 

The substance decomposes on heating or on burning producing nitrogen oxides and oxygen, which increases fire hazard •The substance is a strong oxidant and reacts with combustible and reducing materials, causing fire and explosion hazard

 

SODIUM NITRITE

7632-00-0

 

May explode on heating above 530°C •The substance decomposes on contact with even weak acids producing toxic fumes (nitrogen oxides) •The substance is a strong oxidant and reacts with combustible and reducing materials causing fire and explosion hazard

5.1

SODIUM PEROXIDE

1313-60-6

 

 

5.1

Table 104.20 Physical & chemical properties

Chemical Name

CAS-Number

Colour/Form

Boiling Point (°C)

Melting Point (°C)

Molecular Weight

Solubility in Water

Relative Density (water=1)

Relative Vapour Density (air=1)

Vapour Pressure/ (Kpa)

Inflam. Limits

Flash Point (°C)

Auto Ignition Point (°C)

AMMONIA

7664-41-7

colourless gas, liquid

-33.35

-77.7

17.03

sol

0.7710

0.59

1013  @26°C

16 ll 25 ul

flammable gas

651

AMMONIUM BICARBONATE

1066-33-7

colourless rhombic or monoclinic crystals; shiny, hard, colourless or white prisms or crystalline mass

 

107.5

79.06

14%  @10°C

1.57

 

 

 

 

 

AMMONIUM CHLORIDE

12125-02-9

colourless crystals or crystalline masses; or white,granular powder; cubic crystals; a white, fine or coarse, crystalline powder

520

338 decomp

53.50

sol

1.5274  @25°C

 

0.13  @160°C

 

 

 

AMMONIUM FLUORIDE

12125-01-8

leaflets or needles; hexagonal prisms by sublimation; colourless hexagonal crystals; white crystals

 

 

37.04

45.3g/100g  @25°C

1.015

 

 

 

 

 

AMMONIUM HYDROXIDE

1336-21-6

colourless liquid

 

-77

35.05

misc

0.90  @25°C

 

 

 

 

 

AMMONIUM NITRATE

6484-52-2

colourless rhombic crystals; monoclinic when temp is greater than 32.1°C; transparent crystals or white granules; five solid phases exist at normal pressure; orthorhombic at room temp; colourless (pure) to gray or brown (fertilizer grade).

210 decomp

169.6

80.06

118.3g/ 100ml  @0°C; 871g/100ml  @100°C

1.725  @25°C

 

 

 

 

 

CALCIUM

7440-70-2

lustrous, silver-white surface (when freshly cut); face-centered cubic structure below 300°C; acquires bluish-gray tarnish on exposure to moist air

1440

850

40.08

 

1.54

 

10mmHg  @983°C

 

 

 

CALCIUM BROMATE

10102-75-7

white crystalline powder

149

38.2

313.90

v sol

3.329

 

 

 

 

 

CALCIUM CARBIDE

75-20-7

grayish-black, irregular lumps or orthorhombic crystals; colourless tetragonal crystals

 

2300

64.10

reacts

2.22

 

 

 

 

 

CALCIUM CARBONATE

1317-65-3

white powder or colourless crystals

825 decomp

 

 

sl sol

2.7-2.95

 

 

 

 

 

CALCIUM CHLORATE

10137-74-3

 

 

340 ± 10

206.99

sol

2.710  @0°C

 

 

 

 

 

CALCIUM CHLORIDE

10043-52-4

cubic crystals, granules or fused masses; colourless

1, 935

772

110.98

74.5g/100ml

2.152  @15°C/4°C

 

 

 

 

 

CALCIUM HYDRIDE

7789-78-8

grayish-white lumps or crystals

675 decomp

 

42.10

decomposes

1.7

 

 

 

 

 

CALCIUM HYDROXIDE

1305-62-0

crystals or softgranules or powder; colourless, hexagonal; rhombic, trigonal, colourless crystals; white powder

580 decomp

580

74.10

insol

2.24

 

 

 

 

 

CALCIUM NITRATE

10124-37-5

granules; colourless, cubic crystals; white mass

 

560

164.10

v sol

2.504  @18°C

 

 

 

 

 

CALCIUM NITRITE

13780-06-8

colourless or yellowish crystals

 

100

150.11

sol

2.23  @34°C

 

 

 

 

 

CALCIUM OXIDE

1305-78-8

colourless cubic crystals; white orgrayish white lumps, orgranular powder

2850

2570

56.08

 

3.32-3.35

 

 

 

 

 

CARBONIC ACID, CALCIUM SALT

471-34-1

fine, white, microcrystalline powder; powder or crystals; aragonite: orthorhombic; calcite: hexagonal-rhombohedral

 

825 decomp

102.10

insol

2.7-2.9

 

 

 

 

 

DIAMMONIUM PHOSPHATE

7783-28-0

colourless, monoclinic; white crystals or powder

decomp

155 decomp

132.07

1g/1.7ml

1.619

 

 

 

 

 

LITHIUM

7439-93-2

silvery-white metal; body-centered cubic structure; becomes yellowish on exposure to moist air; tarnishes tograyish-white on exposure to air

1342

180.54

6.941

reacts

0.534

 

0.133  @723°C:

 

 

 

LITHIUM CARBONATE

554-13-2

white, light powder; monoclinic

1310 decomp

618-723

73.89

insol

2.11

 

 

 

 

 

LITHIUM CHLORIDE

7447-41-8

cubic crystals, granules or crystalline powder; white

1360

613

42.40

1g/1.3ml

2.07

 

 

 

 

 

LITHIUM HYDRIDE

7580-67-8

commercial product is usuallygray; white, translucent, crystalline mass or powder

850 decomp

680

7.95

reacts

0.76-0.77

 

0mmHg

 

highly flammable

200

LITHIUM HYDROXIDE

1310-65-2

crystals

decomp

450-471

 

12.8g/100ml

1.46

 

 

 

 

 

LITHIUM HYDROXIDE MONOHYDRATE

1310-66-3

crystals

 

450-471

 

10.9g/100ml

1.51

 

 

 

 

 

PERCHLORIC ACID, POTASSIUM SALT

7778-74-7

colourless crystals or white, crystalline powder; colourless, rhombic crystals

 

400 decomp

138.55

sol in 65 parts

2.52

 

 

 

 

 

POTASSIUM

7440-09-7

soft, silvery-white metal; body-centered cubic structure

765.5

63.2

39.098

 

0.856

 

8mmHg  @432°C

 

 

 

POTASSIUM BROMATE

7758-01-2

white crystals or granules; colourless, trigonal crystals

 

434

167.01

7.53g/100g  @25°C

3.27  @17.5°C

 

 

 

 

 

POTASSIUM BROMIDE

7758-02-3

colourless crystals or white granules or powder; cubic crystals

1435

730

119.01

1g/1.5ml

2.75  @25°C

 

 

 

 

 

POTASSIUM CARBONATE

584-08-7

granules or granular powder; colorless, monoclinic crystals; white granular powder; granular translucent powder

 

891

140.82

112 g/100 ml cold

2.29

 

 

 

 

 

POTASSIUM CHLORATE

3811-04-9

colourless, lustrous crystals or white granules or powder

400 decomp

368

122.55

1g/16.5ml

2.32

 

 

 

 

 

POTASSIUM FLUORIDE

7789-23-3

colourless cubic deliquescent

1505

858

58.10

v sol

2.48

 

 

 

 

 

POTASSIUM HYDROXIDE

1310-58-3

white or slightly yellow lumps, rods, pellets; sticks, flakes, or fused masses; white rhombic crystals; colourless watery liquid

1324

380

56.11

100g/90ml  @25°C

2.044mg/ml

 

0.13  @714°C

 

 

 

POTASSIUM IODATE

7758-05-6

white crystals or crystalline powder; colourless monoclinic crystals

 

560

214.02

4.74g/100ml

3.93  @32°C/4°C

 

 

 

 

 

POTASSIUM IODIDE

7681-11-0

colourless or white, cubical crystals, white granules, or powder; hexahedral crystals, either transparent or somewhat opaque

1330

680

166.02

sol 1g/0.7ml

3.13

 

 

 

 

 

POTASSIUM NITRATE

7757-79-1

colourless, rhombic or trigonal crystals; white granular or crystalline powder

400 decomp

334

101.10

1g/2.8ml  @25°C

2.109  @16°C

 

 

 

 

 

POTASSIUM NITRITE

7758-09-0

white or slightly yellow granules or rods; white yellowish prism

 

441; decomp  @351

85.10

v sol

1.915

 

 

 

 

 

POTASSIUM OXIDE

12136-45-7

crystalline powder

 

350

 

reacts

2.3

 

 

 

 

 

POTASSIUM PERIODATE

7790-21-8

small colourless crystals or whitegranular powder

 

582

230

sl sol

3.168

 

 

 

582

 

SODIUM

7440-23-5

light, silvery-white metal; body-centered cubic structure; lustrous when freshly cut

881.4

97.82

22.99

 

0.968

 

1.2mmHg  @400°C

 

 

115 in dry air

SODIUM BICARBONATE

144-55-8

white, monoclinic prisms; white crystalline powder orgranules

 

- CO2  @270

84.01

sol in 10 parts  @25°C; 12 parts  @18°C

2.159

 

 

 

 

 

SODIUM BROMATE

7789-38-0

colourless cubic crystals; white granules or crystalline powder

 

381

150.90

27.5g/100ml  @0°C 90.9g/100ml  @100°C

3.339  @17.5°C

 

 

 

 

 

SODIUM CARBONATE

497-19-8

white powder; grayish-white powder or lumps containing up to 99% sodium carbonate.

 

- 851

106.00

sol in 3.5 parts

2.53

 

 

 

 

 

SODIUM CHLORATE

7775-09-9

colourless; cubic or trigonal crystals; white powder; pale yellow to white crystals; colourless powder; colourless crystals or white granules

122

248

106.5

 

2.490g/ml  @15°C

3.7

 

 

 

 

SODIUM CHLORIDE

7647-14-5

colourless, transparent crystals or white, crystalline powder

1413

801

58.44

35.7g/100ml  @0°C; 9.2g/100ml  @100°C

2.165  @25°C/4°C

 

1mmHg  @865°C

 

 

 

SODIUM CHLORITE

7758-19-2

white crystalline solid; crystals or flakes

 

180-200

90.44

34g/100g  @5°C 39g/100g  @17°C

2.468g/ml in crystalline form

 

 

 

 

 

SODIUM ETHYLATE

141-52-6

white or yellowish powder; white powder sometimes having brownish tinge

 

 

68.06

 

 

 

 

 

 

 

SODIUM HYDROXIDE

1310-73-2

lumps, chips, pellets, sticks; white flakes or cake; fused solid with cryst fracture

1390

318.4

40.01

1g/ 0.9ml

2.13  @25°C

 

0.13  @739°C

 

 

 

SODIUM HYPOCHLORITE

7681-52-9

in solution only; greenish yellow liquid

 

 

74.44

sol

1.21

 

 

 

 

 

SODIUM IODIDE

7681-82-5

colourless, cubic crystals; white crystals orgranules; white powder

1304

651

149.92

184g  @25°C

3.67

 

1mmHg  @767°C

 

 

 

SODIUM METHYLATE

124-41-4

amorphous, free flowing powder

 

127 decomp

54.03

reacts

0.45

 

 

 

 

70-80

SODIUM MONOHYDROGEN PHOSPHATE

 7558-79-4

colourless, or white, granular salt

 

 

141.98

sol 8 parts 25°C

 

 

 

 

 

 

SODIUM NITRATE

7631-99-4

colourless, trigonal or rhombohedron crystals; whitegranules or powder

380 decomp

308

85.01

92.1g/100ml  @25°C

2.26

 

 

 

 

 

SODIUM NITRITE

7632-00-0

colourless-yellow rhombohedral prisms; white or slightly yellow granules, rods, or powder; slightly yellowish or white crystals, pellets, sticks or powder

320 decomp

271

69.00

sol

2.26

 

 

 

 

 

SODIUM PEROXIDE

1313-60-6

yellowish-white, granular powder; white powder turning yellow on exposure to atmosphere; yellowish-white powder turns yellow when heated

657 decomp

460 decomp

77.99

v sol

2.805

 

 

 

 

 

SODIUM PHOSPHATE

7601-54-9

 

 

 

163.94

8.8g /100ml

2.536  @17.5°C

 

 

 

 

 

SODIUM TRIPOLYPHOSPHATE

7758-29-4

powder and granules; white powder

 

 

367.86

sol

 

 

 

 

 

 

TETRAMETHYLAMMONIUM CHLORIDE

75-57-0

white crystalline solid

 

420

109.6

sol

1.1690

 

 

 

 

 

AMIDES

The amides are a class of organic compounds which can be regarded as having been derived from either acids or amines. For example, the simple aliphatic amide acetamide  (CH3-CO-NH2) is related to acetic acid in the sense that the -OH group of acetic acid is replaced by an -NH2 group. Conversely, acetamide can be regarded as being derived from ammonia by replacement of one ammonia hydrogen by an acyl group. Amides can be derived not only from aliphatic or aromatic carboxylic acids but also from other types of acids—for example, sulphur- and phosphorus-containing acids.

The term substituted amides may be used to describe those amides having one or both hydrogens on the nitrogen replaced by other groups—for example, N,N-dimethylacetamide. This compound could also be regarded as an amine, acetyl dimethyl amine.

Amides are generally quite neutral in reaction compared with the acid or amine from which they are derived, and they are occasionally somewhat resistant to hydrolysis. The simple amides of aliphatic carboxylic acids (except formamide) are solids at room temperature, while the substituted aliphatic carboxylic acid amides may be liquids with relatively high boiling points. The amides of aromatic carboxylic or sulphonic acids are usually solids. A wide variety of methods are available for the synthesis of amides.

Uses

The unsubstituted aliphatic carboxylic acid amides have wide use as intermediates, stabilizers, release agents for plastics, films, surfactants and soldering fluxes. The substituted amides such as dimethylformamide and dimethylacetamide have powerful solvent properties.

Dimethylformamide is primarily used as a solvent in organic synthesis. It is also used in the preparation of synthetic fibres. It is a selective medium for the extraction of aromatics from crude oil and a solvent for dyes. Both dimethylformamide and dimethylacetamide are ingredients in paint removers. Dimethylacetamide is also used as a solvent for plastics, resins and gums, and in many organic reactions.

Acetamide is used for denaturing alcohol and as a solvent for many organic compounds, as a plasticizer, and an additive in paper. It is also found in lacquers, explosives and soldering flux. Formamide is a softener for paper and glues, and a solvent in the the plastics and pharmaceutical industries.

Some unsaturated aliphatic amides, such as acrylamide, are reactive monomers used in polymer synthesis. Acrylamide is also used in the synthesis of dyes, adhesives, paper and textile sizing, permanent press fabrics, and sewage and waste treatment. It is utilized in the metal industry for ore processing, and in civil engineering for the construction of dam foundations and tunnels. The polyacrylamides find extensive use as flocculants in water and sewage treatment, and as strengthening agents during paper manufacture in the paper and pulp industry. Aromatic amide compounds form important dye and medicinal intermediates. Some have insect repellent properties.

Hazards

The wide variety of possible chemical structures of amides is reflected in the diversity of their biological effects. Some appear entirely innocuous—for example, the longer-chain simple fatty acid amides such as stearic or oleic acid amides. On the other hand, several of the members of this family are classified as Group 2A (probable human carcinogens) or Group 2B (possible human carcinogens) by the International Agency for Research on Cancer (IARC). Neurologic effects have been noted in humans and experimental animals with acrylamide. Dimethylformamide and dimethylacetamide have produced liver injury in animals, and formamide and monomethylformamide have been shown experimentally to be teratogens.

Although a considerable amount of information is available on the metabolism of various amides, the nature of their toxic effects has not yet been explained on a molecular or cellular basis. Many simple amides are probably hydrolyzed by non-specific amidases in the liver and the acid produced excreted or metabolized by normal mechanisms.

Some aromatic amides—for example, N-phenylacetamide (acetanilide)—are hydroxylated on the aromatic ring and then conjugated and excreted. The ability of a number of amides to penetrate the intact skin is especially important in considering safety precautions.

Neurological effects

Acrylamide was initially made in Germany in 1893. Practical use of this compound had to wait until the early 1950s, when commercial manufacturing processes became available. This development occurred primarily in the United States. By the mid-1950s it was recognized that workers exposed to acrylamide developed characteristic neurologic changes primarily characterized by both postural and motor difficulties. Reported findings included tingling of the fingers, tenderness to touch, coldness of the extremities, excessive sweating of the hands and feet, a characteristic bluish-red discolouration of the skin of the extremities, and a tendency toward peeling of the skin of the fingers and hands. These symptoms were accompanied by weakness of the hands and feet which led to difficulty in walking, climbing stairs and so on. Recovery generally occurs with cessation of exposure. The time for recovery varies from a few weeks to as long as 1 year.

Neurologic examination of individuals suffering from acrylamide intoxication shows a rather typical peripheral neuropathy with weakness or absence of tendon reflexes, a positive Romberg test, a loss of position sense, a diminution or loss of vibration sense, ataxia, and atrophy of the muscles of the extremities.

Following recognition of the symptom complex associated with acrylamide exposure, animal studies were carried out in an attempt to document these changes. It was found that a variety of animal species including rat, cat and baboon were capable of developing peripheral neuropathy with disturbance of gait, disturbance of balance and a loss of position sense. Histopathologic examination revealed a degeneration of the axons and myelin sheaths. The nerves with the largest and longest axons were most commonly involved. There did not appear to be involvement of the nerve cell bodies.

Several theories have been advanced as to why these changes occur. One of these has to do with possible interference with the metabolism of the nerve cell body itself. Another theory postulates interference with the intracellular transport system of the nerve cell. An explanation is that there is a local toxic effect on the entire axon, which is felt to be more vulnerable to the action of acrylamide than is the cell body. Studies of the changes taking place within the axons and myelin sheaths have resulted in a description of the process as a drying back phenomenon. This term is used to describe more accurately the progression of changes observed in the peripheral nerves.

While the described symptoms and signs of the characteristic peripheral neuropathy associated with acrylamide exposure are widely recognized from exposure in industry and from animal studies, it appears in humans that, when acrylamide has been ingested as a contaminant in drinking water, the symptoms and signs are of involvement of the central nervous system. In these instances drowsiness, disturbance of balance, and mental changes characterized by confusion, memory loss and hallucinations were paramount. Peripheral neurological changes did not appear until later.

Skin penetration has been demonstrated in rabbits, and this may have been a principal route of absorption in those cases reported from industrial exposures to acrylamide monomer. It is felt that the hazard from inhalation would be primarily from exposure to aerosolized material.

Hepatotoxic effects

The good solvent action of dimethylformamide results in drying and defatting of the skin on contact, with resultant itching and scaling. Some complaints of eye irritation have resulted from vapour exposure in industry. Complaints by exposed workers have included nausea, vomiting and anorexia. Intolerance to alcoholic beverages after exposure to dimethylformamide has been reported.

Animal studies with dimethylformamide have shown experimental evidence of liver and kidney damage in rats, rabbits and cats. These effects have been seen from both intraperitoneal administration and inhalation studies. Dogs exposed to high concentrations of the vapour exhibited polycythemia, decrease of the pulse rate, and a decline in systolic pressure, and showed histologic evidence of degenerative changes in the myocardium.

In humans this compound is capable of being readily absorbed through the skin, and repeated exposures can lead to cumulative effects. In addition, like dimethylacetamide, it may facilitate the percutaneous absorption of substances dissolved in it.

It should be mentioned that dimethylformamide will readily penetrate both natural and neoprene rubber gloves, so that prolonged use of such gloves is inadvisable. Polyethylene provides better protection; however, any gloves used with this solvent should be washed after each contact and discarded frequently.

Dimethylacetamide has been studied in animals and has been shown to exhibit its principal toxic action in the liver on repeated or continued excessive exposure. Skin contact may cause the absorption of dangerous quantities of the compound.

Carcinogenesis

Acetamide and thioacetamide are prepared by heating ammonium acetate and aluminium sulphide, and are used in the laboratory as analytical reagents. Both compounds have been shown to produce hepatomas in rats on prolonged dietary feeding. Thioacetamide is more potent in this respect, is carcinogenic also to mice, and can also induce bile duct tumours in rats. While human data on these chemicals are not available, the extent of the experimental animal data is such that both of these substances are now considered possible human carcinogens. (Thioacetamide can also be found in the article “Sulphur compounds, organic” in this chapter.) Dimethylformamide is also classified as a Group 2B possible human carcinogen by IARC.

Acrylamide is classified as a probable human carcinogen (Group 2A) by IARC. This decision is supported by the results of bioassays in mice by several routes and yielding multiple sites of cancer, by data on genotoxicity, and by acrylamide’s ability to form adducts. The chemical structure of acrylamides also supports the probability that the chemical is a human carcinogen.

Safety and Health Measures

The potential toxic properties of any amide should be carefully considered before use or exposure commences. Owing to the general tendency of amides (especially those of lower molecular weight) to be absorbed percutaneously, skin contact should be prevented. Inhalation of dusts or vapours should be controlled. It is desirable that persons with exposure to amides be under regular medical observation with particular reference to the functioning of the nervous system and liver. The possible or probable cancer status of some these chemicals dictates that extremely prudent working conditions are needed.

Amides tables

Table 104.21 Chemical identification

CHEMICAL

SYNONYMS

UN CODE

CAS-NUMBER

CHEMICAL FORMULA

ACETAMIDE

Acetic acid amide; Acetimidic acid; Ethanamide; Methanecarboxamide

60-35-5

2-ACETYLAMINOFLUORENE

2-Acetaminofluorene; Acetoaminofluorene; N-Acetyl-2-aminofluorene; 2-(Acetylamino)fluorene; 2-Fluorenylacetamide

53-96-3

ACRYLAMIDE

Acrylic amide; Ethylenecarboxamide; Propenamide; 2-Propenamide; Vinyl amide

UN2074

79-06-1

BENZOTHIAZYL-2-CYCLOHEXYLSULFENAMIDE

N-Cyclohexyl-2-benzothiazolesulfenamide; N-Cyclohexyl-2-benzothiazylsulfenamide

95-33-0

2-CHLOROACETAMIDE

Chloroacetamide; α-Chloroacetamide; 2-Chloroethanamide

79-07-2

2-CHLORO-N-HYDROXYMETHYLACETAMIDE

Chloracetamide-N-metholol

2832-19-1

COLCHICINE

Acetamide, N-(5,6,7,9-Tetrahydro-1,2,3,10-tetramethoxy-9-oxobenzo-α-(heptalen-7-yl)-; N-Acetyl trimethylcolchicinic acid methylether; Benzo(a)heptalen-9(5h)-one, 7-acetamido-6,7-dihydro-1,2,3,10-tetramethoxy-

64-86-8

CYCLOHEXIMIDE

β-(2-(3,5-Dimethyl-2-oxocyclohexyl)-2-hydroxyethyl)glutarimide; 3-(2-(3,5-Dimethyl-2-oxocyclohexyl)-2-hydroxyethyl)glutarimide

66-81-9

CYCLOPHOSPHAMIDE

Cyclophosphane; N,n-bis(2-chloroethyl)-N',o-propylenephosphoric acid ester diamide; N,N-Bis(2-chloroethyl)tetrahydro-2h-1,3,2-oxazaphosphorin-2-amine 2-oxide; Bis(2-chloroethyl)phosphoramide-cyclic propanolamide ester

50-18-0

4,4'-DIACETYLBENZIDINE

4,4'-Diacetamidobiphenyl; 4,4'-Diacetylaminobiphenyl; Diacetylbenzidine; N,N'-Diacetyl benzidine

613-35-4

DIETHYLCARBAMOYL CHLORIDE

Diethylcarbamic chloride; N,N-Diethylcarbamoyl chloride; Diethylcarbamyl chloride; Diethylchloroformamide; N,N-Diethylchloroformamide

88-10-8

DIMETHYL ACETAMIDE

Acetdimethylamide; Acetic acid, dimethylamide; N,N-Dimethylacetamide; Dimethylacetone amide; Dimethylamide acetate

127-19-5

DIMETHYL CARBAMOYL CHLORIDE

Chloroformic acid dimethylamide; (Dimethylamino)carbonyl chloride; Dimethylcarbamic acid chloride; Dimethylcarbamic chloride; Dimethylchloroformamide

UN2262

79-44-7

DIMETHYLFORMAMIDE

N,N-Dimethyl formamide; N,N-Dimethylmethanamide; N-Formyldimethylamine

UN2265

68-12-2

N,N'-ETHYLENE BIS(STEARAMIDE)

1,2-Bis(octadecanamido)ethane; N,N'-Ethylene distearylamide; N,N'-Ethylene bis(octadecanamine)

110-30-5

FORMAMIDE

Carbamaldehyde; Methanamide

75-12-7

METHYLFORMAMIDE

N-Methylformamide; Monomethylformamide

123-39-7

SODIUM AMIDE

 

7782-92-5

Table 104.22 Health hazards

Chemical Name

     CAS-Number

ICSC Short-Term Exposure

ICSC Long-Term Exposure

ICSC Routes of Exposure and Symptoms

US NIOSH Target Organs & Routes of Entry

US NIOSH Symptoms

ACETAMIDE

     60-35-5

eyes; skin; resp tract

 

Inhalation: cough, shortness of breath

Skin: redness, pain

Eyes: pain, redness, blurred vision

Ingestion: sore throat, burning sensation

 

 

2-ACETYLAMINOFLUORENE

     53-96-3

 

 

 

Liver; bladder; kidneys; pancreas; skin; lungs (in animals: tumors of the liver; bladder, pancreas, skin lungs)

Inh, abs, ing, con

Reduced function of liver, kidneys, bladder, pancreas (carc)

ACRYLAMIDE

     79-06-1

skin; resp tract; CNS; liver

PNS; CNS

Inhalation: cough, sore throat, weakness

Skin: may be absorbed, redness, pain

Eyes: redness, pain

Ingestion: abdominal pain, weakness

CNS; PNS; skin; eyes, repro sys (in animals: tumors of the lungs, testes, thyroid & adrenal glands)

Inh, abs, ing, con

Irrit eyes, skin; ataxia, numb limbs, pares; musc weak; absent deep tendon reflex; hand sweat; ftg, leth; repro effects (carc)

2-CHLOROACETAMIDE

     79-07-2

eyes; skin; resp tract; heart; liver; spleen

skin

Inhalation: burning sensation, cough, sore throat

Skin: redness, pain

Eyes: redness, pain

Ingestion: sore throat

 

 

CYCLOPHOSPHAMIDE

     50-18-0

eyes; skin; resp tract; kidneys; bladder; CVS; CNS; GI tract; liver; heart; blood

skin

Inhalation: diarrhoea, dizziness, loss of hair, darkening of skin and finger nails, nausea, vomiting

Skin: may be absorbed

 

 

DIMETHYL ACETAMIDE

     127-19-5

eyes; skin; resp tract

skin; liver; kidneys

Inhalation: headache, nausea, vomiting

Skin: may be absorbed, redness

Eyes: Vapour will be absorbed, redness, pain

CNS; liver; skin

Inh, abs, ing, con

irrit skin; jaun, liver damage; depres, leth, halu, delusions

DIMETHYLFORMAMIDE

     68-12-2

eyes; skin; resp tract; liver; CNS

liver

Inhalation: loss of appetite, abdominal pain, diarrhoea, dizziness, nausea, vomiting, nervous agitation, facial flushing and alcohol intolerance

Skin: may be absorbed, dry skin, redness, roughness

Eyes: redness, pain

Eyes; liver; kidneys; CVS; skin; resp sys

Inh, abs, ing, con

Irrit eyes, skin, resp sys; nau, vomit, colic; liver damage, enlarged liver; high BP; face flush; derm; in animals: kidney, heart damage

FORMAMIDE

     75-12-7

lungs; CNS

liver

Inhalation: drowsiness, headache, nausea, unconsciousness

Skin: may be absorbed, redness

Eyes: redness

Ingestion: abdominal pain

Eyes; skin; resp sys; CNS; repro sys

Inh, ing, con

Irrit eyes, skin, muc memb; drow, ftg; nau, acidosis; skin eruptions; in animals: repro effects

Table 104.23 Physical & chemical hazards

For UN Class: 1.5 = very insensitive substances which have a mass explosion hazard; 2.1 = flammable gas; 2.3 = toxic gas; 3 = flammable liquid; 4.1 = flammable solid; 4.2 = substance liable to spontaneous combustion; 4.3 = substance which in contact with water emits flammable gases; 5.1 = oxidizing substance; 6.1 = toxic; 7 = radioactive; 8 = corrosive substance

Chemical Name

CAS-Number

Physical

Chemical

UN Class or Division /  Subsidiary Risks

ACETAMIDE

60-35-5

 

The substance decomposes on heating, producing toxic fumes •The solution in water is a strong base, it reacts violently with acid and is corrosive •Reacts with oxidants, reducing agents, bases, and acids

 

ACRYLAMIDE

79-06-1

 

The substance may polymerize violently due to heating or under the influence of light •The substance decomposes on heating producing toxic gases (nitrous oxides) •Reacts violently with oxidants

6.1

2-CHLOROACETAMIDE

79-07-2

 

The substance decomposes on heating producing toxic fumes including nitrogen oxides and chlorine •Reacts with strong oxidants, strong reducing agents, strong acids and strong bases

 

CYCLOPHOSPHAMIDE

50-18-0

 

The substance decomposes on heating, on contact with moisture, light, producing toxic fumes •Reacts with strong oxidants, strong acids, strong bases

 

DIMETHYL ACETAMIDE

127-19-5

 

The substance decomposes on heating producing toxic fumes (nitrogen oxides) •Attacks many plastics

 

DIMETHYL CARBAMOYL CHLORIDE

79-44-7

 

 

8

DIMETHYLFORMAMIDE

68-12-2

 

On combustion, forms toxic gases (carbon monoxide, dimethylamine and oxides of nitrogen) •Reacts with oxidants

3

N,N'-ETHYLENE BIS(STEARAMIDE)

110-30-5

Dust explosion possible if in powder or granular form, mixed with air

On combustion, forms toxic gases •The substance decomposes on heating and on burning producing toxic fumes (nitrogen oxides) •Reacts with strong oxidants

 

FORMAMIDE

75-12-7

 

On combustion, forms toxic gases (nitrogen oxides) •The substance decomposes on heating at 200°C or above producing ammonia, water, carbon monoxide and hydrogen cyanide •Reacts vigorously with oxidizing materials •Attacks copper and natural rubber •Incompatible with iodine, pyridine and sulfur trioxide

 

Table 104.24 Physical & chemical properties

Chemical Name

CAS-Number

Colour/Form

Boiling Point (°C)

Melting Point (°C)

Molecular Weight

Solubility in Water

Relative Density (water=1)

Relative Vapour Density (air=1)

Vapour Pressure/ (Kpa)

Inflam. Limits

Flash Point (°C)

Auto Ignition Point (°C)

ACETAMIDE

60-35-5

deliquescent hexagonal crystals; trigonal monoclinic crystals

222

81

59.07

1g/0.5ml

1.159

 

<0.1

 

 

 

2-ACETYLAMINOFLUORENE

53-96-3

tan, crystalline solid

 

194

223.26

insol

 

 

 

 

 

 

ACRYLAMIDE

79-06-1

flake-like crystals from benzene;white crystalline solid; leaf crystals from benzene

125

84.5

71.08

v sol

1.122

2.45

1 Pa

 

138 cc

424

BENZOTHIAZYL-2- CYCLOHEXYLSULFENAMIDE

95-33-0

cream-coloured powder

 

93-100

264.41

insol

1.27

 

 

 

 

 

2-CHLOROACETAMIDE

79-07-2

crystals

225

120

93.5

sol

 

3.2

0.007

 

 

 

COLCHICINE

64-86-8

 

 

156

399.42

v sol

 

 

 

 

 

 

CYCLOHEXIMIDE

66-81-9

plates from amyl acetate, water or 30% methanol; colourless crystals

 

119.5-121

281.34

 

 

 

 

 

 

 

CYCLOPHOSPHAMIDE

50-18-0

fine, white, crystalline powder; liquifies on loss of its water of crystallization

 

49.5-53

261.10

1/25 parts

 

 

 

 

112

 

4,4'-DIACETYLBENZIDINE

613-35-4

 

 

328.3

268.30

 

 

 

 

 

 

 

DIETHYLCARBAMOYL CHLORIDE

88-10-8

liquid

187

-44

135.6

sol

 

4.1

 

 

 

 

DIMETHYL ACETAMIDE

127-19-5

colourless oily liquid

165

-20

87.12

misc

0.9366  @25°C/4°C

3.01

0.33

1.8 ll 11.5 ul

70 oc

490

DIMETHYL CARBAMOYL CHLORIDE

79-44-7

liquid

167

-33

107.5

 

1.1678

3.73

 

 

 

 

DIMETHYLFORMAMIDE

68-12-2

colourless to very slightly yellow liquid; water-white liquid

153

-60.4

73.09

misc

0.9445  @25°C/4°C

2.51

0.36

2.2 ll 15.2 ul

67 oc

354

N,N'-ETHYLENE BIS(STEARAMIDE)

110-30-5

solid

 

135-146

593.04

insol

0.97

 

 

 

280 oc

 

FORMAMIDE

75-12-7

slightly viscous, colourless oily liquid

210.5 decomp

2.55

45.04

misc

1.1334

1.6

2 Pa

 

154 oc

>500

METHYLFORMAMIDE

123-39-7

 

180-185

-3.8

59.07

v sol

1.011  @19°C

 

3.08x 10-2 mm Hg  @25°C

 

 

 

SODIUM AMIDE

7782-92-5

white crystalline powder

400

210

39.02

sol

1.39

 

 

 

 

 

AMINES, ALIPHATIC

Aliphatic amine compounds are formed when one or more hydrogen atoms in ammonia (NH3) are replaced by one, two or three alkyl or alkanol radicals. The lower aliphatic amines are gases like ammonia and freely soluble in water, but the higher homologues are insoluble in water. All the aliphatic amines are basic in solution and form salts. The salts are odourless, non-volatile solids freely soluble in water.

According to the number of hydrogens substituted, the amines may be primary (NH2R), secondary (NHR2) or tertiary (NR3).

Uses

Aliphatic amines are found in the chemical, pharmaceutical, rubber, plastics, dye-stuff, textile, cosmetics and metal industries. These chemicals are used as intermediates, solvents, rubber accelerators, catalysts, emulsifiers, synthetic cutting fluids, corrosion inhibitors and flotation agents. Several are used in the manufacture of herbicides, pesticides and dyes. In the photography industry, triethylamine and methylamine are used as accelerators for developers. Diethylamine is a corrosion inhibitor in the metal industries and a solvent in the petroleum industry. In the tanning and leather industries, hexamethylenetetramine is used as a tanning preservative; methylamine, ethanolamine and diisopropanolamine are softening agents for hides and leather.

2-Dimethylaminoethanol functions as a control agent for the acidity of boiler water treatment. Triethanolamine, isopropanolamime, cyclohexylamine and dicyclohexylamine are used in dry-cleaning soaps. Triethanolamine is used extensively in industry for the manufacture of surface-active agents, waxes, polishes, herbicides and cutting oils. It is also used to recover hydrogen sulphide from sour natural gas and sour crude petroleum. Ethanolamine extracts both carbon dioxide and hydrogen sulphide from natural gas.

Ethylamine acts as a stabilizer for rubber latex and as a dye intermediate, while butylamine is a pesticide and a strong alkaline liquid used in the rubber, pharmaceutical and dye-stuff industries. Ethylenediamine is another strongly alkaline liquid used in the preparation of dyes, rubber accelerators, fungicides, synthetic waxes, pharmaceuticals, resins, insecticides and asphalt wetting agents. Dimethylamine and isobutanolamine find use in the rubber industry as vulcanization accelerators. Dimethylamine is also used in the tanning industry and in the manufacture of detergent soaps.

Ethylenimine is an important compound found in the paper, textile, petroleum, lacquer and varnish, cosmetics and photography industries. Diethanolamine is a scrubbing agent for gases, a chemical intermediate, and an emulsifier in agricultural chemicals, cosmetics and pharmaceuticals. Other widely used emulsifying agents include isobutanolamine, isopropanolamine and cyclohexylamine.

