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 Table of Contents

1. INTRODUCTION ....................................................................................................................1
1.1 SCOPE ..............................................................................................................................1
1.2 CHLORINE INSTITUTE STEWARDSHIP PROGRAM ..................................................................1
1.3 HISTORY ...........................................................................................................................1
1.4 DISCLAIMER ......................................................................................................................2
1.5 APPROVAL .........................................................................................................................2
1.6 REVISIONS ........................................................................................................................2
1.7 REPRODUCTION.................................................................................................................2
PART A: "REACTIONS OF CHLORINE AND HYDROGEN: A BIBLIOGRAPHY" ...............3

2. SUMMARY .............................................................................................................................3
2.1 CHAIN REACTIONS .............................................................................................................3
2.2 METHODS OF INITIATING THE REACTION OF HYDROGEN AND CHLORINE ..............................3
2.3 EXPLOSIVE LIMITS .............................................................................................................6
3. SELECTED REFERENCES...................................................................................................6

4. ABSTRACTS .......................................................................................................................11

PART B: "REACTION CHARACTERISTICS OF HYDROGEN ADMIXED WITH

CHLORINE, OXYGEN AND INERT GASES".........................................................22

5. SUMMARY ...........................................................................................................................22

6. DISCUSSION .......................................................................................................................22

7. IGNITION LIMITS.................................................................................................................24

8. EXPLOSIONS AND DETONATIONS ..................................................................................26

9. SELECTED REFERENCES.................................................................................................30

APPENDIX A ..............................................................................................................................31

i
 EXPLOSIVE PROPERTIES OF GASEOUS MIXTURES
CONTAINING HYDROGEN AND CHLORINE 1

1. INTRODUCTION

1.1 SCOPE

This pamphlet is presented in two parts:

Part A: Reactions of Chlorine and Hydrogen: A Bibliography, aims to bring together in a

single source all known pertinent, published references on explosive properties of
gaseous mixtures containing hydrogen and chlorine. References for each of those
published reports are found in Section 3 of this pamphlet. In addition, a number of
selected abstracts are included (See Section 4). The availability of an abstract will be
indicated by a number in parenthesis [e.g. (46-1)] following the document’s citation in the
text.

Part B: Reaction Characteristics of Hydrogen Admixed with Chlorine, Oxygen and Inert
Gases, is based on the literature review of reaction characteristics of hydrogen with
chlorine and with mixtures of chlorine and oxygen, and represents an attempt to
graphically show ignition and detonation zones for the systems hydrogen-chlorine-
oxygen and hydrogen-chlorine-air. In addition the effects of inert gases, nitrogen, water
vapor, hydrogen chloride and carbon dioxide on the ignition limits of the hydrogen-
chlorine system are illustrated.

1.2 CHLORINE INSTITUTE STEWARDSHIP PROGRAM

The Chlorine Institute, Inc. (CI) exists to support the chlor-alkali industry and serve the
public by fostering continuous improvements to safety and the protection of human
health and the environment connected with the production, distribution and use of
chlorine, sodium and potassium hydroxides, and sodium hypochlorite; and the
distribution and use of hydrogen chloride. This support extends to giving continued
attention to the security of chlorine handling operations.

Chlorine Institute members are committed to adopting CI safety and stewardship

initiatives, including pamphlets, checklists, and incident sharing, that will assist members
in achieving measurable improvement. For more information on the Institute’s
stewardship program, visit the CI website at www.chlorineinstitute.org.

1.3 HISTORY

A predecessor group of the Institute's Properties, Analysis and Specifications Committee

(PAS) met in September, 1968, to discuss a proposal for a study to be sponsored by the
Institute made by D.S. Rosenberg in a memorandum of February 1, 1968 entitled,
"Hydrogen Explosion Hazards in Chlorine Storage Tanks". The conferees agreed to the
desirability of exploring the subject further, and requested that the Institute obtain any
additional data which might be available.
2 PAMPHLET 121

Part A of this pamphlet is based on a review of the literature by D.S. Rosenberg in April,
1969, updated through mid-1977 by L.E. Tufts and other members of the PAS, and
again through mid-1989 by H.J. Hoenes, Jr. It includes information on availability of
published papers on the subject, with abstracts where available.

Part B of this pamphlet was originally prepared by L.E. Tufts of the Institute's Properties,
Analysis and Specifications Committee. This edition has included some minor revisions.

1.4 DISCLAIMER

The information in this pamphlet is drawn from sources believed to be reliable. The
Institute and its members, jointly and severally, make no guarantee, and assume no
liability, in connection with any of this information. Moreover, it should not be assumed
that every acceptable procedure is included, or that special circumstances may not
warrant modified or additional procedures. The user should be aware that changing
technology or regulations may require a change in the recommendations herein.
Appropriate steps should be taken to ensure that the information is current when used.
These suggestions should not be confused with federal, state, provincial, municipal or
insurance requirements, or with national safety codes.

1.5 APPROVAL

The Institute's Health, Environment, Safety and Security (HESS) Issue Team approved
Edition 3 of this pamphlet on January 23, 2009.

1.6 REVISIONS

Suggested additions and/or revisions should be directed to the Secretary of the Institute.

1.6.1 Significant Revisions in Current Edition

This edition is the pamphlet’s first update since July 1992. A new literature search was
not conducted. If you are aware of new research on this topic please submit copies of
documents and/or references to the Secretary of the Institute. Significant updates to this
revision as approved include:

• Deletion of Section 2.4 – Plant Operations, and Section 2.5 – Hydrogen

Control in Plant Design. Portions of the information found in Sections 2.4 and
2.5 have been inserted into CI Pamphlet 86.

• Section 5 was amended to note that pressures above 1 atmosphere can

impact the explosivity of the Cl2/H2/O2 mixtures.

1.7 REPRODUCTION

The contents of this pamphlet are not to be copied for publication, in whole or in part,
without Institute permission.
4 PAMPHLET 121

2.2.1 Thermal Ignition

In any purely adiabatic system the heat from an exothermic reaction, no matter how
slow, will cause an acceleration of both rate of reaction and temperature increase. Only
at low concentrations of one of the components is the heat capacity of the hydrogen-
chlorine system sufficient to absorb the heat of reaction without massive increases in
both temperature and pressure.

For mixtures with low concentrations of hydrogen or of chlorine the maximum

temperature reached and the fraction of minor reactant consumed will depend on the
initiating conditions, the initial composition, and on the conditions promoting chain
termination. In cases where the potential for reaction of large amounts of hydrogen-
chlorine mixtures exist, particularly near the equivalence point, strong explosions and
violent detonations accompanied by temperatures as high as 4532°F (2500°K) result
upon adiabatic reaction. Reaction under such conditions is essentially complete. When
the chlorine is considerably in excess of the hydrogen the temperature reached by rapid
adiabatic reaction is significantly reduced because of the energy absorbed in
dissociation of the excess chlorine.

The thermal reaction of hydrogen and chlorine has been studied in considerable detail
by Pease and his associates. In their system, the reaction was quite slow at
temperatures as high as 680°F (360°C). The data was explained in terms of a Nernst
chain (See Section 2.1) starting and ending on the walls, with an estimated chain length
of 104 for stoichiometric proportions of the pure reactants.

Thermal initiation of the hydrogen-chorine reaction was also studied by Kunin and
Serdyukov (46-1) using a platinum coil to which a thermo-couple was fastened. The
maximum coil temperature of 2192°F (1200°C) was needed to produce an explosive
reaction with 7% H2 in a H2-Cl2 mixture. As the H2 content was increased, the coil
temperature needed to produce an explosion dropped to 440°F (227°C) at 19% H2. The
difference in thermal reaction behavior in these experiments as compared to those of
Pease can be attributed to the nature and locus of the surface on which the free radicals
are formed for initiating the reaction.

The thermal reaction in a flame front is very rapid. Flames have been studied in
considerable detail in various types of equipment by Kunin and Serdyukov (46-1) and by
Bartholome (49-1). Flame velocities measured by Bartholome are higher than those of
Serdyukov, but in both cases are significantly lower than for H2-air systems. The data
indicate that detonation waves are less severe for H2-Cl2 than for H2-O2 systems.
 EXPLOSIVE PROPERTIES OF GASEOUS MIXTURES
CONTAINING HYDROGEN AND CHLORINE 5

2.2.2 Chain Ignition

In studies of the explosive characteristics of the H2-Cl2 reaction the reaction is initiated
by formation of chlorine free radicals, although an excellent study of academic interest
by Martin and Diskowski (56-4) employed thermally excited hydrogen atoms. Reaction
initiation thus precedes any thermal effects. The behavior of a given reaction mixture,
i.e. the rate at which the reaction proceeds and the fraction of limiting reactant
consumed are functions of the concentration of free radicals generated by the initiating
source.

The most effective method of initiating chlorine free radicals is by irradiation with light of
wave length less than 4,850oA. Selected regions of the mercury arc spectrum are
usually employed, such as filtered light of wave length 3,650°A and 4,060°A. An
excellent study of the oxygen-free system is given by Ritchie and Taylor (42-1). The
reaction has also been used to reduce the concentration of hydrogen in electrolytic cell
gas (67-1). It is greatly inhibited by O2. The reaction chain length of a stoichiometric
mixture can be as high as 106, but can be reduced to 103 with 1% O2.

