Carson Ph., Mumford C. Hazardous Chemicals Handbook (Справочник по опасным химическим веществам)

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Sodium hydroxide E G G E E

Aliphatic hydrocarbons

Hydraulic oil F G F G E

Paraffins F G E G E

Petroleum ether F G E F G

Pine oil G G E G E

Aromatic hydrocarbons

(2)

Benzene NR F G F G

Naphtha NR F F F G

Naphthalene G G E G E

Toluene NR F G F G

Turpentine F G R F G

Xylene NR F G F G

(1)

Halogenated hydrocarbons

(2)

Benzyl chloride F F G F G

Carbon tetrachloride F F G F G

Chloroform F F G F G

Ethylene dichloride F F G F G

Methylene chloride F F G F G

Perchloroethylene F F G F G

Trichloroethylene F F G F G

Esters

Amyl acetate F G G F G

Butyl acetate F G G F G

Ethyl acetate F G G F G

Ethyl butyrate F G G F G

Methyl butyrate F G G F G

Ethers

Diethyl ether F G E F G

Aldehydes

Acetaldehyde G E E E E

Benzaldehyde F F E G E

Formaldehyde G E E E E

Ketones

Acetone G G G F G

Diethyl ketone G G G F G

Methyl ethyl ketone G G G F G

Alcohols

Amyl alcohol E E E E E

Butyl alcohol E E E E E

Ethyl alcohol E E E E E

Ethylene glycol G G E E E

Glycerol G G E E E

Isopropyl alcohol E E E E E

Methyl alcohol E E E E E

Amines

Aniline F G E E E

Butylamine G G E E E

Ethylamine G G E E E

Ethylaniline F G E E E

Methylamine G G E E E

Methylaniline F G E E E

Triethanolamine G E E E E

Table 13.12 Cont’d

Glove material

Chemical Natural rubber Neoprene Nitrile Normal PVC High grade PVC

PERSONAL PROTECTION 439

440 OPERATING PROCEDURES

Miscellaneous

Animal fats F G G G E

Bleaches NR G G G E

Carbon disulphide NR F G F G

Degreasing solution F F G F G

Diesel fuel NR F G F E

Hydraulic fluids F G G G E

Mineral oils F G E G E

Ozone F E G E E

Paint and varnish removers F G G F G

Petrol NR G G F G

Photographic solutions G E E G E

Plasticizers F G E G E

Printing inks G G E G E

Refrigerant solutions G G E F G

Resin oil F G G G E

Vegetable oils F G G G E

Weed killers G E E G E

White spirit F G G F G

Wood preservatives NR G G F G

E Excellent

F Fair

G Good

NR Not recommended

(1)

Resistance not absolute, but the best available.

(2)

Aromatic and halogenated hydrocarbons will attack all types of natural and synthetic gloves. Should swelling occur, switch

to another pair, allowing the swollen gloves to dry and return to normal.

Impervious clothing is essential when handling corrosive chemicals, liquids liable to cause

dermatitis, or chemicals toxic by skin absorption.

All protective clothing should be maintained in a sound condition, cleaned/washed/replaced

regularly as appropriate, and be stored apart from everyday clothing. With toxic chemicals a

double locker system is advisable. With highly toxic substances, e.g. lead compounds or asbestos-

based substances, separate storage of personal clothing and protective clothing is specifically required.

Protective footwear

Protective footwear includes shoes, boots with steel toecaps, full boots, e.g. Wellingtons. The

choice of material determines durability, acid resistance, oil resistance, heat resistance, non-slip

characteristics, impact resistance etc.