Hazards

Since the amines are bases and may form strongly alkaline solutions, they can be damaging if splashed in the eye or if allowed to contaminate the skin. Otherwise they have no specific toxic properties, and the lower aliphatic amines are normal constituents of body tissues, so that they occur in a large number of foods, particularly fish, to which they impart a characteristic odour. One area of concern at present is the possibility that some aliphatic amines may react with nitrate or nitrite in vivo to form nitroso compounds, many of which are known to be potent carcinogens in animals, as is discussed more fully in the accompanying box.

Allylamine. The vapour is intensely irritating. In animals there is evidence of effects on the heart and circulatory system. Myocardial and vascular legions have been observed. Some of allylamine’s toxicity has been attributed to the formation of acrolein in vivo. There is also a definite risk of explosion over a wide range of concentrations in air.

Butylamine is the most important isomer commercially. Its vapour has been observed to have severe effects on the central nervous system (CNS) of animals exposed to it. It has intense effects on humans. It is extremely irritating to the eyes and respiratory tract. It also affects the CNS and can cause depression and even unconsciousness. Chest pains and severe coughing have also been reported. Butylamine is readily absorbed through the skin. Any absorbed butylamine is readily metabolized.

A main toxic effect of cyclohexylamine is to act as an irritant. It may damage and sensitize the skin. Cyclohexylamine is also a weak methaemoglobin inducer. This amine is also a principal metabolite of cyclamate.

Diethanolamine is irritating to the skin and mucous membranes. Exposure can lead to nausea and vomiting.

Dimethylamine vapours are both flammable and irritating. The solutions which it forms are strongly alkaline.

Ethanolamine may be weakly irritating but is not associated with major toxic effects on humans.

Ethylamine can cause eye irritation. Corneal damage may occur in those exposed to the vapour. The compound is excreted unchanged by humans.

Ethylenediamine damages the eyes, skin and respiratory tract. Sensitization may follow vapour exposure.

Methylamine a stronger base than ammonia, and the vapour is irritating to the eyes and respiratory tract. Cases of sensitization (bronchial) have been reported. The warning properties of this chemical are not good, since olfactory fatigue can set in.

Propylamine vapour may be injurious to the eyes and respiratory tract. Transitory visual disturbances have been reported.

Triethanolamine is of low human toxicity and is commonly added to many cosmetics and similar products.

Formation of nitrosamines

Nitrosamines are amines that contain a nitroso- functional group (—N—N=O). These chemicals are formed when a nitrogen (N) and an oxygen (O) from a "nitrosating" compound bind to the amino group nitrogen (N) of the amine compound. For example, the nitrate and nitrite salts used in the salt bath in rubber manufacturing serve as nitrosating agents and combine with amines in the rubber compound to form nitrosamines. Nitrosamines are also formed in vivo during the metabolism of nitrate- or nitrite-containing founds. Rubber compounds that are nitrosamine precursors include sulphenamides, secondary sulphenamides, dithiocarbamates, thiurams and diethylhydroxylamines. Some rubber compounds actually contain a nitrosamine, such as nitrosodiphenylamine (NDPhA), a retarder, or dinitrosopentamethylenetetramine (DNPT), a blowing agent. These nitrosamines are weakly carcinogenic, but they can "transnitrosate", or transfer their nitroso- groups to, other amines to form more carcinogenic nitrosamines. Nitrosamines that have been detected at salt bath operations include: nitrosodimethylamine (NDMA), nitrosopiperidine (NPIP), nitrosomorpholine (NMOR), nitrosodiethylamine (NDEA) and nitrosopyrrolidine (NPYR).

The formation of nitrosamines is a health concern because most nitrosamines are suspected to be human carcinogens, although a causal association between nitrosamine exposure and human cancer has not yet been firmly established. There is, however, circumstantial evidence that nitrosamines could cause cancer in humans. Nitrosamines are potent animal carcinogens; approximately 90% of the 300 tested nitrosamines have shown carcinogenic effects in laboratory animals. Approximately 40 animal species, including mammals, birds, fish and amphibia, have been studied, and none has been resistant. Nitrosamine effects have been demonstrated in multiple organs; the tumour sites depend on the specific nitrosamine, the species tested and the route of administration.

Biochemical, pathological and experimental nitrosamine research provide little evidence that humans might be resistant to the carcinogenic potential of nitrosamines. Human tissues have been shown to metabolize nitrosamines into compounds that bind to DNA, a process that is considered the first step in the development of many cancers, and human liver tissue appears to metabolize nitrosamines with a similar activity to rodent liver tissue. A few human DNA-adduct studies have revealed higher levels of nitrosamine-related DNA adducts in cancer cases than in controls, and studies in experimental animals have shown the formation of similar DNA-adducts to those detected in the human studies.

The International Agency for Research on Cancer (IARC) has classified both NDMA and NDEA as Group 2A carcinogens (probable human carcinogens), and NMOR, NPIP and NPYR as Group 2B carcinogens (possible human carcinogens). The US National Toxicology Program (NTP) has listed all five of these nitrosamines as substances that may be reasonably anticipated to be human carcinogens. In the United States, both the Occupational Safety and Health Administration (OSHA) and the National Institute for Occupational Safety and Health (NIOSH) consider nitrosodimethylamine (NDMA) to be an occupational carcinogen, but no exposure limit has as yet been established. In Germany, Der Ausschub für Gefahrstoffe (AGS) has strict regulations for occupational exposures to nitrosamines. In general industry, the total nitrosamine exposure may not exceed 1 mg/m3. For certain processes, such as rubber vulcanization, total nitrosamine exposures may not exceed 2.5 mg/m3.

Eliminating the nitrosamine formation from operations such as those in the rubber industry can be done by either reformulating the rubber compounds or using alternate methods, such as hot air with glass beads or microwave curing. Both changes require research and development to ensure that the final product has all the same desirable properties as the former rubber product. Another option to reduce exposures is local exhaust ventilation (LEV). Not only does the salt bath need to be enclosed and properly ventilated, but also other areas along the line, such as places where the product is cut or drilled, need sufficient engineering controls to ensure that worker exposures are kept low.

Beth Donovan Reh

Aliphatic amines tables

Table 104.25 Chemical identification

CHEMICAL

SYNONYMS

UN CODE

CAS-NUMBER

CHEMICAL FORMULA

ACETALDEHYDE-OXIME

Acetaldoxime; Aldoxime; Ethanal oxime; Ethylidenehydroxylamine

UN2332

107-29-9

ALLYLAMINE

Allylamine; 3-Aminopropene; 3-Aminopropylene; Monoallylamine; 2-Propenamine

UN2334

107-11-9

1,3-BIS(HYDROXYMETHYL)UREA

N,N'-Bis(hydroxymethyl)urea; N,N'-Dihydroxymethylurea; Dimethanol urea; Dimethylolurea; N,N'-Dimethylolurea; 1,3-Dimethylolurea; Oxymethurea

140-95-4

1,3-BUTANEDIAMINE

1,3-Diaminobutane

590-88-5

BUTYLAMINE

1-Aminobutane; 1-Butanamine; Monobutylamine

UN1125

109-73-9

sec-BUTYLAMINE

2-Aminobutane; 2-Butanamine; 1-Methylpropylamine,

13952-84-6

tert-BUTYLAMINE

2-Aminoisobutane; 2-Amino-2-methylpropane; 1,1-Dimethylethylamine; Trimethylaminomethane

75-64-9

CYCLOHEXYLAMINE

Aminocyclohexane; Aminohexahydrobenzene; Cyclohexanamine; Hexahydroaniline

UN2357

108-91-8

DIALLYLAMINE

Di-2-propenylamine ; N-2-Propenyl 2-propen-1-amine

UN2359

124-02-7

3,3'-DIAMINODIPROPYLAMINE

Aminobis(propylamine); Dipropylenetriamine; Iminobis(propylamine); 3,3'-Iminobis(propylamine)

UN2269

56-18-8

DIBUTYLAMINE

Butyl-1-butanamine; N-Dibutylamine

UN2248

111-92-2

2-DIBUTYLAMINOETHANOL

Dibutylaminoethanol; N,N-Dibutylethanolamine; N,N-Dibutyl-N-(2-hydroxyethyl)amine

UN2873

102-81-8

2,2'-DICHLORO-N-METHYLDIETHYLAMINE

Bis(2-chloroethyl)methylamine; 2-Chloro-n-(2-chloroethyl)-N-methylethanamine; N,N-Di(chloroethyl)methylamine; Methylbis(2-chloroethyl)amine

51-75-2

DICYCLOHEXYLAMINE

N-Cyclohexylcyclohexanamine; N,N-Diclohexylamine; Dodecahydrodiphenylamine

UN2565

101-83-7

DIETHYLAMINE

Diethamine; N,N-Diethylamine; N-Ethyl ethanamine

UN1154

109-89-7

2-DIETHYLAMINOETHANOL

Diethylaminoethanol; Diethylethanolamine; N,N-Diethylethanolamine

UN2686

100-37-8

DIETHYLENETRIAMINE

Aminoethylethandiamine; Bis(2-aminoethyl)amine; 2,2'-Diaminodiethylamine; Ethylamine, 2,2'-Iminobis-; Ethylenediamine-N-(2-aminoethyl)-

UN2079

111-40-0

DIETHANOLAMINE

Bis(2-hydroxyethyl)amine; Diethanolamine; Diethylolamine; 2,2'-Dihydroxydiethylamine ; Di(2-hydroxyethyl)amine

111-42-2

DIISOPROPANOLAMINE

Bis(2-propanol)amine; Bis(2-hydroxypropyl)amine; DIPA; 1,1'-Iminobis-2-propanol; 1,1’-Iminodi-2-propanol

110-97-4

DIISOPROPYLAMINE

N-(1-Methylethyl)-2-propanamine

UN1158

108-18-9

3-DIMETHYLAMINOPROPYLAMINE

1-Amino-3-dimethylaminopropane; N,N-Dimethyl-1,3-propanediamine; N,N-Dimethyl-n-(3-aminopropyl)amine; 3-(Dimethylamino)propylamine; N,N-Dimethyl-1,3-propylenediamine

109-55-7

DIMETHYLAMINE

DMA; Methanamine, N-Methylmethanamine

UN1032

UN1160

124-40-3

DIMETHYLAMINE HYDROCHLORIDE

Dimethylammonium chloride; Hydrochloric acid dimethylamine; N-Methylmethanamine hydrochloride

506-59-2

2-DIMETHYLAMINOETHANOL

Dimethylaminoethanol; Dimethylethanolamine; N,N-Dimethyl-N-(2-hydroxyethyl)amine; DMAE

UN2051

108-01-0

BIS(2-DIMETHYLAMINOETHYL)ETHER

Ethylamine, 2,2'-oxybis(N,N-Dimethyl; NIAX Catalyst A1

3033-62-3

DIPENTYLAMINE

Diamyl amine; Di-N-amylamine; 1-Pentanamine, N-Pentyl

UN2841

2050-92-2

ETHANOLAMINE

2-Aminoethanol; Ethanolamine; Glycinol; 2-Hydroxyethylamine; Monoethanolamine

UN2491

141-43-5

ETHYLAMINE

Aminoethane; 1-Aminoethane; Ethanamine; Monoethylamine

UN1036

UN2270

75-04-7

ETHYLENEDIAMINE

1,2-Diaminoethane; Dimethylenediamine; 1,2-Ethanediamine; Ethylendiamine; Ethylenediamine; 1,2-Ethylenediamine

UN1604

107-15-3

ETHYLENIMINE

Dihydroazirene; Dihydro-1H-azirine; Dimethyleneimine; Dimethylenimine

UN1185

151-56-4

2-ETHYLHEXYLAMINE

2-Ethyl hexylamine

UN2276

104-75-6

ETHYLMETHYLKETONE OXIME

2-Butanone, oxime; Ethyl methyl ketoxime; MEK-oxime; Methyl ethyl ketoxime

96-29-7

HEXAMETHYLENEDIAMINE

1,6-Diaminohexane; Hexamethylenediamine; 1,6-Hexamethylenediamine

UN1783

UN2280

124-09-4

HEXAMETHYLENETETRAMINE

Formamine; Hexaform; 1,6-Hexanediamine; Hexamine; Methamin; Methenamine

UN1328

100-97-0

HYDROXYETHYLETHYLENEDIAMINE

N-Aminoethylethanolamine; Ethanolethylene diamine; N-Hydroxyethyl-1,2-ethanediamine Monoethanolethylenediamine; 2-((2-Aminoethyl)amino)ethanol

111-41-1

ISOBUTANOLAMINE

2-Aminodimethylethanol; 2-Amino-2-methylpropanol; 2-Amino-2-propanol; Isobutanol-2-amine

124-68-5

ISOBUTYLAMINE

1-Amino-2-methylpropane; Monoisobutylamine; 1-Propanamine, 2-methyl-

UN1214

78-81-9

ISOPROPANOLAMINE

α-Aminoisopropyl alcohol; 2-Hydroxypropylamine; Isopropanolamine; 1-Methyl-2-aminoethanol; Mono-iso-propanolamine

78-96-6

ISOPROPYLAMINE

1-Methylethylamine; Monoisopropylamine; 2-Propanamine; sec-Propylamine; 2-Propylamine

UN1221

75-31-0

METHYLAMINE

Aminomethane; Carbinamine; Mercurialin; Monomethylamine

UN1061

UN1235

74-89-5

2-METHYLAMINOETHANOL

N-Methylaminoethanol; Methylethanolamine; Monomethylaminoethanol

109-83-1

1,5-PENTANEDIAMINE

Cadaverin; 1,5-Diaminopentane; Pentamethylenediamine; 1,5-Pentamethylenediamine

462-94-2

1,3-PROPANEDIAMINE

1,3-Diaminopropane; 1,3-Propylenediamine; Trimethylenediamine

109-76-2

PROPYLAMINE

1-Aminopropane; Monopropylamine; Propanamine; 1-Propylamine

UN1277

107-10-8

PROPYLENEDIAMINE1,2-PROPANEDIAMINE

1,2-Diaminopropane; 1,2-Propanediamine; 1,2-Propylenediamine; Propylenediamine

UN2258

78-90-0

TETRAETHYLENEPENTAMINE

D.E.H. 26; 1,4,7,10,13-Pentaazatridecane; 1,2-Ethanediamine, N-(2-aminoethyl)-N'-(2-((2-aminoethyl)amino)ethyl

UN2320

112-57-2

TRIALLYLAMINE

N,N-Di-2-propenyl-2-propen-1-amine; 2-Propen-1-amine, N,N-Di-2-propenyl-

UN2610

102-70-5

TRIBUTYLAMINE

Tributylamine; Tri-N-butylamine; Tris-N-butylamine

UN2542

102-82-9

TRIETHYLAMINE

Diethylaminoethane; N,N-Diethylethanamine; Ethanamine, N,N-Diethyl

UN1296

121-44-8

TRIETHYLENETETRAMINE

N,N-Bis(2-aminoethyl)-1,2-Diaminoethane; N,N'-Bis(2-aminoethyl)ethylenediamine; 1,2-Ethanediamine, N,N'-bis(2-aminoethyl)-; Ethylenediamine, N,N'-Bis(2-aminoethyl)-

UN2259

112-24-3

TRIETHANOLAMINE

Nitrilo-2,2',2''-triethanol; Triethanolamine; Tri(hydroxyethyl)amine; Trihydroxytriethylamine

102-71-6

TRIISOPROPANOLAMINE

Triisopropanolamine; Tris(2-hydroxypropyl)amine; Tris(2-hydroxy-1-propyl)amine

122-20-3

TRIMETHYLAMINE

Methanamine, N,N-dimethyl-; TMA

UN1083

UN1297

75-50-3

TRIPROPYLAMINE

N,N-Dipropyl-1-propanamine

UN2260

102-69-2

Table 104.26 Health hazards

Chemical Name

     CAS-Number

ICSC Short-Term Exposure

ICSC Long-Term Exposure

ICSC Routes of Exposure and Symptoms

US NIOSH Target Organs & Routes of Entry

US NIOSH Symptoms

ALLYLAMINE

     107-11-9

eyes; skin; resp tract; lungs; heart

skin

Inhalation: burning sensation, cough, chest pain, shortness of breath, sore throat

Skin: may be absorbed, redness, pain, blisters

Eyes: severe eye irritation, redness, pain, tear drawing, blurred vision, loss of vision

Ingestion: burning sensation, headache, nausea, weakness

 

 

1-AMINO-2-PROPANOL

     78-96-6

eyes; skin; resp tract; lungs

 

Inhalation: burning sensation, cough, headache, laboured breathing, nausea, sore throat

 

 

BUTYLAMINE

     109-73-9

eyes; skin; resp tract; lungs; CNS

skin

Inhalation: burning sensation, cough, dizziness, unconsciousness

Skin: may be absorbed, redness, roughness, skin burns, burning sensation, blisters

Eyes: pain, burns, loss of vision

Ingestion: cough, dizziness, nausea, unconsciousness, vomiting

Respsys; eyes; skin

Inh, abs, ing, con

Irrit eyes, skin, nose, throat; head; skin flush, burns

sec-BUTYLAMINE

     13952-84-6

eyes; skin; resp tract; lungs

skin

Inhalation: cough, laboured breathing, sore throat, symptoms may be delayed

Skin: redness, skin burns, pain

Eyes: redness, pain, blurred vision, severe deep burns

Ingestion: diarrhoea, sore throat, vomiting

 

 

CYCLOHEXYLAMINE

     108-91-8

eyes; skin; resp tract; lungs; CNS

skin

 

Eyes; skin; resp sys; CNS

Inh, abs, ing, con

Irrit eyes, skin, muc memb, resp sys; eye, skin burns; skin sens; cough, pulm edema; drow, li-head, dizz; diarr, nau, vomit

DIALLYLAMINE

     124-02-7

eyes; skin ; resp tract; lungs; heart

 

burning sensation, cough, sore throat, chest pain, shortness of breath

 

 

DIETHYLAMINE

     109-89-7

eyes; skin; resp tract; lungs

skin

Inhalation: burning sensation, cough, chest pain

Skin: roughness, skin burns, pain

Eyes: pain, blurred vision, severe deep burns

Ingestion: abdominal cramps, abdominal pain, burning sensation, cough, sore throat

Eyes; skin; resp sys; CNS

Inh, abs, ing, con

Irrit eyes, skin, resp sys; in animals: myocardial degeneration

2-DIETHYLAMINOETHANOL

     100-37-8

 

 

Inhalation: cough, laboured breathing, nausea, shortness of breath, sore throat, vomiting

Respsys; skin; eyes

Inh, abs, ing, con

Irrit eyes, skin, resp sys; nau, vomit

DIETHYLENETRIAMINE

     111-40-0

eyes; skin; resp tract; lungs

skin; resp tract

Inhalation: burning sensation, cough, headache, laboured breathing, nausea, sore throat, symptoms may be delayed

Skin: severe skin burns, pain

Eyes: pain, loss of vision, severe deep burns

Ingestion: abdominal pain, sore throat

Eyes; skin; resp sys

Inh, abs, ing, con

Irrit eyes, skin, muc memb, upper resp sys; derm, skin sens; eye, skin nec; cough, dysp, pulm sens

DIETHANOLAMINE

     111-42-2

eyes; skin; resp tract

skin; resp tract

Inhalation: burning sensation, headache, nausea, sore throat, vomiting

Skin: redness, burning sensation

Eyes: redness, pain, severe deep burns

Ingestion: abdominal pain, burning sensation

Eyes; skin; resp sys

Ing, ing, con

irrit eyes, skin, nose, throat; eye burns, corn nec; skin burns; lac, cough, sneez

DIISOPROPANOLAMINE

     110-97-4

eyes; skin

skin

Skin: redness, burning sensation

Eyes: redness, pain, blurred vision

 

 

DIISOPROPYLAMINE

     108-18-9

eyes; resp tract; lungs

skin

Inhalation: cough, laboured breathing, nausea, sore throat

Skin: may be absorbed, dry skin, redness, burning sensation

Eyes: redness, pain, temporary or even permanent loss of vision

Ingestion: corrosive, abdominal cramps, cough, nausea, sore throat

Eyes; skin; resp sys

Inh, abs, ing, con

Irrit eyes, skin, resp sys; nau, vomit; head; vis dist

DIMETHYLAMINE

     124-40-3

eyes; skin; resp tract; lungs

skin

Inhalation: abdominal pain, burning sensation, cough, diarrhoea, laboured breathing, shortness of breath, sore throat

Skin: redness, skin burns, pain

Eyes: redness, pain, blurred vision, severe deep burns

Respsys; skin; eyes

Inh, con, (liq)

Irrit nose, throat; sneez, cough, dysp; pulm edema; conj; derm; liq: frostbite

2-DIMETHYLAMINOETHANOL

     108-01-0

eyes; skin; resp tract; lungs

skin

Inhalation: cough, laboured breathing, symptoms may be delayed

Skin: may be absorbed, redness, pain

Eyes: pain, severe deep burns

Ingestion: abdominal pain, nausea, vomiting

 

 

DIPENTYLAMINE

     2050-92-2

eyes; skin; resp tract

 

Inhalation: cough

 

 

1,2-ETHANEDIAMINE

     107-15-3

eyes; skin; resp tract; lungs; liver; kideys

skin; resp tract

Inhalation: burning sensation, cough, laboured breathing, shortness of breath, sore throat

Skin: may be absorbed, redness, skin burns, pain

Eyes: redness, pain, blurred vision

Ingestion: abdominal pain, diarrhoea, sore throat, vomiting

Respsys; liver; kidneys; skin

Inh, abs, ing, con

Irrit nose, resp sys; sens derm; asthma; liver, kidney damage

ETHANOLAMINE

     141-43-5

 

 

 

Respsys; skin; eyes; CNS

Inh, ing, con

Irrit eyes, skin, resp sys; leth

ETHYLAMINE

     75-04-7

eyes; skin; resp tract

kidneys; lungs

Inhalation: cough, laboured breathing, sore throat

Skin: may be absorbed, redness, burning sensation

Eyes: redness, pain

Ingestion: abdominal pain, burning sensation

Respsys; eyes; skin

Inh, abs (liq), ing (liq), con (liq)

Irrit eyes, skin, resp sys; skin burns; derm

ETHYLENIMINE

     151-56-4

eyes; skin; resp tract; lungs; CNS; kidneys; liver

skin

Inhalation: cough, dizziness, headache, laboured breathing, nausea, vomiting, symptoms may be delayed

Skin: may be absorbed, redness, skin burns, blisters

Eyes: redness, pain, severe deep burns

Ingestion: Vomiting

Eyes; lungs; skin; liver; kidneys; resp sys; In animals: lung & liver tumors

Ing, abs, ing, con

Irrit eyes, skin, nose, throat; nau, vomit; head, dizz; pulm edema; liver, kidney damage; eye burns; skin sens; (carc)

HEXAMETHYLENEDIAMINE

     124-09-4

eyes; skin; resp tract

skin

Inhalation: cough, laboured breathing, shortness of breath

Skin: redness, pain

Eyes: redness, pain

Ingestion: abdominal cramps, abdominal pain

 

 

ISOBUTANOLAMINE

     124-68-5

eyes; skin; resp tract; lungs

 

 

 

 

ISOPHORONE DIAMINE

     2855-13-2

eyes; skin; resp tract; lungs

skin; lungs

Inhalation: burning sensation, cough, headache, cardiac dysrhythmia, symptoms may be delayed

Skin: may be absorbed, redness, skin burns, burning sensation, pain

Eyes: redness, pain, blurred vision, loss of vision, severe deep burns

Ingestion: abdominal pain, burning sensation, sore throat

 

 

ISOPROPYLAMINE

     75-31-0

 

 

 

Respsys; skin; eyes

Inh, abs, ing, con

Irrit eyes, skin, nose, throat; pulm edema; vis dist; eye, skin burns; derm

METHYLAMINE

     74-89-5

eyes; skin; resp tract; lungs

skin

Inhalation: abdominal cramps, cough, diarrhoea, laboured breathing, shortness of breath, sore throat, vomiting

Skin: redness, pain

Eyes: redness, pain

Ingestion: abdominal cramps

Respsys; eyes; skin

Inh, abs (soln), ing (soln), con (liq

soln)

irrit eyes, skin, resp sys; cough; skin, muc memb burns; derm; conj; liq: frostbite

PROPYLAMINE

     107-10-8

eyes; skin; resp tract; lungs

 

Inhalation: burning sensation, cough, sore throat, shortness of breath

 

 

TRIETHYLAMINE

     121-44-8

 

 

 

Respsys; eyes; skin; CVS; liver; kidneys

Ing, abs, ing, con

Irrit eyes, skin, resp sys; in animals: myocardial, kidney, liver damage

TRIETHYLENETETRAMINE

     112-24-3

eyes; skin; resp tract; lungs

skin

Inhalation: burning sensation, cough, laboured breathing

Skin: redness, pain, blisters

Eyes: redness, pain, severe deep burns

Ingestion: abdominal pain, burning sensation, weakness

 

 

TRIISOPROPANOLAMINE

     122-20-3

eyes; skin; resp tract; lungs

 

Inhalation: burning sensation, cough, laboured breathing, sore throat

 

 

TRIMETHYLAMINE

     75-50-3

 

 

Inhalation: abdominal pain, burning sensation, cough, diarrhoea, laboured breathing, shortness of breath, sore throat

Skin: redness, skin burns, pain

Eyes: redness, pain, blurred vision, severe deep burns

Eyes; skin; resp sys

Inh, ing (soln), con

Irrit eyes, skin, nose, throat, resp sys; cough, dysp, delayed pulm edema; blurred vision, corn nec; skin burns; liq: frostbite

Table 104.27 Physical & chemical hazards

For UN Class: 1.5 = very insensitive substances which have a mass explosion hazard; 2.1 = flammable gas; 2.3 = toxic gas; 3 = flammable liquid; 4.1 = flammable solid; 4.2 = substance liable to spontaneous combustion; 4.3 = substance which in contact with water emits flammable gases; 5.1 = oxidizing substance; 6.1 = toxic; 7 = radioactive; 8 = corrosive substance

Chemical Name

CAS-Number

Physical

Chemical

UN Class or Division /  Subsidiary Risks

ACETALDEHYDE-OXIME

107-29-9

 

 

3

ALLYLAMINE

107-11-9

The vapour is heavier than air and may travel along the ground; distant ignition possible

The substance decomposes on heating and on burning producing toxic fumes (nitrogen oxides) •Reacts violently with oxidants causing explosion hazard •Reacts violently with acids and acid anhydrides Corrosive to copper (alloys), aluminium, zinc (alloys) and steel

6.1/ 3

BUTYLAMINE

109-73-9

The vapour is heavier than air and may travel along the ground; distant ignition possible

On combustion, forms carbon monoxide and oxides of nitrogen •Reacts with strong oxidants, acids

3/ 8

sec-BUTYLAMINE

13952-84-6

The vapour is heavier than air and may travel along the ground; distant ignition possible

The substance decomposes on burning producing toxic fumes and gases (ammonia, oxides of nitrogen) •The substance is a weak base, forming water-soluble salts with acids •Reacts with strong oxidants and strong acids •Corrosive to tin, aluminum, and some steels

 

CYCLOHEXYLAMINE

108-91-8

The vapour is heavier than air

The substance decomposes on heating producing toxic gases (nitrogen oxides) •The substance is a strong base, it reacts violently with acid and is corrosive •Reacts violently with strong oxidants causing fire hazard

8/ 3

DIALLYLAMINE

124-02-7

The vapour mixes well with air, explosive mixtures are easily formed

May explode on heating •On contact with hot surfaces or flames this substance decomposes forming toxic and corrosive fumes (nitrogen oxides) •The substance is a medium strong base •Reacts violently with oxidants and acids •Attacks copper, tin, aluminium and zinc •Solutions of diallylamine in water may attack glass

6.1/ 3

DIBUTYLAMINE

111-92-2

 

 

8/ 3

DICYCLOHEXYLAMINE

101-83-7

 

 

8

DIETHANOLAMINE

111-42-2

The vapour is heavier than air

The substance decomposes on burning producing toxic fumes •The solution in water is a medium strong base •Reacts violently with oxidants •Reacts violently with strong acids and anhydrides •Attacks copper

 

DIETHYLAMINE

109-89-7

The vapour is heavier than air and may travel along the ground; distant ignition possible

On combustion, forms carbon monoxide and oxides of nitrogen •Upon heating, toxic fumes are formed •The solution in water is a medium strong base •Reacts with oxidants causing fire and explosion hazard

3/ 8

2-DIETHYLAMINOETHANOL

100-37-8

 

On combustion, forms toxic gases (nitrogen oxides) •Reacts violently with oxidants, acids, acid chlorides, and isocyanates •Attacks light metals and copper

3

DIETHYLENETRIAMINE

111-40-0

The vapour is heavier than air

The substance decomposes on burning producing toxic fumes •The solution in water is a strong base, it reacts violently with acid and is corrosive •Reacts violently with strong oxidants, nitric acid, and organic nitro compounds •Attacks many metals in presence of water

8

DIISOPROPYLAMINE

108-18-9

The vapour is heavier than air and may travel along the ground; distant ignition possible

The substance decomposes on heating and on burning producing toxic and corrosive fumes (eg •NOx) •The substance is a medium strong base and reacts violently with strong acids •Reacts violently with strong oxidants •Reacts with a lot of compounds like organic chlorides, nitriles, oxides, etc •Attacks many metals forming combustible gas (Hydrogen): aluminium, zinc, copper and tin

3/ 8

DIMETHYLAMINE

124-40-3

The gas is heavier than air and may travel along the ground; distant ignition possible

The substance decomposes on burning producing toxic fumes (nitrogen oxides) •The substance is a medium strong base •Reacts violently with strong oxidants, such as chlorine •Reacts violently with mercury causing fire and explosion hazard •Attacks plastics, rubber, and coatings

2.1

DIMETHYLETHANOLAMINE

108-01-0

The vapour is heavier than air

Reacts with strong oxidants and many other substances, causing fire and explosion hazard •Attacks copper

8/ 3

3,3'-DIAMINODIPROPYLAMINE

56-18-8

 

 

6.1

DIISOPROPANOLAMINE

110-97-4

Dust explosion possible if in powder or granular form, mixed with air

The substance decomposes on heating andon burning producing toxic gases (nitrogen oxides) •The substance is a strong oxidant and reacts with combustible and reducing materials •The solution in water is a medium strong base and reacts with strong acids •Reacts violently with strong oxidants causing fire and explosion hazard

 

ETHANOLAMINE

141-43-5

 

 

8

ETHYLAMINE

75-04-7

The gas is heavier than air and may travel along the ground; distant ignition possible •Do not use compressed air when filling, emptying, or processing

The substance decomposes on heating producing toxic gases including nitrogen oxides •The solution in water is a strong base •It reacts violently with acid, strong oxidants and organic compounds causing fire and explosion hazard •Attacks many non-ferrous metals and plastics

3/ 8

ETHYLENEDIAMINE

107-15-3

 

The substance decomposes on heating producing toxic fumes (nitrogen oxides) •The substance is a medium strong base •Reacts violently with chlorinated organic compounds strong oxidants

8/ 3

ETHYLENIMINE

151-56-4

The vapour is heavier than air and may travel along the ground; distant ignition possible •The vapour mixes well with air, explosive mixtures are easily formed

The substance may polymerize under the influence of aqueous acidic conditions, acids, oxidising materials •On combustion, forms toxic and irritating fumes including nitrogen oxides •The substance is a medium strong base

6.1/ 3

HEXAMETHYLENEDIAMINE

124-09-4

 

Upon heating, toxic fumes are formed •The solution in water is a strong base, it reacts violently with acid and is corrosive •Reacts with oxidants •Attacks many metals in presence of water

8

ISOBUTYLAMINE

78-81-9

 

 

3/ 8

ISOPHORONE DIAMINE

2855-13-2

 

May explode on heating •Reacts with brass, copper, zinc and tin •Reacts violently with acids •Attacks many metals

8

ISOPROPANOLAMINE

78-96-6

 

On combustion, forms nitrous oxide •Reacts with strong oxidants

 

ISOPROPYLAMINE

75-31-0

 

 

3

METHYLAMINE

74-89-5

The gas is heavier than air and may travel along the ground; distant ignition possible

The substance decomposes on burning producing toxic fumes (nitrogen oxides) •The substance is a medium strong base •Reacts violently with mercury causing fire and explosion hazard •Reacts violently with strong oxidants, such as chlorine

2.1

DIPENTYLAMINE

2050-92-2

 

The substance decomposes on heating producing toxic and irritating gases (nitrogen oxides) •Reacts with oxidants

 

PROPYLAMINE

107-10-8

The vapour is heavier than air and may travel along the ground; distant ignition possible

The substance decomposes on heating or on burning producing toxic gases (nitrogen oxides) •The substance is a medium strong base •Reacts violently with oxidants and mercury causing fire and explosion hazard, Reacts violently with concentrated acids, nitroparrafins, halogenated hydrocarbons, alcohols and many other compounds •Attacks many metals and alloys, especially copper •Is corrosive to copper (alloys), aluminium, zinc (alloys) and galvanised surfaces •Solutions of propylamine in water may attack glass

3/ 8

TETRAETHYLENEPENTAMINE

112-57-2

 

 

8

TRIALLYLAMINE

102-70-5

 

 

3/ 8

TRIBUTYLAMINE

102-82-9

 

 

8

TRIETHYLAMINE

121-44-8

 

 

3/ 8

TRIETHYLENETETRAMINE

112-24-3

 

On combustion, forms toxic fumes of carbon monoxide and nitrogen oxides •The substance is a medium strong base •Reacts violently with oxidants causing fire and explosion hazard •Reacts with acid chlorides, acid anhydrides, aldehydes, ketones, halogenated organic compounds and acrylates •Attacks metals such as aluminium, zinc, copper and its alloys

 

TRIISOPROPANOLAMINE

122-20-3

 

On combustion, forms toxic gases of carbon and nitrogen oxides •Reacts with strong oxidants and acids

 

TRIMETHYLAMINE

75-50-3

The gas is heavier than air and may travel along the ground; distant ignition possible

The substance decomposes on burning producing toxic gases (nitrous oxides) •The substance is a medium strong base •Reacts violently with mercury causing fire and explosion hazard •Reacts violently with strong oxidants, such as chlorine

2.1

TRIPROPYLAMINE

102-69-2

 

 

3/ 8

Table 104.28 Physical & chemical properties

Chemical Name

CAS-Number

Colour/Form

Boiling Point (°C)

Melting Point (°C)

Molecular Weight

Solubility in Water

Relative Density (water=1)

Relative Vapour Density (air=1)

Vapour Pressure/ (Kpa)

Inflam. Limits

Flash Point (°C)

Auto Ignition Point (°C)

ACETALDEHYDE-OXIME

107-29-9

needles; two crystalline modifications

115

47

59.07

sol

0.9656

 

10mmHg  @25.8°C

 

<22

 

ALLYLAMINE

107-11-9

colourless to light yellow liquid

55-58

-88

57.09

misc

0.76

2.0

26.4

2.2 ll 22 ul

-29 cc

370

BUTYLAMINE

109-73-9

clear, colourless liquid

77.8

-50

73.1

misc

0.7414

2.5

10.9

1.7 ll 9.80 ul

-1 oc

312

sec-BUTYLAMINE

13952-84-6

colourless liquid

63

-104

73.14

misc

0.724

2.52

18

1.7 ll 9.8 ul

- 9

378

tert-BUTYLAMINE

75-64-9

colourless liquid

44

-72.65

73.1

misc

0.6951

2.5

362mmHg  @25°C.