The usual method of reaction initiation for study of explosive limits is with a high-voltage
spark. This procedure was used by Lindeijer (37-2), Weissweiler (36-1), Umland (54-1),
Eichelberger, Smura and Bergenn (61-1), Davies (58-1), Suzuki and Fukunaga (56-1),
van Diest and DeGraff (65-1), and Kunin and Serdyukov (46-1).

Only two major studies have employed heated wires. Rozlovskiy (56-2, 56-3) used a
platinum spiral to give a maximum temperature of 2192°F (1200°C). Grelecki and Mann
(68-1) heated a Parr wire to fusion. Explosive limits are narrower for hot wire ignition
than for spark ignition.

The nature of the ignition source is very important in the study of detonations. In order
for a reaction in a flammable mixture to degenerate from a deflagration to a detonation,
the flame front must travel a certain distance, termed the run-up distance. This distance
is greater for hot wire ignition than for spark ignition. Thus, in studies carried out by
Grelecki and Mann (68-1) with hot wire ignition in a 6 foot stainless steel tube, no
detonations were observed until the H2 content reached 29% to 39%, while Davies (58-
1) observed detonations at H2 concentrations as low as 12% in a 3 foot tube with spark
ignition. It should be noted, however, that the experimental techniques similar to those
of Grelecki and Mann were much more sophisticated than those of Davies. In the work
of Eichelberger, et. al. spark ignition was used with experimental techniques similar to
those of Grelecki and Mann, giving detonation limits somewhat lower than with hot wire
ignition. The reaction tube was 20 feet long.

In studies by Weissweiler (36-1), who carried out the major definitive investigation in this
field, a transition from an explosion to detonation was observed with about 18% H2 using
pure, dry reactants. His studies were carried out in a glass flask or bomb, using spark
ignition.
6 PAMPHLET 121

2.3 EXPLOSIVE LIMITS

The definition of the explosive limit as the lowest concentration of hydrogen that will give
an appreciable pressure rise when the reaction is initiated has been accepted by major
investigators in this field. It is the definition used for the extensive studies of Weissweiler
(36-1) and Umland (54-1). J. Van Diest and DeGraff (65-1) use temperature rise.

Other investigators have attempted to define the limit as that at which a flame front
appears. This definition was used by Lindeijer and gives much higher values (8% to
10% H2). Moreover, the H2-Cl2 flame is difficult to observe. With great care, Weissweiler
observed a flame at H2 concentrations as low as 7%.

3. SELECTED REFERENCES

All references in this Section 3 are related to explosion and detonation limits in the Cl2-
H2 system. The number at the left of the reference indicates the availability of an
abstract in Section 4 of this pamphlet. The following references are directly referenced
in Part A of this pamphlet.

# Abstract

49-1 Bartholome, E. Zur Methodik der Messung von Flammengeschwindigkeit. Zeit

Electrochemie, 53, 191-196 (1949); [German]

58-1 Davis, I.P.W. Hydrogen-Chlorine Explosions in Tail Gas, B.P. Chemicals Ltd.,
Murgatroyds Works, Oct. 30, 1958

67-1 Eichelberger, W.C. and Hartford, W.H. The Photochemical Reaction of Hydrogen
and Chlorine in Electrolytic Cell Gas, Elect. Technology, 5, 104-107 (1967)

61-1 Eichelberger, W.C., Smura, B.B. and Bergenn, W.R. Explosions and Detonations in
Chlorine Production. Chem Engrg. Prog., 57:8, 94-97 (1961)

68-1 Grelecki, C.J. and Mann, D.J. Flammability Studies on Mixtures of Hydrogen with
Chlorine Residual Gases. RMD Report 2298, Thiokol Chem. Corp. (1968)

46-1 Kunin, T.I. and Serdyukov, J. Chlorine and Hydrogen Explosion Temperatures and
Limits in Hydrogen Chloride. Zhur. Obshchey Khimii, 16:9, 1421-1430 (1946)
[Russian, English Translation by Foreign Technology Division.] WP-AFB (Astia AD
292616)
 EXPLOSIVE PROPERTIES OF GASEOUS MIXTURES
CONTAINING HYDROGEN AND CHLORINE 7

37-2 Lindeijer, E. W. Explosive Limits of Hydrogen and Chlorine with Oxygen, Carbon
Monoxide and Nitrous Oxide etc. Rec. Trav. Chem., 56, 97 (1937) and 56, 105-118
(1937)

56-4 Martin, H. and Diskowski, H. Der Vorgang H + Cl2 -- HCl + Cl als

Molekularstrahlreaktion. Zeit Elecktrochemie, 60, 964-970 (1956) [German]

42-1 Ritchie, M. and Taylor, D. The Photocombination of Hydrogen and Chlorine. Proc.
Roy. Soc., 180, 423-451 (1942)

56-2 Part III. Normal Combustion of Chlorine Hydrogen Mixtures. ZFK 30, 2489 (1956)

56-3 Part IV. Kinetics and Mechanism of Reaction in Flame ZFK 30, 2713 (1956)

56-1 Suzuki, O. and Fukunaga, T. Explosion Limits of Ternary Mixtures of Hydrogen-

Chlorine-Air. J. Elec. Soc. Japan, 24, 104-108 (1956) [Japanese with English
abstract]

54-1 Umland, A.W. Explosive Limits of Hydrogen-Chlorine Mixtures. J. Elec. Soc.,

101:12, 626-631 (1954)

65-1 Van Diest, J. and DeGraff, R. Methode nouvelle de determination des limits
d'inflammabilite de melanges gazeux de chlore et d'hydrogene. Industrie Chimique
Belge 30:11, 1195-1203 (1965) [French]

36-1 Weissweiler, A. Versuche zur Bestimmung der Explosionsgrenzen von Chlor-

Wasserstoffgemischen. Zeit Elektrochemie, 42, 499-503 (1936), [German]

Other references dealing with the subject matter of Part A are:

# Abstract

Angel, G., Lunden, T., Brannland, R. and Dahlerus, S. Influence of Impurities in the
Electrolyte in Chlorine-Caustic Electrolysis by the Mercury Cell Process. S. Elect,
Soc., 99, 435 (1952); 100, 39 (1953); 102, 124 (1955); 104, 167 (1957)

74-1 Antonov, V.N., Frolor, Yu E., Rozlovski, A.I. Maltseva, A.S. Explosion Hazard of
Hydrogen and Chlorine Mixture. U.S.S.R.O. Kim Prom. 3, 205-208 (1974) [Moscow]

Antweiler, et. al. Chemie-Ing. Techn., 34, 387 (1962)

8 PAMPHLET 121

53-2 Ashmore, P.G. Explosions in Mixtures of Hydrogen, Chlorine and Nitrogen

Trichloride. Nature, 172, 449-450 (9/5/53). (Abs. in Chem. Abs. 48, 1784 (2/25/54)

Ashmore, P.G. Sensitized ignitions in Mixtures of Hydrogen and Chlorine. 5th

Symposium on Combustion, New York (1955) p. 700

50-1 Bartholeme, E. Die Flammengeschwindigkeit in sehr heissen Flammen. Zeit

Electrochemie, 54, 169-172 (1950), [German]

Bartkowiak, A. and Zabetakis, M.G. Flammability Limits of Methane and Ethane in

Chlorine at Ambient and Elevated Temperatures and Elevated Temperatures and
Pressures. U.S. Bu. Mines Rept. 5610 (1960)

Becker, R. Uber Detonationen. Zeit Electrochemie, 42, 457 (1936) [German]

Bodenstein, M. Hundert Jahre Photochemie de Chlorknallgases. Ber. dtsch. Chem.

Ges. 75, 119 (1942) [German]

Bodenstein, M. Abschlussarbeiten am Chlorknallgases. Z. Phys. Chemie, 48, 239

(1940-41) [German]

Bodenstein, M. Die Reaktionskinetischen Grundlagen der Verbrenn ung suorgange.

Zeit Elektrochemie, 42, 439 (1936) [German]

78-1 Casson, H.V. and Loftfield, R.E. Electrolytic Cell. U.S. Patent US 4087344,
2 May 1978, 7pp.

Coward, H.F. and Jones, G.W., Limits of Flammability of Gases and Vapors. U.S.
Bureau of Mines Bull 503, 19-23 (1952)

Cowley, et. al. Trans. Inst. Chem. Engrs., 41, 372 (1963)

Cummings, D. and Leighton, J. Separations of Gases. S. African Patent ZA

73/9427, 27 Sep 1974, 15pp.

