Health and Safety Executive

The interpretation and use of flashpoint information

Guidance Note CS24
This is a free-to-download, web-friendly version of CS24 (First edition, published 1999). This version has been adapted for online use from HSEs current printed version. You can buy the document at www.hsebooks.co.uk and most good bookshops. ISBN 978 0 7176 2418 8 Price 5.00 This guidance provides information on the problems associated with the determination of flashpoint during the classification of substances. It discusses the principles and pitfalls in the test methods used in the classification. The guidance is aimed at those directly responsible for the classification of the flammability hazard, ie manufacturers and suppliers. It can also help the end-user of a substance to interpret the flammability information given by the safety data sheet and the label on the packaging.

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Crown copyright 1999 First published 1999 ISBN 978 0 7176 2418 8 All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means (electronic, mechanical, photocopying, recording or otherwise) without the prior written permission of the copyright owner. Applications for reproduction should be made in writing to: The Office of Public Sector Information, Information Policy Team, Kew, Richmond, Surrey TW9 4DU or e-mail: licensing@opsi.gov.uk This guidance is issued by the Health and Safety Executive. Following the guidance is not compulsory and you are free to take other action. But if you do follow the guidance you will normally be doing enough to comply with the law. Health and safety inspectors seek to secure compliance with the law and may refer to this guidance as illustrating good practice.

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Contents
Introduction 4 Classification of hazards 4 Flammability principles 5 Incidents resulting from inadequate flammability data 8 Flashpoint measurement 10 The interpretation of flashpoint 16 Important points to bear in mind 17 References 18 Further information 19

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Introduction
1 This guidance provides information on the problems associated with the determination of flashpoint during the classification of substances. It discusses the principles and the pitfalls present in the test methods used in the classification. 2 The important points to bear in mind, whether you are a user or a supplier of a substance, are summarised at the end of the guidance. 3 The guidance recommends a procedure for correctly classifying a substance in relation to its flammability. It is important that the classification of the hazard is correct, otherwise the label, safety data sheet and possibly the packaging may be incorrectly assigned. This can have potentially serious consequences for a subsequent user of the substance. Relatively little guidance is given in the UN Manual of tests and criteria.1 4 The guidance is aimed at those directly responsible for the classification of flammability hazard, ie manufacturers and suppliers. It can also help the end-user of a substance to interpret the flammability information given by the safety data sheet and the label on the packaging. 5 Examples of incidents caused as a result of incorrect flammability classification are given later in the guidance note.

Classification of hazards
6 The classification of chemicals helps to identify the hazards (or dangers) of a chemical substance or preparation. There are many pieces of health and safety legislation which require such classification. These include: (a) (b) (c) the Chemicals (Hazard Information and Packaging for Supply) Regulations 19942 (CHIP) if you supply dangerous chemicals; the Carriage of Dangerous Goods (Classification, Packaging and Labelling) and Use of Transportable Pressure Receptacles Regulations 19963 if you transport dangerous substances; the Notification of New Substances Regulations 19934 before you place new substances on the market. New substances are those which are not listed on the European Inventory of Existing Commercial Chemical Substances (EINECS).

7 Other regulations also rely upon the correct classification of substances and preparations, for example the Highly Flammable Liquids and Liquefied Petroleum Gases Regulations 19725 and the Control of Major Accident Hazards Regulations 1999.6 8 In many cases, there are guides which detail the methods for classifying substances or preparations, for example the Approved requirements and test methods for the classification and packaging of dangerous goods for carriage7 and the Approved guide to the classification and labelling of substances and preparations dangerous for supply.8 The test methods contained in these documents are taken from either the United Nations Recommendations on the transport of dangerous goods: Manual of tests and criteria Second revised edition (UN Publication ST/SG/AC.10/11/Rev2, 1995)1 or Annex V of the Dangerous Substances Directive (67/548/EEC)9 which has been directly adopted in the UK as an Approved Code of Practice.