1.7 ll 8.9 ul

10

380

CYCLOHEXYLAMINE

108-91-8

colourless to yellow liquid

134

-17.7

99.17

sol

0.8191

3.42

1.2

1.5 ll 9.4 ul

31 cc

293

DIALLYLAMINE

124-02-7

liquid

111

-88.4

97.2

8.6g/ 100ml

0.7627  @10°C/4°C

3.35

2.4

 

21

 

1,3-BUTANEDIAMINE

590-88-5

water white liquid

143-150

 

 

 

0.858

 

 

 

516

 

1,5-PENTANEDIAMINE

462-94-2

 

179

9

102.17

sol

0.873 25°C

 

 

 

 

 

1,3-PROPANEDIAMINE

109-76-2

 

140

 

74.12

sol

0.884

 

 

 

 

 

DIBUTYLAMINE

111-92-2

liquid; colourless

160

-60-59

129.24

sol

0.7670

4.46

1.9mmHg

1.1

57 oc

 

2,2'-DICHLORO-N-METHYLDIETHYLAMINE

51-75-2

mobile liquid

87  @18mmHg

-60

156.07

sl sol

1.118  @25°C/4°C

 

 

 

 

 

DICYCLOHEXYLAMINE

101-83-7

colourless liquid

256

-0.1

181.31

sl sol

0.9123

6.25

 

 

110

 

DIETHANOLAMINE

111-42-2

prisms; usually offered as a viscous liquid; crystalline solid

268.8

28

105.1

v sol

1.0966

3.65

< 0.001

 

134 oc

660

DIETHYLAMINE

109-89-7

colourless liquid

55.5

-49.8

73.1

v sol

0.71

2.53

25.9

1.8 ll 10.1. ul

-26 cc

312

2-DIETHYLAMINOETHANOL

100-37-8

colourless liquid

163

-70

117.19

misc

0.8921

4.03

0.19

6.7 ll 11.7 ul

52 cc

250

DIETHYLENETRIAMINE

111-40-0

yellow liquid

207

-39

103.2

misc

0.96

3.56

0.037

1 ll 10 ul

97-102 oc

390-395

DIISOPROPYLAMINE

108-18-9

colourless liquid

84

-61

101.19

sl sol

0.7169

3.5

8.0

0.8 ll 7.1 ul

-1 oc

316

DIMETHYLAMINE

124-40-3

gas at ordinary temperature; colourless gas

7

-92

45.08

v sol

0.680

1.6

206

2.8 ll 14.4 ul

 

402

DIMETHYLAMINE HYDROCHLORIDE

506-59-2

 

 

171

81.54

v sol

 

 

 

 

 

 

3-DIMETHYLAMINOPROPYLAMINE

109-55-7

colourless liquid

123

-70

102.2

sol

0.8100  @30°C

3.5

 

 

 

 

DIMETHYLETHANOLAMINE

108-01-0

colourless liquid

135

-59

89.1

misc

0.8866

3.03

560

 

41oc

220

3,3'-DIAMINODIPROPYLAMINE

56-18-8

 

15  @50°C

-14

131.22

 

0.938  @25°C

 

 

 

 

 

ETHANOLAMINE

141-43-5

viscous, clear, hydroscopic fluid; viscous liquid

171

10.5

61.08

misc

1.0180

2.1

0.26mmHg  @25°C

 

85 cc

410

ETHYLAMINE

75-04-7

colourless liquid or gas

17

-81

45.08

misc

0.689  @15°C/15°C

1.55

121

3.5 ll 14 ul

-17 cc

725

ETHYLENEDIAMINE

107-15-3

colourless liquid; water-white liquid

117

8.5

60.10

v sol

0.8979

2.07

1.2

4.2 ll 14.4 ul

34 cc

385

ETHYLENIMINE

151-56-4

colourless, mobile fluid; oil

56-57

-71.5

43.08

sol

0.8321  @24°C/4°C

1.48

21.3

3.6 ll 46 ul

11 cc

322

2-ETHYLHEXYLAMINE

104-75-6

colourless liquid

 

 

129.24

sol

 

 

1.2

 

60 oc

 

HEXAMETHYLENEDIAMINE

124-09-4

colourless leaflets; rhombic bipyramidal plates

205

42

116.20

v sol

0.93

4.01

200 Pa  @50°C

0.7 ll 6.3 ul

71

310

HYDROXYETHYL ETHYLENEDIAMINE

111-41-1

colourless liquid

238-40

 

104.15

misc

1.0286

3.59

8.19x 10-4 mmHg  @25°C

 

135 cc

 

ISOBUTANOLAMINE

124-68-5

crystalline mass

165

31

89.1

misc

0.934

3.0

 

 

67 cc

 

ISOBUTYLAMINE

78-81-9

colourless liquid

68

-85

73.1

v sol

0.724  @25°C/4°C

2.5

100mmHg  @18.8°C

3.4 ll 9 ul

 

378

ISOPHORONE DIAMINE

2855-13-2

colourless liquid

247

10

170.30

v sol

0.92

 

2 Pa

 

110

 

ISOPROPANOLAMINE

78-96-6

liquid

159.46

1.74

75.11

sol

0.9611

2.6

< 0.2

 

77

374

ISOPROPYLAMINE

75-31-0

colourless liquid

33-34

-101

59.1

misc

0.694  @15°C/4°C

2.04

579.6mmHg  @25°C

2.3 ll 12 ul

-37 oc

402

HEXAMETHYLENETETRAMINE

100-97-0

rhombic crystals from alcohol; crystals or granules or powder; colourless, lustrous crystals or white crystalline powder

 

 

140.19

1g /1.5ml

1.331  @-5°C

 

 

 

 

 

ETHYL METHYL KETONE OXIME

96-29-7

 

152.5

-29.5

87.12

sol

0.9232

 

 

 

 

 

METHYLAMINE

74-89-5

colourless gas or liquid

-6.3

-94

31.1

v sol

0.6628

1.07

290

4.9 ll 20.7 ul

 

430

2-METHYLAMINOETHANOL

109-83-1

viscous liquid

155-156

-4.5

75.11

misc

0.937

2.6

0.7mmHg

 

74 oc

 

2-DIBUTYLAMINOETHANOL

102-81-8

colourless liquid

224-232

 

173.29

 

0.859

 

 

 

933

 

DIISOPROPANOLAMINE

110-97-4

crystals

249-250  @745mmHg

44.5

133.2

sol

0.989

4.6

0.003  @42°C

1.1 ll 5.4 ul

127

374

DIPENTYLAMINE

2050-92-2

colourless to light-yellow liquid

202

-44

157.3

sl sol

0.7771

5.4

 

 

52

 

PROPYLAMINE

107-10-8

colourless liquid

48-49

-83

59.11

sol

0.72

2.0

33.1

2.0 ll 10.4 ul

<-37 oc

317

PROPYLENEDIAMINE

78-90-0

 

119.5

 

74.12

v sol

0.878  @15°C

 

 

 

 

 

TETRAETHYLENEPENTAMINE

112-57-2

viscous, hygroscopic liquid; yellow liquid

340

-30

189.3

sol

0.9980

6.53

8.0x 10-7 mmHg  @25°C

 

163 oc

321

TRIALLYLAMINE

102-70-5

liquid

155.5

-70

137.2

0.25g/100ml

0.809

4.73

 

 

39 oc

 

TRIBUTYLAMINE

102-82-9

colourless liquid; pale yellow liquid

216.5

-70

185.34

sl sol

0.78

6.39

0.29mmHg  @25°C

 

86 oc

 

TRIETHANOLAMINE

102-71-6

viscous liquid; colourless to pale yellow

335

20.5

149.2

misc

1.1242

5.1

< 0.01mmHg

 

 

 

TRIETHYLAMINE

121-44-8

colourless liquid

89

-115

101.19

sol

0.7275

3.49

400mmHg  @31.5°C

1.2 ll 8.0 ul

-667 oc

 

TRIETHYLENETETRAMINE

112-24-3

moderately viscous, yellowish liquid

266.5

12

146.2

v sol

0.9818

5.04

1.3 Pa

1.1 ll >6.4 ul

118-143 cc

338

TRIISOPROPANOLAMINE

122-20-3

crystals

305

45

191.3

sol

1.0

 

<0.001

 

160

320

TRIMETHYLAMINE

75-50-3

colourless gas

3

-117

59.11

v sol

0.6356

2.0

220

2.0 ll 11.6 ul

12 cc

190

TRIPROPYLAMINE

102-69-2

water white liquid

150-156

-94

143.28

 

0.7558

 

 

 

405

 

AROMATIC AMINO COMPOUNDS

The aromatic amino compounds are a class of chemicals derived from aromatic hydrocarbons, such as benzene, toluene, naphthalene, anthracene and diphenyl by the replacement of at least one hydrogen atom by an amino -NH2 group. A compound with a free amino group is described as a primary amine. When one of the hydrogen atoms of the -NH2 group is replaced by an alkyl or aryl group, the resultant compound is a secondary amine; when both hydrogen atoms are replaced, a tertiary amine results. The hydrocarbon may have one amino group or two, more rarely three. It is thus possible to produce a considerable range of compounds and, in effect, the aromatic amines constitute a large class of chemicals of great technical and commercial value.

Aniline is the simplest aromatic amino compound, consisting of one -NH2 group attached to a benzene ring and its derivatives are most widely used in industry. Other common single-ring compounds include dimethylaniline and diethylaniline, the chloroanilines, nitroanilines, toluidines, the chlorotoluidines, the phenylenediamines and acetanilide. Benzidine, o-tolidine, o-dianisidine, 3,3'-dichlorobenzidine and 4-aminodiphenyl are the most important conjoined ring compounds from the point of view of occupational health. Of compounds with ring structures, the naphthylamines and aminoanthracenes have attracted much attention because of problems of carcinogenicity. Strict precautions necessary for handling carcinogens apply to many members of this family.

Azo and diazo dyes

Azo dye is a comprehensive term applied to a group of dyestuffs that carry the azo (-N=N-) group in the molecular structure. The group may be divided into subgroups of monoazo, diazo and triazo dye and further in accordance with the number of the azo group in the molecule. From a toxicological perspective, it is important to take into account that the commercial grade dyestuffs usually contain impurities up to 20% or even higher. The composition and quantity of the impurities are variable depending on several factors such as the purity of the starting materials for the synthesis, the process of synthesis employed and the requirements of the users.

Production

Azos dyes are synthesized by diazotization or tetrazotization of aromatic monoamine or aromatic diamine compounds with sodium nitrite in the HCl medium, followed by coupling with dye intermediates such as various aromatic compounds or heterocyclic compounds. When the coupling component carries an amino group, it is possible to produce long-chained polyazo dye by the repetition of diazotization and coupling. The generalized structural formulae for the first three members of the family are:

     R-N=N-R'     monoazo dye

     R-N=N-R'-N=N-R"     diazo dye

     R-N=N-R'-N=N-R"-N=N-R"'     triazo dye

Tetrazotization of benzidine and coupling with naphthionic acid yields the very popular dye Congo Red.

Uses

Aromatic amino compounds are primarily used as intermediates in the manufacture of dyes and pigments. The largest class of dyestuffs is that of the azo colours, which are made by diazotization, a process by which a primary aromatic amine reacts with nitrous acid in the presence of excess mineral acid to produce a diazo (-N=N-) compound; this compound is subsequently coupled with a phenol or an amine. Another important class of dyestuffs, the triphenylmethane colours, is also manufactured from aromatic amines. In addition to serving as chemical intermediates in the dyestuffs industry, several compounds are employed as dyes or intermediates in the pharmaceutical, fur, hairdressing, textile and photography industries.

o-Aminophenol is used for dyeing furs and hair. It is also a developer in the photography industry and an intermediate for pharmaceuticals. p-Aminophenol is used in dyeing textiles, hair, furs and feathers. It finds use in photographic developers, pharmaceuticals, antioxidants and oil additives. 2,4-Diaminoanisole provides an oxidation base for dyeing fur. o-Toluidine, p-phenylenediamine, diphenylamine and N-phenyl-2-naphthylamine find additional uses as antioxidants in the rubber industry.

Diphenylamine is also employed in the pharmaceutical and explosives industries and as a pesticide. N-Phenyl-2-naphthylamine serves as a vulcanization accelerator, a stabilizer for silicone enamels and a lubricant. It is a component of rocket fuels, surgical plaster, tin-electroplating baths and dyes. 2,4-Diaminotoluene and 4,4'-diaminodiphenylmethane are useful intermediates in the manufacture of isocyanates, basic raw materials for the production of polyurethanes.

The major use of benzidine is in the manufacture of dyestuffs. It is tetrazotized and coupled with other intermediates to form colours. Its use in the rubber industry has been abandoned. Auramine is used in printing inks and as an antiseptic and a fungicide.

o-Phenylenediamine is a photographic developing agent and a hair dye component while p-phenylenediamine is used as a photographic chemical and a dyeing agent for fur and hair. However, p-phenylenediamine has been banned for use as an oxidation dye for hair in some countries. p-Phenylenediamine is also a vulcanization accelerator, a component of gasoline antioxidants. m-Phenylenediamine has numerous functions in the dyestuffs, rubber, textile, hairdressing and photography industries. It finds use in rubber curing agents, ion exchange and decolorizing resins, urethanes, textile fibers, petroleum additives, corrosion inhibitors and hair dyes. It is used as an promoter for adhering tire cords to rubber.

Xylidine serves as a gasoline additive as well as raw material in the manufacture of dyes and pharmaceuticals. Melamine is used in moulding compounds, textile and paper treating resins, and in adhesive resins for gluing lumber, plywood and flooring. In addition, it is useful in organic synthesis and in leather tanning. o-Tolidine is a reagent for the detection of gold.

Anilines

The anilines are primarily used as intermediates for dyes and pigments. Several compounds are intermediates for pharmaceuticals, herbicides, insecticides and rubber processing chemicals, as well. Aniline itself is widely used in the manufacture of synthetic dyestuffs. It is also used in printing and cloth marking inks and in the manufacture of resins, varnishes, perfumes, shoe blacks, photographic chemicals, explosives, herbicides and fungicides. Aniline is useful in the manufacture of rubber as a vulcanizing agent, as an antioxidant, and as an antiozone agent. A further important function of aniline is in the manufacture of  p,p'-methylenebisphenyldiisocyanate (MDI), which is then used to prepare polyurethane resin and spandex fibers and to bond rubber to rayon and nylon.

Chloroaniline exists in three isomeric forms: ortho, meta and para, of these only the first and the last are important for manufacturing dyes, drugs and pesticides. p-Nitroaniline is a chemical intermediate for antioxidants, dyes, pigments, gasoline gum inhibitors and pharmaceuticals. It is used in diazotized form to retain fastness of dyes after washing. 4,4'-Methylene-bis(2-chloroaniline), MbOCA, is used as a curing agent with isocyanate-containing polymers for the manufacture of solid abrasion-resistant urethane rubbers and moulded semi-rigid polyurethane foam articles with a hardened skin. These materials are used in an extensive range of products, including wheels, rollers, conveyor pulleys, cable connectors and seals, shoe soles, antivibration mounts and acoustic components. p-Nitroso-N,N,-dimethylaniline and 5-chloro-o-toluidine are used as intermediates in the dyestuffs industry. N,N-Diethylaniline and N,N-dimethylaniline are used in the synthesis of dyestuffs and other intermediates. N,N-Dimethylaniline also serves as a catalytic hardener in certain fibreglass resins.

Azo compounds

Azo compounds are among the most popular groups of various dyes including direct dyes, acid dyes, basic dyes, naphthol dyes, acid mordant dyes, disperse dyes, etc., and are extensively used in textiles, fabrics, leather goods, paper products, plastics and many other items.

Hazards

The manufacture and use in industry of certain aromatic amines may constitute a grave and sometimes unexpected hazard. However, since these hazards have become better known, there has, over recent years, been a tendency to substitute other substances or to take precautions which have reduced the hazard. Discussion has also taken place concerning the possibility of aromatic amines having health effects either when they exist as impurities in a finished product, or when they may be restored as the result of a chemical reaction taking place during the use of a derivative, or—and this is a totally different case—as the result of metabolic degradation within the organism of persons who may be absorbing more complex derivatives.

Absorption pathways

Generally speaking, the principal risk of absorption lies in skin contact: the aromatic amines are nearly all lipid-soluble. This particular hazard is all the more important because in industrial practice it is one often not sufficiently appreciated. In addition to skin adsorption, there is also a considerable risk of absorption by inhalation. This may be the result of inhaling the vapours, even though most of these amines are of low volatility at normal temperatures; or it may result from breathing in dust from the solid products. This applies particularly in the case of the amine salts such as sulphates and chlorohydrates, which have a very low volatility and lipid solubility: the occupational hazard from the practical point of view is less but their over-all toxicity is about the same as the corresponding amine, and thus the inhalation of their dust and even skin contact must be considered dangerous.

Absorption by way of the digestive tract does represent a potential danger if inadequate eating and sanitary facilities are provided or if workers do not exercise excellent person hygiene practices. Contamination of food and cigarette smoking with dirty hands are two examples of possible ingestion routes.

Many of the aromatic amines are flammable and represent a moderate fire hazard. Combustion products can often be highly toxic. The primary health danger of industrial exposure to aniline arises from the ease with which it can be absorbed, either by inhalation or from skin absorption. Because of these absorptive properties, prevention of aniline poisoning requires high standards of industrial and personal hygiene. The most important specific measure for the prevention of spillage or contamination of the work atmosphere with aniline vapour is proper plant design. Ventilation control of the contaminant should be designed as close to the point of generation as possible. Work clothing should be changed daily and facilities for an obligatory bath or shower at the end of the working period should be provided. Any contamination of skin or clothing should be washed off immediately and the individual kept under medical supervision. Both workers and supervisors should be educated to be aware of the nature and extent of the hazard and to carry out the work in a clean, safe manner. Maintenance work should be preceded with sufficient attention to removal of possible sources of contact with the offending chemicals.

Since many cases of aniline poisoning result from contamination of the skin or clothing that leads to absorption through the skin, contaminated clothing should be removed and laundered. Even when intoxication results from inhalation, the clothing is likely to be contaminated and should be removed. The entire body surface, including hair and fingernails, should be carefully washed with soap and tepid water. Where methaemoglobinemia is present, appropriate emergency precautions should be taken and the occupational health service must be fully equipped and trained to handle such emergencies. Laundry workers should be provided with adequate precautions to avoid contamination from the aniline compounds.

Metabolism

The amines undergo a process of metabolization within the organism. Generally the active agents are the metabolites, some of which induce methaemoglobinaemia, while others are carcinogenic. These metabolites generally take the form of hydroxylamines (R-NHOH), changing to aminophenols (H2N-R-OH) as a form of detoxification; their excretion provides a means of estimating the degree of contamination when the level of exposure has been such that they are detectable.

Health effects

Aromatic amines have various pathological effects, and each member of the family does not share the same toxicological properties. While each chemical must be evaluated independently, certain important characteristics are prominently shared by many of them. These include:

·     cancer of the urinary tract, particularly of the urinary bladder

·     danger of acute poisoning, particularly methaemoglobinaemia, which may ultimately have adverse effects on the red cells

·     sensitization, notably of the skin, but sometimes respiratory.

Toxic effects are also related to chemical characteristics. For example, although an aniline salt has a very similar toxicity to aniline itself, it is not water or lipid soluble and hence not readily absorbed through the skin or by inhalation. Thus, poisoning by aniline salts from industrial exposure are rare.

Acute poisoning generally results from the inhibition of haemoglobin function through the formation of methaemoglobin, leading to a condition called methaemoglobinemia, which is discussed more fully in the Blood chapter. Methaemoglobinemia is more often associated with the single-ring aromatic amino compounds. Methaemoglobin is normally present in the blood at a level of about 1 to 2% of the total haemoglobin. Cyanosis at the oral mucosae begins to become apparent at levels of 10 to 15%, though subjective symptoms are normally not experienced until methaemoglobin levels of the order of 30% are reached. With increases above this level, the patient's skin colour deepens; later, headache, weakness, malaise and anoxia occur, to be succeeded, if absorption continues, by coma, cardiac failure and death. Most cases of acute poisoning react favourably to treatment and the methaemoglobin disappears completely after two to three days. The consumption of alcohol is conducive to and aggravates acute methaemoglobin poisoning. Haemolysis of the red blood cells can be detected after severe poisoning, and is followed by a process of regeneration which is demonstrated by the presence of reticulocytes. The presence of Heinz bodies in the red blood corpuscles may sometimes also be detected.

Cancer. The potent carcinogenic effects of the aromatic amines were first discovered in the workplace as a result of the abnormally high incidence of cancer employees in a dye factory. The cancers were described as "dye cancer", but further analysis very soon pointed to their origin being in the raw materials, of which the most important was aniline. They then became known as "aniline cancers". Later, further definition was possible and β-naphthylamine and benzidine were considered to be the “culprit” chemicals. Experimental confirmation of this was long in coming and difficult. Experimental work on many members of this family has found a number to be animal carcinogens. Since insufficient human evidence is available, they have been classified by the International Agency for Research on Cancer (IARC) for the most part as 2B, probable human carcinogens, that is, having sufficient evidence for animal carcinogenicity but insufficient for human carcinogenicity. In some cases, laboratory work has lead to the discovery of human cancer, as in the case of 4-aminodiphenyl, which was first shown to be carcinogenic for animals (in the liver), after which a number of cases of bladder cancer in humans were brought to light.

Dermatitis. Because of their alkaline nature, certain amines, particularly the primary ones, constitute a direct risk of dermatitis. Many aromatic amines can cause allergic dermatitis, such as that due to sensitivity to the "para-amines" (p-aminophenol and particularly  p-phenylenediamine). Cross-sensitivity is also possible.

Respiratory allergy. A number of cases of asthma due to sensitization to p-phenylenediamine, for example, have been reported.

Haemorrhagic cystitis can result from heavy exposure to o- and p-toluidine, particularly the chlorine derivatives, of which chloro-5-o-toluidine is the best example. These haematuria appear to be short-lived and the relationship to development of bladder tumours is not established.

Liver injuries. Certain diamines, such as toluenediamine and diaminodiphenylmethane, have potent hepatotoxic effects in experimental animals but serious liver damage resulting from industrial exposure has not been a widely reported. In 1966, however, 84 cases of toxic jaundice were reported from eating bread baked from flour contaminated with 4,4'-diaminodiphenylmethane, and cases of toxic hepatitis have also been reported after occupational exposure.

Some of the toxicological properties of the aromatic amines are discussed below. Because the members of this chemical family are very numerous, it is not possible to include them all, and there may be others, not included below, which also have toxic properties.

Aminophenols

Neither o- nor p-aminophenol isomers, which are crystalline solids of low volatility, are readily absorbed through the skin, although both may act as skin sensitizers and cause contact dermatitis, which appears to be the greatest hazard arising from their use in industry. Although both isomers can cause serious, even life-threatening methaemoglobinaemia, this seldom arises from industrial exposure, since their physical properties are such that neither compound is readily absorbed into the body. p-Aminophenol is the major metabolite of aniline in humans and is excreted in the urine in conjugated form. Bronchial asthma from the ortho isomer has been reported as well.

p-Aminodiphenyl is considered a confirmed human carcinogen by IARC. It was the first compound in which the demonstration of carcinogenic activity in experimental animals preceded the first reports of bladder tumours in exposed workers, where it was used as an antioxidant in rubber manufacture. The substance is clearly a potent bladder carcinogen since in one plant with 315 workers, 55 developed tumours as did 11% of 171 workers in another plant manufacturing 4-aminodiphenyl. The tumours appeared 5 to 19 years after initial exposure, and survival ranged in duration from 1.25 to 10 years.

Aniline and its derivatives

It has been demonstrated experimentally that aniline vapour can be absorbed via the skin and respiratory tract in approximately equal amounts; however, the rate of absorption of the liquid through the skin is about 1,000 times greater than that of the vapour. The most frequent cause of industrial poisoning is accidental skin contamination, either directly through accidental contact, or indirectly through contact with soiled clothing or footwear. The use of clean and suitable protective clothing and rapid washing in case of accidental contact constitute the best protection. While the US National Institute for Occupational Health and Safety (NIOSH) recommends that aniline be treated as a suspected human carcinogen, IARC has rated it as a Group 3 chemical, meaning insufficient evidence of animal or human carcinogenicity.

p-Chloroaniline is a potent methaemoglobin-former and eye irritant. Animal experiments have provided no evidence of carcinogenicity. 4,4'-Methylene bis(2-chloroaniline), or MbOCA, can be absorbed from contact with dust or from fume inhalation, and in industry, skin absorption may also be an important route for uptake. Laboratory studies showed MbOCA or its metabolites may cause genetic damage in a variety of organisms. In, addition, long-term subcutaneous administration in rats resulted in liver and lung tumours. Thus, MbOCA is regarded as an animal carcinogen and a probable human carcinogen.

N,N-Diethylaniline and N,N-dimethylaniline are readily absorbed through the skin, but poisoning may also occur through inhalation of vapours. Their hazards may be considered as similar to those of aniline. They are, in particular, potent methaemoglobin-formers.

Nitroanilines. Of the three mono-nitroanilines, the most important is p-nitroaniline. All are used as dye intermediates, but the o- and m- isomers only on a small scale. p-Nitroaniline is readily absorbed through the skin and also by inhalation of dust or vapour. It is a powerful methaemoglobin-former, and is alleged, in serious cases, also to bring about haemolysis, or even liver damage. Cases of poisoning and cyanosis have been reported following exposure while cleaning up spills. The chloronitroanilines are also potent methaemoglobin-formers, leading to haemolysis, and are hepatotoxic. They may give rise to dermatitis by sensitization.

p-Nitroso-N,N-dimethylaniline possesses both primary irritant and skin sensitizing properties, and it is a common cause of contact dermatitis. Although, occasionally, workers who develop dermatitis may subsequently work with this compound without further trouble, most will suffer a severe recurrence of the skin lesions on re-exposure, and, in general, it is wise to transfer them to other work to avoid further contact.

5-Chloro-o-toluidine is readily absorbed through the skin or by inhalation. Although it (and some of its isomers) may cause methaemoglobin formation, the most striking feature is its irritant effect on the urinary tract, resulting in haemorrhagic cystitis characterized by painful haematuria and frequency of micturition. Microscopic haematuria may be present in men exposed to this compound before the cystitis is manifest, but there is no carcinoenic hazard to humans. However, laboratory experiments have cast doubts on the carcinogenicity of other isomers for certain species of animals.

Benzidine and derivatives

Benzidine is a confirmed carcinogen, the manufacture and industrial use of which has caused many cases of papilloma and carcinoma of the urinary tract. Among some working populations, more than 20% of all workers have developed the disease. Recent studies indicate that benzidine may raise the rate of cancer at other sites but there is not agreement on this as yet. Benzidine is a crystalline solid with a significant vapour pressure (that is, it forms vapours readily). Penetration through the skin seems to be the most important pathway for the absorption of benzidine, but there is also a hazard from the inhalation of vapour or fine particles. The carcinogenic activity of benzidine has been established by the many reported cases of bladder tumour in exposed workers and by experimental induction in animals. It is a Group1 confirmed human carcinogen according to IARC ratings. The use of benzidine has been discontinued in most places.

3,3'-Dichlorobenzidine is a probable human carcinogen (IARC Class 2B). This conclusion is based on a statistically significantly increased tumor incidence in rats, mice and dogs and positive data on its genotoxicity. The structural relationship to benzidine, a known, powerful human bladder carcinogen, lends further weight to the probability that it is a human carcinogen.

Diamino-4,4'-diaminodiphenylmethane. The most striking example of the toxicity of this compound was when 84 persons contracted toxic hepatitis as a result of eating bread baked from flour that was contaminated with the substance. Other cases of hepatitis were noted after occupational exposure through skin absorption. It may also give rise to allergic dermatitis. Animal experiments have led to its being a suspected potential carcinogen, but conclusive results have not been obtained. Diaminodiphenylmethane derivatives have been shown to be carcinogens for laboratory animals.

Dimethylaminoazobenzene. The metabolism of DAB has been extensively studied and it has been found that it involves reduction and cleavage of the azo group, demethylation, ring hydroxylation, N-hydroxylation, N-acetylation, protein binding and binding of nucleic acids. DAB shows mutagenic properties after activation. It has carcinogenic power by various routes in the rat and mouse (liver carcinoma), and by oral route it causes carcinoma of the bladder in the dog. The only occupational health observation in humans was of contact dermatitis in factory workers handling DAB.

Technical measures should prevent any contact with the skin and mucous membranes. Workers exposed to DAB should wear personal protective equipment and their work should be carried out only in restricted areas. Clothing and equipment after use should be placed in an impervious container for decontamination or disposal. Pre-employment and periodical examinations should focus on liver function. In the US, DAB has been included by OSHA among the cancer suspect agents for humans.

Diphenylamine. This chemical can be mildly irritating. It appears that under ordinary industrial conditions it offers little hazard, but the potent carcinogen 4-aminodiphenyl may be present as an impurity during the manufacturing process. This may be concentrated to significant proportions in the tars produced at the distillation stage and will constitute a hazard of bladder cancer. While modern manufacturing procedures have enabled the amount of impurities in this compound to be considerably reduced in the commercial product, appropriate prevention must be taken to prevent unnecessary contact.

Naphthylamines

The naphthylamines occur in two isomeric forms, α-naphthylamine and β-naphthylamine.  α-Naphthylamine is absorbed through the skin and by inhalation. Contact may cause burns to the skin and eyes. Acute poisoning does not arise from its industrial use, but exposure to commercial grades of this compound in the past has resulted in many cases of papilloma and carcinoma of the bladder. It is possible that these tumours were attributable to the substantial  β-naphthylamine impurity. This matter is not merely of academic interest, as α-naphthylamine with greatly reduced levels of β-naphthylamine impurity is now available.

β-Naphthylamine is a known human bladder carcinogen. Acute poisoning results in methaemoglobinemia or acute haemorrhagic cystitis. Although at one time extensively used as an intermediate in the manufacture of dyestuffs and antioxidants, its manufacture and use has been almost entirely abandoned throughout the world, and it has been condemned as too dangerous to make and handle without prohibitive precautions. It is readily absorbed through the skin and by inhalation. The question of its acute toxic effects does not arise because of its high carcinogenic potency.

Phenylenediamines

Various isomeric forms of the phenylenediamines exist but only the m- and p-isomers are of industrial importance. While p-phenylenediamine can act as a methaemoglobin-former in vitro, methaemoglobinaemia arising from industrial exposure is unknown. p-Phenylenediamine is notorious for its sensitizing properties of the skin and respiratory tract. Regular skin contact readily causes contact dermatitis. Acne and leukoderma have also been reported. The former problem of "fur dermatitis" is much less frequent now owing to improvements in the dyeing process having the effect of removing all traces of p-phenylenediamine. Similarly, asthma, at one time common among fur dyers using this substance, is now relatively rare after improvements in the control of airborne dust. Even with controls, a preliminary skin test is useful prior to possible occupational exposure. m-Phenylenediamine is a strong irritant to the skin and causes eye and respiratory irritation. Conclusions drawn from experiments conducted on the phenylenediamines and their derivatives (e.g. N-phenyl or 4- or 2-nitro) relating to their carcinogenic potential are, up to the present time, either insufficient, inconclusive or negative. Chlorine derivatives that have been tested seem to have a carcinogenic potential in animal tests.

The carcinogenic potential of commercial mixtures in the past was of great concern because of the presence of β-naphthylamine, which had been found to exist as an impurity in considerable quantities (running into tens or even hundreds of ppm) in some of the older preparations, and by the discovery, in the case of N-phenyl-2-naphthylamine, PBNA, of β-naphthylamine as a metabolic excretion, though in infinitesimal quantities. The experiments point to a carcinogenic potential for the animals tested but do not permit a conclusive judgment to be made, and the degree of significance of the metabolic findings is not yet known. Epidemiological investigations on a large number of persons working under different conditions have not shown any significant increase in the incidence of cancer among workers exposed to these compounds. The amount of β-naphthylamine that is present in the marketed products today is very low—less than 1 ppm and frequently 0.5 ppm. At the present time it is not possible to draw any conclusions as to the true cancer hazard, and for this reason every precaution should be taken, including the elimination of impurities that may be suspect, and technical protective measures in the manufacture and use of these compounds.

Other compounds

Toluidine exists in three isomeric forms but only the o- and p- isomers are of industrial importance. o-Toluidine and p-toluidine are readily absorbed through the skin, or inhaled as dust, fume or vapour. They are powerful methaemoglobin-formers, and acute poisoning may be accompanied by microscopic or macroscopic haematuria, but they are much less potent as bladder irritants than 5-chloro-o-toluidine. There is sufficient evidence of carcinogenicity in animals to classify o-toluidine and p-toluidine as suspected human carcinogens.

Toluenediamines. Among the six isomers of toluenediamine the one most frequently encountered is the 2,4- which accounts for 80% of the intermediate product in the manufacture of toluene diisocyanate, a further 20% being the 2,6- isomer, which is one of the basic substances for the polyurethanes. Attention was drawn to this compound following the experimental discovery of a carcinogenic potential in laboratory animals. Data on humans are not available.

Xylidines. Results of animal experiments indicate that they are primarily liver toxins and act secondarily on the blood. However, other experiments have demonstrated that methaemoglobinaemia and Heinz body formation were readily induced in cats, though not in rabbits.

Azo Dyes

In general, azo dyes as a group represent a relatively low order of general toxicity. Many of them have an oral LD50 of more than 1 g/kg when tested in rats and mice, and the rodents can be given lifetime laboratory diets containing more than 1 g of the test chemical per kg of diet. A few may cause contact dermatitis but usually with only mild manifestations; in practice, it is rather difficult to determine whether the dye per se or co-existing material is responsible for the observed skin lesion. In contrast, increasing attention has been focused on the carcinogenic potentials of the azo dyes. Although confirmative epidemiological observations are as yet rare, the data from long-term experiments have accumulated to show that some azo dyes are carcinogenic in laboratory animals. The main target organ under such experimental conditions is the liver, followed by the urinary bladder. The intestine is also involved in some cases. It is, however, very problematic to extrapolate these findings to humans.

Most of the carcinogenic azo dyes are not direct carcinogens, but pre-carcinogens. That is, they require conversion by in vivo metabolic activation through proximate carcinogens to be ultimate carcinogens. For example, methylaminoazobenzene first undergoes N-hydroxylation and N-demethylation at the amino group, and then sulphate conjugation takes place with the N-hydroxy derivative forming the ultimate carcinogen which is reactive with the nucleic acid.

It should be noted that benzidine-derived diazo dyes may be transformed to the highly carcinogenic chemical benzidine by the body’s normal metabolic processes. The body reduces two azo groups in vivo or by the activity of intestinal bacteria, to benizidine. Thus azo dyes should be handled with prudence.

Safety and Health Measures

The most important specific measure for the prevention of spillage or contamination of the work atmosphere by these compounds is proper plant design. Ventilation control of the contaminant should be designed as close to the point of generation as possible. Work clothing should be changed daily and facilities for an obligatory bath or shower at the end of the working period should be provided. Any contamination of skin or clothing should be washed off immediately and the individual kept under medical supervision. Both workers and supervisors should be educated to be aware of the nature and extent of the hazard and to carry out the work in a clean, safe manner. Maintenance work should be preceded with sufficient attention to removal of possible sources of contact with the offending chemicals.