63-1 Farbwerke - Hoechst Process for Complete Liquefaction of Chlorine. Chem. Ing.
Tech., 35, 41-43 (1963)
Follows, A.G. Reaction of Hydrogen with Chlorine in Cell Gas in the Presence of
Ultraviolet Light. Chlorine Institute Proceedings, 9th Meeting of Chlorine Plant
Managers (2/2/66) 6pp, 8 figures

76-1 Frolov, Y., Mal'tseva, A.S., Serdechki, V.M., Fedotov, K.E., and Rozolovskii, A.I.
Certain Features of the Combustion of Lean Mixtures of Hydrogen with Chlorine.
Khim. Prom-st. (Moscow), (5), 358-60 (1976)
 EXPLOSIVE PROPERTIES OF GASEOUS MIXTURES
CONTAINING HYDROGEN AND CHLORINE 9

Guy, Charles A. Continuous Analysis of Hydrogen in Chlorine Gas. Chlorine Institute

Proceedings, 9th Meeting of Chlorine Plant Managers (2/2/66) 1Opp. 7 figures

Hikata, T. and Urano, I. J. Chem. Soc. Japan 60, 48 (1957) [Japanese]

Jones, G.W. Inflammation Limits and Their Practical Application in Hazardous

Industrial Operations, Chem. Rev. 22, 1 (1938)

Jost, W. Explosion and Combustion Processes in Gases. McGraw Hill,

New York (1946)
Jost, W. Flammenreaktionen and Detonationen. Zeit Elektrochemie, 61, 559 (1957)
[German]

Kandiner, H.J. and Brinkely, S.R. Jr. Ind. Engrg. Chem., 42, 850-855 (1950)

Kistlakowsky, G.B. Initiation of Detonations in Gases. Ind. Engrg Chem., 43, 2794
(1951)

Laffite, P. Explosits 17, 14 (1964)

Lewis, B. and Von Elbe, G. Combustion, Flames and Explosion of Gases.

Cambridge University Press (1938); New York (1951)

74-2 Mal'tseva, A.S., Rozlovskii, A.I., and Frolov, Y.E., Explosion Hazard of Systems
Containing Free and Bound Chlorine. Zh. Vses. Khim. O-va., 19(5), 542-51 (1974)

53-1 Mason, E.A., Bauer, W.C. and Quincy, R.R. Explosions in Chlorine Absorption
Systems. Tappi, 36:6, 274-278 (1953)

Mathieu, P. J. Physique, 7, 166-172, (1917)

Maude, A.H. Anhydrous Hydrogen Chloride. Chem. Ind., 51, 348 (1942)

McGill, P.L. and Luker, J.A. Syracuse Univ. Res. Inst. Rept. No. Ch. E.
273-5611

Mellor, J.W. Comprehensive Treatise on Inorganic and Theoretical Chemistry, Vol.

II, Sup. 1, 373-397, 402. London (1956)

39-1 Morris, J.C. and Pease, R.N. The Thermal Hydrogen - Chlorine Reaction I
Experimental Kinetics. J. Am. Chem. Soc., 61, 391-396 (1939)

39-2 Morris, J.C. and Pease, R.N. The Thermal Hydrogen - Chlorine Reaction II Relation
to the Theory of Chain Reactions. J. Am Chem. Soc., 61, 396-401 (1939)
10 PAMPHLET 121

74-3 Munke, K. Explosive Properties of the System Chlorine-Hydrogen and its

Admixtures. Chem. Tech. (Leipzig) 20:5, 292-295 (1974)

Myers, John C. Explosive Mixtures of Chlorine and Hydrogen in Production and

Processing of Chlorine. Chlorine Institute, Proceedings, 9th Meeting of Chlorine
Plant Managers, (Feb 2, 1966) 13pp

Olsen, N.B. Small Scale Research. Three Experiments with Explosions. Dan.
Kemi, 63(10), 283 (1982)

34-1 Pease, R. Kinetics of The Thermal Hydrogen Chlorine Reaction. J. Am. Chem.
Soc., 56, 2388-2391 (1934)

Rozlovskiy, A.I. Kinetics of the Dark Reactions of the Chlorine-Hydrogen Mixture.

Zhurnal Fizicheskey Khimii, by Foreign Technology Divn., WP-AFB [Russian-ET]

Part I: ZFK 28, 51 (1954)

Part II. ZFK 29, 3 (1955)

Sanders and Gardner. Ind. & Eng. Chem., 45, 1824 (1953)

Sconce, J.S. Chlorine, Its Manufacture, Properties and Uses

(ACS Monograph 154). New York; Reinhold Publishing Co. (pp 139-163) (1962)

Semenov, N. Spontaneous Ignition and Chain Reactions. Russian Chemical

Reviews, 36:1 (1967) [Russian]

Shilov, E.A. On the Catalytic Inflammation of Mixtures of Chlorine with Ethylene and
With Other Combustible Gases. Zurnel Obshchey Chimii, 15, 133 (1945)

Smirnov, N.I., Radun, D.V., Genin, L.S., and Lomakin, I.L. Condensation of Chlorine.
Khim. Prom. (Moscow), 46(9), 680-4 (1970)

73-1 Stephens, T.J.R. and Livingston, C.B. Explosion of a Chlorine Distillate Tower.
Chem. Eng. Prog., 69(4), 45-7 (1973)

87-1 Tabata, Y., Kodama, T., and Kotoyori, T. Explosion Hazards of Chlorine Drying
Towers. J. Hazard. Mater., 17(1), 47-59 (1987)
 EXPLOSIVE PROPERTIES OF GASEOUS MIXTURES
CONTAINING HYDROGEN AND CHLORINE 11

4. ABSTRACTS

# Abstract

34-1 Pease, Robert N.

Kinetics of the Thermal Hydrogen-Chlorine Reaction, J. Amer. Chem. Soc., 56,
2388-2391 (1934)

The thermal reaction of hydrogen and chlorine was studied in a Pyrex glass tube at
temperatures of 250° and 360°C. Retention times varied from 24-150 seconds. In
the absence of oxygen, the reaction is second order. Oxygen is a strong inhibitor (as
it is in the photochemical reaction). Hydrogen chloride is not an inhibitor. (Note:
Additional studies were carried out in a static system and reported by Morris and
Pease; See Abstract 39-1 and 39-2).

36-1 Weissweiler, A.
Versuche zur Bestimmung der Explosiongrenzen von Chlor-Wasserstoffgemischen,
Zeit Elektrochemie, 42, 499-503 (1936) [German]

Two series of studies were carried out in the laboratories of I.G. Farben. In the first,
a glass vessel of 14 cm3 capacity was used containing 2 Pt electrodes with a 5 mm
gap. All glass was brown or lacquered in black to exclude actinic light. Studies were
carried out in a darkened room with very low illumination. The impulse produced by
the reaction was observed by the movement of mercury in a glass tube connected to
the reaction vessel. With dry chlorine there was no visible flame at the lower
explosive limit of 3.5% H2. A flame was observed at 7% H2 and an audible
detonation at 17.5% H2. With moist chlorine (87% relative humidity) the lower
explosive limit was observed at 4% H2, a flame at 7% H2, and a detonation at 24%
H2.

Further studies were carried out in a steel bomb having a heavy glass window sealed
in the bottom. Pressure changes were observed by mounting a mirror on a coil
spring attached to a diaphragm sealed to the vessel. A light beam was directed on
the mirror and the deflection recorded photographically at 1/4 second intervals, giving
a time-pressure curve. Various internal configurations were used to give a volume of
550-810 cm3. Initial pressure was varied from 1-7 atmospheres gauge. The lower
explosive limit was 6% H2 and the upper was 84.5% H2. As the H2 content was
increased from 6% there was a gradual transition from a mild pressure increase to a
detonation. In some cases, an abrupt detonation occurred; in others, there was an
induction period with a transition from a moderate pressure increase to a sharp
pressure burst of 3-4 times the initial pressure. In the pressure range studied, the
explosive limits were independent of initial pressure. A similar study was carried out
with H2-O2 and H2-air mixtures, with comparable behavior observed.
12 PAMPHLET 121

37-2 Lindeijer, E.W.

Explosion Limits of Hydrogen and Chlorine with Oxygen, Carbon Monoxide and
Nitrous Oxide and of Carbon Monoxide and Oxygen with Chlorine and Nitrogen, Also
of Carbon Monoxide with Nitrous Oxide, Rec. Trav. Chim. 56. 105-118 (1937)

Explosive limits were determined using an explosion burette 30 cm long x 1.5 cm

diameter shielded from light. The gas ignited at the top by a spark. A gas mixture
was considered explosive when the reaction initiated by the spark propagated the
length of the burette. The spark intensity was adjusted to be just above the minimum
ignition intensity. In this system the explosion limits for hydrogen and chlorine were
at 10.4 and 83.9% H2. Addition of up to 80% oxygen had no significant effect on the
lower explosive limit. Lindeijer attributed this behavior to the chain reaction
phenomenon first described by N. Semenov in 1932.

Morris, J.C. and Pease, R.N.