Washing facilities

Wherever chemicals are handled, adequate washing facilities are required conveniently situated

with respect to the workplace. These comprise wash-basins or troughs with a constant supply of

hot and cold or warm water; soap or liquid hand cleanser; clean towels or hot-air driers or

disposable paper towels. Typical minimum standards are:

Normal work One wash-basin per 10 workers

Handling toxic or irritant chemicals One wash-basin per 5 workers

Table 13.12 Cont’d

Glove material

Chemical Natural rubber Neoprene Nitrile Normal PVC High grade PVC

Table 13.13 Properties of protective clothing materials

Material Advantages Disadvantages

Cotton Lightweight, reasonably Liable to shrinkage unless Suitable for under-gloves

hard-wearing, no static treated

generation More flammable than wool

Resists penetration of direct Vulnerable to hot splashes

splashes of corrosive

Unaffected by oils

Wool Resists rapid penetration of Not resistant to hot splashes

direct splashes (more Takes up water and dirt

effective than cotton) Difficult to wash

Resists penetration of dust

High absorption and porosity

absorbs perspiration

Artificial fibres Hardwearing Not resistant to hot splashes Ceramic coating of fibres

(nylon, Terylene) Terylene has good acid High initial cost can render dust-proof

resistance Can allow dust to pass through

Static electricity can cause

rapid soiling

PVC Impervious Not resistant to hot splashes Used alone or

Non-flammable Causes sweating unless impregnated on fabric

Chemically and well ventilated For gloves armlets, hats,

biologically resistant bibs, spats, suits

Abrasion resistant

Paper Hygienic (disposable) Liable to wetting if not Possibly used for

Fairly resistant to chemicals treated with polythene disposable underwear

if treated with polythene film or for clothing for

film No strength visitors

Flammable Used under headgear

Not resistant to hot splashes (disposable)

Polythene Hygienic Low abrasion resistance Suitable for disposable

May be disposable Not resistant to hot splashes gloves or headgear

Impervious Low melting point could

cause adhesion to skin

In some circumstances, where clothing has to be changed, bathing facilities, e.g. showers, are

required. The provision of suitable and sufficient washing facilities and showers, if required by

the nature of the work, at readily accessible places is required in the UK under Reg. 21 of the

Workplace (Health, Safety and Welfare) Regulations 1992. Specific needs are also covered in

other legislation, e.g. the Control of Lead at Work Regulations, and the Control of Asbestos at

Work Regulations 1987 (as amended 1998).

Facilities for rest and food

Rest facilities should be provided in readily accessible places. To avoid contamination of food, or

accidental ingestion of chemicals, these should include facilities to eat meals in a separate location.

Medical screening

The medical background of workers must be considered for work involving certain chemicals,

e.g. radioactive substances, sensitizers. (Refer to Chapter 5.)

MEDICAL SCREENING 441

442 OPERATING PROCEDURES

Monitoring standards

Management must institute procedures to assess levels of compliance with agreed standards for

safety. Techniques include environmental and/or biological monitoring, health surveillance, safety

audits, safety inspections, and procedures for accident reporting, investigation and analysis.

Communication is essential, e.g. by provision of information (on specific chemicals, processes,

etc.), safety meetings, notices, safety bulletins etc.

Training

Education, training and supervision are essential for the safe handling of chemicals. Training

requirements vary according to position within the organization, and hence responsibility.

Topics should embrace a knowledge of the hazards and precautions, including the use and

maintenance of protective devices including personal protection, under both normal and abnormal

operating conditions including emergencies.

Marketing

Chemicals vary from commodity substances in bulk to household cleaning products in small

packages. Mixtures of chemicals, such as formulated products, are usually termed ‘preparations’

which constitute 95% of commercially-available dangerous chemicals. Manufacturers, suppliers

and importers of all chemicals have a legal obligation to ensure that their products are fit for use,

properly packed, labelled and transported, and to provide the user with information on the hazards

and precautions to ensure they can be used safely and without harm to the environment. (See

Table 14.1 for UK legislation.) The hazards of dangerous substances, as opposed to dangerous

preparations, must also appear in advertisements for those chemicals.

Important aspects of classification labelling and packaging chemicals are regulated in the UK

by the Chemicals (Hazard Information and Packaging for Supply) Regulations 1994 (‘CHIP’).