Aromatic amino compounds tables

Table 104.29 Chemical identification

CHEMICAL

SYNONYMS

UN CODE

CAS-NUMBER

CHEMICAL FORMULA

o-ACETOTOLUIDINE

Acetamide, acetyl-o-toluidine; o-Methylacetanilide; 2-Methylacetanilide; 2'-Methylacetanilide; N-(2-methylphenyl)acetamide

120-66-1

1-AMINO-2-METHYLANTHRAQUINONE

Acetate fast orange R; Acetoquinone light orange JL; 1-Amino-2-methyl-9,10-anthracenedione

82-28-0

4-AMINODIPHENYL

p-Aminobiphenyl; 4-Aminobiphenyl; p-Aminodiphenyl; Biphenylamine

92-67-1

o-AMINOPHENOL

2-Amino-1-hydroxybenzene; 2-Aminophenol; o-Hydroxyaniline; 2-Hydroxyanaline; Nako yellow 3GA

UN2512

95-55-6

p-AMINOPHENOL

4-Amino-1-hydroxybenzene; 4-Aminophenol; Azol; BASF Ursol P base; p-Hydroxyaniline; 4-Hydroxyaniline

UN2512

123-30-8

ANILINE

Aminobenzene; Benzenamine; Phenylamine

UN1547

62-53-3

ANILINE HYDROCHLORIDE

Aniline chloride; Hydrochloride benzenamide; Phenylamine hydrochloride

UN1548

142-04-1

o-ANISIDINE

o-Aminoanisole; 2-Aminoanisole; 1-Amino-2-methoxybenzene; 2-Anisidine; 2-Methoxy-1-aminobenzene; Methoxyphenylamine

90-04-0

p-ANISIDINE

p-Aminoanisole; 4-Aminoanisole; 1-Amino-4-methoxybenzene; 4-Anisidine; 4-Methoxy-1-aminobenzene; Methoxybenzenamine

104-94-9

o-ANISIDINE HYDROCHLORIDE

2-Aminoanisole hydrochloride; o-Aminoanisole hydrochloride ; o-Anisylamine hydrochloride; C.I. 37115; Fast red BB base; 2-Methoxy-1-aminobenzene hydrochloride; o-Methoxyaniline hydrochloride; 2-Methoxyaniline hydrochloride

134-29-2

AURAMINE

Bis(p-dimethylaminophenyl)methyleneimine; Brilliant oil yellow; 4,4'-Carbonimidoylbis(N,N-Dimethylbenzenamine); C.I. 41000B; C.I. basic yellow; 2, 4,4'-dDmethylaminobenzophenonimide; Glauramine

492-80-8

BENZIDINE

4,4'-Bianiline; 4,4'-Biphenyldiamine; C.I. 37225; C.I. Azoic diazo component 112; 4,4'-Diaminobiphenyl; 4,4'-Diaminodiphenyl; 4,4'-Diphenylenediamine

UN1885

92-87-5

m-BROMOANILINE

 

591-19-5

p-BROMOANILINE

4-Bromobenzenamine; p-Bromophenylamine

106-40-1

2-CHLORO-4-NITROANILINE

1-Amino-2-chloro-4-nitrobenzene; o-Chloro-p-nitroaniline; 4-Nitro-2-chloroaniline

121-87-9

4-CHLORO-o-PHENYLENEDIAMINE

2-Amino-4-chloroaniline; C.I. 76015; 4-Chloro-1,2-benzenediamine; 4-Chloro-1,2-diaminobenzene; 4-Chloro-1,2-phenylenediamine; 1,2-Diamino -4-chlorobenzene; 3,4-Diaminochlorobenzene; 3,4-Diamino-1-chlorobenzene

95-83-0

4-CHLORO-o-TOLUIDINE

2-Amino-5-chlorotoluene; Azogene fast red TR; 3-Chloro-6-aminotoluene; 5-Chloro-2-aminotoluene; 4-Chloro-2-methylaniline; 4-Chloro-6-methylaniline; 2-Methyl-4-chloroaniline

95-69-2

5-CHLORO-o-TOLUIDINE

2H-1-Benzopyran-2-one; 2H-1-Benzopyran, 2-Oxo-; Benzo-α-pyrone; 1,2-Benzopyrone; Cinnamic acid, o-Hydroxy-, δ-lactone; cis-o-Coumarinic acid lactone; Coumarinic anhydride; Cumarin; o-Hydroxycinnamic acid lactone; o-Hydroxycinnamic lactone; NCI C07103; 2-Oxo-1,2-benzopyran; Rattex; Tonka bean camphor

95-79-4

o-CHLOROANILINE

1-Amino-2-Chlorobenzene; 2-Chloroaniline; 2-Chlorobenzenamine

95-51-2

m-CHLOROANILINE

m-Aminochlorobenzene; 1-Amino-3-Chlorobenzene; 3-Chloroaniline; 3-Chlorobenzenamine

108-42-9

p-CHLOROANILINE

1-Amino-4-chlorobenzene; 4-Chlorobenzenamine; 4-Chlorophenylamine

106-47-8

p-CRESIDINE

3-Amino-p-cresol methyl ether; 1-Amino-2-methoxy-5-methylbenzene; 3-Amino-4-methoxytoluene; 2-Amino-4-methylanisole; 5-Methyl-o-anisidine; Azoic red 36

120-71-8

N,N'-DI-2-NAPHTHYL-p-PHENYLENEDIAMINE

Aceto DIPP; Agerite white; N,N'-Bis(2-naphthyl)-p-phenylenediamine; Di-β-naphthyl-p-phenylenediamine; N,N'-Di-β-naphthyl-p-phenylenediamine; DNPD; DNPDA

93-46-9

2,4-DIAMINOANISOLE

C.I. 76050; M-Diaminoanisole 1,3-diamino-4-methoxybenzene; 2,4-Diamino-1-methoxybenzene; Furro l; 4-Methoxy-1,3-benzenediamine

615-05-4

3,3'-DIAMINOBENZIDINE

3,3',4,4'-Biphenyltetramine ; 3,3',4,4'-Diphenyltetramine; 3,3',4,4'-Tetraaminobiphenyl

91-95-2

2,4-DIAMINOPHENOL DIHYDROCHLORIDE

Acrol; amidol; 2,4-Diaminophenol hydrochloride; Dianol; NCI-C60026

137-09-7

2,4-DIAMINOTOLUENE

3-Amino-p-toluidine; 5-Amino-o-toluidine; Azogen developer Hh; Benzofur MT; C.I. 76035; 1,3-Diamino-4-methylbenzene; 2,4-Siamino-1-methylbenzene

UN1709

95-80-7

2,6-DIAMINOTOLUENE

1,3-Benzenediamine, 2-Methyl-; 2,6-toluylenediamine; 2,6-Tolylenediamine

823-40-5

N,N-DIBUTYLANILINE

 

613-29-6

2,3-DICHLOROANILINE

 

608-27-5

2,4-DICHLOROANILINE

Benzenamine, 2,4-Dichloro-

554-00-7

2,5-DICHLOROANILINE

 

95-82-9

2,6-DICHLOROANILINE

 

608-31-1

3,4-DICHLOROANILINE

1-Amino-3,4-Dichlorobenzene; 4,5-Dichloroaniline; 3,4-Dichlorobenzenamine

95-76-1

3,3'-DICHLOROBENZIDINE

C.I. 23060; Curithane C126; DCB; 4,4'-Diamino-3,3'-dichlorobiphenyl; Dichlorobenzidine; 3,3'-Dichloro-4,4'-biphenyldiamine

91-94-1

3,3'-DICHLOROBENZIDINE DIHYDROCHLORIDE

(1,1'-Biphenyl)-4,4'-diamine, 3,3'-Dichloro-, dihydrochloride

612-83-9

DICYCLOHEXYLAMINONITRITE

N-Cyclohexylcyclohexanamine nitrite; Dechan; Diana; Dicyclohexylammonium nitrite

UN2687

3129-91-7

m-DIETHYLAMINOPHENOL

3-(Diethylamino)phenol

91-68-9

N,N-DIETHYLANILINE

N,N-Diethylaminobenzene; Diethylaniline; N,N-Diethylbenzenamine; Diethylphenylamine

UN2432

91-66-7

3,3'-DIMETHOXYBENZIDINE DIHYDROCHLORIDE

o-Dianisidine dihydrochloride; 3,3'-Dimethoxy-4,4'-Diaminobiphenyl dihydrochloride; 3,3'-Dimethoxy-(1,1-biphenyl)-4,4'-diamine dihydrochloride

20325-40-0

N,N-DIMETHYL-p-TOLUIDINE

Benzenamine, N,N,4-Trimethyl-; N,N,4-Trimethylaniline; p-N,N-Trimethylaniline

99-97-8

DIMETHYLAMINOAZOBENZENE

p-Dimethylaminoazobenzene; N,N-Dimethyl-4-aminoazobenzene, Benzeneazodimethylaniline, 4-Dimethylaminoazobenzene,4-Dimethylaminoazobenzol; DAB

60-11-7

DIMETHYLANILINE

Dimethylaminobenzene; N,N-Dimethylbenzenamidne; Dimethylphenylamine

UN2253

121-69-7

2,4-DINITROANILINE

2,4-Dinitraniline; 2,4-Dinitrobenzenamine

97-02-9

N,N'-DIPHENYL-p-PHENYLENEDIAMINE

Agerite; Agerite DPPD; 1,4-Bis(phenylamino)benzene; Diphenyl-p-phenylenediamine; DPPD; Flexamine g; JZF; Nonox DPPD

74-31-7

DIPHENYLAMINE

Anilinobenzene; benzene C.I. 10355; No scald; No scald DPA 283; N-Phenylaniline; N-Phenylbenzenamine

122-39-4

1,3-DIPHENYLGUANIDINE

Diphenylguanidine; N,N'-Diphenylguanidine

102-06-7

N-ETHYLANILINE

Anilinoethane; N-Ethylaminobenzene; Ethylaniline; N-Ethylbenzenamine; Ethylphenylamine

UN2272

103-69-5

N-ISOPROPYL-N'-PHENYL-p-PHENYLENEDIAMINE

Cyzone; Elastozone 34; Flexzone 3c; 4-Isopropylaminodiphenylamine; N-Phenyl-N'-isopropyl-p-phenylenediamine; N-2-propyl-N'-phenyl-p-phenylenediamine; Santoflex 36

101-72-4

N-ISOPROPYLANILINE

 

768-52-5

MELANINE

Aero; Ammelide; Cyanuramide; Cyanuric triamide; 4,6-Triamino-1,3,5-Triazine; 1,3,5-Triazine-2,4,6-triamine

108-78-1

p-METHYLAMINOPHENOL

4-(Methylamino)phenol

150-75-4

METHYLANILINE

Anilinomethane; (Methylamino)benzene; Methylphenylamine; Monomethylaniline

UN2294

100-61-8

4,4’-METHYLENE-BIS CHLOROANILINE

Bis-amine; Bis-amine A; Bisamine S; Bis(4-amino-3-chlorophenyl)methane; Bis(3-chloro-4-aminophenyl)methane; CL-MDA; Buamine M; MBOCA; MOCA

101-14-4

4,4'-METHYLENEBIS(2-METHYLANILINE)

Bis(4-amino-3-methylphenyl)methane; 3,3'-Dimethyl-4,4'-diaminodiphenylmethane; MBOT; Me-MDA; 4,4'-Methylenebis(2-methylbenzenamine)

838-88-0

2,4'-METHYLENEDIANILINE

2',4-Bis(aminophenyl)methane; o,p'-Diaminodiphenylmethane; 2,4'-Diaminodiphenylmethane; 2,4'-Diphenylmethanediamine

1208-52-2

4,4-METHYLENEDIANILINE

Ancamine tl; Araldite hardener 972; Bis(p-aminophenyl)methane; Bis(4-aminophenyl)methane; Curithane; DADPM; DAPM; DDM; Diaminodiphenylmethane; Dianilinomethane; 4,4'-Diphenylmethanediamine

UN2651

101-77-9

MICHLER'S BASE

4,4'-Bis(dimethylamino)diphenylmethane; Bis(p-dimethylaminophenyl)methane; Michler's methane; Reduced Michler's ketone; Tetramethyldiaminodiphenylmethane

101-61-1

MICHLER'S KETONE

Bis(p-(N,N-dimethylamino)phenyl)ketone; Bis(4-(dimethylamino)phenyl)methanone; 4,4'-Bis(dimethylamino)benzophenone; Tetramethyldiaminobenzophenone

90-94-8

1,5-NAPHTHALENEDIAMINE

1,5-Diaminonaphthalene; 1,5-Naphthylenediamine; NCI-C03021

2243-62-1

α-NAPHTHYLAMINE

1-Naphthylamine; 1-Aminonaphthalene; C.I. Azoic diazo component 114; Naphthalidam; Naphthalidine

 UN2077

134-32-7

β-NAPHTHYLAMINE

2-Aminonaphthalene; C.I. 37270; Fast scarlet base B; 2-Naphthylamine; 2-Naphthalenamine; 6-Naphthylamine

UN1650

91-59-8

o-NITROANILINE

1-Amino-2-nitrobenzene; 2-Nitroaniline

UN1661

88-74-4

m-NITROANILINE

1-Amino-3-nitrobenzene; Nitranilin; m-Nitroaniline; 3-Nitroaniline; 3-Nitrobenzenamine

UN1661

99-09-2

p-NITROANILINE

p-Aminonitrobenzene; 1-Amino-4-nitrobenzene; 4-Nitroaniline; 4-Nitrobenzenamine

UN1661

100-01-6

4,4'-OXYDIANILINE

4-Aminophenyl ether; Diaminodiphenyl ether; 4,4'-Diaminophenyl oxide; 4,4'-Oxybisaniline; 4,4'-Oxybisbenzenamine

101-80-4

N-PHENYL-1-NAPHTHYLAMINE

1-Anilinonaphthalene; Phenylnaphthylamine; Phenyl-α-naphthylamine

90-30-2

N-PHENYL-β-NAPHTHYLAMINE

Anilinonaphthalene; 2-Anilinonaphthalene; N-(2-Naphthyl)aniline; Phenylaminonaphthalene

135-88-6

m-PHENYLENEBIS(METHYLAMINE)

1,3-Bis(aminomethyl)benzene; MXDA; m-Xylene-a,a'-Diamine; m-Xylylenediamine

1477-55-0

o-PHENYLENEDIAMINE

2-Aminoaniline; o-Benzenediamine; 1,2-Benzenediamine; C.I. 76010; C.I. oxidation base 16; o-Diaminobenzene; 1,2-Diaminobenzene; o-Phenylenediamine; 1,2-Phenylenediamine

UN1673

95-54-5

m-PHENYLENEDIAMINE

m-Aminoaline; 3-Aminoaniline; m-Benzenediamine; 1,3-Benzenediamine; C.I. 76025; Developer 11; m-Diaminobenzene; 1,3-diaminobenzene; m-Phenylenediamine; Metaphenylenediamine; 1,3-Phenylenediamine

UN1673

108-45-2

p-PHENYLENEDIAMINE

p-Aminoaniline; 4-Aminoaniline; p-Benzenediamine; 1,4-Benzenediamine; Benzofur D; C.I. 76060; Pelagol D

UN1673

106-50-3

p-PHENYLENEDIAMINE HYDROCHLORIDE

p-Aminoaniline dihydrochloride; 4-Aminoaniline dihydrochloride; p-Benzenediamine dihydrochloride; 1,4-Benzenediamine dihydrochloride; C.I. 76061; C.I. oxidation base 10A; p-Diaminobenzene dihydrochloride; 1,4-Diaminobenzene dihydrochloride

624-18-0

N-PHENYLETHANOLAMINE

Aniline, N-(2-hydroxyethyl)-; 2-(Phenylamino)ethanol; N-Phenylethanolamine

122-98-5

o-TOLIDINE

Bianisidine; (1,1'-Biphenyl)-4,4'-diamine-3,3'-Dimethyl-; 4,4'-bi-o-toluidine; C.I. 37230; C.I. Azoic diazo component 113; 4,4'-Diamino-3,3'-dimethylbiphenyl; 4,4'-Diamino-3,3'-dimethyldiphenyl; 3,3'-Dimethylbenzidin

119-93-7

o-TOLUIDINE

1-Amino-2-methylbenzene; o-aminotoluene; 2-Aminotoluene; C.I. 37077; 1-Methyl-2-aminobenzene; o-Methylaniline

UN1708

95-53-4

m-TOLUIDINE

3-Amino-1-methylbenzene; 3-Aminophenylmethane; m-Aminotoluene; 3-Aminotoluene; m-Methylaniline; 3-Methylaniline

UN1708

108-44-1

p-TOLUIDINE

4-Amino-1-methylbenzene; p-Aminotoluene; 4-Aminotoluene; C.I. 37107; C.I. Azoic coupling component 107; p-Methylaniline; 4-Methylaniline; p-Methylbenzenamine; 4-Methylbenzenamine

UN1708

106-49-0

2,4,5-TRIMETHYLANILINE

1-Amino-2,4,5-trimethylbenzene; 1,2,4-Trimethyl-5-Aminobenzene; 2,4,5-Trimethylaniline

137-17-7

TRIPHENYLAMINE

N,N-Diphenylaniline; N,N-Diphenylbenzenamine

603-34-9

XYLIDINE

Acid leather brown 2G; Acid orange 24; Aminodimethylbenzene; Dimethylaminobenzene; Dimethylaniline; Dimethylphenylamine

UN1711

1300-73-8

2,3-XYLIDINE

2,3-Dimethylaniline; 2,3-Dimethylbenzenamine; 2,3-Dimethylphenylamine; o-Xylidine; 2,3-Xylylamine

87-59-2

2,4-XYLIDINE

1-Amino-2,4-dimethylbenzene; 4-Amino-1,3-Dimethylbenzene; 4-Amino-3-methyltoluene; 4-Amino-1,3-xylene; 2,4-Dimethylaniline; 2,4-Dimethylbenzenamine

95-68-1

3,4-XYLIDINE

3,4-Dimethylaminobenzene; 3,4-Dimethylaniline; 3,4-Dimethylbenzenamine; 3,4-Dimethylphenylamine; 3,4-Xylylamine

95-64-7

Table 104.30 Health hazards

Chemical Name

     CAS-Number

ICSC Short-Term Exposure

ICSC Long-Term Exposure

ICSC Routes of Exposure and Symptoms

US NIOSH Target Organs & Routes of Entry

US NIOSH Symptoms

4-AMINODIPHENYL

     92-67-1

eyes; bladder

 

Inhalation: dullness, headache

Skin: may be absorbed

Eyes: redness

Bladder; skin (bladder cancer)

Inh; abs; ing; con

Head, dizz; leth, dysp; ataxia, weak; methemo; urinary burning; acute hemorrhagic cystitis; (carc)

o-AMINOPHENOL

     95-55-6

blood

skin

Inhalation: blue lips or finger nails, blue skin, cough, dizziness, headache, laboured breathing, unconsciousness, symptoms may be delayed

Eyes: Redness

 

 

ANILINE

     62-53-3

eyes; blood; CNS

liver; kidneys; spleen; skin; blood

Inhalation: blue lips or finger nails, blue skin, headache, dizziness, laboured breathing, convulsions, increased heartbeat, vomiting, weakness, unconsciousness

Skin: may be absorbed

Eyes: redness

Blood; CVS; eyes; liver; kidneys; resp sys  (in animals: tumors of the spleen)

Inh; abs; ing; con

Head, weak, dizz; cyan; ataxia; dysp on effort; tacar; irrit eyes; methemo; cirr; (carc)

ANILINE HYDROCHLORIDE

     142-04-1

eyes; skin; resp tract; blood

skin; spleen; kidneys; blood

Inhalation: blue lips or finger nails, blue skin, cough, dizziness, headache, nausea, shortness of breath, sore throat, unconsciousness, vomiting, weakness

Skin: may be absorbed, redness

Eyes: redness, pain

Ingestion: abdominal pain

 

 

o-ANISIDINE

     90-04-0

blood

blood

Inhalation: blue lips or finger nails, blue skin, dizziness, drowsiness, headache, nausea, vomiting

Skin: may be absorbed

Blood; kidneys; liver; CVS; CNS

Inh; abs; ing; con

Head, dizz; cyan; RBC Heinz bodies; (carc)

p-ANISIDINE

     104-94-9

blood

blood

Inhalation: blue lips or finger nails, blue skin, dizziness, drowsiness, headache, laboured breathing, nausea, vomiting

Skin: may be absorbed, blue lips or fingernails, blue skin

Ingestion: blue lips or fingernails, blue skin

Blood; kidneys; liver; CVS; CNS

Inh; abs; ing; con

Head, dizz; cyan; RBC Heinz bodies; (carc)

BENZIDINE

     92-87-5

 

 

 

Bladder; kidneys; liver; skin; blood  (liver, kidney and bladder cancer)

Inh; abs; ing; con

Hema; secondary anemia from hemolysis; acute cystitis; acute liver disorders; derm;  painful, irreg urination; (carc)

o-CHLOROANILINE

     95-51-2

eyes; skin

skin; liver; kidneys; blood

Inhalation: blue lips or finger nails, blue skin, convulsions, diarrhoea, dizziness, headache, nausea, shortness of breath, vomiting, weakness

Skin: may be absorbed, redness

Eyes: redness, pain

Ingestion: abdominal pain

 

 

m-CHLOROANILINE

     108-42-9

eyes; skin; resp tract; liver; kidneys

blood

Inhalation: blue lips or finger nails, blue skin, dizziness, drowsiness, headache, nausea, shortness of breath, unconsciousness

Skin: may be absorbed, redness, burning sensation

Eyes: redness, pain, severe deep burns

Ingestion: abdominal pain,

 

 

p-CHLOROANILINE

     106-47-8

eyes; skin; resp tract; blood

skin ; blood; liver; kidneys; spleen ; bone marrow

Inhalation: blue lips or finger nails, blue skin, dizziness, headache, laboured breathing

Skin: may be absorbed, redness

Eyes: redness, pain

Ingestion: nausea

 

 

2,4-DIAMINOTOLUENE

     95-80-7

eyes; skin; resp tract; lungs; heart; liver; blood

skin

Inhalation: blue lips or finger nails, blue skin, dizziness, increased heart rate, laboured breathing, nausea, vomiting, convulsions, respiratory depression

Skin: may be absorbed, redness on contact with molten material - skin burns, blisters

Eyes: redness

Ingestion: abdominal pain, blue skin, headache, nausea, vomiting

Eyes, skin, resp sys, blood, CVS, liver, CNS  (in animals: liver, skin & mammary gland tumors)

Inh; abs; ing; con

Irrit eyes, skin, nose, throat; derm; ataxia, tacar, nau, vomit, convuls, resp depres; methemo, cyan, head, ftg, dizz, bluish skin; liver inj; (carc)

2,6-DIAMINOTOLUENE

     823-40-5

eyes; skin; resp tract; blood

skin

Inhalation: blue lips or finger nails, blue skin, cough, dizziness, headache, shortness of breath

Skin: redness

Eyes: redness, pain

Ingestion: laboured breathing

 

 

2,3-DICHLOROANILINE

     608-27-5

liver; kidneys

skin ; blood

Inhalation: blue lips or finger nails, blue skin, convulsions, diarrhoea, dizziness, headache, shortness of breath, vomiting, weakness

Skin: may be absorbed, redness

Eyes: redness, pain

 

 

2,4-DICHLOROANILINE

     554-00-7

liver; kidneys

skin ; blood

Inhalation: blue skin, dizziness, headache, shortness of breath

Skin: may be absorbed, redness, skin burns

Eyes: redness, pain, severe deep burns

Ingestion: abdominal pain, nausea

 

 

2,5-DICHLOROANILINE

     95-82-9

liver; kidneys

skin ; blood

Inhalation: blue skin, dizziness, headache, shortness of breath

Skin: may be absorbed, redness, skin burns

Eyes: redness, pain, severe deep burns

Ingestion: abdominal pain, nausea

 

 

2,6-DICHLOROANILINE

     608-31-1

liver; kidneys

skin ; blood

Inhalation: blue skin, dizziness, headache, shortness of breath

Skin: may be absorbed, redness

Eyes: redness, pain

 

 

3,4-DICHLOROANILINE

     95-76-1

liver; kidneys

skin; blood

Inhalation: blue skin, dizziness, headache, shortness of breath

Skin: may be absorbed, redness, burning sensation

Eyes: redness, pain, severe deep burns

Ingestion: abdominal pain, nausea

 

 

3,3'-DICHLOROBENZIDINE

     91-94-1

resp tract

skin; liver

Inhalation: cough, sore throat

Skin: may be absorbed

Bladder; liver; lung ; skin; GI tract  (in animals: liver & bladder cancer)

Inh; abs; ing; con

Skin sens, derm; head, dizz; caustic burns; frequent urination, dysuria; hema; GI upset; upper resp infection; (carc)

DIMETHYLANILINE

     121-69-7

blood

skin

Inhalation: abdominal pain, blue skin, dizziness, headache, ringing in the ears, laboured breathing, unconsciousness, vomiting, visual disturbance

Skin: may be absorbed, redness

Eyes: redness, pain

Blood; kidneys;liver; CVS

Inh; abs; ing; con

Anoxia symptoms; cyan, weak, dizz, ataxia; methemo

DIMETHYLAMINOAZOBENZENE

     60-11-7

 

 

 

Skin; resp sys; liver; kidneys; bladder ( in animals: liver & bladder tumors)

Inh; abs; ing; con

Enlarged liver; liver, kidney dysfunc; contact derm; cough, wheez, dysp; bloody sputum; bronchial secretions; frequent urination, hema, dysuria; (carc)

N,N-DIMETHYL-p-TOLUIDINE

     99-97-8

blood; brain; kidneys

 

Inhalation: blue lips or finger nails, blue skin, dizziness, headache, shortness of breath, weakness

Skin: may be absorbed

 

 

2,4-DINITROANILINE

     97-02-9

eyes; skin; resp tract; blood

blood

Inhalation: blue lips or finger nails, blue skin, cough, dizziness, headache, laboured breathing, nausea, sore throat

Skin: may be absorbed, redness, blue lips or fingernails, blue skin

Eyes: redness, pain

Ingestion: unconsciousness

 

 

DIPHENYLAMINE

     122-39-4

eyes; skin; resp tract

kidneys

Inhalation: cough, sore throat

Skin: redness

Eyes: redness

Eyes; skin; resp sys; CVS; blood; bladder; repro sys

Inh; abs; ing; con

Irrit eyes, skin muc memb; eczema; tacar, hypertension; cough, sneez; methemo; incr BP, heart rate; prot, hema, bladder inj; in animals: terato effects

N-ISOPROPYLANILINE

     768-52-5

skin; blood; brain; kidneys

skin ; blood

Inhalation: blue lips or finger nails, blue skin, dizziness, headache, laboured breathing

Skin: may be absorbed, blue lips or fingernails, blue skin

Eyes: redness, pain, blurred vision

Ingestion: nausea

Eyes; skin; resp sys; blood; CVS; liver; kidneys

Inh; abs; ing; con

Irrit eyes, skin; head, weak, dizz; cyan; ataxia; dysp on effort; tacar; methemo

N-ISOPROPYL-N'-PHENYL-p-PHENYLENEDIAMINE

     101-72-4

eyes; skin

skin

Inhalation: cough, irritant

Skin: redness, irritant

Eyes: redness, irritant

 

 

METHYLANILINE

     100-61-8

eyes; skin; resp tract; blood; brain; kidneys

skin; blood

Inhalation: blue lips or finger nails, blue skin, cough, dizziness, headache, laboured breathing, sore throat

Skin: may be absorbed, redness, pain

Eyes: redness, pain, blurred vision

Ingestion: abdominal pain, blue lips or fingernails, blue skin, dizziness, headache, laboured breathing, nausea

Resp sys; liver; kidneys; blood; CNS

Inh; abs; ing; con

Weak, dizz, head; dysp, cyan; methemo; pulm edema; liver, kidney damage

1,5-NAPHTHALENEDIAMINE

     2243-62-1

 

skin

Skin: may be absorbed

 

 

α-NAPHTHYLAMINE

     134-32-7

 

 

 

Bladder; skin  (bladder cancer)

Inh; abs; ing; con

Derm; hemorrhagic cystitis; dysp, ataxia, methemo; hema; dysuria; (carc)

β-NAPHTHYLAMINE

     91-59-8

 

 

 

Bladder; skin  (bladder cancer)

Inh; abs; ing; con

Derm; hemorrhagic cystitis; dysp; ataxia; methemo, hema; dysuria; (carc)

o-NITROANILINE

     88-74-4

blood

 

Inhalation: blue lips or finger nails, blue skin, dizziness, drowsiness, headache, laboured breathing, nausea, shortness of breath, unconsciousness, weakness

Skin: may be absorbed, blue lips or fingernails, blue skin

 

 

m-NITROANILINE

     99-09-2

blood

 

Inhalation: blue lips or finger nails, blue skin, dizziness, drowsiness, headache, laboured breathing, nausea, shortness of breath, unconsciousness, weakness

Skin: may be absorbed, blue lips or fingernails, blue skin

 

 

p-NITROANILINE

     100-01-6

blood

liver

Inhalation: blue lips or finger nails, blue skin, dizziness, drowsiness, headache, laboured breathing, nausea, shortness of breath, unconsciousness, weakness

Skin: may be absorbed, blue lips or fingernails, blue skin

Resp sys; blood; heart; liver; abs; ing; con

Irrit nose, throat; cyan, ataxia; tacar, tachypnea; dysp; irrity; vomit, diarr; convuls; resp arrest; anemia; methemo; jaundice

N-PHENYL-1-NAPHTHYLAMINE

     90-30-2

 

skin

Skin: redness

 

 

p-PHENYLENEDIAMINE

     106-50-3

resp tract; blood; kidneys

skin; resp tract

Inhalation: cough, dizziness, headache, laboured breathing

Skin: redness

Eyes: redness, blurred vision, even permanent loss of vision

Ingestion: abdominal pain, blue lips or fingernails, blue skin, vomiting, weakness, convulsions, coma, death

Respsys ; skin

Inh; abs; ing; con

Irrit pharynx, larynx; bronchial asthma; sens derm

p-PHENYLENEDIAMINE HYDROCHLORIDE

     624-18-0

eyes; skin; resp tract; blood; brain; kidneys

skin; resp tract; liver

Inhalation: cough, dizziness, laboured breathing, see ingestion

Skin: redness

Eyes: blurred vision, even permanent loss of vision

Ingestion: abdominal pain, blue lips or fingernails, blue skin, vomiting, weakness, swelling of the face and neck, convulsions, coma, death

 

 

o-TOLIDINE

     119-93-7

eyes; skin; resp tract

skin; blood

Inhalation: cough, weak irritant

Skin: may be absorbed

Eyes; resp sys; liver; kidneys; (in animals: liver, bladder & mammary gland tumors)

Inh; abs; ing; con

Irrit eyes, nose; in animals: liver, kidney damage; (carc)

o-TOLUIDINE

     95-53-4

 

 

 

Eyes; skin; blood; kidneys; liver; CVS  (in animals: liver, bladder & mammary gland tumors)

Inh; abs; ing; con

Irrit eyes; anoxia, head, cyan; weak, dizz, drow; micro hema, eye burns; derm;  (carc)

XYLIDINE

     1300-73-8

eyes; skin; resp tract; blood

kidneys; liver; red blood cells

Inhalation: blue lips or finger nails, blue skin, dizziness, headache, laboured breathing

Skin: may be absorbed

Eyes: redness, pain, blurred vision

Ingestion: blue lips or fingernails, blue skin, dizziness, headache

Resp sys; blood; liver; kidneys; CVS

Inh; abs; ing; con

Anoxia, cyan, methemo; lung, liver, kidney damage

Table 104.31 Physical & chemical hazards

For UN Class: 1.5 = very insensitive substances which have a mass explosion hazard; 2.1 = flammable gas; 2.3 = toxic gas; 3 = flammable liquid; 4.1 = flammable solid; 4.2 = substance liable to spontaneous combustion; 4.3 = substance which in contact with water emits flammable gases; 5.1 = oxidizing substance; 6.1 = toxic; 7 = radioactive; 8 = corrosive substance

Chemical Name

CAS-Number

Physical

Chemical

Un Class/Div /  Subsidiary Risks

4-AMINODIPHENYL

92-67-1

 

On combustion, forms toxic gases: COx, NOx • The solution in water is a weak base • Reacts with strong oxidants • Forms salts with acids such as hydrochloric acid, sulfuric acid, etc. 

 

p-AMINOPHENOL

123-30-8

 

 

6.1

o-AMINOPHENOL

95-55-6

 

The substance decomposes on heating producing toxic fumes (nitrogen oxides) •Reacts violently with oxidants causing fire and explosion hazard

6.1

ANILINE

62-53-3

 

The substance decomposes on heating at temperatures above 190°C, or on burning producing toxic and corrosive fumes (ammoia and nitrogen oxides) and flammable vapours •The substance is a weak base •Reacts vigorously with strong oxidants, acids, acetic anhydride, chloromelamine monomers, beta-propiolactone and epichlorohydrin causing fire and explosion hazard •Reacts with metals such as sodium, potassium, calcium, producing flammable hydrogen gas •Attacks copper and its alloys

6.1

ANILINE HYDROCHLORIDE

142-04-1

The vapour is heavier than air

On combustion, forms toxic fumes including nitrogen oxides •On contact with hot surfaces or flames this substance decomposes forming toxic and corrosive fumes of aniline and chlorine compounds and nitrosis gases •The substance decomposes on heating or on contact with acids producing toxic fumes including aniline and hydrochloric acid •Reacts violently with oxidants causing fire and explosion hazard

 

o-ANISIDINE

90-04-0

 

The substance decomposes on heating producing toxic fumes (nitrogen oxides) •Reacts with strong oxidants causing fire and explosion hazard •Reacts with acids, acid chlorides, acid anydrides, chloroformates •Attacks some forms of plastics, rubber and coatings

6.1

p-ANISIDINE

104-94-9

 

The substance decomposes on heating producing toxic fumes (nitrogen oxides) •Reacts with strong oxidants causing fire and explosion hazard •Reacts with acids, acid chlorides, acid anydrides, chloroformates

6.1

o-ANISIDINE HYDROCHLORIDE

134-29-2

 

 

6.1

1,4-BENZENEDIAMINE DIHYDROCHLORIDE

624-18-0

Dust explosion possible if in powder or granular form, mixed with air

The substance decomposes on heating producing toxic and corrosive fumes (nitrogen oxides, hydrogen chloride)

 

BENZIDINE

92-87-5

 

 

6.1

2-CHLORO-4-NITROANILINE

121-87-9

 

 

6.1

o-CHLOROANILINE

95-51-2

 

The substance decomposes on burning producing toxic fumes (nitrous oxides, hydrogen chloride)

6.1

m-CHLOROANILINE

108-42-9

 

The substance decomposes on burning producing toxic fumes (nitrous oxides, hydrogen chloride) •The solution in water is a weak base •Reacts violently with oxidants causing fire and explosion hazard

6.1

p-CHLOROANILINE

106-47-8

 

The substance decomposes on heating above 160°C and on burning producing toxic and corrosive fumes of nitrogen oxides and hydrogen chloride •Reacts violently with oxidants

6.1

5-CHLORO-o-TOLUIDINE

95-79-4

 

 

6.1

p-CRESIDINE

120-71-8

 

 

8

2,4-DIAMINOTOLUENE

95-80-7

 

On combustion, forms toxic gases and fumes (carbon monoxide and nitrogen oxides) •Reacts with oxidants, acids, acid anhydrides, and acid chlorides

6.1

2,6-DIAMINOTOLUENE

 823-40-5

 

On combustion, forms toxic fumes of nitogen oxides

 

2,3-DICHLOROANILINE

608-27-5

 

The substance decomposes on heating producing toxic fumes (nitrous oxides, hydrogen chloride)

6.1

2,4-DICHLOROANILINE

554-00-7

 

The substance decomposes on heating producing toxic fumes (nitrous oxides, hydrogen chloride)

6.1

2,5-DICHLOROANILINE

95-82-9

 

The substance decomposes on heating producing toxic fumes (nitrous oxides, hydrogen chloride)

6.1

2,6-DICHLOROANILINE

608-31-1

 

The substance decomposes on heating producing toxic fumes (nitrous oxides, hydrogen chloride)

6.1

3,4-DICHLOROANILINE

95-76-1

 

The substance decomposes on heating producing toxic fumes (nitrous oxides, hydrogen chloride)

6.1

3,3'-DICHLOROBENZIDINE

91-94-1

 

The substance decomposes on heating producing toxic and corrosive fumes including nitrogen oxides and hydrogen chloride •Undergoes usual reactions of benzidine derivates, eg •formation of diazonium salts and acyl and alkyl derivates

 

DICYCLOHEXYLAMINONITRITE

3129-91-7

 

 

4.1

N,N-DIETHYLANILINE

91-66-7

 

 

6.1

N,N-DIMETHYL-p-TOLUIDINE

99-97-8

 

On combustion, forms toxic and corrosive gases (NOx) •Reacts violently with strong oxidants causing fire and explosion hazard •Reacts with acids, anhydrides and chlorides •Attacks many plastics

 

DIMETHYLANILINE

121-69-7

 

The substance decomposes on heating or on burning producing highly toxic fumes (aniline, nitrogen oxides) •The substance is a weak base •Reacts with oxidants

6.1

2,4-DINITROANILINE

97-02-9

 

May explode on heating, friction or contamination •The substance decomposes on heating producing toxic fumes (nitrogen oxides) •Reacts violently with oxidants •Reacts violently with chlorine and hydrochloric acid evolving gases

6.1

DIPHENYLAMINE

122-39-4

Dust explosion possible if in powder or granular form, mixed with air

On combustion, forms toxic gases of carbon and nitrogen oxides •Reacts with strong oxidants and acids

 

N-ETHYLANILINE

103-69-5

 

 

6.1

N-ISOPROPYL-N'-PHENYL-p-PHENYLENEDIAMINE

101-72-4

 

On combustion, forms toxic gases (NOx, COx) • The substance decomposes producing toxic fumes (nitrogen oxides)

 

p-METHYLAMINOPHENOL

150-75-4

 

 

6.1

METHYLANILINE

100-61-8

 

The substance decomposes on heating and on burning producing toxic fumes including aniline, nitrogen oxides •Reacts violently with strong acids and oxidants •Attacks some plastic

6.1

1,5-NAPHTHALENEDIAMINE

2243-62-1

 

The substance decomposes on heating producing toxic fumes (nitrogen oxides)

 

α-NAPHTHYLAMINE

134-32-7

 

 

6.1

β-NAPHTHYLAMINE

91-59-8

 