The Thermal Hydrogen-Chlorine Reaction,
39-1 I Experimental Kinetics, J. Am Chem. Soc. 61, 391-396 (1939)
and
39-2 II Relation to the Theory of Chain Reactions ibid, 396-401 (1939)

Studies of the thermal reaction of hydrogen and chlorine were carried out in a static
system using three Pyrex tubes and one tube coated with potassium chloride. The
tubes were 3.5 cm in diameter and 22 cm long, giving a volume of 200 cc. The
reaction temperature was 184°C. Most of the data were explained by treating the
reaction as a Nernst chain starting and ending on the walls. The estimated chain
length is about 104 as compared to as high a 106 for a photochemical reaction in
which the chains are started in the gas phase. The inhibiting effect of oxygen is
much less for thermal than a photochemical reaction, reducing the chain length by 10
as compared to a thousand-fold reduction for a photochemical reaction. An
unexplained phenomenon in these studies was the drop in the initial reaction rate to
a fairly steady-state reaction in two of the Pyrex tubes.

Data obtained are compared with those of other investigators and with rate constants
calculated by collision theory and by statistical thermodynamics. Reasons for the
wide variations are discussed in terms of chain-reaction theory.

42-1 Ritchie, M. and Taylor, D.

The Photocombination of Hydrogen and Chlorine in Oxygen-Free Systems, Proc.
Roy. Soc., A180, 423-51 (1942)

The photochemical reaction of hydrogen and chlorine at 25°C was studied in silica
reaction vessels of 31.3 cc and 178.0 cc capacity irradiated with light of wave length
3,650°A and 4,060°A. A 500-fold variation in intensity of incident light was studied.
 EXPLOSIVE PROPERTIES OF GASEOUS MIXTURES
CONTAINING HYDROGEN AND CHLORINE 13

Data were interpreted in terms of a Nernst chain mechanism. The quantum

efficiency is normally proportional to the hydrogen pressure, since the only reactions
involving H2 atoms are:

Cl + H2 ⇒ HCl + H
H + Cl2 ⇒ HCl + Cl

With increasing partial pressure of chlorine and of diluents such as nitrogen and
argon the quantum efficiency shows a maximum at intermediate partial pressures.
With increasing pressure of HCl the quantum efficiency decreases continually. The
change in intensity exponent 1n increased with increasing pressure, reaching about
0.5 at the higher pressures studied (1 atm total pressure).

46-1 Kunin, T.I. and Serdyukov, V.I.

Chlorine and Hydrogen Explosion Temperatures and Limits in Hydrogen Chloride,
Zhur Obshehey Khimii, 16, 1421-1430 (1946) [Russian]
Translation by Foreign Technology Division, WP-AFB, FTO-TT-62-1415/1+2

The reaction chambers for these studies were glass vessels with a diameter up to 40
mm and a volume up to 500 ml. The vessels were shielded from light by wrapping
with black paper. All tests were conducted at atmospheric pressure. The gas
mixture could be ignited by a spark discharge or a platinum heating coil with a
platinum-rhodium thermocouple attached. After reaction, the gas mixture was
analyzed.

Since the apparatus did not provide for complete mixing of the reactant gases, there
was some scatter in the data. Data for the H2-Cl2 system with spark ignition are
reasonably consistent with later studies by Umland, showing a lower explosive limit
of 5.5% as compared to 4.1% reported by Umland. With hot wire ignition at a coil
temperature of 1200°C the lower explosive limit is reported at a hydrogen content of
7%. As the hydrogen content is raised above 7% the temperature needed to initiate
an explosion drops gradually to 227°C with a H2-Cl2 mixture containing 19%
hydrogen.

Considerable studies were made with systems containing HCl as a diluent. These
studies are not considered pertinent to the problem under consideration.

49-1 Bartholome, E.
and Zur Methodik der Messung von Flammengeschwindigkeit, Zeit Electrochemie 53,
191-196 (1949) [German]
50-1 Die Flammengeschwindigkeit in sehr heissen Flammen, ibid 54, 169-172 (1950)
14 PAMPHLET 121

Burner nozzles from 1-8 mm diameter were fabricated with a proper configuration to
give a flame having the desired conical form. These nozzles were used to observe
various combustible gas mixtures using various ratios of reactants. With H2-Cl2
mixtures the maximum flame velocity was 410 cm/sec as compared to 1,180 cm/sec
for H2-O2 mixtures.

The maximum velocity for a H2-Cl2 flame is obtained with a feed mixture containing
73% hydrogen having a calculated flame temperature of 2,402°K. With equimolar
proportions the calculated flame temperature is 2,500°K and the measured flame
velocity is 350 cm/sec.

53-1 Mason, E.A., Bauer, W.C. and Quincy, R.R.

Explosions in Chlorine Absorption Systems, Tappi, 36, 274-278 (1953)

During a study of explosions occurring in absorption systems used for the

preparation of chlorine bleaching solutions from cell gas, the lower explosive limits for
mixtures of hydrogen, chlorine, and air were determined. The presence of explosive
mixtures of these gases in the absorption towers was established and traced to the
stripping of chlorine from the feed gas. Ignition may have been due to static
electricity. The use of an air bleed into the system and of an anti-foaming agent in
the spray water has been successful in eliminating serous explosions.

53-2 Ashmore, P.G.

Explosions in Mixtures of Hydrogen, Chlorine, and Nitrogen Trichloride, Nature, 172,
449-450 (1953)

The behavior of the systems hydrogen, chlorine, nitrogen trichloride and nitrogen,
chlorine, nitrogen trichloride was studied. The concentration of NCl3 was varied from
0.1% to 2.0 %. Explosions resulting from branched-chain decomposition of NCl3
occurred in both systems when the total pressure was reduced below an upper limit.
The pressure of the upper limit increases with temperature, and is nearly the same
for both systems. The rate of decomposition rises rapidly following a typical S-curve
as the pressure is reduced below the upper limit, giving an explosive reaction after
an induction period. The explosion can be prevented by introduction of trace
quantities of a chain stopper such as nitrosyl chloride.

54-1 Umland, A.W.

Explosive Limits of Hydrogen-Chlorine Mixtures, J. Elec. Soc., 101, 626-631 (1954)

Explosive limits for hydrogen in mixtures of chlorine containing oxygen, nitrogen, and
carbon dioxide were determined at pressure of 0 to 135 psig. The definition used is
the lowest concentration of hydrogen that will give an appreciable pressure rise. The
apparatus employed a stainless steel bomb having an inner diameter of 5 cm and a
length of 20 cm with a volume of 432 ml. A sight glass was mounted in
 EXPLOSIVE PROPERTIES OF GASEOUS MIXTURES
CONTAINING HYDROGEN AND CHLORINE 15

one end and brass rupture disc in the other end. Gases were mixed with a magnetic
stirrer. A recording pressure gauge was used. A spark plug in the lower section
provided ignition with upward flame propagation.

With pure Cl2, the explosive limit dropped from 4.1% to 3.2% H2 as the pressure was
raised from atmospheric to 103 psig. With the various oxygen-containing mixtures
the explosive limit was higher than for pure Cl2, but the effect of pressure was
unpredictable.

56-1 Suzuki, Osamu and Fukunaga, Tomio

Explosion limits of Ternary Mixtures of Hydrogen-Chlorine-Air, Denki Kagakur 24:
104-108 (1956) [Japanese] J. Elec. Soc. Japan

The authors of this paper were acquainted with the extensive studies of Umland (54-
1) relating to mixtures simulating tail gases from chlorine liquefaction systems.
Suzuki and Fukunaga decided to extend the range of compositions to lower limits of
oxygen concentration than studied by Umland. Such compositions may occur in cell
gas. The chlorine-hydrogen mixtures studied were diluted with air. The
compositions studied contained 5, 10, 15, 20, 30, 50, 70, and 90% air. H2- air
mixtures were also tested.

The apparatus contained a brown glass explosion chamber of inside diameter 4.2
cm, 10 cm long with a volume of 145 cc.

Ignition was provided by a spark across a gap of 2.5 mm between two platinum wires
sealed to the bottom of the chamber. The chamber top was covered with a glass
plate weighing 20 g. All studies were made at room temperature and atmospheric
pressure. An explosion was considered to occur when the reaction developed
sufficient pressure to raise the glass plate. Both lower and higher explosive limits
were studied. For the lower limit, the minimum hydrogen content of 4.3% was
obtained with a mixture containing 15%, rising to 5.8% with no air present and to
5.0% with 90% air. Due to the limitations of the experimental technique, the data are
not conclusive, although they are reasonably consistent with the data of Umland.

Rozlovskiy, A.I.
56-2 Kinetics of the Dark Reaction of the Chlorine-Hydrogen Mixture, III and IV, Zhur
and Fizicheskoy Khimii, 30, 2489-2498, 2713-2723 [Russian]
56-3 Translation by Foreign Technology Division, WP-AFB, ATD-TT62-1688/1+2 (April 1,
1963)
16 PAMPHLET 121

Rozlivskiy has carried out and reported extensive studies of the thermal reaction of
hydrogen and chlorine. Flame temperatures were calculated for various H2-Cl2
mixtures, and flame velocities were measure photographically. Velocities are lower
than reported by Bartholome (49-1, 50-1). The deviation is not explained. Flames
with less than 30% chlorine were non-luminous and could not be photographed. The
primary apparatus was a round gas flask 100 mm in diameter with central ignition.
Initial pressures were varied from 35 to 260 mm Hg. Tests in long tubes gave
detonation waves.