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Flammability principles
9 Firstly, it is important to understand the basic principles relating to flammability. Flammability is the term used to describe the ability of a substance to burn or combust with a flame. Combustion is usually a rapid chemical process, described as an oxidation reaction between a fuel and an oxidant which is accompanied by the evolution of light and heat. For combustion to take place, both fuel and oxidant need to be present with an ignition source of sufficient energy to initiate the reaction. The well-known fire triangle provides a useful means of illustrating this requirement, ie all three components must be present for combustion to occur. Removing any one of these components results in a no-fire condition. 10 Common examples of the three components of the fire triangle are wood, air and a match (as in a domestic fire), and petrol, air and a spark (as in a car engine). Although in these examples the fuel element is either a solid or liquid, the combustion reaction between the fuel and the oxidant, with a few exceptions, takes place in the vapour phase. So to start the reaction, ie for ignition to occur, enough energy must be supplied both to vaporise the fuel and to initiate the reaction. For burning to continue, the combustion reaction must produce sufficient heat to propagate the reaction and, in the case of solid or liquid fuels, to maintain the vaporisation process. 11 The amount of heat produced depends on the nature of both the fuel and the oxidant, and also on the respective concentrations in the burning mixture. The mixture of fuel vapour and oxidant is called a flammable atmosphere and may be defined as one through which a flame will be propagated, away from the influence of the ignition source. 12 The oxidant is often the oxygen present in air. However other oxidants can constitute the oxidant element of the fire triangle, and so allow the combustion reaction to occur. These include the gases chlorine and nitrous oxide, and even solids such as ammonium nitrate. 13 In unconfined situations, combustion of a flammable mixture generally results in a fire. Under confined conditions, the heat from the combustion reaction and also the production of gaseous reaction products can cause significant increases in pressure. This can occur in a matter of milliseconds and lead ultimately to an explosion. The severity of the explosion is influenced by a number of factors including the initial pressure, the mixture composition, the degree of confinement, and the degree of congestion. 14 The flammability of a substance is therefore characterised by: (a) the conditions under which the substance can be ignited and those under which it continues to burn - known respectively as the flashpoint and fire point; (b) the concentration range over which the vapour/oxidant mixture is flammable, ie the upper and lower flammability limits. These limits vary depending on the oxidant, and pressure; and (c) the minimum oxygen concentration required for the combustion reaction.

Flammability limits
15 It has been found experimentally that mixtures of flammable gases and vapours in air are only ignitable over a restricted range of concentrations, the limits of which are termed the lower and upper flammability limits (or lower and upper explosive limits). These limits are normally quoted in terms of the volume percentage of

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flammable vapour in air, for example the lower and upper flammability limits of toluene are approximately 1.3% and 7% respectively. If the concentration of toluene vapour in air is less than about 1.3% then combustion will not occur; the mixture of flammable vapour in air is said to be too lean to burn. Conversely, if the concentration of toluene vapour in air is greater than about 7% then combustion again will not occur; the mixture is said to be too rich to burn. 16 These limits have not been satisfactorily explained theoretically, and their measurement has been found to be very apparatus dependent. A wide range of factors influence the limits of flammability or explosibility, for example: (a) (b) (c) actual test conditions (notably the vessel dimensions, energy of the ignition source and the direction of flame propagation); temperature and pressure; and oxidant concentration.

In addition, different criteria may be used to determine whether or not ignition has occurred. For example, a German (BAM) test uses a pressure rise rather than the flame disengaging from the ignition source as the criterion for ignition. This generally results in a wider flammable range than other methods. 17 Flammability limits are not very convenient working tools as it is difficult to interpret volume concentrations in air. It is often more helpful to know the conditions under which flammable mixtures of vapours and gases in air will be formed, and the parameter most used in this context is flashpoint.