 

6.1

o-NITROANILINE

88-74-4

Dust explosion possible if in powder or granular form, mixed with air

On combustion, forms toxic fumes of nitrogen oxides •The substance is a strong oxidant and reacts with combustible and reducing materials •Reacts with organic materials in presence of moisture causing fire hazard

6.1

m-NITROANILINE

99-09-2

Dust explosion possible if in powder or granular form, mixed with air

On combustion, forms toxic fumes of nitrogen oxides •The substance is a strong oxidant and reacts with combustible and reducing materials •Reacts with organic materials in presence of moisture causing fire hazard

6.1

p-NITROANILINE

100-01-6

Dust explosion possible if in powder or granular form, mixed with air

May explode on heating •On combustion, forms toxic fumes of nitrogen oxides •The substance is a strong oxidant and reacts with combustible and reducing materials •Reacts with organic materials in presence of moisture causing fire hazard

6.1

N-PHENYL-1-NAPHTHYLAMINE

90-30-2

 

On combustion, forms toxic fumes (NOx) •The substance decomposes on heating or on burning producing toxic fumes (nitrogen oxides)

 

o-PHENYLENEDIAMINE

95-54-5

 

 

6.1

m-PHENYLENEDIAMINE

108-45-2

 

 

6.1

p-PHENYLENEDIAMINE

106-50-3

 

The substance decomposes on heating and on burning producing toxic fumes (nitrogen oxides) •The substance is a strong reducing agent and reacts violently with oxidants

6.1

o-TOLIDINE

119-93-7

 

The substance decomposes on heating and on burning producing toxic fumes including nitrogen oxides •The substance is degraded by light

 

o-TOLUIDINE

95-53-4

 

 

6.1

m-TOLUIDINE

108-44-1

 

 

6.1

p-TOLUIDINE

106-49-0

 

 

6.1

XYLIDINE

1300-73-8

 

The substance decomposes on burning producing hazardous oxides of nitrogen •Reacts with strong oxidants •Reacts with hypochlorites forming explosive chloramines

6.1

2,3-XYLIDINE

87-59-2

 

 

6.1

2,4-XYLIDINE

95-68-1

 

 

6.1

3,4-XYLIDINE

95-64-7

 

 

6.1

Table 104.32 Physical & chemical properties

Chemical Name

CAS-Number

Colour/Form

Boiling Point (°C)

Melting Point (°C)

Molecular Weight

Solubility in Water

Relative Density (water=1)

Relative Vapour Density (air=1)

Vapour Pressure/ (Kpa)

Inflam. Limits

Flash Point (°C)

Auto Ignition Point (°C)

o-ACETOLUIDINE

120-66-1

crystals; colourless

296

110

149.2

sl sol

1.168  @15°C

 

 

 

 

 

1-AMINO-2-METHYLANTHRAQUINONE

82-28-0

 

 

205.5

237.3

insol

 

 

 

 

 

 

2-AMINOANTHRAQUINONE

177-79-3

red or orange-brown needles

sublimes

303-6

233.23

insol

 

 

 

 

 

 

4-AMINODIPHENYL

92-67-1

colourless crystals which turn purple on contact with air

302

53

169.2

sl sol

1.160

5.8  @boiling point

 

 

153 cc

450

o-AMINOPHENOL

95-55-6

crystals, rapidly becoming brown; white rhombic bipyramidal needles from benzene; colourless rhombic needles or plates

153 sublimes

174

109.12

sol

1.328

 

 

 

190

 

p-AMINOPHENOL

123-30-8

orthorhombic plates from water; white plates from water; colourless crystals; white or reddish yellow crystals

284 decomp

188

109.13

sl sol

 

 

 

 

 

 

ANILINE

62-53-3

oily liquid, colourless when pure; colourless with a bluish fluorescence when freshly distilled

184

-6

93.12

sol

1.022

3.22

0.04

1.2 ll 11 ul

70 cc

615

ANILINE HYDROCHLORIDE

142-04-1

crystals

245

198

526.8

v sol

1.22

4.46

 

 

193

 

o-ANISIDINE

90-04-0

pale yellowish liquid; reddish or yellowish coloured oil; colourless to pink liquid

225

5

123.2

sl sol

1.0923

4.25

<0.133  @30°C

 

118 oc

 

p-ANISIDINE

104-94-9

tablets from water, rhombic plates; crystals; fused crystalline mass

246

57

123.15

sol

1.071  @57°C/4°C

4.28

<13 Pa

 

107

 

AURAMINE

492-80-8

yellow or colourless plates from alcohol

 

136

267.4

insol

 

 

2.5x 10-6 mmHg  @25°C

 

 

 

1,4-BENZENEDIAMINE DIHYDROCHLORIDE

624-18-0

crystals

 

 

181.06

sol

 

6.2

 

 

 

 

BENZIDINE

92-87-5

white or slightly-reddish, crystalline powder; needles, grayish, yellow crystalline powder

400

120

184.23

sl sol

1.250

6.36

 

 

 

 

2-CHLORO-4-NITROANILINE

121-87-9

yellow needles from petroleum ether-carbon disulfide, water, 20% acetic acid

 

108

172.57

misc

 

 

 

 

 

 

o-CHLOROANILINE

95-51-2

amber liquid

208.8

-14

127.57

insol

1.2114  @22°C/4°C

4.41

0.05

 

108

>500

m-CHLOROANILINE

108-42-9

colourless to light amber liquid

230.5

-10

127.57

insol

1.2161

4.4

9 Pa

 

118 cc

>540

p-CHLOROANILINE

106-47-8

orthorhombic crystals from alcohol or petroleum ether; rhombic prisms; colourless crystals

232

72.5

127.6

sol

1.4

4.4

2 Pa

2.2 ll ? ul

120-123

685

4-CHLORO-o-PHENYLENEDIAMINE

95-83-0

 

 

76

142.6

sl sol

 

 

 

 

 

 

5-CHLORO-o-TOLUIDINE

95-79-4

grayish-white solid

237 (@ 722 mm Hg)

26

141.6

 

 

 

 

 

 

 

p-CRESIDINE

120-71-8

white crystals

235

52

137.2

sl sol

 

 

1.02x 10-2 mmHg  @25°C

 

 

 

N,N'-DI-2-NAPHTHYL-p-PHENYLENEDIAMINE

93-46-9

 

 

235

360.43

 

 

 

 

 

 

 

2,4-DIAMINOANISOLE

615-05-4

 

 

67.5

138.16

 

 

 

 

 

 

 

3,3'-DIAMINOBENZIDINE

91-95-2

solid

 

178-180

 

 

 

 

 

 

 

 

4,4'-DIAMINODIPHENYLMETHANE

101-77-9

 

398-399

92.5

198.25

sl sol

 

 

 

 

 

 

2,4-DIAMINOPHENOL DIHYDROCHLORIDE

137-09-7

grayish-white crystals; needles

 

205

197.08

v sol

 

 

 

 

 

 

2,4-DIAMINOTOLUENE

95-80-7

needles from water or crystals from alcohol; prisms; colourless crystals

292

99

122.2

v sol

 

4.2

0.13  @106.5°C

 

149

 

2,6-DIAMINOTOLUENE

823-40-5

colourless crystals

289

106

122.17

sol

 

 

2.13  @150°C

 

 

 

N,N-DIBUTYLANILINE

613-29-6

amber liquid

267-275

 

 

insol

0.904

 

 

 

110

 

2,3-DICHLOROANILINE

608-27-5

needles from petroleum ether icsc: colourless crystals

252

24

162.02

insol

 

5.6

< 0.01 Pa  @25°C

 

>112 cc

 

2,4-DICHLOROANILINE

554-00-7

prisms from acetone; needles from diluted alcohol or petroleum ether

245

64

162.0

sl sol

1.567

5.6

<1 Pa  @25°C

 

 

 

2,5-DICHLOROANILINE

95-82-9

light brown or amber-coloured crystalline mass; needles from petroleum ether

251

50

162.0

sl sol

1.54

5.6

<1 Pa  @25°C

 

139

>540

2,6-DICHLOROANILINE

608-31-1

crystals

97

39

 

insol

 

5.6

 

 

 

 

3,4-DICHLOROANILINE

95-76-1

needles from petroleum ether; fine, light-tan crystals

272

71-72

162.03

insol

1.36

5.6

2 Pa

2.8  @152°C ll 7.2  @179°C ul

166 oc

269

3,3'-DICHLOROBENZIDINE

91-94-1

needles from alcohol or benzene; gray or purple crystalline solid.

402

132-133

253.13

insol

 

 

6x10-7 Pa

 

 

350

DICYCLOHEXYLAMINE NITRITE

3129-91-7

 

 

 

228.32

 

 

 

 

 

 

 

m-DIETHYLAMINOPHENOL

91-68-9

white, crystalline solid

276-280

78

165.23

sol

 

 

 

 

 

 

N,N-DIETHYLANILINE

91-66-7

colourless to yellow liquid; brown oily liquid

216

-38

149.23

sl sol

0.9307

1.0

 

 

 

 

N,N-DIMETHYL-p-TOLUIDINE

99-97-8

liquid

211

 

135.20

insol

0.9366

4.7

0.02

1.2 ll 7 ul

83

 

DIMETHYLAMINOAZOBENZENE

60-11-7

yellow crystalline leaflets

decomp

114-117

225.28

13.6 ppm

 

 

3.3x10-7 mm Hg (est).

 

 

 

DIMETHYLANILINE

121-69-7

oily liquid; pale yellow

194

2.5

121.2

sl sol

0.956

4.17

67 Pa

 

62

371

2,4-DINITROANILINE

97-02-9

yellow needles from diluted acetone, greenish-yellow plates from alcohol.

56.7

188

183.12

insol

1.615g/ml  @14°C

6.31

5.94x 10-7 mmHg  @25°C

 

224 cc

 

N,N'-DIPHENYL-p-PHENYLENEDIAMINE

74-31-7

colourless leaflets from alcohol; commercial grades are greenish-brown; gray powder

220-225  @0.5mmHg

150-151

260.32

insol

1.20

9.0

 

 

 

 

DIPHENYLAMINE

122-39-4

monoclinic leaflets from diluted alcohol; crystals; solid or liquid, very pale tan-amber to brown

302

53

169.2

insol

1.16

5.82

133 Pa  @108°C

 

153 oc

634

1,3-DIPHENYLGUANIDINE

102-06-7

monoclinic needles; white powder

170 D

150

211.3

sl sol

1.13

 

 

 

 

 

N-ETHYLANILINE

103-69-5

colourless liquid; clear to straw-coloured, yellow-brown oil

204.5

-63.5

121.2

insol

0.9625

4.2

1mmHg  @38.5°C

 

 

 

HYDROXYLAMINE

7803-49-8

large white flakes or white needles; colourless liquid

56.5  @22mmHg

32.05

33.04

v sol

1.2255  @0°C/4°C

 

 

 

 

 

HYDROXYLAMINE HYDROCHLORIDE

5470-11-1

crystals

 

decomp

 

83g/100ml  @17°C

1.7

 

 

 

 

 

HYDROXYLAMINE SULPHATE

10039-54-0

colourless crystals

 

177

 

sol

 

 

 

 

 

 

N-ISOPROPYL-N'-PHENYL-p-PHENYLENEDIAMINE

101-72-4

dark gray to black flakes

 

72.5

226.3

insol

1.04  @25°C

 

 

 

 

 

N-ISOPROPYLANILINE

768-52-5

yellowish liquid

203

 

135.2

insol

0.9526 25°C

 

 

 

878

 

MELAMINE

108-78-1

monoclinic prisms; colourless; white

 

<250

126.13

sl sol

1.573  @14°C

4.34

50mmHg  @315°C

 

 

 

p-METHYLAMINOPHENOL

150-75-4

colourless needles

 

87

123.17

sol

 

 

5.77x 10-2 mmHg  @25°C

 

 

 

METHYLANILINE

100-61-8

colourless to reddish-brown oily liquid

196

-57

107.15

insol

0.989

3.70

133 Pa  @36°C

 

795 cc

 

4,4'-METHYLENE BIS(2-CHLOROANILINE)

101-14-4

tan coloured pellets

 

110

267.15

insol

1.44

 

1.3x 10-3 torr  @60°C

 

 

 

MICHLER'S BASE

101-61-1

lustrous leaflets; yellowish leaflets or glistening plates

390

91.5

254.36

insol

 

 

 

 

 

 

MICHLER'S KETONE

90-94-8

white to greenish leaflets; leaf in alcohol, needles in benzene

>360 decomp

172

268.35

insol

 

 

 

 

 

 

1,5-NAPHTHALENEDIAMINE

2243-62-1

colourless crystals

sublimes

190

158.2

sl sol

1.4

 

 

 

 

 

α-NAPHTHYLAMINE

134-32-7

needles from diluted ethanol and ether; yellow rhombic needles; white crystals; needles, become red on exposure to air or a reddish, crystalline mass

300.8

50

143.18

sl sol

1.0228

4.93

1mmHg  @104.3°C

 

157 cc

 

β-NAPHTHYLAMINE

91-59-8

colourless crystals which darken in air to a reddish-purple colour

306

113

143.18

sol

1.061  @98°C/4°C

4.95

1mmHg  @108.0°C

 

157

 

o-NITROANILINE

88-74-4

yellow-orange crystals from boiling water; plates or needles; orange solid

284

71

138.1

sl sol

0.9015  @25°C/4°C

 

133 Pa  @104°C

 

168

521

m-NITROANILINE

99-09-2

yellow crystals from water; yellow rhombic needles

306

114

138.1

sl sol

0.9011  @25°C/4°C

 

0.005 Pa  @25°C

 

 

 

p-NITROANILINE

100-01-6

yellow monoclinic needles; bright yellow powder

332

146

138.12

1g/1250ml

1.424

4.77

0.2 Pa

 

199

180

4,4'-OXYDIANILINE

101-80-4

colourless crystals

>300

186-187

200.2

insol

 

 

3.07x 10-7 mmHg  @25°C

 

 

 

N-PHENYL-1-NAPHTHYLAMINE

90-30-2

powder

335

62

219.27

sl sol

1.2

 

 

 

 

 

N-PHENYL-β-NAPHTYLAMINE

135-88-6

needles from methanol; white to yellowish crystals; gray to tan flakes or powder

395.5

108

219.29

insol

1.24

 

 

 

 

 

m-PHENYLENEBIS(METHYLAMINE)

1477-55-0

colourless liquid

247

 

136.2

v sol

1.052

 

0.03mmHg  @25°C

 

 

 

o-PHENYLENEDIAMINE

95-54-5

brownish-yellow leaf from water; plates from chloroform

257

103

108.14

sol

 

 

 

1.5 ll ? ul

 

 

m-PHENYLENEDIAMINE

108-45-2

white crystals becoming red on exposure to air; colourless needles; rhombic crystals from alcohol; colourless rhombic needles

285

63.5

108.14

v sol

1.139

1.1309  @5ºC

<1mmHg  @99.8°C

 

 

 

p-PHENYLENEDIAMINE

106-50-3

white to slightly red crystals; white plates from benzene, ether

267

146

108.14

sl sol

1.14

3.72

<1mm  @21°C

1.5 ll ? ul

156

 

N-PHENYLETHANOLAMINE

122-98-5

 

286

 

137.17

sl sol

1.0945

 

 

 

 

 

o-TOLIDINE

119-93-7

white to reddish crystals or crystal powder

300

131.5

212.28

sl sol

1

 

 

 

 

 

o-TOLUIDINE

95-53-4

light yellow liquid becoming reddish brown on exposure to air and light; colourless liquid

200.2

-14.7-16.3

107.15

sl sol

1.008

3.69

0.32 torr

 

 

 

m-TOLUIDINE

108-44-1

colourless liquid

203

-30.4

107.15

sl sol

0.9889

3.90

1mmHg  @41°C

 

861

 

p-TOLUIDINE

106-49-0

lustrous plates or leaflets; white solid; colourless leaflets

200.5

44

107.15

sl sol

1.046

3.9

0.34 torr

 

 

 

2,4,5-TRIMETHYLANILINE

137-17-7

white crystals; needles obtained from water as solvent

235

68

135.2

insol

0.957  @25°C

 

 

 

 

 

TRIPHENYLAMINE

603-34-9

monoclinic crystals from methanol, ethyl acetate, benzene; colourless

365

127

245.3

insol

0.774  @0°C/0°C

 

 

 

 

 

XYLIDINE

1300-73-8

exists in 6 isomeric forms varying from a light yellow to a brown liquid; all isomers except ortho-4-xylidine are liquids above 27°C

213-226

-15 - + 51

121.18

sl sol

0.97-0.99

4.17

20 Pa

1 ll 7 ul

91

405

2,3-XYLIDINE

87-59-2

liquid

221.5

-15

121.2

sl sol

0.9931

 

0.1mmHg  @25°C

1.0 ll ? ul

97 cc

 

2,4-XYLIDINE

95-68-1

colourless liquid

214

-14.3

121.2

sl sol

0.9723

 

1mmHg  @52.6°C

 

 

 

3,4-XYLIDINE

95-64-7

plates of prisms from petroleum ether

226

51

121.2

sl sol

1.076  @18°C

 

 

 

 

 

AZIDES

Uses

Azides have varied uses in the chemical, dye-stuff, plastics, rubber and metal industries. Several compounds are used in wastewater treatment and as chemical intermediates, food additives, and sanitizing agents in dishwashing detergent and swimming pools.

1,1'-Azobis(formamide) is a blowing agent for synthetic and natural rubber and ethylene-vinyl acetate copolymers. It is also useful as a foaming agent added to increase the porosity of plastics. Trichlorinated isocyanuric acid and sodium dichloroisocyanurate are used as sanitizing agents for swimming pools and as active ingredients in detergents, commercial and household bleaches, and dishwashing compounds. Sodium dichloroisocyanurate is also used in water and sewage treatment.

Edetic acid (EDTA) has numerous functions in the food, metal, chemical, textile, photography and health care industries. It is an antioxidant in foods. EDTA is used as a chelating agent to remove unwanted metal ions in boiler water and cooling water, in nickel plating and in wood pulping. It also acts as a bleaching agent for film processing in the photography industry, an etching agent in metal finishing and a dyeing agent in the textile industry. EDTA is found in detergents for textiles, industrial germicides, metal cutting fluids, semiconductor production, liquid soaps, shampoos, pharmaceuticals and cosmetics industry products. It is also used in medicine to treat lead poisoning.

Phenylhydrazine, aminoazotoluene and hydrazine are useful in the dye-stuff industry. Phenylhydrazine is also utilized in the preparation of pharmaceutical products. Hydrazine is a reactant in fuel cells for military uses and a reducing agent in plutonium extraction from reactor waste. It is used in nickel plating, wastewater treatment, and electrolytic plating of metals on glass and plastics. Hydrazine is employed for nuclear fuel reprocessing and as a component of high-energy fuels. It is a corrosion inhibitor in boiler feedwater and in reactor cooling water. Hydrazine is also a chemical intermediate and a rocket propellant. Diazomethane is a powerful methylating agent for acidic compounds such as carboxylic acids and phenols.

Sodium azide is used in organic synthesis, explosives manufacture and as a propellant in automobile air-bags. Hydrazoic acid is used to make contact explosives such as lead azide.

Other azides, including methylhydrazine, hydrazobenzene, 1,1-dimethylhydrazine, hydrazine sulphate and diazomethane, are used in numerous industries. Methylhydrazine is a solvent, a chemical intermediate and a missile propellant, while hydrazobenzene is a chemical intermediate and an antisludging additive to motor oil. 1,1-Dimethylhydrazine is used in rocket fuel formulations. It is a stabilizer for organic peroxide fuel additives, an absorbent for acid gases, and a component of jet fuel. Hydrazine sulphate is used in the gravimetric estimation of nickel, cobalt and cadmium. It is an antioxidant in soldering flux for light metals, a germicide and a reducing agent in the analysis of minerals and slags.

Hazards

Diazomethane

Fire and explosion hazards. Either in the gaseous or liquid state, diazomethane explodes with flashes and even at -80 °C the liquid diazomethane may detonate. It has been the general experience, however, that explosions do not occur when diazomethane is prepared and contained in solvents such as ethyl ether.

Health hazards. Diazomethane was first described in 1894 by von Pechmann, who indicated that it was extremely poisonous, causing air hunger and chest pains. Following this, other investigators reported symptoms of dizziness and tinnitus. Skin exposure to diazomethane was reported to produce denudation of the skin and mucous membranes, and it was claimed that its action resembles that of dimethyl sulphate. It was also noted that the vapours from the ether solution of the gas were irritating to the skin and rendered the fingers so tender that it was difficult to pick up a pin. In 1930, exposure of two persons resulted in chest pains, fever and severe asthmatic symptoms about 5 hours after exposure to mere traces of the gas.

The first exposure to the gas may not produce any noteworthy initial reactions; however, subsequent exposures in even minute amounts may produce extremely severe attacks of asthma and other symptoms. The pulmonary symptoms may be explained as either the result of true allergic sensitivity after repeated exposure to the gas, particularly in individuals with hereditary allergy, or of a powerful irritant action of the gas on the mucous membranes.

At least 16 cases of acute diazomethane poisoning, including fatalities from pulmonary oedema, have been reported amongst chemists and laboratory workers. In all cases, symptoms of intoxication included irritating cough, fever and malaise, varying in intensity according to the degree and duration of exposure. Subsequent exposures have led to hypersensitivity.

In animals, exposure to diazomethane at 175 ppm for 10 minutes caused haemorrhagic emphysema and pulmonary oedema in cats, resulting in death in 3 days.

Toxicity. One explanation for the toxicity of diazomethane has been the intracellular formation of formaldehyde. Diazomethane reacts slowly with water to form methyl alcohol and liberate nitrogen. Formaldehyde, in turn, is formed by the oxidation of methyl alcohol. The possibilities of liberation in vivo of methyl alcohol or of the reaction of diazomethane with carboxylic compounds to form toxic methyl esters may be considered; on the other hand, the deleterious effects of diazomethane may be primarily due to the strongly irritant action of the gas on the respiratory system.

Diazomethane has been shown to be a lung carcinogen in mice and rats. Skin application and subcutaneous injection, as well as inhalation of the compound, have also been shown to cause tumour development in experimental animals. Bacterial studies show it is mutagenic. The International Agency for Research on Cancer (IARC), however, places it in Group 3, unclassifiable as to human carcinogenicity.

Diazomethane is an effective insecticide for the chemical control of Triatoma infestations. It is also useful as an algicide. When the ichthyotoxic component of the green alga Chaetomorpha minima is methylated with diazomethane, a solid is obtained which retains its toxicity to kill fish. It is noteworthy that in the metabolism of the carcinogens dimethylnitrosamine and cycasin, one of the intermediary products is diazomethane.

Hydrazine and derivatives

Flammability, explosion and toxicity are major hazards of the hydrazines. For example, when hydrazine is mixed with nitromethane, a high explosive is formed which is more dangerous than TNT. All hydrazines discussed here have sufficiently high vapour pressures to present serious health hazards by inhalation. They have a fishy, ammoniacal odour which is repulsive enough to indicate the presence of dangerous concentrations for brief accidental exposure conditions. At lower concentrations, which may occur during manufacturing or transfer processes, the warning properties of odour may not be enough to preclude low-level chronic occupational exposures in fuel handlers.

Moderate to high concentrations of hydrazine vapours are highly irritating to the eyes, nose and the respiratory system. Skin irritation is pronounced with the propellant hydrazines; direct liquid contact results in burns and even sensitization type of dermatitis, especially in the case of phenylhydrazine. Eye splashes have a strongly irritating effect, and hydrazine can cause permanent corneal lesions.

In addition to their irritating properties, hydrazines also exert pronounced systemic effects by any route of absorption. After inhalation, skin absorption is the second most important route of intoxication. All hydrazines are moderate to strong central nervous system poisons, resulting in tremors, increased central nervous system excitability and, at sufficiently high doses, convulsions. This can progress to depression, respiratory arrest and death. Other systemic effects are in the haematopoietic system, the liver and the kidney. The individual hydrazines vary widely in degree of systemic toxicity as far as target organs are concerned.

The haematological effects are self-explanatory on the basis of haemolytic activity. These are dose dependent and, with the exception of monomethylhydrazine, they are most prominent in chronic intoxication. Bone marrow changes are hyperplastic with phenylhydrazine, and blood cell production outside the bone marrow has also been observed. Monomethylhydrazine is a strong methaemoglobin former, and blood pigments are excreted in the urine. The liver changes are primarily of the fatty degeneration type, seldom progressing to necrosis, and are usually reversible with the propellant hydrazines. Monomethylhydrazine and phenylhydrazine in high doses can cause extensive kidney damage. Changes in the heart muscle are primarily of fatty character. The nausea observed with all of these hydrazines is of central origin and refractory to medication. The most potent convulsants in this series are monomethylhydrazine and 1,1-dimethylhydrazine. Hydrazine causes primarily depression, and convulsions occur much less frequently.

All hydrazines appear to have some kind of activities in some laboratory animal species by some route of entry (feeding in drinking water, gastric intubation or inhalation). IARC considers them Group 2B, possibly carcinogenic in humans. In laboratory animals, with the exception of one derivative not discussed here, 1,2-dimethylhydrazine (or symmetrical dimethylhydrazine), there is a definite dose response. In view of its Group 2B rating, any exposure of humans should be minimized by proper protective equipment and decontamination of accidental spills.

Phenylhydrazine

The pathology of phenylhydrazine has been studied by means of animal experiments and clinical observations. Information about the effects of phenylhydrazine in humans was obtained from the use of phenylhydrazine hydrochloride for therapy. The conditions observed included haemolytic anaemia, with hyperbilirubinaemia and urobilinuria, and the appearance of Heinz bodies; liver damage with hepatomegalia, icterus, and very dark urine containing phenols; sometimes signs of kidney manifestations occurred. Haematological effects included cyanosis, haemolytic anaemia, sometimes with methaemoglobinaemia, and leucocytosis. Among the more general symptoms were fatigue, giddiness, diarrhoea and lowering of the blood pressure. It was also observed that a student, who had received 300 g of the substance on the abdomen and thighs suffered from cardiac collapse with a coma that lasted for several hours. Individuals with hereditary glucose-6-phosphate dehydrogenase (G6PDH) deficiency would be much more susceptible to the haemolytic effects of phenylhydrazine and should not be exposed to it.

With regard to skin damage, there have been reports of acute eczema with vesicular eruption, as well as chronic eczema on the hands and forearms of workers preparing antipyrin. Also described was a case of vesicular dermatosis with the production of phlyctenae on the wrist of an assistant chemist. This appeared 5 or 6 hours after handling and took 2 weeks to heal. A chemical engineer who handled the substance suffered only from a few pimples, which disappeared in 2 or 3 days. Phenylhydrazine is therefore regarded as a potent skin sensitizer. It is very rapidly absorbed by the skin.

Because of reports of carcinogenicity of phenylhydrazine to mice, the US National Institute for Occupational Safety and Health (NIOSH) has recommended its regulation as a human carcinogen. A variety of bacterial and tissue-culture studies have shown it is mutagenic. Intraperitoneal injection of pregnant mice resulted in offspring with severe jaundice, anaemia and a deficit in acquired behaviour.

Sodium azide and hydrazoic acid

Sodium azide is manufactured by combining sodamide with nitrous oxide. It reacts with water to produce hydrazoic acid. Hydrazoic acid vapour may be present when handling sodium azide. Commercially, hydrazoic acid is produced by the action of acid on sodium azide.

Sodium azide appears to be only slightly less acutely toxic than sodium cyanide. It may be fatal if inhaled, swallowed or absorbed through skin. Contact may cause burns to skin and eyes. A lab technician accidentally ingested what was estimated to be a “very small amount” of sodium azide. Symptoms of tachycardia, hyperventilation and hypotension were observed. The authors note that the minimal hypotensive dose in humans lies between 0.2 and 0.4 µg/kg.

Treatment of normal individuals with 3.9 mg/day of sodium azide for 10 days produced no effects other than a heart-pounding sensation. Some hypertensive patients developed sensitivity to azide at 0.65 mg/day.

Workers exposed to 0.5 ppm hydrazoic acid developed headaches and nasal congestion. Additional symptoms of weakness and eye and nasal irritation developed from exposure to 3 ppm for less than 1 hour. Pulse rate was variable and blood pressure was low or normal. Similar symptoms were reported among workers making lead azide. They had definite low blood pressure which became more pronounced during the work day and returned to normal after leaving work.

Animal studies showed a rapid but temporary fall in blood pressure from single oral doses of 2 mg/kg or more of sodium azide. Associated haematuria and cardiac irregularities were observed at levels of 1 mg/kg IV in cats. Symptoms observed in animals after relatively large doses of sodium azide are respiratory stimulation and convulsions, then depression and death. The LD50 for sodium azide is 45 mg/kg in rats and 23 mg/kg in mice.

Exposure of rodents to hydrazoic acid vapour causes acute inflammation of the deep lung. Hydrazoic acid vapour is about eight times less toxic than hydrogen cyanide, with a concentration of 1,024 ppm being fatal in mice after 60 minutes (compared to 135 ppm for hydrogen cyanide).

Sodium azide was mutagenic in bacteria, although this effect was reduced if metabolizing enzymes were present. It was also mutagenic in mammalian cell studies.

Azides tables

Table 104.33 Chemical identification

CHEMICAL

SYNONYMS

UN CODE

CAS-NUMBER

CHEMICAL FORMULA

3-AMINO-9-ETHYLCARBAZOLE

3-Amino-N-ethylcarbazole

132-32-1

AMINOAZOTOLUENE

o-Aminoazotoluene; 2-Amino-5-azotoluene; 4-Amino-2',3-dimethylazobenzene; 4'-Amino-2,3'-dimethylazobenzene; 2-Methyl-4-((2-methylphenyl)azo)benzenamine; Toluazotoluidine; 4-(o-tolylazo)-o-toluidine

97-56-3

3-AMINO-1,2,4-TRIAZOLE

Aminotriazole; 2-Aminotriazole; 3-Aminotriazole; 3-Amino-S-triazole; 3-Amino-1,2,4-triazole; 2-Amino-1,3,4-triazole; 3-Amino-1h-1,2,4-triazole; Amitrole; Amitrol-t; Triazolamine; 1h-1,2,4-Triazol-3-amine

61-82-5

AZASERINE

Azaserin; Azaserine; Diazoacetate (ester) L-Serine; L-Diazoacetate (ester) serine

115-02-6

1,1'-AZOBIS(FORMAMIDE)

Azobiscarboxamide; Azodicarbamide; Azodicarboxylic acid diamide

123-77-3

AZOBENZENE

Azobenzide; Azobenzol; Azodibenzeneazofume; Azofume; Benzeneazobenzene; Benzene, azodi; Benzofume; Diazobenzene; Diphenyldiazene; 1,2-Diphenyldiazene; Diphenyldiimide

103-33-3

CYANURIC CHLORIDE

Chlorotriazine; Cyanurchloride; Cyanuric acid chloride; Trichlorocyanidine; 1,3,5-Trichlorotriazine; 2,4,6-Trichloro-1,3,5-triazine; Tricyanogen chloride

UN2670

108-77-0

DIAZOMETHANE

Azimethylene; Diazirine; Diazomethane

334-88-3

1,2-DIETHYLHYDRAZINE

N-N'-Diethylhydrazine; Hydrazoethane; Hydroazoethane

1615-80-1

1,2-DIMETHYLHYDRAZINE

N,N'-Dimethylhydrazine; sym-Dimethylhydrazine; Hydrazomethane

UN2382

540-73-8

1,1-DIMETHYLHYDRAZINE

Dimethylhydrazine; N,N-Dimethylhydrazine

UN1163

57-14-7

EDETIC ACID

3,6-Bis(carboxymethyl)-; N,N'-1,2-Ethanediylbis(N-(carboxymethyl)glycine); 3,6-Diazaoctanedioic acid; Ethylenediaminetetraacetic acid; Ethylenediamine-N,N,N',N'-Tetraacetic acid

60-00-4

HYDRAZINE  

UN2029

302-01-2

HYDRAZINE HYDRATE

Hydrazine, monohydrate

7803-57-8

HYDRAZINE HYDROCHLORIDE

Hydrazine monochloride; Hydrazinium chloride; Hydrazinium monochloride

2644-70-4

HYDRAZINE SULPHATE

Hydrazine monosulfate; Hydrazinium sulfate; Hydrazonium sulfate

10034-93-2

2-HYDRAZINOETHANOL

Hydroxyethyl hydrazine; β-Hydroxyethylhydrazine; N-(2-Hydroxyethyl)hydrazine

109-84-2

HYDRAZOBENZENE

N,N'-Diphenylhydrazine; sym-Diphenylhydrazine; 1,2-Diphenylhydrazine; Hydrazine, 1,2-diphenyl-

122-66-7

HYDRAZOIC ACID

Azoimide; Diazoimide; Hydrogen azide; Hydronitric acid

7782-79-8

METHYLHYDRAZINE

Hydrazomethane; 1-Methylhydrazine; Monomethylhydrazine

UN1244

60-34-4

METHYLHYDRAZINE HYDROCHLORIDE

 

7339-53-9

PHENYLHYDRAZINE

Hydrazine-benzene; Hydrazinobenzene

UN2572

100-63-0

PHENYLHYDRAZINE HYDROCHLORIDE

Phenylhydrazine hydrochloride; Phenylhydrazinium chloride

59-88-1

SODIUM AZIDE  

UN1687

26628-22-8

SODIUM DICHLOROCYANURATE

Dichloroisocyanuric acid sodium salt; Isocyanuric acid, dichloro-, sodium salt; Sodium dichlorisocyanurate; Sodium dichloroisocyanurate; sym-Triazine-2,4,6(1H,3H,5H)-Trione, dichloro-, sodium salt

2893-78-9

1,2,4-TRIAZOLE

sym-Triazole

288-88-0

TRICHLOROISOCYANURIC ACID

Trichlorinated isocyanuric acid; Trichloroisocyanic acid; Trichloroisocyanurate; Trichloroisocyanuric acid; 1,3,5-Trichloroisocyanuric acid; 1,3,5-Trichloro-2,4,6-trioxohexahydro-sym-triazine

UN2468

87-90-1

Table 104.34 Health hazards

Chemical Name

     CAS-Number

ICSC Short-Term Exposure

ICSC Long-Term Exposure

ICSC Routes of Exposure and Symptoms

US NIOSH Target Organs & Routes of Entry

US NIOSH Symptoms

1,1'-AZOBIS(FORMAMIDE)

     123-77-3

eyes; resp tract

skin; resp tract

Inhalation: cough, headache, fatigue, shortness of breath, sore throat, cramps

Skin: redness

Eyes: redness, pain

 

 

DIAZOMETHANE

     334-88-3

 

 

 

eyes; resp sys

Inh; con (liq)

Irrit eyes; cough, short breath; head, ftg; flush skin, fever; chest pain, pulm edema, pneuitis; asthma; liq: frostbite

DIMETHYL-p-AMINOAZOBENZENE

     60-11-7

 

 

 

Liver; skin; bladder; kidneys; resp sys (in animals: liver &bladder tumors)

Inh; abs; ing; con

Enlarged liver; liver, kidney dysfunc; contact derm; cough, wheez, dysp; bloody sputum; bronchial secretions; frequent urination, hema, dysuria; (carc)

EDETIC ACID

     60-00-4

eyes; skin; resp tract

 

Inhalation: burning sensation, cough

Skin: redness

Eyes: redness

Ingestion: burning sensation

 

 

HYDRAZINE

     302-01-2

eyes; skin; resp tract; liver; kidneys; CNS

skin; liver; kidneys; CNS; genes

 

Eyes; skin; resp sys; CNS; liver; kidneys (in animals: tumors of the lungs, liver, blood vessels & intestine)

Inh; ing; abs; con

Irrit eyes, skin, nose throat; temporary blindness; dizz, nau; derm; eye, skin burns; in animals: bron, pulm edema; liver, kidney damage; convuls; (carc)

METHYLHYDRAZINE

     60-34-4

 

 

 

CNS; resp sys; liver; blood; CVS; eyes; skin

Inh; abs; ing; con

Irrit eyes, skin, resp sys; vomit, diarr, tremor, ataxia; anoxia, cyan; convuls; (carc)

PHENYLHYDRAZINE

     100-63-0

eyes; skin; resp tract; blood; kidneys

skin; blood

Inhalation: cough, laboured breathing, sore throat, cyanosis

Skin: may be absorbed, dry skin, redness, pain

Eyes: redness, pain, blurred vision

Ingestion: abdominal pain, diarrhoea, nausea, vomiting, weakness, vertigo

Blood; resp sys; liver; kidneys; skin (in animals: tumors of the lungs, liver, blood vessels & intestine)