Rozlovskiy presents considerable discussion of data in terms of the chain

mechanisms propounded by Semenov. The reaction rate data are considered
consistent with a reaction mechanism in which energy branching results from
collisions between chlorine molecules and excited HCl molecules.

56-4 Martin, H. and Diskowski, H.

Der Vorgang H + Cl2 ───> HCl + Cl als Molekularstrahlreakton, Zeit Elektrochemie
60, 964-970 (1956) [German]

The reaction of chlorine at very low pressures with thermally excited hydrogen atoms
was observed to determine the collision yield of HCl. Measurements at 2,300°K and
at 2,490°C activation temperature gave a relative activation energy of 9.4 ± 0.4 Kcal.

58-1 Davies, I.P.W.

Hydrogen-Chlorine Explosions in Tail Gas, B.P. Chemicals Limited, Murgatroyds
Works, October 30, 1958

The rate of flame propagation and violence of combustion as a function of hydrogen

concentration in tail gas were measured in a glass tube 1 inch in diameter and 3 feet
long. Gases were fed to one end of the tube through a tee. The gas velocity was 3-
4 cm/sec. The mixture was ignited by a spark from an induction coil. Initial
combustion of the gas mixture was observed at about 4.7% H2. The rate of flame
propagation was observed visually. It increased progressively to about 200 cm/sec
at 11% H2, and then rose rapidly until detonation occurred at 11.8% H2. As the
hydrogen concentration was increased, the reaction became progressively more
violent.

A flame trap was tested, consisting of a bed of gravel about 20 cm deep attached to
the inlet end of the tube. The ignition spark was placed in the gas feed tube at the
base of the bed. At hydrogen contents below 10.5%, a steady flame burnt at the top
of the gravel. A stable flame could not be maintained below 6.4% H2. At H2
concentrations above 12.5%, detonation occurred and the flame struck back through
the gravel bed to the point of mixture of the two gases. At 18.1% H2, the gravel was
blown from the trap. It was concluded that a trap of this type would prevent
instantaneous passage of a flame in gas mixtures containing less than 10.5%
hydrogen.
 EXPLOSIVE PROPERTIES OF GASEOUS MIXTURES
CONTAINING HYDROGEN AND CHLORINE 17

61-1 Eichelberger, W.C., Smura, B.B. and Bergenn, W.R.

Explosions and Detonations in Chlorine Production, Chem Eng. Progress 57, 94-94
(1961) (Also additional data from files of ADI 6809)

Two reaction chambers were used to study explosions and detonation of mixtures of
hydrogen with gas mixtures corresponding to tail gas from chlorine liquefaction
plants. Laboratory tests were carried out in a stainless steel bomb made of 1.25 inch
pipe, 14 inches long (350 cc) and plant tests in a 1 inch pipe 20 feet long. Various
packing materials in the bomb did not appear to affect the nature of the reaction.

Fifty-four tests were made with 51 gas mixtures. The transition from explosion to
detonation was detected audibly. Twenty-nine mixtures gave detonations and
twenty-five gave explosions. Pressure traces were made with an oscilloscope. The
maximum observed detonation pressure rise was about 2,400 psi occurring about 30
milliseconds after gas ignition using a mixture containing 38.02% H2, 28.0% Cl2 and
7.1% O2. The calculated pressures of the reflected waves and explosion waves
corresponded closely to the observed pressures. The hydrogen concentration at the
boundary between explosions and detonations rises with increasing chlorine
concentration from 18.6% for H2-air mixtures to 28% H2 for mixtures containing 50%
chlorine.

63-1 Farbwerke - Hoechst Process for Complete Liquefaction of Chlorine, Chem. Ing.
Tech. 35, 41-43 (1963)

Chlorine from electrolytic cells is compressed to 1.5-2 atm gauge and liquefied in a
multi-stage refrigerated cooling system with a final coolant temperature of about -
60°C. In the first stage (-15 to -20°C) about 90% of the chlorine is liquefied, giving an
exhaust gas having about 4% hydrogen. This gas composition was not explosive. In
the second stage, virtually all of the chlorine is liquefied, giving a gas phase
containing about 16% hydrogen, which is in the explosive region. This zone is filled
with a multitude of baffles to prevent detonation waves. The system is grounded and
is designed to withstand the maximum explosion pressure.

65-1 Van Diest, J. and DeGraaf, R.

Methode Nouvelle de determination des limites d'inflammabilite de melanges gazeux
de chlore et d'hydrogene Industrie Chimique Belge, 1195-1203 (1965)

The apparatus for these experiments employed a vertical stainless steel explosion
chamber 82 mm inner diameter and 1200 mm long, tested for a hydraulic pressure of
40 kg/cm2 (approximately 40 atms). The tube was jacketed and insulated to control
the initial gas temperature. Chromel-alumel thermocouples were mounted below
and above the ignition spark and a pressure tap was mounted below the rupture disc
at the top. The platinum electrodes for spark ignition had a variable gap from 0-10
mm. A stirrer was mounted in the bottom of the chamber to mix the gases.
18 PAMPHLET 121

This system was then designed to observe flammability limits is measured by an

increase in temperature of the reaction gases rather than explosive limits. With
measuring devices of equal sensitivity, the results will be the same by either method.

In addition to the primary test chamber described above, two other chambers were
used for determination of lower flammability limits, one 16 mm in diameter and 600
mm long and the other 130 mm in diameter and 1800 mm long. A fourth chamber 82
mm in diameter and 130 mm long was also used for the upper flammability limit. As
the tube diameter is increased, the reaction approaches adiabatic conditions, giving
higher terminal temperatures and pressures. However, the flammability limits were
the same in all chambers.

The initial temperature was varied from -60°C to 100°C. The lower flammability limit
for H2-Cl2 mixtures dropped from 5.0% to 3.0% H2 as the initial temperature was
raised from -60°C to 20°C, and stayed at this level up to 100°C. There was no effect
of initial pressure in the range of 0.5 - 1.6 atmospheres.

In summary, the results of these studies are consistent with those of other earlier
investigators, and provide no significant contribution to the bases for safe design of
commercial systems.

67-1 Eichelberger, W.C. and Hartford, W.H.

The Photochemical Reaction of Hydrogen and Chlorine in Electrolytic Cell Gas,
Electrochem Tech., 104-107, March-April, 1967

A photochemical reaction system is defined for removal of 90% to 95% of the

hydrogen in cell gas by irradiation with light from a mercury-arc lamp. Liquefaction
efficiency can be raised from 95% to 99% by such pretreatment.

68-1 Grelecki, C.J. and Mann, D.J.

Flammability Studies on Mixtures of Hydrogen with Chlorine Residual Gases, RMD
Report 2298, Thiokol Chemical Corporation, January 31, 1968 (Private)

Experiments on flammability characteristics of residual gases from chlorine

liquefaction units were conducted for Wyandotte Chemical Corporation by Thiokol
Chemical Corporation. Residual gases were from two sources: the Hooker cell
liquefaction unit and the mercury cell liquefaction unit. Typical composition of gases
from the Hooker cell system was 4.5% H2, 22% Cl2 and 18% O2 (remainder CO2, N2,
CO), and from the mercury cells 6% H2, 17% Cl2, 14% O2 (remainder CO2, N2). The
test unit used a 2" diameter stainless steel tube 6 feet long. The ignition source was
a Parr wire heated to fusion. Pressure and temperature were monitored by signals
transmitted to a Honeywell visicorder. Liquefaction off-gas was diluted with air or
enriched with H2 content.
 EXPLOSIVE PROPERTIES OF GASEOUS MIXTURES
CONTAINING HYDROGEN AND CHLORINE 19

Undiluted Hooker cell gas (4.5% to 5% H2) showed no reaction. There was a very
slight reaction with un-diluted mercury cell gas with a flame propagating at a rate of
about 1 ft/sec. Enrichment of the two residual gases with H2 showed a quite different
behavior, since reaction rates for H2-Cl2 are greater as the composition approaches
the stoichiometric reaction ratio. With Hooker cell residual gases enrichment to 20%
H2 resulted in flame propagation rates of about 1.5 ft/sec. With mercury cell residual
gases enrichment to 20% H2 gave flame velocities of about 6 ft/sec. With both
gases, enrichment to about 30% H2 produced a detonable mixture.

73-1 Stephens, T.J.R. and Livingston, C.B.

Explosion of a Chlorine Distillate Tower. Chem. Eng. Prog., 69(4), 45-7 (1973)

The case history of an explosive failure of a pressure vessel is presented. The

culprit, hydrogen, was formed in a corrosive environment where the chlorine
concentration was low, and then carried to process equipment with high amounts of
chlorine. While molecular hydrogen does not appear to be generated in high
concentrations of chlorine, it can be formed where the chlorine concentration is
lower, and subsequently be carried to process equipment where explosive
concentrations can result. Other analogous incidents experienced during handling of
chlorine at DuPont are discussed.

