Bulletin 627

BuREu OF MiNS

FLAMMABILITY CHARACTERISTICS
OF COMBUSTIBLE GASES AND VAPORS
By Michael G. Zabetacis

Bulletin 627
BUREAU OF MINES

FLAMMABILITY CHARACTERISTICS
OF COMBUSTIBLE GASES AND VAPORS
By Michael G. Zabetakis

This publication has been cataloged as follows:

Zabetakis, Michael George, 1924Flanunability (haraeteristics of combu.tilhe gases and

vapors. rWashingtonj U.S. Dept of the Interior, lureati of
Mines 11965)
121 p. Illus., tables. (U.S. Bureau of Mines. Bulletin 627)
Includes bibliography.

1. Combustion gases. 2. Gases.

Combustible gases. (Series)

TN23.U4 no. 627

3. Vapors.

1. Title. II. Title:

622.06173

U.S. Dept. of the Int. Library.

For sale by the Superintendent of Documents, U.S. Government Printing Office

Washington, D.C., 20402
Price 75 cents

CONTENTS

Page
Abstract -------------------------------------Introduction---------------------------------I
Definitions and theory ------------------------2
Limits of flammability ----------------------2
Ignition -----------------------------------3
Formation of flammiable mixtures -------------4
Presentation of data -------------------------- 9
Deflagration and detonation processes..----------15
Deflagration ------------------------------15
Detonation -------------------------------16
Blast pressore -----------------------------16
Preventive measures -------------------------18
Inerting -----------------------------------1
Flame arrestors and relief diaphragms-------18
Flammability characteristics ------- -----------20
Paraffin hydrocarbons -----------------------20
Limits in air----------------------------20
Limits in other atmospheres ---------------27
Autoignition ----------------------------32
Burning rate ----------------------------42
Unsaturated hydrocarbons ------------------47
Limits in air---------------------------47
Limits in other atmospheres ----------------50
Autoignition ----------------------------50
Burning rate -----------------------------51
Stability ---------------------------- ---- 51
Acetylenic hydrocarbons------- ------------653
Limits in air -----------------------------3
55
Limits in other attmospheres ------- --------0
Autoignition -----------------------------56
Burni~ng rate ----------------------------57
Stability-- - - ---------------------------59
Aromictic hydrocarbons.--------------------59
Limrits in air --------------------------

Flammability characteristics-Continued
Pape
Aromatic hydrocarbons- Continued
Limits in other atmospheres---------------60
Autoignition -----------------------------62
Burning rate ----------------------------62
Alicyclic hydrocarbons ---------------------63
Limits in air ----------------------------63
Limits in other atmospheres ---------------64
Alcohols----------------------------------65
Limits in air ----------------------------65
Limits in other atmospheres ---------------66
Autoignition -----------------------------67
Burning rate -----------------------------68
Ethers ------------------------------------69
Limits in air -----------------------------69
Limits in other atmospheres ----------- -- ---- 69
Autoignition ---- ------------------------70
Esters ------------------------------------70
Aldehydes and ketones ---------------------73
Sulfur compounds --------------------------74
Fuels and fuel blends ----------------------74
aimmonia and related compounds ---------74
Boron hydrides---------------------------82
Gasolines, diesel and jet fuels --------------82
Hydrogen ------------------------------89
Hydraulic fluids and engin) , oils -------------95
Miscellaneous -----------------------------97
Acknowledgments---------------------------106
Bibliography -------------------------------- 107
114
Appendix A. Siirnmary limits of flammabilitypnix.-oihoticom
ston---17
118
Appendix C. -11eat contents of gases ----------119
Appendix 1). -Definitions of principal symbolsSubject index--------------------------------120

ILLUSTRATONS
Fig.
1 . Ignitibility curve and limits of flammiability for methane-air mixtures at atmosphieric pressure and 26* C-

2. FfI~tv

Page

of tempe-rature onl limits of flinniatdlity of a conmbustibile vapor in air at a constant initial pins-