Inh; abs; ing; con

Skin sens, hemolytic anemia, dysp, cyan; jaun; kidney damage; vascular thrombosis; (carc)

SODIUM AZIDE

     26628-22-8

eyes; skin; resp tract; CNS

CNS; genes

Inhalation: cough, headache, nasal stuffiness, blurred vision, shortness of breath, unconsciousness, slowing heartbeat, fall in blood pressure

Skin: redness, blisters

Eyes: redness, pain

Ingestion: abdominal pain, headache, nausea, unconsciousness, sweating

Eyes; skin; CNS; CVS; kidneys

Inh; abs; ing; con

Irrit eyes, skin; head, weak, dizz, blurred vision; dysp; low BP, bradycardia; kidney changes

SODIUM DICHLOROCYANURATE

     2893-78-9

eyes; skin; resp tract; lungs

skin; lungs

Inhalation: cough, dullness, headache, nausea, shortness of breath, sore throat, vomiting, symptoms may be delayed

Skin: redness, skin burns, pain

Eyes: redness, pain, loss of vision, severe deep burns

Ingestion: burning sensation, cough, headache, sore throat

 

 

1,2,4-TRIAZOLE

     288-88-0

eyes; skin

 

 

 

 

Table 104.35 Physical & chemical hazards

For UN Class: 1.5 = very insensitive substances which have a mass explosion hazard; 2.1 = flammable gas; 2.3 = toxic gas; 3 = flammable liquid; 4.1 = flammable solid; 4.2 = substance liable to spontaneous combustion; 4.3 = substance which in contact with water emits flammable gases; 5.1 = oxidizing substance; 6.1 = toxic; 7 = radioactive; 8 = corrosive substance

Chemical Name

CAS-Number

Physical

Chemical

UN Class or Division /  Subsidiary Risks

1,1'-AZOBIS(FORMAMIDE)

123-77-3

 

The substance decomposes on heating or on burning producing toxic fumes (nitrogen oxides)

 

CYANURIC CHLORIDE

108-77-0

 

 

8

1,1-DIMETHYLHYDRAZINE

57-14-7

The vapour is heavier than air and may travel along the ground; distant ignition possible

The substance may spontaneously ignite on contact with air in the presence of oxidizing agents •Reacts vigorously with oxidizing material such as air; vapour is inflammable in air •On combustion, forms toxic and/or flammable fumes including nitrogen oxides, hydrogen, ammonia, dimethylamine and hydrazoic acid •toxic fumes nitrogen •The substance is a strong reducing agent and reacts violently with oxidants like nitrogen tetroxide, hydrogen peroxide and nitric acid •The substance is a strong base, it reacts violently with acid and is corrosive •Reacts with oxygen causing fire and explosion hazard •Attacks plastic

3

1,2-DIMETHYLHYDRAZINE

540-73-8

 

 

6.1/ 3

EDETIC ACID

60-00-4

 

The substance decomposes on heating producing nitrous oxides •Reacts with strong oxidants, strong bases, copper, copper alloys and nickel

 

HYDRAZINE

302-01-2

 

 

3/ 3/ 6.1

METHYLHYDRAZINE

60-34-4

 

 

6.1/ 3/ 8

METHYLHYDRAZINE HYDROCHLORIDE

7339-53-9

 

 

6.1/ 3/ 8

PHENYLHYDRAZINE

100-63-0

 

The substance decomposes on heating and on burning producing toxic fumes including nitrogen oxides •Reacts with oxidants •Reacts violently with lead dioxide

6.1

PHENYLHYDRAZINE HYDROCHLORIDE

59-88-1

 

 

6.1

SODIUM AZIDE

26628-22-8

 

May explode on heating above melting point, especially on rapid heating causing fire and explosion hazard •The solution in water is a weak base •Reacts with copper, lead, silver, mercury and carbon disulfide to form particularly shock-sensitive compounds •Reacts with acids, forming toxic and explosive hydrogen azide •Very corrosive to aluminium

6.1

SODIUM DICHLOROCYANURATE

2893-78-9

 

The substance decomposes on heating, on contact with water, producing toxic fumes •The substance is a strong oxidant and reacts violently with combustible and reducing materials •The substance is a strong reducing agent and reacts with oxidants •The solution in water is a weak acid •Reacts violently with many substances causing fire and explosion hazard

5.1

1,2,4-TRIAZOLE

288-88-0

Dust explosion possible if in powder or granular form, mixed with air

The substance decomposes on boiling •Upon heating, toxic fumes are formed •Reacts with strong oxidants and strong bases

 

TRICHLOROISOCYANURIC ACID

87-90-1

 

 

5.1

Table 104.36 Physical & chemical properties

Chemical Name

CAS-Number

Colour/Form

Boiling Point (°C)

Melting Point (°C)

Molecular Weight

Solubility in Water

Relative Density (water=1)

Relative Vapour Density (air=1)

Vapour Pressure/ (Kpa)

Inflam. Limits

Flash Point (°C)

Auto Ignition Point (°C)

3-AMINO-9-ETHYLCARBAZOLE

132-32-1

crystalline compound

 

127

210.3

 

 

 

 

 

 

 

AMINOAZOTOLUENE

97-56-3

golden crystals; reddish-brown to yellow crystals; yellow leaves from alcohol

 

102

225.28

7.64mg/l  @25°C

 

 

7.5x 10 -7 mmHg  @25°C

 

 

 

AZASERINE

115-02-6

orthorhombic, pale yellow togreen crystals from 90% ethanol.

 

157

173.13

1.36x105mg/l  @25°C

 

 

1.53x 10-10 mmHg  @25°C

 

 

 

1,1'-AZOBIS(FORMAMIDE)

123-77-3

orange-red crystals; yellow powder

 

212 decomp

116.08

sl sol

1.65

 

 

 

 

 

AZOBENZENE

103-33-3

orange-red leaflets; solid, orange-red crystals; yellow or orange crystals

293

68

182.22

insol in water

1.203  @20 º C/4 º C

 

1mmHg  @103 º C

 

 

 

CYANURIC CHLORIDE

108-77-0

crystals from ether or benzene; colourless, monoclinic crystals

190

154

184.41

insol

1.32

6.36

2mmHg  @70°C

 

 

 

DIAZOMETHANE

334-88-3

yellowgas

-23

-145

42.04

 

1.45

1.45

 

 

 

 

1,2-DIETHYLHYDRAZINE

1615-80-1

 

85.5

 

88.15

 

0.797  @26°C

 

 

 

 

 

1,1-DIMETHYLHYDRAZINE

57-14-7

clear, colourless liquid

63.9

-58

60.1

v sol

0.7914  @22°C/4°C

1.94

16.4

2 ll 95 ul

-15 cc

249

1,2-DIMETHYLHYDRAZINE

540-73-8

clear, colourless liquid

81  @753mmHg

-9

60.10

misc

0.8274

 

68mmHg  @24.46°C

 

< 23 cc

 

EDETIC ACID

60-00-4

white crystalline powder

 

240 decomp

292.24

0.50g/l  @25°C

 

 

 

 

 

 

HYDRAZINE

302-01-2

colourless oily liquid; white crystals

113

2.0

32.05

misc

1.011  @15°C/4

1.1

2.1

4 ll 100 ul

38 cc

270

HYDRAZINE HYDROCHLORIDE

2644-70-4

white crystalline flakes

190 decomp

81-87

 

sol

 

 

 

 

 

 

HYDRAZINE SULPHATE

10034-93-2

orthorhombic crystals;glass like plates or prisms; white crystalline powder; colourless rhombic crystals

 

254

130.12

v sol

1.378  @25°C

 

 

 

 

 

2-HYDRAZINOETHANOL

109-84-2

 

218-220  @754mmHg

-70

76.10

v sol

1.119  @25°C

 

 

 

 

 

HYDRAZOBENZENE

122-66-7

tablets from alcohol & ether

 

131

184.2

 

1.158  @16°C/4°C

 

1 torr  @103°C

 

 

 

HYDRAZOIC ACID

7782-79-8

colourless volatile liquid

37

-80

 

 

 

 

 

 

 

 

METHYLHYDRAZINE

60-34-4

colourless liquid

87.5

-52.4

46.07

sol

0.874  @25°C

1.6

49.6mmHg  @25°C

2.5 ll 97 ul

0 oc

194

PHENYLHYDRAZINE

100-63-0

monoclinic prisms or oil; colourless, oily liquid; colourless to pale yellow solid or liquid

243.5

19.5

108.14

sol

1.098

3.7

0.133  @71.8 °C

 

88 cc

174

PHENYLHYDRAZINE HYDROCHLORIDE

59-88-1

 

sublimes

243-246 decomp

144.60

v sol

 

 

 

 

 

 

SODIUM AZIDE

26628-22-8

white, crystalline solid; colourless hexagonal crystals

 

275 decomp

65.02

v sol

1.846

 

 

 

 

 

SODIUM DICHLOROCYANURATE

2893-78-9

white, crystalline powder

 

240-250 decomp

- 220.96

25g/100ml

>1

 

 

 

 

 

1,2,4-TRIAZOLE

288-88-0

needles

260

120-121

 

v sol

 

 

 

 

 

 

TRICHLOROISOCYANURIC ACID

87-90-1

needles from ethylene chloride; white crystalline powder orgranules

 

246.7 decomp

232.4

sol

> 1 (solid)

 

 

 

 

 

BORANES

David L. Hinkamp

Uses

Boron and boranes have varied functions in the electronics, metalworking, chemical, pulp and paper, ceramics, textile and construction industries. In the electronics industry, boron, boron tribromide and boron trichloride are used as semiconductors. Boron is an igniter in radio tubes and a degasifying agent in metallurgy. It is also used in pyrotechnic flares. Diborane, pentaborane and decaborane are utilized in high-energy fuel. Boron trichloride, diborane and decaborane are rocket propellants, and triethylboron and boron serve as igniters for jet and rocket engines. 10Boron is employed in the nuclear industry as a constituent of neutron-shielding material in reactors.

In the metalworking industry, many of the boranes are used in welding and brazing. Other compounds are employed as flame retardants and as bleaching agents in the textile, paper and pulp, and paint and varnish industries. Boron oxide is a fire-resistant additive in paints and varnishes, while sodium tetraborate, borax and trimethyl borate are fireproofing agents for textile goods. Both borax and sodium tetraborate are used for the fireproofing and artificial aging of wood. In the construction industries, they are components of fibreglass insulation. Sodium tetraborate also serves as an algicide in industrial water and as an agent in the tanning industry for curing and preserving skins. Borax is a germicide in cleaning products, a corrosion inhibitor in antifreeze, and a powdered insecticide for crack and crevice treatment of food-handling areas. Decaborane is a rayon delustrant and a mothproofing agent in the textile industry, and sodium borohydride is a bleaching agent for wood pulp.

In the ceramics industry, boron oxide and borax are found in glazes, and sodium tetraborate is a component of porcelain enamels and glazes. Sodium perborate is employed for bleaching textile goods and for electroplating. It is used in soaps, deodorants, detergents, mouthwash and vat dyes. Boron trifluoride is used in food packaging, electronics, and in the nuclear industry’s breeder reactors.

Health Hazards

Boron is a naturally occurring substance that is commonly found in food and drinking water. In trace amounts it is essential to the growth of plants and certain types of algae. Although it is also found in human tissue, its role is unknown. Boron is generally regarded as safe (GRAS) for use as an indirect food additive (e.g., in packaging), but compounds containing boron can be highly toxic. Boron is present in a number of industrially useful compounds, including borates, boranes and boron halides.

Boron toxicity in humans is seen most commonly following chronic use of medicines containing boric acid and in cases of accidental ingestion, especially among young children. Occupational toxicity usually results from exposure of the respiratory system or open skin wounds to dusts, gases or vapours of boron compounds.

Acute irritation of eyes, skin and the respiratory tract can follow contact with almost any of these materials in usual concentrations. Absorption can affect the blood, respiratory tract, digestive tract, kidneys, liver and central nervous system; in severe cases, it can result in death.

Boric acid is the most common of the borates, which are compounds of boron, oxygen and other elements. Acute exposure to boric acid in liquid or solid forms can cause irritation, the severity of which is determined by the concentration and duration of exposure. Inhalation of borate dusts or mists can directly irritate the skin, eyes and respiratory system.

Symptoms of this irritation include eye discomfort, dry mouth, sore throat and productive cough. Workers usually report these symptoms after acute boric acid exposures over  10 mg/m3; however, chronic exposures of less than half this can also cause irritant symptoms.

Workers exposed to borax (sodium borate) dust have reported chronic productive cough, and, in those who have experienced long exposures, obstructive abnormalities have been detected, though it is unclear whether these are related to exposure.

Borates are readily absorbed through open skin wounds and from the respiratory and digestive tracts. After absorption borates exert predominant actions upon the skin, central nervous system and digestive tract. Symptoms generally develop rapidly, but may take hours to evolve following skin exposures. Following absorption, the skin or mucous membranes may develop abnormal redness (erythema), or surface tissue may be shed. Chronic exposure may cause eczema, patchy hair loss and swelling around the eyes. These dermatologic effects may take days to develop after exposure. The individual may experience abdominal pain, nausea, vomiting and diarrhoea. Vomitus and diarrhoea may be blue-green in colour and may contain blood. Headache, excitement or depression, seizures, lethargy and coma may develop.

In instances of acute poisoning, anaemia, acidosis and dehydration develop, accompanied by rapid, weak pulse and low blood pressure. These effects may be followed by irregular heart rhythm, shock, kidney failure and, in rare cases, liver damage. Victims appear pale, sweaty and acutely ill. Most of these severe findings have been present just before death from acute borate toxicity. However, when victims are diagnosed and treated in time, the effects usually are reversible.

The reproductive effects of borates are still unclear. Boric acid exposure inhibited sperm motility in rats and, at higher levels, led to testicular atrophy. Animal and tissue studies of genotoxicity have been negative, but infertility has been demonstrated in both males and females after chronic boric acid feedings. Offspring have shown delayed and abnormal development including abnormal rib development. In humans, there is only suggestive evidence of decreased fertility among the few workers who have been evaluated in uncontrolled studies.

Boron trihalides—boron trifluoride, boron chloride and boron bromide—can react violently with water, liberating hydrogen halides such as hydrochloric and hydrofluoric acids. Boron trifluoride is a severe irritant of the lungs, eyes and skin. Animals studied after lethal exposures showed kidney failure and kidney tubule damage, pulmonary irritation and pneumonia. Examinations of a small number of exposed workers showed some decreases in pulmonary function, but it was unclear whether these were related to exposure.

Boranes (boron hydrides)—diborane, pentaborane and decaborane—are extremely reactive compounds which can explode on contact with oxygen or oxidizing agents. As a group they are severe irritants which can quickly cause chemical pneumonia, pulmonary oedema and other respiratory injuries. In addition, boranes have been reported to cause seizures and neurological damage with long-lasting neurological deficits and psychological symptoms. These compounds must be handled with extreme caution.

There is no evidence of boron or the borates causing cancer in chronic experiments with animals or in studies of exposed humans.

Boranes tables

Table 104.37 Chemical identification

CHEMICAL

SYNONYMS

UN CODE

CAS-NUMBER

CHEMICAL FORMULA

BORON

 

7440-42-8

BORIC ACID, DISODIUM SALT

Anhydrous borax; Borates, tetra, sodium salt; Sodium biborate; Sodium tetraborate

1330-43-4

BORON OXIDE

Boric anhydride; Boron sesquioxide; Boron trioxide; Diboron trioxide

1303-86-2

BORON TRIBROMIDE

Boron bromide

UN2692

10294-33-4

BORON TRICHLORIDE

Boron chloride

UN1741

10294-34-5

BORON TRIFLUORIDE

Boron fluoride

UN1008

7637-07-2

BORON TRIFLUORIDE ETHERATE

 

109-63-7

DECABORANE

UN1868

17702-41-9

DIBORANE

Boroethane; Boron hydride; Diborane; Diboron hexahydride

UN1911

19287-45-7

PENTABORANE

UN1380

19624-22-7

SODIUM PERBORATE

Sodium borate; Sodium peroxoborate

7632-04-4

SODIUM TETRABORATE DECAHYDRATE

Borates, tetra, sodium salt, borax decahydrate; Sodium biborate; Sodium biborate decahydrate; Sodium pyroborate; Sodium pyroborate decahydrate; Sodium tetraborate

1303-96-4

SODIUM BOROHYDRIDE

Sodium borohydride; Sodium tetrahydroborate

UN1426

16940-66-2

TRIETHYLBORANE

Triethylborane; Triethylborine

97-94-9

TRIMETHYL BORATE

Boric acid, trimethyl ester; ethyl borate; Trimethoxyborine; Trimethyl borate

 UN2416

121-43-7

Table 104.38 Health hazards

Chemical Name

     CAS-Number

ICSC Short-Term Exposure

ICSC Long-Term Exposure

ICSC Routes of Exposure and Symptoms

US NIOSH Target Organs & Routes of Entry

US NIOSH Symptoms

BORON OXIDE

     1303-86-2

eyes; skin; resp tract

kidneys

Inhalation: cough, sore throat

Skin: redness

Eyes: redness, pain

Ingestion: abdominal cramps, diarrhoea, nausea, vomiting, shock

Eyes, skin; resp sys

Inh; ing; con

Irrit eyes, skin, resp sys; cough; conj; skin eryt

BORON TRIBROMIDE

     10294-33-4

eyes; skin; resp tract; lungs

 

Inhalation: cough, laboured breathing, sore throat

Skin: Redness, burns, pain

Eyes: redness, pain, severe deep burns

Ingestion: burns to mouth and upper gastrointestinal tract, abdominal pain, burning sensation vomiting

Eyes, skin; resp sys

Inh; ing; con

Irrit eyes, skin, resp sys; skin, eye burns; dysp, pulm edema

BORON TRICHLORIDE

     10294-34-5

eyes; skin; resp tract

 

Inhalation: burning sensation, cough, laboured breathing, shortness of breath, sore throat

Skin: Redness, burns, burning sensation, pain, blisters

Eyes: redness, pain, loss of vision

 

 

BORON TRIFLUORIDE

     7637-07-2

eyes; skin; resp tract; lungs

lungs; kidneys

Inhalation: corrosive, burning sensation, cough, laboured breathing

Skin: redness, burning sensation, pain, on contact with liquid: frostbite

Eyes: redness, pain, blurred vision

Resp sys; kidneys; eyes; skin

Inh; con

Irrit eyes, skin, nose, resp sys; epis; eye, skin burns; in animals: pneu; kidney damage

DECABORANE

     17702-41-9

eyes; resp tract; CNS

CNS

Inhalation: cough, dizziness, drowsiness, headache, tremors, convulsions, nausea, weakness, incoordination, symptoms may be delayed

CNS; liver; kidneys

Inh; abs; ing; con

Dizz, head, nau, li-head, drow; inco, local musc spasm, tremor, convuls; ftg; in animals: weak; dysp; liver, kidney damage

DIBORANE

     19287-45-7

eyes; skin; resp tract; lungs

lungs

Inhalation: cough, dizziness, laboured breathing, nausea, sore throat, weakness

Skin: serious frostbite

Eyes: severe deep burns

Resp sys; CNS; liver; kidneys

Inh

Chest tight, precordial pain, short breath, non-productive cough, nau; head, li-head, verti, chills, fever, ftg, weak, tremor, musc fasc; in animals: liver, kidney damage; pulm edema; hemorr

PENTABORANE

     19624-22-7

resp tract; CNS

 

Inhalation: nausea, drowsiness, headache, dizziness, blurred vision, tremors, convulsions; symptoms may be delayed

Ingestion: nausea, vomiting

CNS; eyes; skin

Inh; abs; ing; con

Irrit eyes, skin, dizz, head, drow, li-head, inco, tremor, convuls, behavioral changes; tonic spasm face, neck, abdom, limbs

SODIUM TETRABORATE DECAHYDRATE

     1303-96-4

mucous membranes; eyes; liver; kidneys; CNS

skin

Inhalation: nose bleeding, cough, chest tightness, shortness of breath, sore throat

Skin: dry skin

Eyes: redness

Ingestion: abdominal pain, confusion, diarrhoea, drowsiness, headache, nausea, vomiting, weakness

Eyes, skin, resp sys

Inh; ing; con

Irrit eyes, skin, upper resp sys; derm; epis; cough, dysp

TRIMETHYL BORATE

     121-43-7

eyes; resp tract

 

Inhalation: cough, sore throat

Ingestion: abdominal pain, burning sensation

 

 

Table 104.39 Physical & chemical hazards

For UN Class: 1.5 = very insensitive substances which have a mass explosion hazard; 2.1 = flammable gas; 2.3 = toxic gas; 3 = flammable liquid; 4.1 = flammable solid; 4.2 = substance liable to spontaneous combustion; 4.3 = substance which in contact with water emits flammable gases; 5.1 = oxidizing substance; 6.1 = toxic; 7 = radioactive; 8 = corrosive substance

Chemical Name

CAS-Number

Physical

Chemical

UN Class or Division / Subsidiary Risks

BORON OXIDE

1303-86-2

 

Reacts slowly with water to form boric acid •Corrosive to metals in the presence of oxygen

 

BORON TRIBROMIDE

10294-33-4

The vapour is heavier than air

May explode on heating •The substance decomposes on contact with alcohol producing toxic and corrosive fumes (hydrogen bromide) •The solution in water is a strong acid, it reacts violently with bases and is corrosive to metals, rubber and wood •Reacts violently with water producing hydrogen gas, causing explosion hazard

8

BORON TRICHLORIDE

10294-34-5

The gas is heavier than air

Reacts violently with water •On contact with air it emits hydrogen chloride •Attacks many metals in presence of water

2.3/ 8

BORON TRIFLUORIDE

7637-07-2

The gas is heavier than air

The substance will polymerize unsaturated compounds •The substance decomposes on contact with water and moisture, producing toxic and corrosive fumes including hydrogen fluoride, fluoroboric acid and boric acid •Reacts violently with metals such as sodium, potassium and calcium, and with alkyl nitrates •Attacks many metals in presence of water

2.3/ 8

BORON TRIFLUORIDE ETHERATE

109-63-7

 

 

8/ 3

DECABORANE

17702-41-9

Dust explosion possible if in powder or granular form, mixed with air

May explode on heating or contact with flames •The substance decomposes slowly on heating to 300°C to form boron and the flammable gas, hydrogen, and on burning producing toxic fumes (boron oxides) •Reacts with halogenated materials and ethers to form impact-sensitive materials •Undergoes explosive reaction with oxidants •Reacts with water or moisture to form flammable gas •Attacks natural rubber, some synthetic rubbers, some greases and some lubricants •Ignites in oxygen at 100°C •Reacts with amides, acetone, butyraldehyde, acetonitrile at room temperature

4.1/ 6.1

DIBORANE

19287-45-7

The gas mixes well with air, explosive mixtures are easily formed •Will ignite spontaneously in moist air at room temperature

The substance will polymerize to form liquid pentaborane •The substance decomposes at red heat to boron and hydrogen, and at lower temperatures to hydrogen and boron hydrides •Reacts spontaneously with chlorine and forms hydrides with aluminum and lithium which may ignite spontaneously in air •Reacts with many oxidized surfaces as a strong reducing agent

2.3/ 2.1

PENTABORANE

19624-22-7

The vapour is heavier than air

The substance decomposes slowly on heating to 150°C to form boron and the flammable gas hydrogen, and on burning producing toxic fumes (boron oxides) •Reacts with oxidants and halogens causing fire and explosion hazard •Impure material ignites spontaneously in air •Shock-sensitive solutions are formed with solvents such as ketones, ethers, esters

4.2/ 6.1

SODIUM BOROHYDRIDE

16940-66-2

 

 

4.3

SODIUM TETRABORATE DECAHYDRATE

1303-96-4

 

The substance decomposes on heating above 400°C producing metaborates •The substance is a weak base

 

TRIMETHYL BORATE

121-43-7

The vapour is heavier than air and may travel along the ground; distant ignition possible

On combustion, forms toxic gases of carbon and boron oxides •Reacts with oxidants causing fire and explosion hazard •Reacts with water, moist air and acids to form methanol and boric acid

3

Table 104.40 Physical & chemical properties

Chemical Name

CAS-Number

Colour/Form

Boiling Point (°C)

Melting Point (°C)

Molecular Weight

Solubility in Water

Relative Density (water=1)

Relative Vapour Density (air=1)

Vapour Pressure/ (Kpa)

Inflam. Limits

Flash Point (°C)

Auto Ignition Point (°C)

BORON

7440-42-8

polymorphic: alphα-rhombohedral form, clear red crystals; beta-rhombohedral form, black; alpha-tetragonal form, black, opaque crystals with metallic luster; amorphous form, black or dark brown powder; other crystal forms known

2550

2300

10.81

insol

Amorphous, 2.3g/cm3; alpha-rhombohedral, 2.46g/cm3; alpha-tetragonal, 2.31g/cm3; beta-rhombohedral, 2.35g/cm3

 

1.56x 10-5 @2140°C

 

 

580

BORIC ACID, DISODIUM SALT

1330-43-4

powder orglass-like plates; white, free-flowing crystals; lightgrey solid

1575

741

201.3

2.56g/100g

2.367

 

 

 

 

 

BORON OXIDE

1303-86-2

rhombic crystals; colourless, semitransparent lumps or hard, white crystals

1860

450

69.6

2.77g/100g

1.8 (amorphous); 2.46 (crystalline)

 

 

 

 

 

BORON TRIBROMIDE

10294-33-4

colourless liquid

90

-46.0

250.57

reacts

2.6431  @18.4°C/4°C

8.6

5.3  @14°C

 

 

 

BORON TRICHLORIDE

10294-34-5

 

12.5

-107

117.16

 

1.35  @12°C/4

4.03

2.99 Pa  @12.4°C

 

 

 

BORON TRIFLUORIDE

7637-07-2

colourlessgas

-99.9

-126.8

67.82

reacts

3.08g/1.57 l  @4°C

2.4

10mmHg  @-141°C. (solid); 760mmHg 110.7°C (liquid)

 

 

 

BORON TRIFLUORIDE ETHERATE

109-63-7

liquid; colourless

125.7

-60.4

141.94

 

1.3572

 

 

 

64 oc

 

DECABORANE

17702-41-9

white crystals; orthorhombic crystals; colourless or white crystalline needles

213

99.5

122.21

sl sol

solid: 0.94  @25°C; liquid: 0.78  @100°C

4.2

6.65 Pa  @25°C

 

80 cc

149

DIBORANE

19287-45-7

colourlessgas

-92.5

-165

27.69

sl sol

0.210  @15°C

0.96

224mmHg  @-112°C

0.8 ll 88 ul

flammable gas

40-50

PENTABORANE

19624-22-7

colourless liquid

60

-46.6

63.2

reacts

0.61  @0°C/4°C

2.2

22.8

0.42 ll 98 ul

30 cc

35

SODIUM PERBORATE

7632-04-4

white, amorphous powder

 

 

81.80

 

 

 

 

 

 

 

SODIUM TETRAHYDROBORATE

16940-66-2

white cubic crystal; white togray-white microcrystalline powder or lump

400 decomp slowly; 500 decomp rapidly

36

37.8

v sol

1.07

 

 

 

 

 

SODIUM TETRABORATE DECAHYDRATE

1303-96-4

colourless, monoclinic crystals; hard crystals,granules or crystalline powder; white,gray, bluish orgreenish white streak, vitreous or dull luster

320

75

381.4

5.92g/100g

1.73

 

 

 

 

 

TRIETHYLBORANE

97-94-9

colourless liquid

95-96

-92.9

98.00

 

0.6961mmHg  @23°C

 

 

 

 

 

TRIMETHYL BORATE

121-43-7

water-white liquid

67-68

-29.3

103.9

reacts

0.91

3.6

137mmHg  @25 º

 

< 27 cc

 

CYANO COMPOUNDS

This class of compounds is characterized by the presence of a C≡N (cyano) group and includes the cyanides and nitriles (R-C≡N) as well as related chemicals such as cyanogens, isocyanates and cyanamides. They primarily owe their toxicity to the cyanide ion, which is capable of inhibiting many enzymes, especially cytochrome oxidase, when released in the body. Death, which may be more or less rapid depending on the rate at which the cyanide ion is released, results from chemical asphyxia at the cellular level.

Inorganic Cyanides

Inorganic cyanides are readily hydrolyzed by water and decomposed by carbon dioxide and mineral acids to form hydrogen cyanide, which can also be produced by certain naturally occurring bacteria. Hydrogen cyanide is evolved in coke and steel-making, and can be generated in fires where polyurethane foam is incinerated (e.g., furniture, partitions and so on). It can be generated accidentally by the action of acids on cyanide-containing wastes (lactonitrile evolves hydrocyanic acid when in contact with an alkali, for example.), and intentionally in gas chambers for capital punishment, where cyanide pellets are dropped into bowls of acid to create a lethal atmosphere.

Nitriles

Nitriles (also called organic cyanides) are organic compounds which contain a cyano group  (-C≡N) as the characteristic functional group and have the generic formula RCN. They may be regarded as hydrocarbon derivatives wherein three hydrogen atoms attached to a primary carbon are replaced by a nitrilo group, or as derivatives of carboxylic acids (R—COOH) in which the oxo and hydroxyl radicals are replaced by a nitrilo group (R—C≡N). Upon hydrolysis, they yield an acid which contains the same number of carbon atoms and which, therefore, is usually named by analogy with the acid rather than as a derivative of hydrogen cyanide. They are very dangerous when heated to decomposition because of the release of hydrogen cyanide.

Saturated aliphatic nitriles up to C14 are liquids having a rather pleasant odour like the ethers. Nitriles of C14 and higher are odourless solids and generally colourless. Most nitriles will boil without decomposition at temperatures lower than those for the corresponding acids. They are extremely reactive compounds and are used extensively as intermediates in organic synthesis. They are widely used starting materials in the synthesis of various fatty acids, pharmaceuticals, vitamins, synthetic resins, plastics and dyes.

Uses

The inorganic cyano compounds have varied uses in the metal, chemical, plastics and rubber industries. They are utilized as chemical intermediates, pesticides, metal cleaners, and as agents for extracting gold and silver from ores.

Acryonitrile (vinyl cyanide, cyanoethylene, propene nitrile), a flammable and explosive colourless liquid, is found in surface coatings and adhesives and is used as a chemical intermediate in the synthesis of antioxidants, pharmaceuticals, pesticides, dyes and surface-active agents.

Calcium cyanamide (nitrolim, calcium carbimide, cyanamide) is a blackish-grey, shiny powder used in agriculture as a fertilizer, herbicide, pesticide and a defoliant for cotton plants. It is also used in steel hardening and as a desulphurizer in the iron and steel industry. In industry, calcium cyanamide is used for the manufacture of calcium cyanide and dicyandiamide, the raw material for melamine.

Cyanogen, cyanogen bromide and cyanogen chloride are used in organic syntheses. Cyanogen is also a fumigant and a fuel gas for welding and cutting heat-resistant metals. It is a rocket or missile propellant in mixtures with ozone or fluorine; and it may also be present in blast furnace emissions. Cyanogen bromide is utilized in textile treatment, as a fumigant and pesticide, and in gold extraction processes. Cyanogen chloride serves as a warning agent in fumigant gases.

Hydrogen cyanide finds use in the manufacture of synthetic fibres and plastics, in metal polishes, electroplating solutions, metallurgical and photographic processes, and in the production of cyanide salts. Sodium cyanide and potassium cyanide are used in electroplating, steel hardening, extraction of gold and silver from ores, and in the manufacture of dyes and pigments. In addition, sodium cyanide functions as a depressant in the froth flotation separation of ores.

Potassium ferricyanide (red prussiate of potash) is used in photography and in blueprints, metal tempering, electroplating and pigments. Potassium ferrocyanide (yellow prussiate of potash) is used in the tempering of steel and in process engraving. It is employed in the manufacture of pigments and as a chemical reagent.

Calcium cyanide, malononitrile, acetone cyanohydrin (2-hydroxy-2-methylproprionitrile), cyanamide and acrylonitrile are other useful compounds in the metal, plastics, rubber and chemical industries. Calcium cyanide and malononitrile are leaching agents for gold. In addition, calcium cyanide is used as a fumigant, a pesticide, a stabilizer for cement, and in the manufacture of stainless steel. Acetone cyanohydrin is a complexing agent for metal refining and separation, and cyanamide is used in metal cleaners, the refining of ores and the production of synthetic rubber. Ammonium thiocyanate is used in the match and photography industries and for double-dyeing fabrics and improving the strength of silks weighted with tin salts. It is a stabilizer for glues, a tracer in oil fields, and an ingredient in pesticides and liquid rocket propellants. Potassium cyanate serves as a chemical intermediate and as a weed killer.

Some of the more important organic nitriles in industrial use include acryonitrile (vinyl cyanamide, cyanethylene, propene nitrile), acetonitrile, (methyl cyanamide, ethanenitrile, cyanomethane), ethylene cyanohydrin, proprionitrile (ethyl cyanide), lactonitrile, glycolonitrile (formaldehyde cyanohydrin, hydroxyacetonitrile, hydroxymethylcyanide, methylene cyanohydrin), 2-methyl-lactonitrile, and adiponitrile.

Hazards

Cyanide compounds are toxic to the extent that they release the cyanide ion. Acute exposure can cause death by asphyxia, as the result of exposure to lethal concentrations of hydrogen cyanide (HCN) whether by inhalation, ingestion or percutaneous absorption; in the last case, however, the dose required is higher. Chronic exposure to cyanides at levels too low to produce such serious symptoms may cause a variety of problems. Dermatitis, often accompanied by itching, an erythematous rash and papules, has been a problem for workers in the electroplating industry. Severe irritation of the nose may lead to obstruction, bleeding, sloughs and, in some cases, perforation of the septum. Among fumigators, mild cyanide poisoning has been recognized as the cause of symptoms of oxygen starvation, headache, rapid heart rate, and nausea, all of which were completely reversed when the exposure ceased.

Chronic systemic cyanide poisoning may occur, but is rarely recognized because of the gradual onset of the disability, and symptoms which are consistent with other diagnoses. It has been suggested that excessive thiocyanate in extracellular fluids might explain chronic illness due to cyanide, since the symptoms reported are similar to those found when thiocyanate is used as a drug. Symptoms of chronic disease have been reported in electroplaters and silver polishers after several years of exposure. The most prominent were motor weakness of arms and legs, headaches and thyroid diseases; these findings have also been reported as complications of thiocyanate therapy.

Toxicity

Cyanides

The cyanide ion of soluble cyanide compounds is rapidly absorbed from all routes of entry—inhalation, ingestion and percutaneous. Its toxic properties result from its ability to form complexes with heavy metal ions which inhibit the enzymes required for cellular respiration, primarily cytochrome oxidase. This prevents the uptake of oxygen by the tissues, causing death by asphyxia. The blood retains its oxygen, producing the characteristic cherry-red colour of the victims of acute cyanide poisoning. Cyanide ions combine with the approximately 2% of methaemoglobin normally present—a fact that has helped to develop the treatment of cyanide poisoning.

If the initial dose is not fatal, part of the cyanide dose is exhaled unchanged, while rhodanase, an enzyme widely distributed in the body, converts the remainder to the much less harmful thiocyanate, which remains in extracellular body fluids until it is excreted in the urine. Urinary levels of thiocyanate have been used to measure the extent of the intoxication, but they are non-specific and are elevated in smokers. There may be an effect on thyroid function due to the affinity of thiocyanate ion for iodine.

There are variations in the biological effects of the compounds in this group. At low concentrations, hydrogen cyanide (hydrocyanic acid, prussic acid) and the halogenated cyanide compounds (i.e., cyanogen chloride and bromide) in vapour form produce irritation of the eyes and the respiratory tract (the respiratory effects, including pulmonary oedema, may be delayed). Systemic effects include weakness, headaches, confusion, nausea and vomiting. In mild cases, the blood pressure remains normal despite increase in the pulse rate. The respiratory rate varies with the intensity of exposure—rapid with mild exposure, or slow and gasping with severe exposure.