74-1 V.N. Antonov, Yu E. Frolov, A.I. Rozlovskil and A.S. Maltseva

Explosion Hazard of Hydrogen and Chlorine Mixture, U.S.S.R.O. Kim Prom.
(Moscow), 205-208 (1974)

The authors investigated hydrogen - chlorine explosions of mixtures containing up to

15% hydrogen and at initial pressures of 1, 2 and 3 atmospheres. They calculated
the theoretical pressure rise expected for the various hydrogen - chlorine mixtures
tested (making allowance for the dissociation of excess chlorine at high
temperatures). Mixtures with up to 8% hydrogen were found to develop far less than
the theoretical pressure, while the more rapid reactions at 15% hydrogen developed
pressures essentially equal to the theoretical limit for adiabatic reactions. They did
not determine whether the reactions with low concentrations of hydrogen failed to
reach the theoretical pressures because of incomplete reaction or because of heat
losses during the relatively slow reactions. They concluded that the pressures
developed on explosion of mixtures containing up to 8% hydrogen would not be
greater than twice the initial pressure and would be insufficient to damage industrial
equipment. They did not investigate the explosive properties of 8% hydrogen
admixed with gases low in chlorine and high in oxygen and nitrogen. Such
compositions are more representative of the residual gases leaving the final stage of
condensation in chlorine liquefaction plants. The authors also did not mention the
hazards of stationary flames which might result from ignition of a flow of chlorine gas
containing 8% hydrogen.
20 PAMPHLET 121

74-2 Mal'tseva, A.S., Rozlovskii, A.I., and Frolov, Y.E.

Explosion Hazard of Systems Containing Free and Bound Chlorine.
Zh. Vses. Khim. O-va., 19(5), 542-51 (1974)

The determination of explosion limits of binary and ternary mixtures of chlorinated

hydrocarbons with oxygen and air, some combustible gases with oxygen and HCl,
organic compounds with free chlorine, and explosiveness of chlorine-hydrogen
mixtures are reviewed and discussed. Includes 59 references.

74-3 Munke, K.
Explosive Properties of the System Chlorine-Hydrogen and its Admixtures. Chem
Tech. (Leipzig) 20:5, 292-295 (1974)

This paper is a critical and selective review of the published data on explosive
properties of hydrogen mixed with chlorine, oxygen, and various inert diluent gases.
The emphasis of the paper is directed toward selection of the best values for ignition
limits of the gaseous mixtures. Effects of variations in temperature and pressure on
ignition limits also are reviewed. Detonation limits are mentioned only briefly.

76-1 Frolov, Y., Mal'tseva, A.S., Serdechki, V.M., Fedotov, K.E., and Rozolovskii, A.I.
Certain Features of the Combustion of Lean Mixtures of Hydrogen with Chlorine.
Khim. Prom-st., (5), 358-60 (1976) (Moscow)

The effect of O2 and CO2 on the explosion danger of hydrogen-chlorine mixtures, the
completeness of combustion of lean hydrogen-chlorine mixtures, and the effect of
the gas motion on the combustion stability were studied. In a fast gas stream, the
unstable combustion of hydrogen-chlorine mixtures with a subcritical ratio becomes
stable (independently of the pressure increase). The inducted turbulence of the
burning mixture in the fast stream stabilizes the flame, as does free convection.

78-1 Casson, H.V. and Loftfield, R.E.

Electrolytic Cell. U.S. Patent US 4087344, 2 May 1978, 7pp.

The title designed cell for brine electrolysis has a removable casing dividing the cell
into a separate cell chamber and a cooling and concentrating chamber. The latter is
made for circulating the electrolyte from the cell chamber to the cooling and
concentrating chamber without circulating the gas between said chambers. The
gases evolved in the cell are combined and an excess over the flammability limit of
hydrogen in air is avoided. This cell by virtue of its construction uses less outside
energy because the heat developed during electrolysis is utilized in concentrating
and evaporation processes.
 EXPLOSIVE PROPERTIES OF GASEOUS MIXTURES
CONTAINING HYDROGEN AND CHLORINE 21

87-1 Tabata, Y., Kodama, T., and Kotoyori, T.

Explosion Hazards of Chlorine Drying Towers. J. Hazard. Mater. 17(1), 47-59 (1987)

Three chlorine drying towers made of PVC exploded suddenly and violently in a
Mercury Amalgam Cell Chlorine Plant. Because of failure of the electric power
system, a current breaker tripped out, the Hg pumps stopped, and the steel bottom
plates in the cells became exposed. The alarm did not work, since both the AC
power supply to the mercury pumps and that for the alarm system were taken from
the same source. Meanwhile the DC power and the brine supply to the cells were
not interrupted. Therefore, the hydrogen generated at the steel plate cathode and
oxygen at the anode at a mole ratio of 4:1, forming an explosive gas mixture, passed
to the chlorine drying towers. Concentrated sulfuric acid is used for drying the wet
chlorine gas. The most likely source of ignition in the towers was a discharged spark
from an electrostatic charge caused by sulfuric acid drops. The actual electrostatic
charge of a PVC chlorine drying tower was measured. A static potential of minus 5
kV was detected constantly near the hole that was drilled in the side wall of the
space below the Raschig ring layer. The main conclusion of the study was that
towers should be constructed of an acid-proof conductive material so they can be
maintained at ground potential to prevent electrostatic charges.
22 PAMPHLET 121

PART B: "REACTION CHARACTERISTICS OF HYDROGEN ADMIXED WITH

CHLORINE, OXYGEN AND INERT GASES"

5. SUMMARY

The literature reporting reaction characteristics of hydrogen with chlorine, and with
mixtures of chlorine and oxygen has been reviewed with particular attention to ignition
limits and explosion and detonation conditions. Data selected from several reports were
used to draw the figures found in Appendix A in which reaction characteristics for the
systems hydrogen-chlorine-oxygen and hydrogen-chlorine-air are summarized. A third
figure shows the effects of the inert gases nitrogen, water vapor, hydrogen chloride and
carbon dioxide on the ignition limits of the hydrogen-chlorine system.

The apparatus for determining ignition limits has been refined over many years.
Investigators, using apparatus meeting the critical criteria, report data which agree well
on the location of these limits. Hence, it is felt that the ignition limits shown in the figures
are accurate and cover adequately the conditions encountered in industrial practice. It
has been noted by at least one organization (Euro Chlor) that the influence of pressure
on the ignition limits and explosion and detonation conditions of hydrogen, chlorine,
oxygen mixtures is relatively small between 0.25 and 11.5 absolute bars (3.6 and 166.8
psia). Since the effect of pressure is not known it is recommended that experimental
measurements be collected and evaluated prior to operating at higher pressures.

Relatively meager data on detonation limits have been reported, and the best apparatus
for determining these limits is not yet clearly defined. Hence, the lines for detonation
limits are located with far less confidence than for the ignition limits. In particular, the
upper detonation limits are based on only one datum point plus the assumption that
consumption of equal amounts of hydrogen will reach the detonation condition for all
mixtures of chlorine and oxygen and of chlorine and air.

The lines which indicate the limits of compositions which on ignition will develop not
more than twice the initial pressure are based on similar assumptions as discussed
below. However, even with these assumptions it seems probable that these lines for
high hydrogen concentrations are nowhere in error by more than 2% hydrogen. Also,
the lines at low hydrogen concentrations are more likely to exclude compositions which
will not reach twice the initial pressure rather than to include compositions which will on
ignition significantly exceed twice the initial pressure.

6. DISCUSSION

In the following discussion all compositions are given in percent by volume.

The terms "ignition limits", "flammable limits", and "explosive limits" have been used by
several investigators to describe gaseous compositions which when ignited under
optimum conditions will barely sustain reaction. In the following text only the term
 EXPLOSIVE PROPERTIES OF GASEOUS MIXTURES
CONTAINING HYDROGEN AND CHLORINE 23

ignition limit is used. This is defined as a composition of gas which when ignited by an
adequate point source of energy, such as strong spark, will barely continue to propagate
the reaction in an upward direction to the limits of the container. Such reactions should
not be called flames or explosions, since they do not emit light and give only slight
pressure surges and minor increases in temperature.

The ignition limit is very dependent upon the nature of the ignition source. A
composition which is at the ignition limit for strong spark ignition will not be ignited by a
hot wire or a weak spark. Unpublished Hooker Chemicals & Plastics Corporation
research may explain this difference:

In experiments to react out traces of hydrogen in chlorine by catalysis

with ultraviolet light it was found that mild explosions may occur at
hydrogen contents somewhat below the 4% ignition limit shown in the
Figures found in Appendix A. A flow of chlorine was passed through a
transparent tubular reaction zone continuously illuminated with a strong
flux of ultraviolet light. The hydrogen content of the chlorine stream
entering the reaction zone was gradually increased in small increments.
When the hydrogen concentration reached 3.0% to 3.5% an audible
explosion occurred - often with sufficient force to blow rubber tubing from
the slip-on connections. The ultraviolet light passed throughout the entire
volume of the reaction chamber. Hence, the absorption of photons with
the attendant generation of chlorine free radicals also extended
throughout the chamber. Under such conditions it is to be expected that,
once started, an explosion would progress rapidly throughout the entire
volume rather than in an upward direction only. The explosions which
resulted were, therefore, much more violent than the comparatively mild
reactions at 4% hydrogen reported as the ignition limit with spark
initiation. It seems evident that the very mild reaction after spark ignition
of a 4% hydrogen-in-chlorine mixture must leave much of the hydrogen
unreacted. Also, it seems that a strong flux of ultraviolet light is more
effective in initiating the reaction than are the strong sparks used in most
investigations. It may be that the flash of ultraviolet light from a strong
spark contributes materially to initiation of the reaction. This could explain
why strong sparks are more effective than hot wires in initiating the
reaction of hydrogen with chlorine.