'i. ini d ilay Iaforv ignition of N PN ini air at 1 000)1pa ig in the tem pira ture range from 1510* to 21 0* C, .
,.1 Logar i ini of time delay bewfore ign itijon of NJi N in air at 1,0001 psig iinitial pressur---------------- -------------------------.. Simiplified nixer----------------------------------------6. Comnposition of gas in chamlber 2, figure 5 (instantaneous muixing)- - - ---------------------- ------7, Coiiiposition of gas in chambher 2, figure 5 (delayed mixing) ----------------------------------------.. Variation in, lower limits oft tlaininatilitv of various comibustibles in air Ps a function of droplet diameter
FVnn i in ahi lit 3 di agrain for the systveiIin i(t Iiate-oxy g(il-nit rogetYi atI at Inospli e pressure and 26' C v (i 5grin for the syst iiii iii(-ithaoi'(-oxy'geni- nitrogeni at at n osph eric pressure and~ 2110 C
10
n.FlanmiiaI ilitY
i
I perit uri on liit s of flai iiiability of it coin hust ii d vapor- iii rt-a ir syst lii itt atmnosen
i. F; icrt o f iuiitia
-- ---- - - ----lpheric pr(-&ur-- -- -- ----------- I------- -------------- ------------------1
12. Ictrict oif initial pressure on liimits of' flaiinahility of JP-4 in air at 26' C ------------

5
6
7
7
7
7
f

Iv

CONTENTrS

13. Effect of temperature and pressure on limits of flammability of a combustible vapor lin a specified
oxident ----------------------------------------------------------------------------------12
14. Flammability diagram for the system gasoline vapor-water vapor-air at 700 F and at 2120 F anid atinlospherio pressure----------------------------------I -I-------------------------13
15. Pressure produced by Ignition of a 9,6 volumec-percent mietbanie-air mixture in a 9-liter cylinld(r -----15
16. D~etonation velocity I, V'; 9tatic pressure, 11,; and reflected pressure, I',, dleveloped b)'Ya detonation
waverating
through byxd ogen-oxygen mixtures in at cylindrical tube at atmzosphieric pressure
and
---X--0 F ---a9-a I ------------ --- --- --- --- --- --- --- --- --- --- 16
17. Pressure variation following ignition of a flanimiable mixtu re ini unp)rotected arid prot;ect ei eiielosures~
i
18
18. P~ressure produced by Ignition of at flamninal le mixture in a vonted oven .-- -- -- ------------it9
19. Effect of molecular weight onl lower limits or flammnability of paraffin hydrocarbons at 250 C ----------- 20
20. Effect of temperature onl lower limit of flainniability of mnethane in Peir tit atmniperic presilr-------22
21. Effect of temperature onl lower limits of flamnmability of it0 pairaffin hydrocarbons init ir ait atmlospheric
pressure.
.
.
-------------2:3
22. Effect of temperature on lower limits of flamnnialnility of 10 parailin liydi darhoiis init;, ti a i )nopl-rie
pressure by wveight------------------------ ----------------------------24
23. Effect of temperature on L,1/ 2 ,,- ratio of paraffin hydrocarbons lin tir tit atinoplicric pressure --.
25
24. Effect of temperature onl (71 7/U.sraitio of liaril
hydrocarbons ini air at atmnospheric pressure in the
absence of cool flames----------------------------------------------------------26
25. Effect of pressure on limits of flammnability of pentane, hexane, and hept aite tin air ait 260 (C------------26
26. Effect of pressure on limits of flammnability of natural gas in air tit 280 C----------------------------27
27. Effect of pressure onl lower temperature limits Of flammiability of pent'ane, blexance, beptanle. and octanle
litair ----------------------------------------------------------------------_ - --- --28
28. Limits of flammability of various methane-inert gas-mnir mixtures ait 250 C and attmiospheric pressure_.29
29. Limits of flamnmability of ethano-carbon dioxide-air anni cthaine-nitrogen-air mixtures ait 250 C and
atmospheric pressure-----------------------------------------------------------------------30
30. Limits of flammability of propane-carboni ioxitie-air and propaoc-nitrogen-air mixtures at 25' C and
atmospheric pressuire-------------------------------------31
31. Limits of flammabilityofbtn-rbndoiearadbt
-nton-rmiuest25Cad
1
atmospheric pressure ----------------------------------------------------------------------32
32. Limits of flammability of various n-pentane-inert gas-air nmixtu- i a
tt 250 C and atmospheric pressure33