Flashpoint
18 The flashpoint of a liquid is an important and practical flammability characteristic, and is one of the main properties used to determine fire and explosion hazard. The flashpoint is defined as: the lowest temperature, corrected to a pressure of 101.325 kPa, at which a liquid evolves vapours, under the conditions defined in the test method, in such an amount that a flammable vapour/air mixture is produced in the test vessel. You should note that at the flashpoint, continuous combustion does not occur; this takes place at a higher temperature commonly referred to as the fire point. 19 Obviously flashpoint is linked to the flammability or explosibility limits and therefore the factors mentioned earlier will have an affect on its value. In addition, other relevant parameters are: (a) test equipment design; (b) size of sample; (c) ignition source and distance from the liquid surface; (d) ambient pressure; (e) viscosity of the material; and (f) operator interpretation (for some materials it can be difficult to determine when a propagating flame occurs). 20 The hazard being determined is the ability of a substance or preparation to evolve a flammable vapour/air mixture where the introduction or presence of an ignition source would cause a flash. The method of identifying this hazard is to perform a flashpoint test using one of the approved methods. 21 Following the initial ignition, combustion may be sustained. A combustibility test, using an approved method, can confirm whether the combustion is sustained. This test must be carried out if the determined flashpoint lies within certain critical ranges.
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22 There can be problems in determining the flashpoint of multicomponent blends and mixtures (eg minor proportions of an organic flammable solvent present in a mixture), emulsions, some halogenated solvents, viscous liquids and products that form a skin. 23 The flashpoint can be regarded as a lower temperature limit of flammability. This can then help to obtain the temperature range over which a closed vessel can contain a flammable atmosphere in the presence of excess liquid. 24 If a liquid is below its flashpoint temperature, a flammable atmosphere will not be formed. However, if there is a fine-droplet mist or aerosol of a flammable substance, this may produce a flammable atmosphere. Fine-droplet mists or aerosols are known to be flammable at temperatures at least 100 C below the flashpoint. Such mists may form due to mechanical means or during cooling. Similarly, foams may be flammable below the flashpoint temperature. 25 Factors affecting the flashpoint include atmospheric pressure and the composition of the liquid. As the atmospheric pressure decreases, the flashpoint decreases and vice versa. This can be illustrated by considering the flashpoint of toluene as measured in the UK at sea level and at Denver in the mountains of Colorado. UK (sea level) Atmospheric pressure 101.3 kPa Atmospheric pressure 83.3 kPa Flashpoint 4.5 C Flashpoint 1.0 C

Denver (1685 metres)

26 Flashpoint measurements can be corrected for atmospheric pressure by using the following empirical equation: FPt = 0.25(101.3 - P)

where FPt is the difference in flashpoint between that measured at a pressure P (in kPa) and that at a pressure of 101.3 kPa.

27 Flashpoint values quoted in the literature, in general, are for pure substances. The presence of contaminants can have a significant effect on the flashpoint, particularly if the contaminant is relatively more volatile. For example, pure ethylene glycol has a flashpoint of 111 C. However, the flashpoint is reduced to 29 C when acetaldehyde at a level of only 2% is present. 28 Adding water to a solvent can raise the flashpoint, provided the solvent is miscible with water. If sufficient water is added, the aqueous liquor can be rendered non-flammable. This is illustrated in Table 1.
Table 1 Variation of flashpoint with percentage ethanol in water % ethanol in water 100 90 75 50 25 10 5 Flashpoint (C) 13.0 14.5 20.5 23.5 31.5 47.5 61.5

For solvents which are immiscible in water, the flashpoint will be largely unaffected by the addition of water.

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Incidents resulting from inadequate flammability data

29 These four incidents highlight the wide discrepancies that may result in the measurement of flashpoint, depending on the method chosen. In particular, there are the substances that are viscous, and the mixtures that contain only a relatively minor component of a volatile, flammable solvent. Both these require care when choosing the most appropriate test apparatus and method. In these circumstances, the measured flashpoints can vary substantially with the test method. Three of the incidents also demonstrate the serious consequences that can arise when incorrect flashpoint test data is provided, and when too much reliance is placed on that information without further considering the composition of the products.

Incident 1
A half-full 205-litre metal drum contained a proprietary pre-polymer blend used in the manufacture of foams. It was opened and stirred with a flat disc stirrer attached to a standard electric drill. During this process, flammable vapours released from the blend built up in the drum and were ignited by a spark from the stirrer motor. The resulting fireball erupted from the drum, engulfing the head and shoulders of an employee. The pre-polymer formulation consisted of a viscous mixture of polymers, surfactants, catalysts and a pentane blowing agent. The replacement of nonflammable CFC-type blowing agents by flammable alternatives is becoming increasingly widespread, primarily because of the restrictions imposed by environmental legislation. The safety data sheet for the pre-polymer blend stated that the flashpoint was 38 C; the test method used was not quoted. It also stated that the material did not support combustion. The results of independent flashpoint tests carried out with different test apparatus gave the following results: Test method ISO 2719: 1988 ISO 3679: 1983 ISO 1523: 1983 Flashpoint (C) 27.4 17.0 <10.0

The material proved not to support combustion when tested in accordance with Schedule 2 of the Highly Flammable Liquids and Liquefied Petroleum Gases Regulations 1972. This illustrates the wide spread of flashpoint temperatures for a given sample. In terms of CHIP, two of the tests would result in the material being classified as highly flammable; while the other test procedure would result in it being classified as non-hazardous in terms of flammability. The results of the combustibility test can exempt material from being classified as flammable, if the flashpoint is between 21 C and 55 C.