The mild explosions reported above with ultraviolet initiation of 3.0% to 3.5% hydrogen-
in-chlorine occurred only when the system was essentially free of oxygen. A few tenths
of a percent of oxygen in the mixture prevented the explosions and increased the
hydrogen content in the gas leaving the reaction zone.
24 PAMPHLET 121

7. IGNITION LIMITS

Several investigators have reported results obtained in experiments to determine the

ignition limits and the explosive properties of mixtures of hydrogen, chlorine, oxygen, air
and several inert gases. From a comparison of the reports it is evident that variations in
apparatus can cause large differences in the values obtained for both the upper and
lower ignition limits. It is now generally agreed that for acceptable accuracy the
apparatus should provide for upward flame propagation. A spherical test chamber
should be at least 20 cm in diameter, while a vertical cylindrical chamber should be at
least 5 cm in diameter with a height of at least four times the diameter. Spark ignition is
preferred with the electrodes located on the center line of the test chamber and 20% to
30% of the height from the bottom. The electrodes should be at least 5 mm apart, and
the spark energy should be 10-2 joule or more. Such strong sparks are required only
when the gas composition is near an ignition limit. Mixtures of hydrogen and chlorine
near the equivalence point are ignited by sparks of only 10-7 joule. Since the flames are
invisible near the ignition limits, sensitive and fast response measurement of the
pressure rise on ignition is the preferred means to determine if ignition has occurred.

The ignition limits reported by investigators (J. Van Diest; A.W. Umland; A. Weissweiler;
O. Suzuki) using apparatus meeting the above criteria are in relatively good agreement.
The ignition limits shown in the Figures A-1, A-2 and A-3 were obtained with such
apparatus. In general, such apparatus gives lower concentrations of hydrogen at the
lower ignition limit and lower concentrations of oxidant at the upper ignition limit than
have been reported by investigators using apparatus failing some aspects of the above
criteria. It appears unlikely that any further modification of test apparatus will
significantly decrease the lower ignition limits or increase the upper ignition limits.
Hence, it seems safe to conclude that the ignition limits drawn in Figures A-1, A-2 and A-
3 are essentially accurate.

The data found in Table 7-1, as determined by J. Van Diest and DeGraff, shows the
effect of initial temperature on the ignition limits. Except for the upper ignition limit of
hydrogen - air mixtures only minor changes in the ignition limits occur within the
temperature range from 140°F to 212°F (60°C to 100°C).
 EXPLOSIVE PROPERTIES OF GASEOUS MIXTURES
CONTAINING HYDROGEN AND CHLORINE 25

Table 7-1 Effect of Initial Temperature on Ignition Limits

(Hydrogen Content, % by Volume)

H2 - Cl2 H2 - Air H2 - O2

Temperature (°C) Lower Upper Lower Upper Lower Upper

Limit Limit Limit Limit Limit Limit

-60 5.0* 90 4.0 69 4.0 96

-40 4.0* 90.5 4.0 71 4.0 96

-20 4.0 91.5 4.0 72 4.0 96

0 3.5 92 4.0 73 4.0 96

20 to 25* 3 92.5 4.0 75 4.0 96

50 3 93 3.7 76 4.0 96

100 3 93 3.0 80 4.0 97

* The results reported for 20°C to 25oC check well with those reported by others (A.W.
Umland; A. Weissweiler; O. Suzuki).

J. Van Diest and DeGraff also reported the effects of inert gases on the ignition limits of
hydrogen - chlorine mixtures at 212°F (100°C). Their results are shown in Figure A-3.
The same apparatus, which gave accurate values for the ignition limits for hydrogen -
chlorine, hydrogen - air, and hydrogen - oxygen, was used for development of this data.
Hence, it seems probable that Figure A-3 is an accurate presentation of the ignition
limits of hydrogen - chlorine mixtures diluted with the indicated inert gases.

Umland reported the small increase in hydrogen content of the lower ignition limits which
maximizes at 15% to 20% chlorine. He suggests that this is due to the transition from a
predominately hydrogen - oxygen reaction to a hydrogen - chlorine reaction. Umland
also investigated the pressure range from 1 to 10.5 atm, finding only minor changes in
the lower ignition limit. For mixtures of both hydrogen and oxygen and hydrogen and
chlorine he found the lower ignition limit to change from 4% hydrogen at 1 atm to about
3% hydrogen at 7.8 atm. Some gas mixtures showed small increases in the hydrogen
content at the lower ignition limit as the pressure was increase to 10.5 atm. This
increase usually was less than 2% hydrogen. This increase also may be associated with
transition from a hydrogen - oxygen reaction to a hydrogen - chlorine reaction as the
partial pressure of chlorine was raised with increasing total pressures.
26 PAMPHLET 121

8. EXPLOSIONS AND DETONATIONS

When the reaction rate in a gas system is so fast that heat is liberated more rapidly than
it can be dissipated to the surroundings (by radiation, conduction or convention) the
temperature and pressure in the system rise. When the pressure rise is significant the
reaction may become an explosion. Once a reaction in a gas system is initiated, the
reaction rate may accelerate for two reasons: first, because the absolute reaction rate is
dependent on temperature, as defined by the Arrhenius reaction rate equation, and
second, because a chain reaction with chain branching may occur, as in the hydrogen -
chlorine reaction. If the reaction rate is sufficiently rapid, full adiabatic heat release may
occur. If the reaction takes place uniformly throughout the reaction mass, the resultant
pressure rise can be calculated.

If an explosive reaction is initiated at a point in a gas system, a pressure pulse is

generated which moves through the gas at the velocity of sound. However, this
pressure pulse heats the gas by adiabatic compression. Since the velocity of sound
increases with temperature, the pressure pulse moves more rapidly in the heated zone
than through the colder zone ahead of it. As a result, the back of the pressure wave
moves faster than the front and tends to catch up with it to form a single large abrupt
pressure pulse, known as a shock wave. Shock waves also can be generated by
mechanical impulse, as in shock tubes.

If a very rapid and highly exothermic reaction takes place in the generated wave front,
the reaction zone will move through the gas at a velocity many times that of the speed of
sound, accelerating to a constant maximum velocity if the reaction path is sufficiently
long. This reaction front of constant velocity is defined as a detonation wave. Its speed
is dependent on the composition and the properties of the gas mixture, and is relatively
little influenced by the initial temperature and pressure or by the method of initiation.

The front of a detonation wave is the boundary between the reacted and unreacted
gases. There are extremely sharp temperature and pressure gradients across this wave
front. When the wave front reaches a boundary surface, it strikes with a force equal to
the sum of the adiabatic pressure rise in the system and the force of flow of the mass of
gas behind the wave front. The magnitude of this impulse depends on the velocity of the
impact wave. For a mild shock wave, it may be only 1.5 to 2.0 times that of the adiabatic
pressure rise in the system. For a detonation wave, the impulse may be 10 to 20 times
the adiabatic pressure rise.

Detonation studies are usually made in long tubes with a spark initiator at one end. For
hydrogen - air mixtures at atmospheric pressure the detonation limit is about 18.5%
hydrogen. Below this concentration of hydrogen, the detonation wave is not stable, and
the velocity actually decreases as the wave moves down the tube. Nevertheless, a
shock wave is produced in a tubular reactor at hydrogen concentrations below the lower
detonation limit, although at concentrations below 10% only mild explosions are
observed.
 EXPLOSIVE PROPERTIES OF GASEOUS MIXTURES
CONTAINING HYDROGEN AND CHLORINE 27

In the oxygen - hydrogen system detonation waves with velocities over 4,000 meters per
second have been observed. In the chlorine - hydrogen system detonation wave
velocities are considerably lower, with a maximum of 1,850 meters per second reported
for hydrogen contents of 66% to 75% (vol).

The only reported study of detonation limits in the H2 - O2 - Cl2 system is that of
Eichelberger, Smura, and Bergenn. Studies were carried out in a 1 inch pipe 20 feet
long, using spark initiation. The impulse was picked up with a pressure transducer and
observed on a cathode ray oscilloscope. The initial pressure of 3.4 atm was the same
for all experiments. The initial temperature was not reported, but probably was near
ambient. The purpose of this study was to evaluate the potential hazards in handling the
residual gas from chlorine liquefaction operations.