These are applicable to any substance dangerous for supply excluding specific categories, e.g.

cosmetic products, controlled drugs, foods, medicines and medical products, munitions, wastes,

radioactive substances.

Classification

If a chemical is hazardous it is first classified into an appropriate category of danger to assist in

the provision of the correct information and packaging.

This can be done by:

• use of the classification given to it by the supplier. (A check is necessary that the classification

is accurate and also that processing has not invalidated it);

• use of an Approved Supply List from the UK Health and Safety Executive which covers most

chemicals but not mixtures; or

• classification by reference to relevant information.

A list of danger categories is given in Table 14.2. Note that chemicals may possess several

hazards, e.g. nitric acid is classed as both an oxidizer and a corrosive. If a chemical is not in one

of these categories it is not generally considered to be dangerous. If the hazards of a new chemical

have not been established it should be labelled ‘Caution – substance not yet fully tested’. Mixtures

can be classified either from results from tests on the preparation, or by calculation to predict the

health effects of the product based on the properties of individual components and their concentration

in the mixture. Preparations need to be classified for both physico-chemical and health effects

but, to date, not for environmental effects.

Under CHIP there is a requirement for suppliers to exercise all due diligence in classifying a

444 MARKETING

Table 14.1 Legislation affecting the classification, packaging, labelling and carriage of dangerous substances in Great

Britain (including their movement in harbours and harbour areas)

The Chemicals (Hazard Information and Packaging for Supply)

Regulations 1994 as amended

The Carriage of Dangerous Goods by Road Regulations

1996

The Carriage of Dangerous Goods (Classification,

Packaging and Labelling) and Use of Transportable

Pressure Receptacles Regulations 1996

The Carriage of Dangerous Goods by Road (Driver

Training) Regulations 1996

The Carriage of Explosives by Road Regulations 1996

The Carriage of Dangerous Goods by Rail Regulations

1996

The Packaging, Labelling and Carriage of Radioactive

Materials by Rail Regulations 1996

Radioactive Material (Road Transport) (Great Britain)

Regulations 1996

The Health and Safety at Work etc. Act 1974 (Application

to Environmentally Hazardous Substances) Regulations

1996 as amended

The Ionizing Radiations Regulations 1999

The Dangerous Substances in Harbour Areas Regulations

1987 (‘DSHA’)

Control the classification, provision of labels and safety data

sheets, and safe packaging of chemicals by supplier.

Covers the mode of dispatch of dangerous goods by road

including bulk and tanker transport; suitability of containers

and vehicles; examination and testing; information

requirements; loading and unloading; procedures for

emergencies and parking; exemptions.

Governs the classification of dangerous goods; consignment

in packages and their markings/labelling; the design,

manufacture, modification and repair of transportable

pressure receptacles and their approval and certification,

marking and filling; the role of approved persons and the

need for records.

Addresses the instruction, training and certification of drivers

of road vehicles used for the carriage of dangerous goods.

Scope includes mode of transport in both passenger vehicles

and bulk carriage; suitability of vehicle and container;

approval; quantity limits; mixed loads; information and

documentation; safety and security during carriage;

equipment; precautions against fire and explosion and in

the event of accidents and emergencies; age limits for

those engaged in the carriage.

Governs the transport of dangerous goods by rail in small

containers, large containers, tanks and wagons. Covers

classification of dangerous goods; suitability, examination

and testing of container; information including labelling.

Also included is training and instruction; loading and

unloading; marshalling; prohibition of overfilling, mixed

loads and temperature-controlled substances; security and

emergency procedures and special requirements for

carriage of explosives.

Covers package design, approval, test procedures, notification

of consignment, information requirements (for package

and transport container).

Includes radiation limits, prior approval, QA programmes,

testing procedures, information/documentation

requirements, and marking/labelling/placarding.