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Incident 2
A company manufactures polyurethane precursors to various specifications. Due to reformulation with a flammable blowing agent, the company undertook a flashpoint determination as part of the classification exercise. The company normally used test ISO 3679 but because the data for a competitors sample had been taken from a test using ISO 1523, they decided to subject all the samples to both tests. All samples were taken from a large-scale evaluation and were replicated. All replicates gave good agreement by the same test method, and the tests were carried out on the same day. The results were as follows: Sample A B C Flashpoint (C) ISO 3679 27 15 7.5 ISO 1523 3 1.5 -8.5

Both ISO 3679 and ISO 1523 are test methods contained in Annex V of the Dangerous Substances Directive as equilibrium methods suitable for determining the flashpoint of viscous liquids.

Incident 3
A man was killed when a storage tank exploded during welding work nearby. The tank contained a waste product from another company which this company then treated to produce agricultural chemicals. The waste product was essentially an aqueous mixture of acetic and phosphoric acids. However it was the product of a solvent extraction process with toluene. Although essentially aqueous there were small amounts of toluene present in the mixture which allowed flammable vapours to build up in the head space of the tank. The parent company had quoted a flashpoint on the safety data sheet as 91 C. Further tests of the flashpoint were undertaken during the investigation. The results were as follows: Test method ISO 3679 ISO 1523 Flashpoint (C) 55 - 65 28 - 33

Incident 4
An explosion occurred in a heated product storage tank containing recycled motor oil, seriously injuring an employee. Tests during the investigation showed that waste motor oil normally contains approximately 0.5% w/w of petrol. This results in a significant lowering of the measured flashpoint. A comparison between the flashpoints of oil contaminated with petrol measured by equilibrium and rapid equilibrium methods is shown here: Nominal petrol addition to unused oil (%w/w) 0 0.5 1.0 1.5 Flashpoint (C) ISO 3679 ISO 1523 >>110 92 65.5 47.5 >>110 68 49 32

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Flashpoint measurement
30 Flashpoints can be measured in two modes, equilibrium or non-equilibrium, and in essentially two types of apparatus, closed cup and open cup apparatus. The most extensively used apparatus are: the Abel closed cup; the Pensky-Martens closed cup; the Tag open and closed cups; the Setaflash apparatus; and the Cleveland open cup. 31 Closed cup measurements can be equilibrium or non-equilibrium methods, whereas the open cup measurements are non-equilibrium methods. 32 Closed cup flashpoints are normally several degrees lower than those determined by open cup methods, the difference being more marked when a closed cup equilibrium procedure is used. This is because they are determined on a saturated vapour/air mixture, whereas in the open cup test, the vapour has free access to the air. Consequently, with the open cup test, the vapour is slightly less concentrated at a given temperature due to vapour losses to the surrounding atmosphere. 33 The closed cup flashpoint test roughly approximates to a situation where the top closure of a drum containing a liquid substance is opened, and a light is used to see if the drum is full or empty. When the light is of a type that can ignite the vapours in the drum, an explosion is likely if the temperature is at or slightly above the closed cup flashpoint of the liquid substance. 34 Likewise, the open cup flashpoint condition is compared to the potential ignition of vapours above a pool of spilt liquid substance on the floor in the absence of draughts. Table 2 shows the comparative flashpoints measured in open and closed cup apparatus for pure liquids.
Table 2 Comparison of flashpoints measured in open and closed cup apparatus Material Closed cup Acetic acid Acetone n-butanol Methanol Toluene 40 Flashpoint (oC) Open cup 43 -9 44 16 7

-17
29 10 4

35 The ability of a liquid to produce a flammable vapour/air mixture within precisely defined conditions, which will cause a flash at a certain temperature, is an intrinsic property of the liquid. The flashpoint test methods which identify this property do not measure flashpoints under such precisely defined condition. They have differing constants in each test method which effectively reflect differing conditions of use. 36 Flashpoint measurement is an empirical approach, and therefore it is important when quoting flashpoints to define the measurement technique. Because it is an empirical measurement, you cannot compare values of flashpoint obtained from different methods. However good agreement should exist if comparing equilibrium methods together, or non-equilibrium methods together, particularly with pure (single component) liquids. 37 The major difference between equilibrium and non-equilibrium methods is not merely that the apparatus for equilibrium methods has a cover over the sample vessel, so containing the vapours produced. It is also the different way in which the temperature of the liquid is attained.