Nitriles

The toxicity of nitriles varies greatly with their molecular structure, ranging from comparatively non-toxic compounds (e.g., the saturated fatty acid nitriles) to highly toxic materials, such as α-aminonitriles and α-cyanohydrins, which are considered to be as toxic as hydrocyanic acid itself. The halogenated nitriles are highly toxic and irritant, and cause considerable lacrimation. Nitriles such as acrylonitrile, propionitrile and fumaronitrile are toxic and may cause severe and painful dermatitis in exposed skin.

Exposure to toxic nitriles may rapidly cause death by asphyxiation similar to that resulting from exposure to hydrogen cyanide. Individuals who survived exposure to high concentrations of nitriles were said to have no evidence of residual physiological effects after the recovery from the acute episode; this has led to the opinion that the person either succumbs to the nitrile exposure or recovers completely.

Medical surveillance should include pre-employment and periodic examinations focused on skin disorders and the cardiovascular, pulmonary and central nervous systems. A history of fainting spells or convulsive disorders might present an added risk for nitrile workers.

All nitriles should be handled under carefully controlled conditions and only by personnel having a thorough understanding and knowledge of safe handling techniques. Leather should not be used for protective garments, gloves and footwear, since it may be penetrated by acryonitrile and other similar compounds; rubber protective equipment should be washed and inspected frequently to detect swelling and softening. The eyes should be protected, proper respirators worn, and all splashes immediately and thoroughly washed away.

Acrylonitrile. Acrylonitrile is a chemical asphyxiant like hydrogen cyanide. It is also an irritant, affecting the skin and mucous membranes; it may cause severe corneal damage in the eye if not rapidly washed away by copious irrigation. IARC has classified acrylonitrile as a Group 2A carcinogen: the agent is probably carcinogenic to humans. The classification is based on limited evidence of carcinogenicity in humans and sufficient evidence of carcinogenicity in animals.

Acrylonitrile may be absorbed by inhalation or through the skin. In gradual exposures, victims may have significant levels of cyanide in the blood before symptoms appear. They derive from tissue anoxia and include, roughly in order of onset, limb weakness, dyspnoea, burning sensation in the throat, dizziness and impaired judgement, cyanosis and nausea. In the later stages, collapse, irregular breathing or convulsions and cardiac arrest may occur without warning. Some patients appear hysterical or may even be violent; any such deviations from normal behaviour should suggest acryonitrile poisoning.

Repeated or prolonged skin contact with acrylonitrile may produce irritation after hours of no apparent effect. Since acrylonitrile is readily absorbed into leather or clothing, blistering may appear unless the contaminated articles are removed promptly and the underlying skin washed. Rubber clothing should be inspected and washed frequently because it will soften and swell.

An important hazard is fire and explosion. The low flashpoint indicates that sufficient vapour is evolved at normal temperatures to form a flammable mixture with air. Acrylonitrile has the ability to polymerize spontaneously under the action of light or heat, which may lead to explosion even when it is kept in closed containers. It must therefore never be stored uninhibited. The danger of fire and explosion is intensified by the lethal nature of the fumes and vapours evolved, such as ammonia and hydrogen cyanide.

Calcium cyanamide. Calcium cyanamide is encountered chiefly as a dust. When inhaled, it will cause rhinitis, pharyngitis, laryngitis and bronchitis. Perforation of the nasal septum has been reported after long exposure. In the eyes, it may cause conjunctivitis, keratitis and corneal ulceration. It may cause an itchy dermatitis which, after a time, may present slowly-healing ulcerations on the palms of the hand and between the fingers. Skin sensitization may occur.

Its most notable systemic effect is a characteristic vasomotor reaction featuring diffuse erythema of the body, face and arms which may be accompanied by fatigue, nausea, vomiting, diarrhoea, dizziness and sensations of cold. In severe cases, circulatory collapse may ensue. This vasomotor reaction may be triggered or exaggerated by consumption of alcohol.

In addition to adequate exhaust ventilation and personal protective equipment, a waterproof barrier cream may provide added protection for face and exposed skin. Good personal hygiene, including showers and changes of clothing after each shift, is important.

Cyanates. Some of the more important cyanates in industrial use include sodium cyanate, potassium cyanate, ammonium cyanate, lead cyanate and silver cyanate. Cyanates of such elements as barium, boron, cadmium, cobalt, copper, silicon, sulphur and thallium may be prepared by reactions between solutions of a cyanate and the corresponding salt of the metal. They are dangerous because they release hydrogen cyanide when heated to decomposition or when in contact with acid or acid fumes. Personnel handling these materials should be provided with respiratory and skin protection.

Sodium cyanate is used in organic synthesis, the heat treatment of steel, and as an intermediate in the manufacture of pharmaceuticals. It is considered to be moderately toxic, and workers should be protected against dust inhalation and skin contamination.

Cyanate compounds vary in toxicity; therefore, they should be handled under controlled conditions, taking standard precautions to protect personnel against exposure. When heated to decomposition or when placed in contact with acid or acid fumes, the cyanates emit highly toxic fumes. Adequate ventilation must be provided, and air quality at the worksite should be closely monitored. Personnel should not inhale contaminated air nor allow skin contact with these materials. Good personal hygiene is essential for those working in areas where such compounds are handled.

Safety and Health Measures

Scrupulous attention to proper ventilation is necessary. Complete enclosure of the process is recommended, with supplementary exhaust ventilation available. Warning signs should be posted near entrances to areas in which hydrogen cyanide may be released into the air. All shipping and storage containers for hydrogen cyanide or cyanide salts should bear a warning label that included instructions for first aid; they should be in a well-ventilated area and handled with great care.

Those working with cyanide salts should fully understand the hazard. They should be trained to recognize the characteristic odour of hydrogen cyanide and to evacuate the work area immediately if it is detected. Workers entering a contaminated area must be supplied with air-supplied or self-contained respirators with canisters specific for cyanides, goggles if full-face masks are not worn, and impervious protective clothing.

For those who work with acrylonitrile, the usual precautions for carcinogens and for highly flammable liquids are necessary. Steps must be taken to eliminate the risk of ignition from sources such as electrical equipment, static electricity and friction. Because of the toxic, as well as the flammable, nature of the vapour, its escape into the worksite air must be prevented by enclosure of the process and exhaust ventilation. Continuous monitoring of the workplace air is necessary to ensure that these engineering controls remain effective. Personal respiratory protection, preferably of the positive pressure type, and impermeable protective clothing are necessary when there is a possibility of exposure, as from a normal but non-routine operation such as a pump replacement. Leather should not be used for protective clothing since it is readily penetrated by acrylonitrile; rubber and other types of clothing should be inspected and washed frequently.

Acrylonitrile workers should be educated about the chemical’s dangers and trained in rescue, decontamination, life-support procedures and the use of amyl nitrate. Skilled medical attention is required in emergencies; principal requirements are an alarm system and plant personnel trained to support the activities of the health professionals. Supplies of specific antidotes should be available on site and at adjacent hospital centres.

Medical surveillance of workers potentially exposed to cyanides should focus on the respiratory, cardiovascular and central nervous systems; liver, kidney and thyroid function; condition of the skin; and a history of fainting or dizzy spells. Workers with chronic diseases of the kidneys, respiratory tract, skin or thyroid are at greater risk of developing toxic cyanide effects than healthy workers.

Medical control requires training in artificial resuscitation and the use of drugs prescribed for emergency treatment of acute poisoning (e.g., inhalations of amyl nitrite). As soon as possible, contaminated clothing, gloves and footwear should be removed and the skin washed to prevent continuing absorption. First-aid kits with drugs and syringes should be placed appropriately at hand and checked frequently.

Unfortunately, some widely distributed handbooks suggest that methylene blue is useful in cyanide poisoning because, at certain concentrations, it forms methaemoglobin, which, because of its affinity for the cyanide ion, might reduce the toxic effect. The use of methylene blue is not recommended since at other concentrations it has the reverse effect of converting methaemoglobin to haemoglobin, and analyses to verify that its concentration is appropriate are not feasible under the conditions created by the cyanide emergency.

Treatment

Individuals exposed to toxic levels of nitriles should be immediately removed to a safe area and given amyl nitrite by inhalation. Any indications of respiratory problems would indicate oxygen inhalation and, if necessary, cardiopulmonary resuscitation. Contaminated clothing should be removed and the areas of skin copiously washed. Extended flushing of the eyes with neutral solutions or water is advised if there is lacrimation or any evidence of conjunctival irritation. Properly trained physicians, nurses and emergency medical technicians should be summoned to the scene promptly to administer definitive treatment and keep the victim under close observation until recovery is complete.

Cyano compounds tables

Table 104.41 Chemical identification

CHEMICAL

SYNONYMS

UN CODE

CAS-NUMBER

CHEMICAL FORMULA

ACETONITRILE

Ethanenitrile; Ethyl nitrile; Methanecarbonitrile; Methyl cyanide

UN1648

75-05-8

ACRYLONITRILE

Cyanoethylene; Propenenitrile; 2-Propenenitrile; Vinyl cyanide

UN1093

107-13-1

ADIPONITRILE

Adipic acid dinitrile; Adipic acid nitrile; 1,4-Dicyanobutane; Hexanedinitrile; Tetramethylene cyanide

UN2205

111-69-3

ALLYL ISOTHIOCYANATE

Allyl isosulphocyanate; Allyl isothiocyanate; 3-Isothiocyanato-1-propene; 2-Propenyl isothiocyanate

UN1545

57-06-7

AMMONIUM THIOCYANATE

Ammonium rhodanate; Ammonium sulfocyanide; Ammoniumthiocyanate; Thiocyanic acid, ammonium salt

1762-95-4

BENZONITRILE

Benzenenitrile; Benzoic acid nitrile; Cyanobenzene; Phenyl cyanide

UN2224

100-47-0

BUTYRONITRILE

Butanenitrile; Butyric acid nitrile; N-butyronitrile; 1-Cyanopropane; Propyl cyanide

UN2411

109-74-0

CALCIUM CYANAMIDE

Calcium carbimide; Calcium cyanamid; Cyanamid; Cyanamide

UN1403

156-62-7

CALCIUM CYANIDE

Calcium cyanide; Calcyan; Calcyanide; Cyanogas

UN1575

592-01-8

CHLOROACETONITRILE

2-Chloroacetonitrile; Chloromethyl cyanide; Monochloroacetonitrile; Monochloromethyl cyanide

UN2668

107-14-2

o-CHLOROBENZYLIDENE MALONONITRILE

2-Chlorobenzalmalononitrile; 2-Chlorobenzylidene malononitrile; Propanedinitrile, ((2-Chlorophenyl)methylene)

2698-41-1

CYANAMIDE

Carbamonitrile; Carbimide; Cyanoamine; N-cyanoamine; Cyanogenamide; Cyanogen nitride; Hydrogen cyanamide

420-04-2

CYANIDE

Hydrocyanic acid, ion(1-); Isocyanide

UN1935

57-12-5

CYANOGEN

Carbon nitride; Ethanedinitrile; Nitriloacetonitrile; Oxalic acid dinitrile

UN1026

460-19-5

CYANOGEN BROMIDE

Bromine cyanide; Bromocyan; Bromocyanide; Cyanobromide; Cyanogen monobromide

UN1889

506-68-3

CYANOGEN CHLORIDE

Chlorine cyanide; Chlorocyan; Chlorocyanide; Chlorocyanogen

UN1589

506-77-4

ETHYL 2-CYANOURATE

ACE-E 50; ACE-EE; Acrylic acid, adhesive 502; aron alpha d; Black max; ethyl cyanoacrylate; Ethyl alpha-cyanoacrylate; Ethyl 2-cyano-2-propenoate; Super glue

7085-85-0

DIALLYL CYANURATE

 

1081-69-2

DICYANODIAMIDE

Cyanoguanidine; Dicyandiamide

461-58-5

HYDRACRYLONITRILE

2-cyanoethanol; Ethylene cyanohydrin; 3-hydroxypropanenitrile; 3-hydroxypropionitrile; Methanolacetonitrile

109-78-4

2-HYDROXY-2-METHYLPROPIONITRILE

Acetone cyanohydrin; 2-methyllactonitrile

UN1541

75-86-5

HYDROGEN CYANIDE

Carbon hydride nitride; Hydrocyanic-acid

UN1051

UN1613

UN1614

74-90-8

HYDROXYACETONITRILE

Cyanomethanol; Formaldehyde cyanohydrin; Glycolic nitrile; 2-hydroxyacetonitrile; Hydroxymethylnitrile

107-16-4

IODINE CYANIDE

Cyanogen iodide; Jodcyan

506-78-5

ISOBUTYRONITRILE

2-cyanopropane; Dimethylacetonitrile; Isopropyl cyanide; 2-methylpropanenitrile; 2-methylpropionitrile

UN2284

78-82-0

ISOCYANURIC ACID

Cyanuric acid; Tricyanic acid; Trihydroxycyanidine; 2,4,6-trihydroxy-1,3,5-triazine

108-80-5

LACTONITRILE

 

78-97-7

MALONONITRILE

Cyanoacetonitrile; Dicyanomethane; Malonic acid dinitrile; Malonic dinitrile

UN2647

109-77-3

MANDELONITRILE

Acetonitrile, hydroxyphenyl-; Benzaldehyde cyanohydrin; Glycolonitrile, phenyl-; Mandelic acid nitrile

532-28-5

METHYLACRYLONITRILE

2-cyanopropene-1; Isopropene cyanide; Isopropenylnitrile; 2-methylpropenenitrile

UN3079

126-98-7

METHYL-2-CYANOACRYLATE

2-Cyanoacrylic acid, methyl ester; Methyl cyanoacrylate; Methyl alpha-cyanoacrylate;

137-05-3

4-MORPHOLINEACETONITRILE

Acetonitrile, morpholino-; N-cyanomethylmorpholine

5807-02-3

PHENYLACETONITRILE

Benzeneacetonitrile (9CI); Benzyl cyanide; Benzyl nitrile; Benzyl cyanide; Cyanomethyl)benzene; α-Cyanotoluene; o-Cyanotoluene; Phenylacetonitrile, liquid (DOT); 2-Phenylacetonitrile; Phenyl acetyl nitrile; Toluene, α-Cyano-; α-Tolunitrile

UN2470

140-29-4

m-PHTHALODINITRILE

m-dicyanobenzene; 1,3-dicyanobenzene; Isophthalodinitrile; Isophthalonitrile; m-phthalodinitrile; 1,3-benzenedicarbonitrile

626-17-5

PHTHALONITRILE

o-dicyanobenzene; 1,2-dicyanobenzene; Phthalic acid dinitrile; Phthalodinitrile; o-phthalodinitrile

91-15-6

POTASSIUM CYANATE

 

590-28-3

POTASSIUM CYANIDE

Hydrocyanic acid, potassium salt

UN1680

151-50-80

POTASSIUM THIOCYANATE

Potassium isothiocyanate; Potassium rhodanate; Potassium sulfocyanate; Potassium thiocyanide

333-20-0

PROPIONITRILE

Cyanoethane; Ethyl cyanide; Hydrocyanic ether; Propanenitrile; Propionic nitrile

UN2404

107-12-0

SODIUM CYANIDE

Hydrocyanic acid, sodium salt

UN1689

143-33-9

SUCCINONITRILE

Butanedinitrile; Ethylene cyanide; Ethylene dicyanide; Succinic acid dinitrile; Succinodinitrile

110-61-2

TETRAMETHYLSUCCINONITRILE

Tetramethylbutanedinitrile; Tetramethylsuccinic acid dinitrile; Tetramethylsuccinodinitrile; Tetramethylsuccinonitrile

3333-52-6

Table 104.42 Health hazards

Chemical Name

     CAS-Number

ICSC Short-Term Exposure

ICSC Long-Term Exposure

ICSC Routes of Exposure and Symptoms

US NIOSH Target Organs & Routes of Entry

US NIOSH Symptoms

ACETONITRILE

     75-05-8

eyes; skin; resp tract

 

Inhalation: abdominal pain, convulsions, laboured breathing, sore throat, unconsciousness, vomiting, weakness, symptoms may be delayed

Skin: may be absorbed, redness

Eyes: redness, pain

Kidneys; liver; CVS; CNS; lungs; skin; eyes; resp sys

Inh; abs; ing; con

Irrit nose, throat; asphy; nau, vomit; chest pain; weak; stupor, convuls; in animals: liver, kidney damage

ACRYLONITRILE

     107-13-1

eyes; skin; resp tract; liver; CNS

CNS; liver

Inhalation: dizziness, headache, nausea, vomiting, weakness, tremor and uncoordinated movements

Skin: may be absorbed, redness, pain, blisters

Eyes: redness, pain, blurred vision

Ingestion: abdominal pain, headache, nausea, shortness of breath, vomiting, weakness

CVS; liver; kidneys; CNS; skin; brain; lungs; bowels; eyes

Inh; abs; ing; con

Irrit eyes, skin; asphy; head; sneez; nau, vomit; weak, li-head; skin vesic; scaling derm; (carc)

ALLYL ISOTHIOCYANATE

     57-06-7

eyes; skin; resp tract

skin

Inhalation: sore throat, cough, laboured breathing

Skin: redness, pain

Eyes: pain, redness, blurred vision

Ingestion: sore throat, burning sensation, nausea, vomiting

 

 

BENZONITRILE

     100-47-0

eyes; resp tract;

 

Inhalation: headache, laboured breathing, unconsciousness

Eyes: redness, pain

Ingestion: nausea, vomiting

 

 

CALCIUM CYANIDE

     592-01-8

eyes; skin; resp tract; lungs; CNS; blood; heart

skin; reproduction

Inhalation: burning sensation, cough, dizziness, headache, red colouration of the skin, laboured breathing, nausea, shortness of breath, unconsciousness, vomiting, convulsions, coma, death

Skin: may be absorbed, skin burns, pain, itching, papules

Eyes: pain, blurred vision, possible permanent loss of vision, severe deep burns

Ingestion: confusion, burning sensation in the mouth, numbness or tightness in throat, salivation, convulsions followed by paralysis

 

 

CHLOROACETONITRILE

     107-14-2

eyes; skin; resp tract

 

Inhalation: cough, headache, laboured breathing, sore throat, unconsciousness

Skin: may be absorbed, redness

Eyes: redness

Ingestion: burning sensation

 

 

o-CHLOROBENZYLIDENE MALONONITRILE

     2698-41-1

 

 

 

Resp sys; skin; eyes

Inh; abs; ing; con

Pain, burn eyes, lac, conj; eryt eyelids, blepharospasm; irrit throat, cough, chest tight; head; eryt, vesic skin

CYANAMIDE

     420-04-2

eyes; skin; resp tract

skin; reproduction

Inhalation: cough, shortness of breath

Skin: may be absorbed, redness

Eyes: redness, pain

Ingestion: abdominal pain

Eyes; skin; resp sys; CNS

Inh; abs; ing; con

Irrit eyes, skin, resp sys; eye, skin burns; miosis, salv, lac, twitch; Antabuse-like effects

CYANOGEN BROMIDE

     506-68-3

eyes; skin; resp tract; lungs

lungs

Inhalation: abdominal pain, burning sensation, confusion, convulsions, dizziness, headache, laboured breathing, shortness of breath, unconsciousness, vomiting, asphyxia, anxiety, irregular heartbeat

Skin: may be absorbed, redness, pain, blisters

Eyes: redness, pain, severe deep burns, tear drawing

Ingestion: abdominal cramps, burning sensation

 

 

CYANOGEN CHLORIDE

     506-77-4

eyes; skin; resp tract; lungs; skin

 

Inhalation: confusion, drowsiness, nausea, sore throat, irritation, unconsciousness, vomiting, symptoms may be delayed

Skin: redness, pain, the liquid may be absorbed, on contact with liquid: frostbite

Eyes: on contact with liquid: frostbite, redness, pain

Eyes; skin; resp sys; CNS; CVS

Inh; abs (liq); con (liq)

Irrit eyes, upper resp sys; cough, delayed pulm edema; weak, head, gidd, dizz, conf, nau, vomit; irreg heartbeat; irrit skin (liq)

DICYANODIAMIDE

     461-58-5

 

 

Inhalation: abdominal pain, dizziness, nausea, shortness of breath

Skin: redness, skin burns

Eyes: loss of vision, severe deep burns

 

 

HYDROGEN CYANIDE

     74-90-8

 

 

Inhalation: numbness or tightness in throat and stiffness in lower jaw, confusion, dizziness, headache, laboured breathing, nausea, unconsciousness, vomiting, weakness

Skin: may be absorbed

Eyes: vapour will be absorbed, see inhalation

Ingestion: burning sensation

CVS; CNS; thyroid; blood

Inh; abs; ing; con

Asphy; weak, head, conf; nau, vomit; incr rate and depth of respiration or respiration slow and gasping; thyroid, blood changes

2-HYDROXY-2-METHYLPROPIONITRILE

     75-86-5

eyes; skin; resp tract; intracellular oxygen metabolism

 

Inhalation: confusion, dizziness, headache, laboured breathing, nausea, unconsciousness, vomiting, weakness

Skin: may be absorbed, redness

Eyes: redness

Ingestion: confusion, dizziness, laboured breathing, unconsciousness, vomiting

Eyes; skin; resp sys; CNS; CVS; liver; kidneys; GI tract

Inh; abs; ing; con

Irrit eyes, skin, resp sys; dizz, weak, head, conf, convuls; liver, kidney inj; pulm edema, asphy

IODINE CYANIDE

     506-78-5

eyes; skin; resp tract; lungs; intracellular oxygen metabolism

 

Inhalation: confusion, cough, dizziness, headache, laboured breathing, nausea, unconsciousness, vomiting, weakness

Skin: may be absorbed, redness

Eyes: redness

Ingestion: confusion, dizziness, laboured breathing, unconsciousness, vomiting

 

 

POTASSIUM CYANIDE

     151-50-8

eyes; skin; resp tract

thyroid gland

Inhalation: confusion, convulsions, dizziness, headache, laboured breathing, nausea, shortness of breath, unconsciousness, vomiting, weakness, asphyxiant, anxiety, irregular heart beat, tightness in the chest

Skin: may be absorbed, redness

Eyes: vapour will be absorbed, redness

Ingestion: salivation, abdominal cramps, burning sensation

CVS; CNS; eyes; skin; thyroid; blood

Inh; abs; ing; con

Irrit eyes, skin; asphy; weak, head, conf; nau, vomit; incr resp rate; slow gasping respiration; thyroid, blood changes

PROPIONITRILE

     107-12-0

eyes; skin; resp tract; cellular metabolism; CNS

skin; birth defects

Inhalation: confusion, asphyxia dizziness, dullness, headache, nausea, vomiting

Skin: may be absorbed, dry skin, pain

Eyes: severe deep burns

Ingestion: unconsciousness

Eyes; skin; resp sys; CNS; CNS; liver; kidneys

Inh; abs; ing; con

Irrit eyes, skin, resp sys; nau, vomit; chest pain; weak; stupor; convuls; in animals: liver, kidney damage

SODIUM CYANIDE

     143-33-9

 

 

Inhalation: burning sensation, headache, shortness of breath, sore throat, unconsciousness, weakness, seizure

Skin: may be absorbed, skin burns, burning sensation, pain

Eyes: pain, severe deep burns

Ingestion: abdominal cramps, diarrhoea, vomiting

CVS; CNS; eyes; skin; thyroid; blood

Inh; abs; ing; con

Irrit eyes, skin; asphy; weak, head, conf; nau, vomit; incr resp rate; slow gasping respiration; thyroid, blood changes

TETRAMETHYLSUCCINONITRILE

     3333-52-6

CNS

 

Inhalation: convulsions, dizziness, headache, nausea, unconsciousness, vomiting

Skin: may be absorbed

CNS; liver; kidneys; GI tract

Inh; abs; ing; con

Head, nau; convuls, coma; liver, kidney, GI effects

Table 104.43 Physical & chemical hazards

For UN Class: 1.5 = very insensitive substances which have a mass explosion hazard; 2.1 = flammable gas; 2.3 = toxic gas; 3 = flammable liquid; 4.1 = flammable solid; 4.2 = substance liable to spontaneous combustion; 4.3 = substance which in contact with water emits flammable gases; 5.1 = oxidizing substance; 6.1 = toxic; 7 = radioactive; 8 = corrosive substance

Chemical Name

CAS-Number

Physical

Chemical

UN Class or Division /  Subsidiary Risks

ACETONITRILE

75-05-8

The vapour is heavier than air and may travel along the ground; distant ignition possible •The vapour mixes well with air, explosive mixtures are easily formed •As a result of flow, agitation, etc, electrostatic charges can be generated

On combustion, forms toxic fumes of hydrogen cyanide and nitrogen oxides •The substance decomposes on contact with acids, water and steam producing toxic fumes and flammable vapour •On contact with strong oxidants causes fire and explosion hazard •Attacks some forms of plastic, rubber and coating

3

ACRYLONITRILE

107-13-1

The vapour is heavier than air and may travel along the ground; distant ignition possible

The substance polymerizes due to heating, under the influence of light, bases and peroxides •Heating may cause violent combustion or explosion •The substance decomposes on heating producing toxic fumes including nitrogen oxides, hydrogen cyanide •Reacts violently with strong oxidants and strong bases causing fire and explosion hazard

3/ 6.1

ADIPONITRILE

111-69-3

 

 

6.1

ALLYL ISOTHIOCYANATE

57-06-7

 

The substance decomposes on heating producing cyanhydric acid vapours •Reacts with strong oxidants

6.1

BENZONITRILE

100-47-0

 

The substance decomposes on heating or on burning on contact with acids, producing very toxic fumes (hydrogen cyanide, nitrous oxides) •Reacts violently with strong acids producing highly toxic hydrogen cyanide •Attacks some plastics

6.1

BUTYRONITRILE

109-74-0

 

 

3/ 6.1

CALCIUM CYANAMIDE

156-62-7

 

 

4.3

CALCIUM CYANIDE

592-01-8

 

The substance decomposes on heating above 350°C producing toxic fumes (hydrogen cyanide, nitrous oxides) •Reacts violently with water, moist air, carbon dioxide, acids, acidic salts producing highly toxic and flammable hydrogen cyanide •Reacts violently when heated with nitrites, nitrates, chlorates and perchlorates

6.1

CHLOROACETONITRILE

107-14-2

The vapour is heavier than air

On contact with hot surfaces or flames this substance decomposes forming toxic and flammable vapours •Reacts with strong oxidants, reducing agents, acids, bases, steam, producing highly toxic and flammable fumes

6.1/ 3

CYANAMIDE

420-04-2

 

The substance may polymerize at temperatures above 122°C •Substance decomposes on warming above 49°C, on contact with acids, bases and moisture producing toxic fumes including nitrogen oxides and cyanides •Reacts with acids, strong oxidants, strong reducing agents and water causing explosion and toxic hazard •Attacks various metals

 

CYANOGEN

460-19-5

 

 

2.3/ 2.1

CYANOGEN BROMIDE

506-68-3

The vapour is heavier than air

The substance decomposes on heating or on contact with acids, producing highly toxic and flammable hydrogen cyanide and corrosive hydrogen bromide •Reacts slowly with water and water vapour, forming hydrogen bromide and hydrogen cyanide

 

CYANOGEN CHLORIDE

506-77-4

The gas is heavier than air

The substance may polymerize violently if contaminated with hydrogen chloride or ammonium chloride •The substance decomposes on heating producing toxic and corrosive fumes (hydrogen cyanide, hydrochloric acid, nitrogen oxides) •Reacts slowly with water or water vapour to form hydrogen chloride •Attacks copper and brass

 

DIALLYL CYANURATE

1081-69-2

 

 

2.3/ 8

DICYANODIAMIDE

461-58-5

 

The substance decomposes on heating producing toxic gases •Reacts violently with strong oxidants, causing fire and explosion hazard •Reacts with acids to form toxic gases

2.3/ 2.1

2-HYDROXY-2-METHYLPROPIONITRILE

75-86-5

 

The substance decomposes on heating and on burning producing hydrogen cyanide •Reacts with strong oxidants, strong bases and strong acids •Reacts violently with alkali metals causing fire and explosion hazard

6.1

HYDROGEN CYANIDE

74-90-8

The gas mixes well with air, explosive mixtures are easily formed

The substance may polymerize due to heating above 184°C or under the influence of bases, 2-5% water or if not chemically stabilized with fire or explosion hazard •On combustion, forms carbon monoxide and nitrogen oxides •The substance decomposes on contact with bases, causing fire and explosion hazard •The substance is a weak acid •The solution in water is a weak acid •Reacts violently with excess of strong acid causing fire and explosion hazard •Attacks many metals in presence of water

6.1/ 3

IODINE CYANIDE

506-78-5

 

The substance may polymerize due to heating or under the influence of acids, producing very toxic gas (hydrogen cyanide) •The substance decomposes slowly on contact with water or humidity producing very toxic gas (hydrogen cyanide) •Reacts violently with strong oxidants •May decompose on exposure to light

 

ISOBUTYRONITRILE

78-82-0

 

 

3/ 6.1

ISOCYANURIC ACID

108-80-5

 

 

6.1/ 8

MALONONITRILE

109-77-3

 

 

6.1

METHYLACRYLONITRILE

126-98-7

 

 

3/ 6.1

PHENYLACETONITRILE

140-29-4

 

 

6.1

SODIUM CYANIDE

143-33-9

 

The substance decomposes on burning producing toxic fumes (nitrogen oxides) •The substance is a strong base, it reacts violently with acid and is corrosive to metals (aluminum and zinc) •Reacts violently with strong oxidants such as nitrates and chlorates causing fire and explosion hazard •The substance decomposes in the presence of air, moisture or carbon dioxide producing highly toxic and flammable gas (hydrogen cyanide) •Contact with acids and acids salts causes immediate formation of highly toxic and flammable hydrogen cyanide gas

6.1

PROPIONITRILE

107-12-0

The vapour mixes well with air, explosive mixtures are easily formed

The substance decomposes on heating producing toxic fumes including nitrogen oxides and hydrogen cyanide •Reacts violently with strong oxidants causing fire and explosion hazard •Reacts with acids, steam, warm water giving off toxic and flammable hydrogen cyanide

3/ 6.1

POTASSIUM CYANIDE

151-50-8

 

The substance decomposes on contact with water, humidity, alkali carbonates, and acids, producing very toxic hydrogen cyanide gas •The solution in water is a strong base, it reacts violently with acid and is corrosive

6.1

TETRAMETHYLSUCCINONITRILE

3333-52-6

 

The substance decomposes on heating producing toxic fumes (hydrogen cyanide, nitrogen oxides) •Reacts with strong oxidants causing fire and explosion hazard

 

Table 104.44 Physical & chemical properties

Chemical Name

CAS-Number

Colour/Form

Boiling Point (°C)

Melting Point (°C)

Molecular Weight

Solubility in Water

Relative Density (water=1)

Relative Vapour Density (air=1)

Vapour Pressure/ (Kpa)

Inflam. Limits

Flash Point (°C)

Auto Ignition Point (°C)

ACETONITRILE

75-05-8

colourless, limpid liquid

81.6

-45

41.05

misc

0.7857

1.42

87mmHg  @24C

3.0 ll 16.0 ul

128 cc

524

ACRYLONITRILE

107-13-1

clear, colourless liquid

77.3

-83.5

53.06

7g/100ml

0.8060

1.13  @25°C

11.0

3 ll 17 ul

-1 cc

481

ADIPONITRILE

111-69-3

needles from ether; colourless liquid

295

1

108.1

sl sol

0.9676

3.73

6.8x 10-4 mmHg  @25°C

1.0  @200°C

 

550

ALLYL ISOTHIOCYANATE

57-06-7

colourless to pale yellow, oily liquid

152

-80

99.15

sl sol

1.0126

3.41

1.3 Pa  @38.3°C

 

461

 

AMMONIUM THIOCYANATE

1762-95-4

colourless, monoclinic crystals

 

149.6

76.12

128g/100ml  @0°C; v sol in hot water

1.3057g/ml

 

 

 

 

 

BENZONITRILE

100-47-0

liquid; transparent colourless oil

191

-13

103.1

sl sol

1.010  @15°C/15°C

3.6

0.1

 

75 cc

550

BUTYRONITRILE

109-74-0

colourless liquid

117.5

-112

69.10

sl sol

0.7936

2.4

19.5mmHg  @25°C

1.65 ll ? ul

 

501

CALCIUM CYANAMIDE

156-62-7

pure calcium cyanamide occurs as glistening, hexagonal crystals belonging to the rhombohedral system; colourless crystals or powder

 

1340

80.11

insol

2.29

 

 

 

 

 

CALCIUM CYANIDE

592-01-8

white powder; rhombohedric crystals or powder

 

>350 decomp

92.12

sol

1.853 (solid)

 

 

 

 

 

CHLOROACETONITRILE

107-14-2

colourless liquid

126

 

75.50

insol

1.1930

2.61

1.15

1.0 ll ? ul

56

 

o-CHLOROBENZYLIDENEMALONONITRILE

2698-41-1

white crystalline solid

310-315

93-95

188.62

insol

 

 

3.4x 10-5 mmHg

 

 

 

CYANAMIDE

420-04-2

orthorhombic, elongated, six-sided tablets from dimethyl phthalate; crystallizes from a variety of solvents as somewhat unstable, colourless, orthorhombic, deliquescent crystals.

83  @0.5mmHg

45-46

42.04

v sol

1.282

1.45

 

 

141

 

METHYL 2-CYANOACRYLATE

137-05-3

colourless, viscous liquid

47-48  @1.8mmHg

 

111.10

2.95x 10+5 mg/l

1.1012

 

0.179mmHg  @25°C.

 

 

 

CYANOGEN

460-19-5

colourless gas

-21.1

-27.9

52.0

sol

0.9537  @-21.17°C/4°C

1.8

760mmHg  @-21.0°C

6.6 ll 32 ul

 

 

CYANOGEN BROMIDE

506-68-3

cubes; colourless or white needle-like crystals

61.5

52

105.0

sol

2.015

3.62

12.3

 

 

 

CYANOGEN CHLORIDE

506-77-4

colourless liquid or gas

13

-6.5

61.5

sol

1.186

2.16

1987  @21.1°C

 

 

 

DICYANODIAMIDE

461-58-5

monoclinic prismatic crystals from water or alcohol; pure white crystals

 

211

84.08

sol

1.400  @25°C/4°C

 

 

 

 

 

HYDRACRYLONITRILE

109-78-4

water-white liquid; straw-coloured liquid

230

-46

71.08

misc

1.041

2.45

0.08mmHg  @25°C

 

1294 oc

505

2-HYDROXY-2-METHYLPROPIONITRILE

75-86-5

colourless liquid

95

-19

85.10

v sol

0.9267  @25°C/4

2.93

106 Pa

2.2 ll 12.0. ul

63-74 cc

688

HYDROGEN CYANIDE

74-90-8

colourless gas or liquid; water-white liquid below 26.5°C; colourless to bluish white liquid

26

-13.4

27.0

misc

0.6876

0.94

81.8

5.6 ll 40.0 ul

-1778 cc

538

HYDROXYACETONITRILE

107-16-4

colourless, water-white, oily liquid

183 decomp

<-72

57.06

v sol

1.10

1.96

1mmHg  @63°C

 

 

 

IODINE CYANIDE

506-78-5

crystals

>45 sub

146.5

152.92

reacts

2.84  @18°C

5.3

0.13  @25.2°C

 

 

 

ISOBUTYRONITRILE

78-82-0

colourless liquid

103.8

-71.5

69.1

sl sol

0.7608  @30°C/4°C

2.38

32.7mmHg  @25°C

 

8 cc

482

ISOCYANURIC ACID

108-80-5

anhydrous crystals from concn hydrochloric acid or sulfuric acid; crystalline powder

 

360

129.08

1g/200ml

2.500

 

 

 

 

 

LACTONITRILE

78-97-7

yellow liquid; straw-colored liq

102 ° C  @ 30 mm Hg

-40

71.1

sol

0.9877  @ 20 ° C/4 ° C

 

17 mm Hg at 90 ° C

 

 

 

MALONONITRILE

109-77-3

white powder; colourless solid

218.5

32

66.06

sol

1.1910

 

11mmHg  @99°C

 

 

 

MANDELONITRILE

532-28-5

oily, yellow liquid

170

-10

 

 

1.1165

 

 

 

 

 

METHYLACRYLONITRILE

126-98-7

colourless liquid

90.3

-35.8

67.10

insol

0.8001

2.31

71.2mmHg  @25°C

2 ll 6.8 ul

13 oc

 

PHENYLACETONITRILE

140-29-4

colourless oily liquid

233.5

-23.8

117.14

insol

1.0214  @15°C/15°C

 

1mmHg  @60.0°C

 

 

 

m-PHTHALODINITRILE

626-17-5

 

265 sub

162

128.13

sl sol

0.992  @40°C

 

 

 

 

 

PHTHALONITRILE

91-15-6

needles from water or petroleum ether; buff-coloured crystals

 

141

128.1

sl sol

 

 

 

 

 

 

POTASSIUM CYANATE

590-28-3

white crystalline powder; colourless, tetragonal/crystal

 

315

81.12

75 G/100 CC  @ 25 ° C

2.056  @ 20 ° C

 

 

 

 

 

SODIUM CYANIDE

 143-33-9

colourless cubes; white solid in form of granules, flakes, or eggs

1496

563.7

49.02

48g/100ml  @10°C

1.6

 

 

 

 

 

POTASSIUM THIOCYANATE

333-20-0

 

 

 

97.18

 

 

 

 

 

 

 

PROPIONITRILE

107-12-0

colourless liquid

97.1

-92

55.08

v sol

0.7818

1.9

5.2

3.1 ll ? ul

6 cc

 

POTASSIUM CYANIDE

151-50-8

white, granular powder or fused pieces; white amorphous lumps or crystalline mass; colourless cubes

 

634

65.11

decomposes

1.553

 

 

 

 

 

SUCCINONITRILE

110-61-2

 

266

54.5

80.09

v sol

0.9867  @60°C

 

 

 

 

 

TETRAMETHYLSUCCINONITRILE

3333-52-6

solid

1.070

170 sub

136.19

insol

1.070 @25°C

4.7

 

 

 

 

EPOXY COMPOUNDS

Janet L. Collins

Epoxy compounds are those that consist of oxirane rings (either one or more). An oxirane ring is essentially one oxygen atom linked to two carbon atoms. These will react with amino, hydroxyl and carboxyl groups as well as inorganic acids to yield relatively stable compounds.