Extends the scope of Health and Safety at Work etc. Act 1974

to include environmentally-hazardous substances including

transportation of such dangerous goods and the control

of volatile organic carbon emissions from storage and

distribution of petrol.

Apply to all work activities with radioactive materials, including

transport. The main provisions relevant to transport are

those relating to driver training and the need, under some

circumstances, to prepare contingency plans for

emergencies and enforced stoppages.

Control the carriage, loading, unloading and storage of all

classes of dangerous substances, including explosives, in

all harbours and harbour areas in Great Britain. Movement

of dangerous substances by road, rail and sea is covered.

substance. Checks which may be required if reliance is placed on classification by a manufacturer

are:

• reference to the Approved Supply List;

• use of experience about the reliability and experience of the supplier;

• use of common sense and experience;

• comparison with similar substances or preparations;

• comparison with any classification for carriage;

• enquiries with the supplier or other competent persons;

• checking with information in reference textbooks.

Packaging

A hazardous chemical must be supplied/conveyed in a package (drum, keg, cylinder, bottle, etc.)

suitable for the purpose. In particular:

• The receptacle and any associated packaging must be designed, constructed, maintained and

closed so as to prevent the escape of any of the contents of the receptacle when subjected to the

stresses and strains of normal handling. A suitable safety device (e.g. pressure relief valve) may

be fitted.

• The receptacle and any associated packagings (in so far as they are likely to come into contact

with the dangerous substance) must be made of materials (a) which are not liable to be

adversely affected by the substance, and (b) which are not liable to react with the substance to

form any other dangerous substance.

• Where the receptacle is fitted with a replaceable closure, the closure must be designed so that

the receptacle can be repeatedly reclosed without the contents escaping.

• The packaging of certain dangerous chemicals (e.g. those labelled ‘toxic’, ‘very toxic’ or

‘corrosive’ must be fitted with child-resistant closures, or tactile danger warnings (for the

blind) if sold to the public.

Suppliers should perform a hazard analysis on each product. For example, aerosols can pose fire,

explosion or inhalation risk. Basic precautions with an aerosol dispenser are:

• Assume that the aerosol contains a liquid of flammability equivalent to that of petrol and treat

it as such.

• Do not use an aerosol spray when smoking, or near any other source of ignition, e.g. an electric

fire, hot-plate, open-flame heater or boiler etc.

• Do not throw used aerosol dispensers onto bonfires.

• Do not let young children have access to aerosol dispensers, full or empty.

Table 14.1 Cont’d

Require that explosives shall not be transported unless they

have been classified by the classifying authority (i.e. the

HSE, and the MOD for military explosives, in the UK)

(except for journeys made specifically for classification

and then only under certain conditions).

The Classification and Labelling of Explosives Regulations

1983 (‘CLER’)

PACKAGING 445

446 MARKETING

Table 14.2 Indication of dangers with chemical products

Category of danger Indication of Symbol Symbol

danger letter

Physico-chemical Explosive Explosive E

Oxidizing Oxidizing O

Extremely Extremely

F+

flammable flammable

Highly flammable Highly flammable F

Flammable Flammable –

Health Very toxic Very toxic T+

Toxic Toxic T

Harmful Harmful Xn

Corrosive Corrosive C

Irritant Irritant Xi

Harmful Xn

Sensitizing

Irritant Xi

Carcinogenic Toxic T

Categories 1 and 2

Category 3 Harmful Xn

Mutagenic Toxic T

Categories 1 and 2

Category 3 Harmful Xn

Toxic for

reproduction Toxic T

Categories 1 and 2

Category 3 Harmful Xn

Environmental Dangerous for the Dangerous for the N

environment environment

EXPLOSIVE

It is the responsibility of the supplier to draw these precautions to the attention of the user in the

best way practicable.

Labelling

If a dangerous chemical is supplied in a package then the package must be labelled. Clearly this

is not practical if the chemical is delivered in bulk or via a pipeline.