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38 Essentially in non-equilibrium methods, the temperature is increased slowly over a given range with the source of ignition being presented to the vapour at intervals until the flash is observed. In equilibrium methods, the temperature is stepped to a given value or increased at a very slow rate, and the vessel allowed to equilibrate for a fixed period of time before the source of ignition is introduced. 39 The test is therefore at equilibrium because this time interval allows the temperature of the vapour to be the same as that of the liquid, so achieving an almost steady state. In actual fact, true equilibrium is not achieved because in all accepted test methods, the lid of the vessel is not heated. Consequently there is a temperature gradient in the vapour space of the apparatus. Since the measurement of flashpoint is empirical, this effect matters little in practice and the material is deemed to be at equilibrium. 40 However in test apparatus which operates with a large cup and a fluid which contains only a small proportion of a low flashpoint material then the equilibrium effect, coupled to the rate of release of the volatile components, may be appreciable.

What do the Regulations require?

41 As discussed earlier, the Regulations state that substances and preparations should be classified so as to determine their hazard. The applicable test methods for the measurement of flashpoint are stated in the relevant guides, and in the approved codes for transport and supply (see paragraph 8). 42 The principle for all the flashpoint test methods is, (normally) after suitably cooling or warming the test material to a few degrees below the test temperature, to place the liquid in a test vessel. The substance is then heated to the test temperature according to the procedure described in the individual test method contained in the various standards. Ignition trials are then carried out in order to ascertain whether or not the sample flashes at the test temperature. 43 The methods quoted in the Regulations recognise the two modes of test, and state applicable test methods for each mode. These test methods are as follows: Equilibrium test methods ISO 1516: 1981 ISO 3680: 1983 ISO 1523: 1983 ISO 3679: 1983 Paints, varnishes, petroleum and related products flash/no flash test closed cup equilibrium method Paints, varnishes, petroleum and related products flash/no flash test rapid equilibrium method Paints, varnishes, petroleum and related products - determination of flashpoint - closed cup equilibrium method Paints, varnishes, petroleum and related products - determination of flashpoint - rapid equilibrium method

Non-equilibrium test methods 44 Many of the standards listed here have equivalent national standards which obviously can be used instead of those quoted: BS 2000: Part 170 EN57 Flashpoint by the Abel apparatus (non-statutory method) Determination of flashpoint - Abel-Pensky closed tester

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ASTM D56

Tag apparatus Determination of flashpoint - Pensky-Martens closed cup method

ISO 2719: 1988

45 Only certain test methods are applicable for determining the flashpoint of viscous fluids. These are ISO 3679, ISO 3680, and ISO 1523. 46 The various pieces of legislation have different classification categories and different transition temperatures, and these are discussed in the following paragraphs. Classification of flammability for supply 47 Under the CHIP regulations,2 substances are essentially classified for flammability into three categories of danger according to their flashpoints: (a) extremely flammable - (b) highly flammable (c) flammable - - those liquids with a flashpoint lower than 0 C and a boiling point (or initial boiling point) lower than or equal to 35 C; liquids which have a flashpoint below 21 C but are not extremely flammable; liquids which have a flashpoint equal to or greater than 21 C and less than or equal to 55 C and which support combustion when tested in the prescribed manner (given in Schedule 2 of the Highly Flammable Liquids and Liquefied Flammable Gases Regulations 19725) at 55 C.