33. Limits of flammability of various n-hexane-inert gas-air mixtur -s ait 250 C anid atmospheric pressure34
34. Limits of flammability of n-heptane-water vapor-air mixtures at 1000 and 2000 C and atmospheric
pressure ---------- f-----------------------------------------------------------------------35
3.Approxiate limits offlammability of higher paraffin hydrocarbons (C.112 ,+ 2, n2!5) in carbon dioxideair and nitrogen-air mixtures at 250 C and atmospheric pressuire---------------------------------36
36. Effect of pressure upon limits of flammability of natural gats-nitrogen-air mixtures at 260 C -----------37
37. Effect of pressure onl limits of flammability of ethane-carbon dioxide-air mixtures at 260 C -----------38
38. Effect of pressure on limits of flammability of ethane-nitrogen-air mixtures at 260 C----------------39
39. Effect of pressure onl limits of flammiability of propane-carbon flioxide-air mixtures--------------------40
40. Effect of pressure onl limits of flammiability of propanie-nitrogen-air mixtures -------------------------41
41. Effect of pressure on minimum oxygen requirements for flame propagation through natural gas-nlitrogenair, ethane-nitrogen-air, and propanie-nitrogen-air mixtures at 260 C -----------------------------42
42. Low-temperature limit of flammiability of decane-air, dodecane-air, anid mecan-dodecane-air mixtures43. Minimum autoignition temperatures of paraffin hydrocarbons in air ats at function of average carbon
chain length------------------------------------------------------------------------------44
44. Burning velocities of miethane-, ethane-, propane-, and n-hceptane vapor-air mixtures at atmospheric
pressure and room temperature - --------------------------------------------------------4
45. Burning velocities of methane-, ethanne-, and propane-oxygen mixtures ait atmospheric pressure and room
temperature -------- ---------------------------------------------------------------------46
46. Variation in horning v'elocity of stoichiometric methane-aiir and propane-air mixtures with pressuii: at
260 C--------------------------------------------------------------------------------47
47. Variation in burning velocity of stoichiornetric methane- andl ethyl cne-oxygen mixtures with presstire
4
4
a t 26 ' C - - - - - - 48. Effect of temperature on burning velocities of four paraffin hydrocarbons in air at atmospheric pressure49
49. Detoiation velocities of mnethane-air mixtures ait atmospheric pressure-----------------------------49
50. D)etonation velocities of methane-, ethane-, propane-, butane-, and hexane-oxygen mixtures at atmospheric pressure ------------------------------------------------------------------------4
51. D~etonation velocities of n-heptatne vapor in WFNA (white funming nitric acid) -nitrogen gas mixtures at
atmospheric pressure arnd 4000 K ---------------------------------------------------------50)
52. Relation between liquid-burning rate. (large-pool diameter) and ratio of net heat of combustion to
sensible heat of vaporization----------------------------------------------------------------50
53. Effect of temperature on lower limit of flammnability of ethylene in air at atmospheric pressure..-----50
54. Limits of flammability of ethylene-carbon (lioxide-air and ethylene-nitrogeni-air mixtures at atmospheric
pressure andl 26'0 C--------------------------------------------------------------5
55. Limits of flammability of propylene-carboni dioxide-air and propylene-nitrogen-air mixtures at atmosphieric ressure and 26' C-------- ------------ ---------------------------------------------51
.56. Limits of flainmability of inobutylerie-carbori dioxide-air and isobutylene-nitrogenl-air mlixtures lit
52
C -------------------------------------------------------------ieric pressurremandl26'
attmnlosp
57 . 5Limits
of flammnability
of isobuitylene-water vapor-oxygen inixtures at I 5)O C and atmospheric pressumre53
58. Limits of flaminmibility of bmtene- I-carbon dioxide-air 1111d bUteme- I-nitrogen-air mixtures ait atniospl(briC
pressure and 26* --- ------------------------------------------------------------------54
59. Limits of flammnability of 3 miethyl butemie-l-carbom dioxide-,dr and 3 miethyl-buiteie- I-nitrogeni-air
mixtures at atmospheric pressure and 260 C--------------------------------------------------54