The elements of a label are:

• Full name and address and phone number of supplier.

• Chemical name or, if a preparation, the trade name.

• Indication of danger and associated symbol.

• Risk and safety phrases.

Requirements for labelling of containers for supply may differ from those for conveyance. Key

features of a supply label are to identify the substance (the chemical name in most cases) and any

hazards and safety precautions. Supply labels are black on yellow/orange. In Europe the classification,

packaging and labelling of dangerous substances is covered by Directive 67/548/EEC as amended.

This requires labels to identify appropriate risk and safety phrases (Tables 14.3 and 14.4) depending

upon product properties. A substance is considered dangerous if in Part 1A of an approved list or

if it exhibits hazardous properties as defined in Schedule 1 for supply, or Schedule 2 for conveyance

as shown in Tables 14.5 and 14.6. Substances not tested should be labelled ‘Caution – substance

not yet fully tested’. Criteria for risk phrases are provided, e.g. as in Table 14.7 for toxic compounds.

Explosive chemicals tend to be governed by separate legislation, e.g., in the UK, The Classification

and Labelling of Explosives Regulations 1983. These require the HSE to classify any explosive

before it may be supplied. Under the scheme, explosives are labelled according to a classification

based on hazard division (Table 14.8), and on compatibility (Table 14.9), which takes into account

their sensitivity, explosivity and chemical nature. Labels are diamond shaped: the top half is

reserved for the pictograph and division number, the bottom half shows the hazard code and the

classification number. Figure 14.1 shows the label for Class 1, Division 1.1, 1.2 or 1.3 explosive.

Figure 14.1

Example of label for explosive (Division 1.1, 1.2 or 1.3)

LABELLING 447

448 MARKETING

Table 14.3 ‘Risk’ phrases from the Approved List

1. Explosive when dry

2. Risk of explosion by shock, friction, fire or other sources of ignition

3. Extreme risk of explosion by shock, friction, fire or other sources of ignition

4. Forms very sensitive explosive metallic compounds

5. Heating may cause an explosion

6. Explosive with or without contact with air

7. May cause fire

8. Contact with combustible material may cause fire

9. Explosive when mixed with combustible material

10. Flammable

11. Highly flammable

12. Extremely flammable

13. Extremely flammable liquefied gas

14. Reacts violently with water

15. Contact with water liberates extremely flammable gases

16. Explosive when mixed with oxidizing substances

17. Spontaneously flammable in air

18. In use, may form flammable/explosive vapour–air mixture

19. May form explosive peroxides

20. Harmful by inhalation

21. Harmful in contact with skin

22. Harmful if swallowed

23. Toxic by inhalation

24. Toxic in contact with skin

25. Toxic if swallowed

26. Very toxic by inhalation

27. Very toxic in contact with skin

28. Very toxic if swallowed

29. Contact with water liberates toxic gas

30. Can become highly flammable in use

31. Contact with acids liberates toxic gas

32. Contact with acids liberates very toxic gas

33. Danger of cumulative effects

34. Causes burns

35. Causes severe burns

36. Irritating to eyes

37. Irritating to respiratory system

38. Irritating to skin

39. Danger of very serious irreversible effects

40. Possible risk of irreversible effects

41. Risk of serious damage to eyes

42. May cause sensitization by inhalation

43. May cause sensitization by skin contact

44. Risk of explosion if heated under confinement

45. May cause cancer

46. May cause heritable genetic damage

47. May cause birth defects

48. Danger of serious damage to health by prolonged exposure

49. May cause cancer by inhalation

50. Very toxic to aquatic organisms

51. Toxic to aquatic organisms

52. Harmful to aquatic organisms

53. May cause long-term adverse effects in the aquatic environment

54. Toxic to flora

55. Toxic to fauna

56. Toxic to soil organisms

57. Toxic to bees

58. May cause long-term adverse effects in the environment

59. Dangerous for the ozone layer