48 The transition temperatures between the various categories of danger are therefore critical, and there are specific methods for measuring the flashpoint. When a flashpoint is determined by a non-equilibrium method and the value is found to be 02 C, 212 C or 552 C, the flashpoint should be confirmed by using an equilibrium method. 49 In practice, for a liquid which possesses a flashpoint, the limiting criteria for classification as extremely flammable will normally be determined by the boiling point criterion. So the relationship between flashpoint and boiling point is such that: for a liquid with a flashpoint and with a boiling point (or initial boiling point) below 35 C, its flashpoint will be lower than 0 C. Classification of flammability for transport 50 Under the Carriage of Dangerous Goods (Classification, Packaging and Labelling) and Use of Transportable Pressure Receptacles Regulations 1996,3 liquids are essentially considered as flammable if: the flashpoint is 61 C or less and, when their flashpoint is above 35 C, they support combustion when tested in the prescribed manner at 60.5 C or 75 C.

The prescribed manner is given in Appendix B of the Approved requirements and test methods for the classification and packaging of dangerous goods for carriage.7 A substance with a flashpoint above 61 C, but actually transported at a temperature at or above its flashpoint, is also considered a flammable liquid. 51 The thresholds for the categories of flammability hazard are:

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I II

(high hazard) (medium hazard)

- - -

those liquids with a boiling point (or initial boiling point) lower than or equal to 35 C and a flashpoint not exceeding 61 C; those liquids with a boiling point (or initial boiling point) above 35 C and a flashpoint of 23 C or less unless they meet the criteria of III(c) below; and (a) (b) (c) those liquids with an initial boiling point above 35 C and a flashpoint of 23 C or above but not exceeding 61 C; or liquids with an initial boiling point above 35 C and a flashpoint above 61 C carried or offered for carriage at a temperature above their flashpoint; or viscous liquids with a flashpoint of 23 C or below unless excluded because they meet certain solvent separation, composition and viscosity requirements specified in the regulations.

III (low hazard)

52 As in the case of supply, the transition temperatures between the various categories of danger are critical, and at these temperatures there are specific methods for the measurement of flashpoint. When a flashpoint is determined by a non-equilibrium method and the value is found to be 232 C or 612 C, or the substance is viscous, the flashpoint should be confirmed by the use of an equilibrium method. Classification of flammability in the Highly Flammable Liquids and Liquefied Petroleum Gases Regulations 19725 53 The Highly Flammable Liquids and Liquefied Petroleum Gases Regulations 1972,5 as amended by CHIP,2 define highly flammable liquids as any liquid, liquid solution, emulsion or suspension: (a) (b) with a flashpoint less than 32 C measured by any one of the approved methods specified in Part III of Schedule 1 to the CHIP Regulations;2 and which when tested in the manner specified in Schedule 2 to the Highly Flammable Liquids and Liquefied Petroleum Gases Regulations 19725 (ie at 50 C) supports combustion.

Ammonia, liquefied flammable gas and liquefied petroleum gas are excluded from this definition. 54 As with supply and transport, an equilibrium method is required only if the flashpoint is determined by a non-equilibrium method and lies within 2 C of the critical temperature, ie within the range 30-34 C.

How do the equilibrium methods differ?

ISO 1523 55 This test method is used to determine the actual temperature of the liquid when ignition of the vapours first occurs, ie by definition the flashpoint of a material. The standard can be applied to assessing the flashpoint of a paint, varnish, paint binder,

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solvent, petroleum or a related product. It is suitable for viscous liquids but there are no limits set for the viscosity quoted in the standard. The method is suitable for testing over the temperature range 5 to 110 C. Any of the following test apparatus can be used: (a) (b) (c) (d) Abel; Abel-Pensky; Pensky-Martens; Tag.