Uses

Epoxy compounds have found wide industrial use as chemical intermediates in the manufacture of solvents, plasticizers, cements, adhesives and synthetic resins. They are commonly used in various industries as protective coatings for metal and wood. The alpha-epoxy compounds, with the epoxy group (C-O-C) in the 1,2 position, are the most reactive of the epoxy compounds and are primarily used in industrial applications. The epoxy resins, when converted by curing agents, yield highly versatile, thermosetting materials used in a variety of applications including surface coatings, electronics (potting compounds), laminating, and bonding together of a wide variety of materials.

Butylene oxides (1,2-epoxybutane and 2,3-epoxybutane) are used for the production of butylene glycols and their derivatives, as well as for the manufacture of surface active agents. Epichlorohydrin is a chemical intermediate, insecticide, fumigant and solvent for paints, varnishes, nail enamels and lacquers. It is also used in polymer coating material in the water supply system and in raw material for high wet-strength resins for the paper industry. Glycidol (or 2,3-epoxypropanol) is a stabilizer for natural oils and vinyl polymers, a dye-leveling agent and an emulsifier.

1,2,3,4-Diepoxybutane. Short-term (4-hour) inhalation studies with rats have caused watering of the eyes, clouding of the cornea, laboured breathing and lung congestion. Experiments in other animal species have demonstrated that diepoxybutane, like many of the other epoxy compounds, can cause eye irritation, burns and blisters of the skin, and irritation of the pulmonary system. In humans, accidental “minor” exposure caused swelling of the eyelids, upper respiratory tract irritation, and painful eye irritation 6 hours after exposure.

Skin application of D,L- and the meso- forms of 1,2,3,4-diepoxybutane have produced skin tumours, including squamous-cell skin carcinomas, in mice. The D- and L- isomers have produced local sarcomas in mice and rats by subcutaneous and intraperitoneal injection respectively.

Several epoxy compounds are employed in the health care and food industries. Ethylene oxide is used to sterilize surgical instruments and hospital equipment, fabric, paper products, sheets and grooming instruments. It is also a fumigant for foodstuffs and textiles, a rocket propellant, and a growth accelerator for tobacco leaves. Ethylene oxide is used as an intermediary in the production of ethylene glycol, polyethylene terephthalate polyester film and fibre, and other organic compounds. Guaiacol is a local anaesthetic agent, antioxidant, stimulant expectorant, and a chemical intermediate for other expectorants. It is used as a flavouring agent for non-alcoholic beverages and food. Propylene oxide, or 1,2-epoxypropane, has been used as a fumigant for the sterilization of packaged food products and other materials. It is a highly reactive intermediary in the production of polyether polyols, which, in turn, are used to make polyurethane foams. The chemical is also used in the production of propylene glycol and its derivatives.

Vinylcyclohexene dioxide is used as a reactive diluent for other diepoxides and for resins derived from epichlorohydrin and bisphenol A. Its use as a monomer for the preparation of polyglycols containing free epoxide groups or for polymerization to a tridimensional resin has been investigated.

Furfural is used in screening tests for urine, solvent refining of petroleum oils, and manufacturing of varnishes. It is a synthetic flavouring agent, a solvent for nitrated cotton, a constituent of rubber cements, and a wetting agent in the manufacture of abrasive wheels and brake linings. Furfuryl alcohol is also a flavouring agent, as well as a liquid propellant and solvent for dyes and resins. It is used in corrosive-resistant sealants and cements, and foundry cores. Tetrahydrofuran is used in histology, chemical synthesis, and in the fabrication of articles for packaging, transporting and storing foods. It is a solvent for fat oils and unvulcanized rubber. Diepoxybutane has been used to prevent spoilage of foodstuffs, as a polymer curing agent, and for cross-linking textile fibres.

Hazards

There are numerous epoxy compounds in use today. Specific commonly used ones are individually discussed below. There are, however, certain characteristic hazards shared by the group. In general, the toxicity of a resin system is a complicated interplay between the individual toxicities of its various component ingredients. The compounds are known sensitizers of the skin, and those with the highest sensitization potential are those of lower relative molecular weight. Low molecular weight is also generally associated with increased volatility. Delayed and immediate allergic epoxy dermatitis and irritant epoxy dermatitis have all been reported. The dermatitis usually first develops on the hands between the digits, and can range in severity from erythema to marked bullous eruption. Other target organs reportedly adversely affected by epoxy compound exposure include the central nervous sysstem (CNS), the lungs, the kidneys, the reproductive organs, the blood and the eyes. There is also evidence that certain epoxy compounds have mutagenic potential. In one study, 39 of the 51 epoxy compounds tested induced a positive response in the Ames/Salmonella assay. Other epoxides have been shown to induce sister-chromatid exchanges in human lymphocytes. Animal studies looking at associated epoxide exposures and cancers are ongoing.

It should be noted that certain of the curing agents, hardeners and other processing agents used in the production of the final compounds have associated toxicities as well. One in particular, 4,4-methylenedianiline (MDA), is associated with hepatotoxicity and with damage to the retina of the eye, and has been known to be an animal carcinogen. Another is trimellitic anhydride (TMA). Both are discussed elsewhere in this chapter.

One epoxy compound, epichlorohydrin, has been reported to cause a significant increase of pulmonary cancer in exposed workers. This chemical is classified as a Group 2A chemical, probably carcinogenic to humans, by the International Agency for Research on Cancer (IARC). One long-term epidemiological study of workers exposed to epichlorohydrin at two US facilities of the Shell Chemical Company was reported to demonstrate a statistically significant (p < .05) increase in deaths due to respiratory cancer. Like the other epoxy compounds, epichlorohydrin is irritating to the eyes, skin and respiratory tract of exposed individuals. Human and animal evidence has demonstrated that epichlorohydrin may induce severe skin damage and systemic poisoning following extended dermal contact. Exposures to epichlorohydrin at 40 ppm for 1 h have been reported to cause eye and throat irritation lasting 48 h, and at 20 ppm caused temporary burning of the eyes and nasal passages. Epichlorohydrin-induced sterility in animals has been reported, as have liver and kidney damage.

Subcutaneous injection of epichlorohydrin has produced tumours in mice at the injection site but has not produced tumours in mice by skin-painting assay. Inhalation studies with rats have shown a statistically significant increase in nasal cancer. Epichlorohydrin has induced mutations (base-pair substitution) in microbial species. Increases in the chromosomal aberrations found in the white blood cells of workers exposed to epichlorohydrin have been reported. As of 1996 the American Conference of Governmental Industrial Hygienists (ACGIH) established a TLV of 0.5 ppm, and it is considered an A3 carcinogen (animal carcinogen).

1,2-Epoxybutane and isomers (butylene oxides). These compounds are less volatile and less toxic than propylene oxide. The major documented adverse effects in humans have been irritation of the eyes, nasal passages and skin. In animals, however, respiratory problems, pulmonary haemorrhage, nephrosis and nasal-cavity lesions were noted in acute exposures to very high concentrations of 1,2-epoxybutane. No consistent teratogenic effects have been demonstrated in animals. IARC has determined that there is limited evidence for the carcinogenicity of 1,2-epoxybutane in experimental animals.

When 1,2-epoxypropane (propylene oxide) is compared to ethylene oxide, another epoxy compound commonly used in sterilization of surgical/hospital supplies, propylene oxide is considered to be far less toxic to humans. Exposure to this chemical has been associated with irritant effects on the eyes and skin, respiratory tract irritation, and CNS depression, ataxia, stupor and coma (the latter effects have thus far been significantly demonstrated only in animals). In addition, 1,2-epoxypropane has been shown to act as a direct alkylating agent in various tissues, and thus the possibility of carcinogenic potential is raised. Several animal studies have strongly implicated the compound’s carcinogenicity as well. The major adverse effects which have thus far been definitively demonstrated in humans involve burning or blistering of the skin when prolonged contact with non-volatilized chemical has occurred. This has been shown to occur even with low concentrations of propylene oxide. Corneal burns attributed to the chemical have also been reported.

Vinylcyclohexene dioxide. The irritation produced by the pure compound after application on rabbit skin resembles the oedema and reddening of first-degree burns. Skin application of vinylcyclohexene dioxide in mice produces a carcinogenic effect (squamous-cell carcinomas or sarcomas); intraperitoneal administration in rats caused analogous effects (sarcomas of the peritoneal cavity). The substance has proved to be mutagenic in Salmonella typhimurium TA 100; it also produced a significant increase in mutations in Chinese hamster cells. It should be treated as a substance with carcinogenic potential, and appropriate engineering and hygienic controls should be in place.

In industrial experience vinylcyclohexene dioxide has been shown to have skin irritant properties and to cause dermatitis: a severe vesiculation of both feet has been observed in a worker who had put on shoes contaminated by the compound. Eye injury is also a definite hazard. Studies on chronic effects are not available.

2,3-Epoxypropanol. Based on experimental studies with mice and rats, glycidol was found to cause eye and lung irritation. The LC50 for a 4-h exposure of mice was found to be 450 ppm, and for an 8-h exposure of rats it was 580 ppm. However, at concentrations of 400 ppm of glycidol, rats exposed for 7 h a day for 50 days showed no evidence of systemic toxicity. After the first few exposures, slight eye irritation and respiratory distress were noted.

Ethylene oxide (ETO) is a highly dangerous and toxic chemical. It reacts exothermically and is potentially explosive when heated or placed in contact with alkali metal hydroxides or highly active catalytic surfaces. Therefore when in use in industrial areas it is best if it is tightly controlled and confined to closed or automated processes. The liquid form of ethylene oxide is relatively stable. The vapour form, in concentrations as low as 3%, is very flammable and potentially explosive in the presence of heat or flame.

A wealth of information exists regarding the possible human health effects of this compound. Ethylene oxide is a respiratory, skin and eye irritant. At high concentrations it is also associated with central nervous system depression. Some individuals exposed to high concentrations of the chemical have described a strange taste in their mouths after the exposure. Delayed effects of high acute exposures include headache, nausea, vomiting, shortness of breath, cyanosis and pulmonary oedema. Additional symptoms that have been reported after acute exposures include drowsiness, fatigue, weakness and incoordination. Ethylene oxide solution can cause a characteristic burn on exposed skin anywhere from 1 to 5 h post-exposure. This burn often progresses from vesicles to coalescent blebs and desquamation. The skin wounds will often spontaneously resolve, with increased pigmentation resulting at the burn site.

Chronic or low-to-moderate prolonged exposures to ethylene oxide are associated with mutagenic activity. It is known to act as an alkylating agent in biological systems, binding to the genetic material and other electron-donating sites, such as haemoglobin, and causing mutations and other functional damage. ETO is associated with chromosomal damage. The ability of damaged DNA to repair itself was adversely affected by low but prolonged exposure to ETO in one study of exposed human subjects. Some studies have linked ETO exposure with increased absolute lymphocyte counts in exposed workers; however, recent studies are not supportive of this association.

The carcinogenic potential of ethylene oxide has been demonstrated in several animal models. IARC has classified ethylene oxide as a Group 1 known human carcinogen. Leukaemia, peritoneal mesothelioma and certain brain tumours have been associated with long-term inhalation of ETO in rats and monkeys. Studies of exposure in mice have linked inhalation exposures to lung cancers and lymphomas. Both the US National Institute for Occupational Safety and Health (NIOSH) and the US Occupational Safety and Health Administration (OSHA) have concluded that ethylene oxide is a human carcinogen. The former conducted a large-scale study of over 18,000 ETO-exposed workers over a 16-year period and determined that the exposed individuals had greater than expected rates of blood and lymph cancers. Subsequent studies have found that no increased rates of these cancers have been associated with exposed workers. One of the major problems with these studies, and a possible reason for their contradictory nature, has been the inability to accurately quantify levels of exposure. For example, much of the available research on human carcinogenic effects of ETO has been done using exposed hospital sterilizer operators. Individuals who worked in these jobs prior to the 1970s most likely experienced higher exposures to ETO gas due to the technology and lack of local control measures in place at that time. (Safeguards in the use of ETO in health care settings are discussed in the Health care facilities and services chapter in this volume.)

Ethylene oxide has also been associated with adverse reproductive effects in both animals and humans. Dominant lethal mutations in reproductive cells have resulted in higher embryonic death rates in the offspring of ETO-exposed male and female mice and rats. Some studies have linked ethylene oxide exposure to increased rates of miscarriage in humans.

Adverse neurological and neuropsychiatric effects resulting from ethylene oxide exposure have been reported in animals and humans. Rats, rabbits and monkeys exposed to 357 ppm of ETO over a period of 48 to 85 days developed impairment of sensory and motor function, and muscle wasting and weakness of the hind limbs. One study found that human workers exposed to ETO demonstrated impaired vibratory sense and hypoactive deep tendon reflexes. The evidence of impaired neuropsychiatric functioning in humans exposed to low but prolonged levels of ethylene oxide is uncertain. Some studies and an increasing body of anecdotal evidence suggest that ETO is linked to CNS dysfunction and cognitive impairment—for example, clouded thinking, memory problems and slowed reaction times on certain types of tests.

One study of individuals exposed to ethylene oxide in a hospital setting suggested an association between that exposure and the development of ocular cataracts.

An additional hazard associated with exposure to ethylene oxide is the potential for the formation of ethylene chlorohydrin (2-chloroethanol), which may be formed in the presence of moisture and chloride ions. Ethylene chlorohydrin is a severe systemic poison, and exposure to the vapour has caused human fatalities.

Tetrahydrofuran (THF) forms explosive peroxides when exposed to air. Explosions may also occur when the compound is brought into contact with lithium-aluminium alloys. Its vapour and peroxides may cause irritation of the mucous membranes and skin, and it is a strong narcotic.

While limited data are available on the industrial experiences with THF, it is interesting to note that investigators that were engaged in animal experiments with this compound complained of severe occipital headaches and dullness after each experiment. Animals subjected to lethal doses of tetrahydrofuran fell into narcosis quickly, which was accompanied by muscular hypotonia and disappearance of corneal reflexes, and followed by coma and death. Single toxic doses caused giddiness, irritation of mucous membranes with copious flow of saliva and mucous, vomiting, a marked fall in blood pressure, and muscular relaxation, followed by prolonged sleep. Generally, the animals recovered from these doses and showed no evidence of biological changes. After repeated exposures, the effects included irritation of the mucous membranes, which may be followed by renal and hepatic alteration. Alcoholic beverages enhance the toxic effect.

Safety and Health Measures

The primary purposes of control measures for the epoxy compounds should be to reduce the potential for inhalation and skin contact. Wherever feasible, control at the source of contamination should be implemented with enclosure of the operation and/or the application of local exhaust ventilation. Where such engineering controls are not sufficient to reduce airborne concentrations to acceptable levels, respirators may be necessary to prevent pulmonary irritation and sensitization in exposed workers. Preferred respirators include gas masks with organic vapour cannisters and high-efficiency particulate filters or supplied-air respirators. All body surfaces should be protected against contact with epoxy compounds through the use of gloves, aprons, face shields, goggles and other protective equipment and clothing as necessary. Contaminated clothing should be removed as soon as possible and the affected areas of the skin washed with soap and water.

Safety showers, eyewash fountains and fire extinguishers should be located in areas where appreciable amounts of epoxy compounds are in use. Handwashing facilities, soap and water should be made available to involved employees.

The potential fire hazards associated with epoxy compounds suggest that no flames or other sources of ignition, such as smoking, be permitted in areas where the compounds are stored or handled.

Affected workers should, as necessary, be removed from emergency situations, and if the eyes or skin have been contaminated they should be flushed with water. Contaminated clothing should be promptly removed. If exposure is severe, hospitalization and observation for 72 h for delayed onset of severe pulmonary oedema is advisable.

When the epoxy compounds, such as ethylene oxide, are extremely volatile, stringent safeguards should be taken to prevent fire and explosion. These safeguards should include the control of ignition sources, including static electricity; the availability of foam, carbon dioxide or dry chemical fire extinguishers (if water is used on large fires, the hose should be equipped with a fogging nozzle); the use of steam or hot water to heat ethylene oxide or its mixtures; and storage away from heat and strong oxidizers, strong acids, alkalis, anhydrous chlorides or iron, aluminium or tin, iron oxide, and aluminium oxide.

Proper emergency procedures and protective equipment should be available to deal with spills or leaks of ethylene oxide. In case of a spill, the first step is to evacuate all personnel except those involved in the clean-up operations. All ignition sources in the area should be removed or shut down and the area well ventilated. Small quantities of spilled liquid can be absorbed on cloth or paper and allowed to evaporate in a safe place such as a chemical fume hood. Ethylene oxide should not be allowed to enter a confined space such as a sewer. Workers should not enter confined spaces where ethylene oxide has been stored without following proper operating procedures designed to ensure that toxic or explosive concentrations are not present. Whenever possible, ethylene oxide should be stored and used in closed systems or with adequate local exhaust ventilation.

All substances having carcinogenic properties, such as ethylene oxide and vinylcyclohexene dioxide, must be handled with extreme care to avoid contact with the workers’ skin or being inhaled during both production and use. Prevention of contact is also promoted by designing the work premises and process plant so as to preclude any leakage of the product (application of a slight negative pressure, hermetically sealed process and so on). Precautions are discussed more fully elsewhere in this Encyclopaedia.

Epoxy compounds tables

Table 104.45 Chemical identification

CHEMICAL

SYNONYMS

UN CODE

CAS-NUMBER

CHEMICAL FORMULA

ALLYL GLYCIDYL ETHER

Allyl 2,3-epoxypropyl ether; 1-(Allyloxy)-2,3-epoxypropane; 1,2-Epoxy-3-allyloxypropane; Glycidyl allyl ether

UN2219

106-92-3

BUTYL GLYCIDYL ETHER

Butyl glycidyl ether; 2,3-Epoxypropyl butyl ether; Ether, butyl 2,3-epoxypropyl; Ether, butyl glycidyl; Glycidyl butyl ether

2426-08-6

CRESYL GLYCIDYL ETHER

Cresol glycidyl ether; Cresylglycide ether; Glycidyl methylphenyl ether; Propane, 1,2-epoxy-3-(tolyloxy)-

26447-14-3

1,2:3,4-DIEPOXYBUTANE

Butadiene diepoxide; 1,3-Butadiene diepoxide; Diepoxybutane; 2,4-Diepoxybutane

1464-53-5

DIGLYCIDYL ETHER

Di(2,3-epoxy)propyl ether

2238-07-5

1,1-DIMETHYLETHYL GLYCIDYL ETHER

tert-Butyl glycidyl ether; Propane, 1-tert-Butoxy-2,3-epoxy-; Oxirane, ((1,1-dimethylethoxy)methyl)-

7665-72-7

EPICHLOROHYDRIN

3-Chloro-1,2-epoxypropane; 1-Chloro-2,3-epoxypropane; (Chloromethyl)ethylene oxide; 3-Chloro-1,2-propane oxide

UN2023

106-89-8

1,2-EPOXYBUTANE

1-Butene oxide; Butylene oxide; 1,2-Butylene oxide; Epoxybutane

UN3022

106-88-7

1,2-EPOXYETHYLBENZENE

1,2-Epoxy-1-phenylethane; Epoxystyrene; 1-Phenyl-1,2-epoxyethane; Phenylethylene oxide; Phenyl oxirane

96-09-3

1,2-EPOXYPROPANE

2,3-Epoxypropane; Methyl ethylene oxide; Propene oxide; Propylene oxide

UN1280

75-56-9

2,3-EPOXYPROPANOL

Epihydrin alcohol; 2,3-Epoxy-1-propanol; Glycidyl alcohol; 3-Hydroxy-1,2-epoxypropane

556-52-5

(2,3-EPOXYPROPYL)TRIMETHYLAMMONIUM CHLORIDE

Glycidyl-trimethyl-ammonium chloride; Oxiranemethanaminium, trimethylglycidylammonium chloride; N,N,N-Trimethyloxiranemethanaminium chloride

3033-77-0

ETHYLENE OXIDE

Dimethylene oxide; Epoxyethane; 1,2-Epoxyethane; Ethene oxide

UN1040

75-21-8

2-ETHYLHEXYL GLYCIDYL ETHER

Glycidyl 2-ethylhexyl ether

2461-15-6

FURFURAL

2-Furanaldehyde; 2-Furancarbonal; 2-Furancarboxaldehyde; 2-Furfural; 2-Furylaldehyde

UN1199

98-01-1

FURFURYL ALCOHOL

Furanmethanol; Furfural alcohol; Furfuralcohol; Furyl alcohol

UN2874

98-00-0

GUAIACOL

Hydroxyanisole

90-05-1

HYDROQUINONE DIGLYCIDYL ETHER

 

2425-01-6

ISOPROPYL GLYCIDYL ETHER

Glycidyl isopropyl ether; Isopropyl glycidyl ether; 3-Isopropyloxypropylene oxide; ((1-Methylethoxy)methyl)oxirane

4016-14-2

DIBENZO-p-DIOXIN

Dibenzodioxin; Dibenzo(1,4)dioxin; Dibenzo(b,e)(1,4)dioxin; Diphenylene dioxide

262-12-4

PHENYL GLYCIDYL ETHER

1,2-Epoxy-3-phenoxypropane; 2,3-Epoxypropylphenyl ether; Phenol glycidyl ether; 3-Phenoxy-1,2-epoxypropane; Phenyl 2,3-epoxypropyl ether

122-60-1

RESORCINOL DIGLYCIDYL ETHER

1,3-Bis(2,3-epoxypropoxy)benzene; m-Bis(glycidyloxy)benzene; 1,3-Diglycidyloxybenzene; Diglycidyl resorcinol ether; Resorcinyl diglycidyl ether

101-90-6

TETRAHYDRODIMETHYLFURAN

Tetrahydrodimethyl furane

1320-94-1

TETRAHYDROFURAN

Butylene oxide; Cyclotetramethylene oxide; Diethylene oxide; 1,4-Epoxybutane; Tetramethylene oxide

UN2056

109-99-9

VINYL CYCLOHEXENE DIOXIDE

1,2-Epoxy-4-(epoxyethyl)cyclohexane; 1-Epoxyethyl-3,4-epoxycyclohexane; 4-Vinyl-1,2-cyclohexene diepoxide; 1-Vinyl-3-cyclohexene dioxide; 4-Vinyl-1-cyclohexene dioxide

106-87-6

Table 104.46 Health hazards

Chemical Name

     CAS-Number

ICSC Short-Term Exposure

ICSC Long-Term Exposure

ICSC Routes of Exposure and Symptoms

US NIOSH Target Organs & Routes of Entry

US NIOSH Symptoms

ALLYL GLYCIDYL ETHER

     106-92-3

eyes; skin; resp tract

skin

 

Eyes; resp sys; skin; liver; kidneys

Inh; abs; ing; con

Irrit eyes, skin, nose, muc memb; pulm edema; in animals: liver, kidney inj

BUTYL GLYCIDYL ETHER

     2426-08-6

skin

 

 

Eyes; skin; resp sys; CNS; blood

Inh; ing; con

Irrit eyes, skin, nose; sens; narco; possible hemato effects; CNS depres

DIGLYCIDYL ETHER

     2238-07-5

 

 

 

Skin; eyes; resp sys; repro sys (in animals: skin tumors)

Inh; abs; ing; con

Irrit eyes, skin, resp sys; skin burns; in animals: hemato sys, lung, liver, kidney damage; repro effects; (carc)

EPICHLOROHYDRIN

     106-89-8

eyes; skin; resp tract; lungs; CNS

skin; asthma; genes; reproduction system

Inhalation: pain, burning sensation, cough, laboured breathing, shortness of breath, vomiting, headache, unconsciousness

Skin: may be absorbed, pain, redness, severe skin burns

Eyes: pain, blurred vision, severe deep burns

Ingestion: burning sensation, abdominal cramps, abdominal pain, nausea, vomiting, unconsciousness

Resp sys; skin; kidneys; eyes; liver; repro sys (in animals: nasal cancer)

Inh; abs; ing; con

Irrit eyes, skin with deep pain; nau, vomit; abdom pain; resp distress, cough; cyan; repro effects; (carc)

1,2-EPOXYBUTANE

     106-88-7

eyes; skin; resp tract; lungs

 

Inhalation: burning sensation, confusion, headache, laboured breathing, nausea, unconsciousness, symptoms may be delayed

Skin: may be absorbed, redness

Eyes: redness

Ingestion: abdominal pain

 

 

1,2-EPOXYPROPANE

     75-56-9

 

 

 

Eyes; skin; resp sys (in animals: nasal tumors)

Inh; ing; con

Irrit eyes, skin, resp sys; blisters, burns; (carc)

2,3-EPOXYPROPANOL

     556-52-5

eyes; skin; resp tract; lungs; CNS

skin

Inhalation: cough, irritant, dizziness, narcotic, laboured breathing

Skin: may be absorbed, redness, irritant

Eyes: redness, severe irritant, pain

Ingestion: abdominal pain, irritant

Eyes; skin; resp sys; CNS

Inh; ing; con

Irrit eyes, skin, nose, throat; narco

ETHYLENE OXIDE

     75-21-8

 

 

 

Eyes; blood; resp sys; liver; CNS; kidneys; skin; repro sys (peritoneal cancer, leukemia)

Inh; ing (liq); con

Irrit eyes, skin, nose, throat; peculiar taste; head; nau, vomit, diarr; dysp, cyan, pulm edema; drow; inco; EKG abnor; eye, skin burns (liq or high vap conc); liq: frostbite; repro effects; (carc); in animals: convuls; liver, kidney damage

FURFURAL

     98-01-1

eyes; skin; resp tract; lungs; CNS

skin; liver; kidneys

Inhalation: cough, headache, laboured breathing, shortness of breath, sore throat

Skin: may be absorbed, redness, pain

Eyes: redness, pain

Ingestion: abdominal pain, diarrhoea, headache, sore throat, vomiting

Eyes; resp sys; skin

Inh; abs; ing; con

Irrit eyes, skin, upper resp sys; head; derm

FURFURYL ALCOHOL

     98-00-0

eyes; skin; resp tract; lungs

skin

Inhalation: cough, shortness of breath, sore throat

Skin: may be absorbed, dry skin, redness

Eyes: redness, pain, lachrymation, blurred vision, swelling of the eyelids

Ingestion: unconsciousness

Resp sys; eyes; skin; CNS

Inh; abs; ing; con

Irrit eyes, muc memb; dizz; nau, diarr; diuresis; resp, body temperature depres; vomit; derm

ISOPROPYL GLYCIDYL ETHER

     4016-14-2

eyes; skin; resp tract; CNS

 

 

Eyes; skin; resp sys; blood; repro sys

Inh; ing; con

Irrit eyes, skin, upper resp sys; skin sens; possible hemato, repro effects

PHENYL GLYCIDYL ETHER

     122-60-1

 

 

 

Eyes; skin; CNS; hemato sys; repro sys (in animals: nasal cancer)

Inh; abs; ing; con

Irrit eyes, skin, upper resp sys; skin sens; narco; possible hemato, repro effects; (carc)

TETRAHYDROFURAN

     109-99-9

eyes; skin; resp tract; CNS

skin; liver; kidneys

Inhalation: dizziness, headache, nausea, unconsciousness

Skin: dry skin, redness, roughness

Eyes: redness, pain

Resp sys; skin; eyes; CNS

Inh; ing; con

Irrit eyes, upper resp sys; nau, dizz, head, CNS depres

VINYL CYCLOHEXENE DIOXIDE

     106-87-6

eyes; skin; resp tract; lungs

 

Inhalation: laboured breathing, sore throat

Skin: may be absorbed, redness, swelling

Eyes: redness

Eyes; skin; resp sys; blood; thymus; repro sys (in animals: skin tumors)

Inh; abs; ing; con

In animals: irrit eyes, skin, resp sys; testicular atrophy; leupen; nec thymus; skin sens; (carc)

Table 104.47 Physical & chemical hazards

For UN Class: 1.5 = very insensitive substances which have a mass explosion hazard; 2.1 = flammable gas; 2.3 = toxic gas; 3 = flammable liquid; 4.1 = flammable solid; 4.2 = substance liable to spontaneous combustion; 4.3 = substance which in contact with water emits flammable gases; 5.1 = oxidizing substance; 6.1 = toxic; 7 = radioactive; 8 = corrosive substance

Chemical Name

CAS-Number

Physical

Chemical

UN Class or Division / Subsidiary Risks

ALLYL GLYCIDYL ETHER

106-92-3

 

 

3

EPICHLOROHYDRIN

106-89-8

 

The substance will polymerize due to heating or under the influence of strong acids, bases and contaminants •On combustion, forms toxic and corrosive fumes •The substance decomposes slowly on contact with water •Reacts violently with strong oxidants •Reacts violently with aluminium, zinc, metal powders, alcohols, phenols, amines (especially aniline) and organic acids causing fire and explosion hazard •Attacks steel in the presence of water

6.1

1,2-EPOXYBUTANE

106-88-7

The vapour is heavier than air and may travel along the ground; distant ignition possible •The vapour mixes well with air, explosive mixtures are easily formed •As a result of flow, agitation, etc, electrostatic charges can be generated

The substance may polymerize on contact with acids, alkalies, tin, aluminium and iron chlorides with fire or explosion hazard

3

1,2-EPOXYPROPANE

75-56-9

 

 

3

2,3-EPOXYPROPANOL

556-52-5

 

The substance decomposes on contact with strong acids and bases, water, salts (aluminium chloride, ferric chloride) or metals (copper, zinc), causing fire and explosion hazard •Attacks plastic and rubber

 

ETHYLENE OXIDE

75-21-8

 

 

6.1 / 2.1

FURFURAL

98-01-1

The vapour is heavier than air

The substance polymerizes under the influence of acid(s) or base(s) with fire or explosion hazard •Reacts violently with oxidants •Attacks many plastics

3

FURFURYL ALCOHOL

98-00-0

 

The substance polymerizes under the influence of acids •Reacts violently with strong oxidants or strong acids, causing fire and explosion hazard

6.1

TETRAHYDROFURAN

109-99-9

The vapour is heavier than air and may travel along the ground; distant ignition possible

The substance can form explosive peroxides •On combustion, forms carbon monoxide •Reacts violently with strong oxidants causing fire and explosion hazard

3

VINYL CYCLOHEXENE DIOXIDE

106-87-6

 

On combustion, forms acrid smoke and irritating fumes •Reacts with active hydrogen compounds (eg, alcohols, amines)

 

Table 104.48 Physical & chemical properties

Chemical Name

CAS-Number

Colour/Form

Boiling Point (°C)

Melting Point (°C)

Molecular Weight

Solubility in Water

Relative Density (water=1)

Relative Vapour Density (air=1)

Vapour Pressure/ (Kpa)

Inflam. Limits

Flash Point (°C)

Auto Ignition Point (°C)

ALLYL GLYCIDYL ETHER

106-92-3

colourless liquid

154

-100

114.1

14.1%

0.9698

3.32  @25°C

4.7mmHg  @25°C

 

 

 

BUTYL GLYCIDYL ETHER

2426-08-6

clear, colourless liquid

164

 

130.2

2% sol

0.918

3.78  @25°C

0.2

 

74 cc

 

CRESYL GLYCIDYL ETHER

26447-14-3

colourless liquid

 

 

164.20

 

 

 

 

 

93 oc

 

1,2:3,4-DIEPOXYBUTANE

1464-53-5

 

138

-19

86.09

v sol

1.113

 

6.9mmHg  @25°C

 

 

 

DIGLYCIDYL ETHER

2238-07-5

colourless liquid

260

 

130.16

 

1.1195

3.78  @25°C

0.09mmHg  @25°C

 

 

 

1,1-DIMETHYLETHYL GLYCIDYL ETHER

7665-72-7

 

152

-70

130.18

 

0.898

 

 

 

 

 

EPICHLOROHYDRIN

106-89-8

colourless, mobile liquid

116

-48

92.5

misc

1.1801

3.29

1.6

3.8 ll 21.0 ul

34 cc

385

1,2-EPOXYBUTANE

106-88-7

colourless liquid

63.3

-150

72.12

95000 ppm  @25°C

0.837  @17°C/4°C

2.2

18.8

3.1 ll 25.1 ul

-17

439

1,2-EPOXYETHYLBENZENE

96-09-3

colourless to pale straw-coloured liquid

194.1

-35.6

120.1

insol

1.0523  @16°C/4°C

4.30

0.3mmHg

 

822 oc

498

1,2-EPOXYPROPANE

75-56-9

colourless ethereal liquid

34.23

-112.13

58.08

v sol

0.8304

2.0

445mmHg

2.3 ll 36 ul

 

449

2,3-EPOXYPROPANOL

556-52-5

colourless, slightly viscous liquid

166-167decomp

-45

74.08

misc

1.115

2.15

0.12  @25°C

 

72 cc

415

ETHYLENE OXIDE

75-21-8

colourless gas at ordinary room temp & pressure; liquid below  12°C

10.7

-112.5

44.06

sol

0.8222  @10°C/10°C

1.49

1095mmHg

3 ll 100 ul

 

 

FURFURAL

98-01-1

an amber-coloured liquid; colourless liquid when freshly prepared; colourless to reddish-brown oily liquid

161.7

-36.5

96.08

sol

1.1594

3.3

0.144

2.1 ll 19.3 ul

60 cc

316

FURFURYL ALCOHOL

98-00-0

colourless-yellow liquid; clear mobile liquid

171

-14.6

98.10

misc

1.1296

1.003

0.051

1.8 ll 16.3 ul

75 oc

490

GUAIACOL

90-05-1

white or slightly yellow crystalline mass or colourless to yellowish; hexagonal prisms; crystals or liquid

205

32

124.13

sl sol

1.1287  @21°C/4°C

 

0.103mmHg  @25°C

 

 

 

ISOPROPYL GLYCIDYL ETHER

4016-14-2

mobile, colourless liquid

137

 

116.18

18.8%

0.9186

4.15

9.4mmHg  @25°C

 

 

 

DIBENZO-p-DIOXIN

262-12-4

 

 

122-123

184.2

1 ppm  @25°C

 

 

4.125x 10-4 mmHg  @25°C

 

 

 

PHENYL GLYCIDYL ETHER

122-60-1

colourless liquid

245

3.5

150.1

0.24%

1.1092

4.37

0.01mmHg

 

 

 

RESORCINOL DIGLYCIDYL ETHER

101-90-6

straw-yellow liquid

172  @0.8mmHg

32-33

222.2

 

1.21  @25°C

 

 

 

177 oc

 

TETRAHYDROFURAN

109-99-9

colourless, mobile liquid

66

-108.3

72.1

sol

0.8892

2.5

19.3

2 ll 11.8 ul

-145

321

VINYL CYCLOHEXENE DIOXIDE

106-87-6

colourless liquid

227

<-55

140.18

v sol

1.0986

4.8

0.13

 

110 oc