This gas is a mixture of H2, Cl2, O2, CO2 and N2, together with other trace diluents. The
gas mixtures studied initially were essentially H2 - air mixtures, with progressive
additions of chlorine. The explosion detonation boundary was 18.6% H2 with no Cl2,
corresponding to data of earlier investigators of the H2 - air system. As chlorine was
added to the mixture the hydrogen content of this lower detonation limit rose to a
maximum of about 25% at 40% chlorine.

For dry mixtures of hydrogen and chlorine (no air or oxygen added). Weissweiler
reported a lower detonation limit of 17.5% hydrogen and an upper detonation limit of
83% hydrogen. Both Eichelberger and Weissweiler recognized that the sharp ping
sound of a detonation wave would serve to determine whether a detonation or a less
violent explosion had occurred. No other data was found in the literature regarding
detonation limits within the range from 50% to 100% chlorine. Therefore, the line over
this range of the lower detonation limit in Figures A-1 and A-2 is merely a graphical
interpolation connecting Weissweiler's result with data obtained by Eichelberger.
Lacking any reason to suspect a sudden change in explosive properties within this
region of high chlorine content, it seems probable that this interpolation is reasonably
accurate.

Weissweiler's report of 83% hydrogen as the upper detonation limit in hydrogen -

chlorine mixtures is the only datum point available to assist in locating this limit. In order
to draw the upper boundary of Zone IV it was assumed that consumption of
approximately equal amounts of hydrogen would occur at all points along this detonation
limit. Hence, the high hydrogen boundaries between Zones III and IV in Figures A-1 and
A-2 are drawn to give oxidant equivalent to 17 to 19% hydrogen. The upper detonation
limit drawn in this way is probably of relatively poor accuracy. However, the size and
shape of equipment containing the explosive mixture may have quite large influence on
the actual composition at the detonation limit in that equipment.

In contrast to the situation with determination of ignition limits, there is relatively little
information concerning the chamber size and shape which is best for determination of
detonation limits. Weissweiler obtained the data he reported using the same small
vertical cylindrical chamber in which he determined ignition limits. Eichelberger ran
preliminary experiments in a similar chamber.
28 PAMPHLET 121

They also packed the chamber with "lead shot, 5 mm glass beads, 0.25 inch Berl
saddles, 0.25 inch Raschig rings, glass wool, steel wool and protruded stainless steel.
The results of these tests showed that explosion pressure rises in the packed bomb are
in almost all cases many times larger than the pressure rise when the bomb is not
packed. The oscilloscope trace of a high hydrogen explosion in a packed bomb showed
that the reaction was approaching a detonation. In no case did the packing appear to
quench the explosion". It appears that the packed bomb would have yielded a lower
hydrogen content for the lower detonation limit than the 20 foot long 1 inch internal
diameter pipe with which the results used to locate the lower detonation limit in Figure A-
1 and A-2 were obtained.

The Farbwerke-Hoechst process for liquefaction of chlorine yields a residual gas

containing about 16% hydrogen. The final stage of liquefaction is at -76°F (-60°C) in
equipment filled with a multitude of baffles to prevent detonation waves in the event
ignition should occur. Here is a situation where the shape of equipment is deliberately
designed to increase the hydrogen content which must be reached before a detonation
can occur.

From the foregoing discussion it is apparent that both the upper and lower detonation
limits of Figures I and II must be regarded as only a rough indication of the actual
situation for a given piece of industrial equipment. A great deal more information is
required concerning optimum chamber shape and dimensions before upper and lower
detonation limits could be drawn with confidence of accuracy comparable to the ignition
limits in the attached figures.

The line at 8% hydrogen in Figures A-1 and A-2 is shown as the upper boundary of low
hydrogen mixtures which will develop not more than twice the initial pressure when
ignited. This line is based on the work of Antonov, Frolov, Rozlovskii, and Maltseva who
investigated hydrogen - chlorine explosions of mixtures containing up to 15% hydrogen
and at initial pressures of 1, 2 and 3 atms. They calculated the theoretical pressure rise
expected for the various hydrogen - chlorine mixtures tested (making allowance for the
dissociation of excess chlorine at high temperatures). Mixtures with up to 8% hydrogen
were found to develop far less than the theoretical pressure, while the more rapid
reactions at 15% hydrogen developed pressures essentially equal to the theoretical limit
for adiabatic reactions. They did not determine whether the reactions with low
concentrations of hydrogen failed to reach the theoretical pressures because of
incomplete reaction or because of heat losses during the relatively slow reactions. They
concluded that the pressures developed on explosion of mixtures containing up to 8%
hydrogen would not be greater than twice the initial pressure and would be insufficient to
damage industrial equipment. They did not investigate the explosive properties of 8%
hydrogen admixed with gases low in chlorine and high in oxygen and nitrogen. Such
compositions are more representative of the residual gases leaving the final stage of
condensation in chlorine liquefaction plants. The 8% hydrogen line is very close to the
lower ignition limit at the maximum found by Umland in the region of 15% to 20%
chlorine.
 EXPLOSIVE PROPERTIES OF GASEOUS MIXTURES
CONTAINING HYDROGEN AND CHLORINE 29

It therefore seems that this 8% hydrogen line should move to near 10% hydrogen in this
region, since such mild explosions probably are reduced in power by the same causes
which increase the lower ignition limit in this area. Hence, it appears that this 8% line
represents a conservative estimate of the hydrogen content which can exist in explosive
mixtures without exceeding twice the initial pressure when ignited.

Antonov recommended that chlorine liquefaction plants be designed to allow up to 8%

hydrogen in the residual gas discharged from the process. This recommendation was
based on the data showing that explosive mixtures of chlorine and hydrogen containing
up to 8% hydrogen would not develop more than twice the initial pressure when ignited.
However, they did not comment on the possibility of damage from the heat of stationary
flames which might result from ignition of a flow of gas containing 8% hydrogen. The
possibility of forming such standing flames and the damage which they could cause
should be evaluated carefully before designing for a maximum of 8% hydrogen in
residual gases from chlorine liquefaction plants.

The line for the lower boundary of the high hydrogen mixtures which will develop not
more than twice the initial pressure when ignited is based on the work of Suzuki and
Fukunaga. They determined the upper ignition limit of hydrogen - chlorine - air mixtures
using apparatus with a relatively insensitive pressure measuring system. They reported
results with hydrogen contents several percent lower than the upper ignition limit drawn
in Figures A-1 and A-2. They also reported that the explosion rapidly became more
violent at only slightly lower hydrogen contents than they found for the ignition limits. In
the light of this information the lower boundaries of Zones II in the high hydrogen areas
of Figures I and II were drawn to show about one percent less hydrogen than Suzuki and
Fukunaga reported from the upper ignition limit. Admittedly, this is at best a rough
estimate of the location of this boundary.
30 PAMPHLET 121

9. SELECTED REFERENCES

The following documents are directly referenced in Part B of this pamphlet.

# Reference

1 -1A Euro Chlor – GEST 91/168 – Physical, Thermodynamic and Selected

Chemical Properties of Chlorine, chapter 9 – Safety

2-1 J. Van Diest and R. DeGraff

Industrie Chimique Belg., 30: 11, 1195-1203 (1965)

3-2 A. W. Umland
J. Electrochem. Soc., 101: 12, 626-631 (1954)

4-3 A. Weissweiler
Z. Electrochem., 42, 499-503 (1936)

5-4 O. Suzuki and t. Fukunaga

J. Electrochem. Soc., 24, 101-108, (1956) (Japan)

6-5 Farbwerke - Hoechst Process for Complete Liquefaction of Chlorine

Chem. Ing. Tech., 35, 41-43 (1963)

7-6 W. Eichelberger, B. Smura and W. Bergenn

Chem. Eng. Prog., 57: 8, 94 (1961)

8-7 V. N. Antonov, Yu. E. Frolov, A. I. Rozlovskii, and A.S. Maltseva (U.S.S.R.)

Khim. Prom. 3, 205-208 (1974) (Moscow)

Other articles dealing with the subject matter of Part B are:

Reference

Gosta Wrangler, Teknisk Tidckrift (Technical Journal) pages 363-370 (1969) (Swedish)

K. Munke, Chem. Tech., 20: 292-295 (1974) (German)

Evans, Marjorie W., and C.M. Ablow, Theories of Detonation. J. Chem. Rev., V129, 129-
178 (1961)

Gibbs, G.J., and H.F. Calcote. Effect of Molecurlar Structure on Burning Velocity.
J.Chem. Eng. Data, V.5, 226-237 (1959)

Zabestakis, M.G., and D.S. Burgess. Research on the Hazards Associated with the
Production and Handling of Liquid Hydrogen. Bumines Dept. of Inv. 5707, 50 pages, (1961)
EXPLOSIVE PROPERTIES OF GASEOUS MIXTURES
CONTAINING HYDROGEN AND CHLORINE 31

APPENDIX A
32 PAMPHLET 121
EXPLOSIVE PROPERTIES OF GASEOUS MIXTURES
CONTAINING HYDROGEN AND CHLORINE 33
34 PAMPHLET 121
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