56 All the above apparatus are similar in that the volume of the cup is relatively large (approximately 50 cm3) and fitted with a close-fitting lid. The test portion is heated in the closed cup by immersion in a suitable bath. The temperature of the bath is slowly raised at such a rate that the difference in temperature between the liquid in the bath and the test portion in the cup never exceeds 2 C. This heating procedure ensures that the temperature of the test portion does not rise more quickly than about 0.5 C in 1.5 minutes. During the heating up period, ignition trials are carried out at intervals of not less than 1.5 minutes. The lowest temperature at which a flash occurs is recorded. The test is repeated using a fresh test portion. The flashpoints are corrected to standard atmospheric pressure. ISO 3679 57 The apparatus specified in this standard allows determination of the flashpoint by a more rapid method and with a smaller test portion (approximately 2 cm3) than the method in ISO 1523. The standard can be applied to assessing the flashpoint of a paint, varnish, paint binder, solvent, petroleum or a related product. It is suitable for viscous liquids but there are no limits set for the viscosity quoted in the standard. The method is suitable for use when the flashpoint is below 110 C. 58 The apparatus is heated to a temperature 3 C below the expected flashpoint. The test portion is then added to the apparatus, and allowed to equilibrate for 60 seconds before carrying out an ignition trial. If no flash is observed, the test is repeated at temperatures in 5 C higher intervals with fresh test portions, until a flash is observed. If a flash is observed at the initial test temperature, the test is repeated at temperatures in 5 C lower intervals with fresh test portions, until no flash is observed. Having established a flash between the two temperatures 5 C apart, the test is repeated again with fresh test portions at 1 C intervals above the lower of the two temperatures until a flash is observed. The flashpoints are corrected to standard atmospheric pressure. ISO 3680 59 This standard uses the apparatus used in ISO 3679 and is applicable for the same types of materials and over the same temperature range. The difference is that it does not determine the actual flashpoint of a liquid, but determines whether the liquid flashes at a specific temperature. It is a so-called flash - no flash method. It can be used therefore to determine the behaviour of a liquid at a selected equilibrium temperature, as required under the regulations relating to the storage, transport or supply of flammable products. 60 The liquid is heated to the specific temperature, and allowed to equilibrate for at least 60 seconds before the ignition trial is carried out. ISO 1516 61 This is the flash - no flash test equivalent to ISO 1523. The difference is that the liquid is allowed to equilibrate at the specific test temperature for 10 minutes

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before the ignition trial. Also if no flash occurs, the test sample is maintained at this temperature for a further 10 minutes and the ignition trial repeated.

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The interpretation of flashpoint

62 Experience has shown that even for pure single component materials, there are discrepancies between the various types of equipment. Table 3 illustrates the average comparative range for a range of different test apparatus. A survey of a number of comparison programmes shows that the Abel closed cup design often gives the lowest results.
Table 3 Comparison of flashpoint temperature ranges between different test apparatus Test apparatus Abel Setaflash Tag Pensky-Martens Abel-Pensky Luchaire-Finances Tag Cleveland Open/closed Closed Closed Closed Closed Closed Semi-open Open Open Average comparative range

about 0 - 6.9 oC higher about 0.5 - 5 oC higher about 1.7 oC lower to 6 oC higher about 0.2 oC lower to 1.4 oC higher about 5.1 - 15.6 oC higher about 6.4 - 16.1 oC higher about 11.7 - 26.1 oC higher

63 The variations will be more marked when procedural changes are introduced (ie equilibrium, rapid equilibrium and non-equilibrium). In general the value of the determined flashpoint increases in the order: equilibrium < rapid equilibrium < non-equilibrium 64 Equilibrium flashpoint procedures tend to be time consuming, and it is often more expedient and convenient to use a small-volume test apparatus with the associated rapid equilibrium test procedure. For many materials, and certainly for pure compounds, this is perfectly adequate. However, as the incidents described in this guidance note show, for certain mixtures an equilibrium procedure is a better means of assessing the flammability hazard. This is particularly so for those mixtures containing relatively low levels of low flashpoint materials, which may be left for relatively long periods in a closed system.

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Important points to bear in mind

The guidance has illustrated the difficulties that can arise with the measurement and interpretation of flashpoint. The following checklist summarises the important points taken from the guidance. These need to be understood in order to correctly apply flashpoint information.

If you are a user of the substance

1

Remember, flashpoint is an empirical measurement of a substance.

2 The flashpoint temperature gives an indication of the flammability hazard, but does not predict the level of safety under specific circumstances of use. Make sure you read the safety data sheet for additional information. 3 (a) (b) (c) (d) (e) (f) Flashpoint values are variable, dependent on: mode of test, ie equilibrium, rapid equilibrium or non-equilibrium; apparatus type and condition; operator interpretation; sampling procedure, particularly for mixtures, halogenated solvents and emulsions; sample conditioning, ie how the sample has been handled and stored before the test; ambient pressure.

4 For pure single component, non-viscous liquids, the determined flashpoint should be comparable between all the approved equilibrium methods.

If you are carrying out a flammability classification of a substance

5 When giving the flashpoint of a substance, always quote the test method used. 6 For multicomponent mixtures, particularly those containing a minor proportion of a volatile low-flashpoint solvent, choose the most appropriate method after consideration of the applicable standards. Do not just use any of the test apparatus that you may have readily available to you. The incidents described in this document suggest that for this type of substance or preparation, true equilibrium test methods using apparatus that contains a relatively large volume of liquid are appropriate, ie ISO 1523 and ISO 1516. 7 Remember there is a duty under the various regulations to classify and label your products correctly. If a flashpoint test is giving non-reproducible results, or if two test methods give conflicting results, then your duty is to resolve these uncertainties satisfactorily - not to classify and label materials on the basis of unsatisfactory results. 8 If there are situations where the risk during use is greater than that suggested by the classification or labelling, this information should be present in the safety data sheet. For example, there could be a substance with a flashpoint of between 21 C and 55 C, and the substance is shown not to support combustion, and so it is not classified as flammable under CHIP.2 However there may be an increased risk of producing a flammable atmosphere by vapour enrichment or accumulation. The safety data sheet could warn users of this danger. The use of risk phrase R18 on the supply label and in the safety data sheet is applicable. Alternatively you could provide information on any flammable components.

The interpretation and use of flashpoint information

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References
1 Recommendations on the transport of dangerous goods: manual of tests and criteria Second revised edition (ST/SG/AC.10/11/Rev.2) United Nations 1995 ISBN 92 1139049 4 2 Chemicals (Hazard Information and Packaging for Supply) Regulations 1994 SI 1994/3247 HMSO 1994 ISBN 0 11 043877 9 as amended by the Chemicals (Hazard Information and Packaging for Supply) (Amendment) Regulations 1996 SI 1996/1092 HMSO 1996 ISBN 0 11 054570 2, the Chemicals (Hazard Information and Packaging for Supply) (Amendment) Regulations 1997 SI 1997/1460 Stationery Office 1997 ISBN 0 11 063750 X, the Chemicals (Hazard Information and Packaging for Supply) (Amendment) Regulations 1998 SI 1998/3106 Stationery Office 1998 ISBN 0 11 079931 3, and the Chemicals (Hazard Information and Packaging for Supply) (Amendment) Regulations 1999 SI 1999/197 Stationery Office 1999 ISBN 0 11 080410 4 3 Carriage of Dangerous Goods (Classification, Packaging and Labelling) and Use of Transportable Pressure Receptacles Regulations 1996 SI 1996/2092 HMSO 1996 ISBN 0 11 062923 X 4 Notification of New Substances Regulations 1993 SI 1993/3050 HMSO 1993 ISBN 0 11 034278 X 5 The Highly Flammable Liquids and Liquefied Petroleum Gases Regulations 1972 SI 1972/917 HMSO 1972 ISBN 0 11 020917 6 6 The Control of Major Accident Hazards Regulations 1999 (due to come into force April 1999) 7 Approved requirements and test methods for the classification and packaging of dangerous goods for carriage. Carriage of Dangerous Goods (Classification, Packaging and Labelling) and Use of Transportable Receptacles Regulations 1996. Approved requirements L88 HSE Books 1996 ISBN 0 7176 1221 X 8 Approved guide to the classification and labelling of substances and preparations dangerous for supply. CHIP97 L100 HSE Books 1997 ISBN 0 7176 1366 6 9 Annex V of the Dangerous Substances Directive (67/548/EEC) which has been directly adopted in the UK as an Approved Code of Practice. While every effort has been made to ensure the accuracy of the references listed in this publication, their future availability cannot be guaranteed.

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Further information
For information about health and safety ring HSEs Infoline Tel: 0845 345 0055 Fax: 0845 408 9566 Textphone: 0845 408 9577 e-mail: hse.infoline@natbrit.com or write to HSE Information Services, Caerphilly Business Park, Caerphilly CF83 3GG. HSE priced and free publications can be viewed online or ordered from www.hse.gov.uk or contact HSE Books, PO Box 1999, Sudbury, Suffolk CO10 2WA Tel: 01787 881165 Fax: 01787 313995. HSE priced publications are also available from bookshops. The Stationery Office publications are available from The Stationery Office, PO Box 29, Norwich NR3 1GN Tel: 0870 600 5522 Fax: 0870 600 5533 e-mail: customer.services@tso.co.uk Website: www.tso.co.uk (They are also available from bookshops.) Statutory Instruments can be viewed free of charge at www.opsi.gov.uk.

Published by HSE 04/10

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