CONTrENTrS
Fig.

60).

,imyits of flatnmabilit 'y of butudlenc-ccirbon dioxide-cur find btitadlene-nitrogon-air mixtures at atmos-

phteric pressure and 260 C -

-- -- - -- - - - - - - - - - - - - - - - - - - - - -

61. Effect of tube dliame'ter onl initial pressure requirements for propagation of dleflagration aind detonation
through acetylene gas ----------------------------_-------62. Range of flammiable mixtures for me(tbylatctylene-propcii(liene-propylenie system at 120' C find at 50
find 100psig-- - ---------------------------------------------------- -------------- -----_
63. Quenched limitsi of flammiability of acetylene-carbon dioxide-air and acetylene-nitrogen-air mixtures
at atmosp~heric pressure find 2t1 C otinced in at 2-inch tube------------------------------------64. Mini ccci autoigi iio temperatures of aceetylene-air aind acctylcne-oxygcn mixtures at atmospheric
and elevated pressures----------------------------------------------------------------------65. Burning velocity of acetylene-air mixtures ait atmospheric pressure and room temperature -------------66. Maximumn LID ratio required for transition of at defl agration to a detonation fin acetylene vapor at 600
F and froto 10 to 70 psia -------------- ----------------------------------------------------#17. Ficcal-to-initial pressure ratios4 developed by acetylene with (letonatijn initiation at various points
aloncgcatube--------------------------------------------------------------------- 68. Limits of fihinicriability of benzver-niethyl bromide-air mixtures at 25' C and benizene-carbon dioxide-air
aind henzene-nitrogen-air mnixtures at 250 aind 15(0' C aind atmospheric pressure ----------------- _ 69. Lilits Of flammablttiility Of ll 2() 2 -C 6lI 4 .(Cl13)h-ll 2O ait 1540 C aind 1 atmosphere pressure ---------------70. Limits of flammnability of 90-weight-perceet llY0 2-C6 11 4.( Clf 3 ) 2-lCOOiI at 154V C and 1 atmosphere
pressure-.---------------------------------------------------------------------------------71. Nliniinuin autoignition temperatures of aroinatic hydrocarbons in air as a function of correlation
paramieter

L ---------

-----------------------------------------------

V
Prg

55

58
58
59

59
60

61
62
63
64

72. Limits of flammllInabili ty of cyclopropan-cacrhon dioxide-air, cyclopropane-nitrogen-air, and cyclopropane65

heliumn-air miixtures ait 250 C aind atmospheric pressure -----------------------------------------73. Limits of flammi
iability of cyclopropatne-hiutni-oxygen aind cyclopropane-nitrous oxide-oxygen mixtures
-----------------66
ait 25' C and atmospheric pressure -----------------------------------------66
74. Limits of flaninability of cyclopropitne,-he(liumt-niitrotus oxide mixtures at 250 C and atmospheric pressure75. Limits of flammability of methyl alcohiol-carbon dioxide-air and methyl alcohol-nitrogen-air mixtures at
25' C and atmospheric pressure ------------------------------------------------------------66
76. Limits of Flammability of methyl alcohol-water vapor-air mixtures at 1000, 2000, and 4000 C and
alnospheric pressure ----------------------------------------------------------------------67
77. Limits Of flammability of ethy) alcohiol-carbon dioxide-air and ethyl alcohol-nitrogen-air mixtures at
251 C and atmospheric pressure ------------------------------------------------------------68
78. Limits of flatmmnability of ethyl alcohiol-wt, vapor-air mixtumres at 1000 C and atmospheric pressure68
79). Limits of flammnability of terf-bcctyl alcohol-water vapor-air mixtures at 1500 C and atmospheric pressure68
80. Limits of flanmmability of terl-butyl alcohiol-carbon dioxide-oxygen mixtures at 1500 C and atmospheric
pressure --------------------------------------------------------------------------------68
81. Limits of flammability of 2-ethiylbtantol-niitrogeni-oxygeni mixtures at 1500 C and atmospheric pressure69
82. Limits of flamniability of dimethyl ether-carbon dioxide-air aind dimethyl ether-nitrogen-air mixtures at
-----------------------------------------------------69
25' C anid atmnospheric presstire------83. Limits of flammability of dilethyl ether-carbon dioxide-air aind diethyl ether-nitrogen-air mixtures at 250
- -69
Cafidatilloqpheric pr'ssccre-------- -----------------------------------------------------84. Limits of flamnability of diethyl ether-helium-oxygen aind diethyl ether-nitrous oxide-oxygen mixtures
ait 25' Canid atmospheric pressuire.-------- --------------------------------------------------70
S5. Limits of flammability of diethvl ether-nitrous oxide-heliumn mixtures ait 25' C and atmospheric pressure70
80i. Limlits of flammnabilit y of mnet hcyl formcvite-cccrbon dioxide,-air aind miethyl formate-iiitrogen-air mixtures71
87. Limits of taimicabilit y of isobut'vi forinate-ecarbon dioxide-air aind isobutyl formate-n1itrogen -air mixtures72
88. Limlits of flitInfilbilit y of flet hI' acetate-carboci dioxide-air aind methyl aetate-nitrogvci-air mnixtumres-72
89). Effu-ct, of temperature onl lower limits of flamomability of MEK-tolumene mixtures in air itt atmosp~heric
ressiirc'---------------- ---------------------------------------------------------------73
90. ICetof teiperattire on lower limits of flammability of TIIF..toluiene mixtures in air at atmospheric
pressur ------- ------------------ ----- ---------------------------------------------------74
91. Effect of liquid composition on lower finciti of flammability of MIEK-tolice mixtures in air at 300 alid
20010 C--------------------------------------------------------------------------------75
02. Effec I of liquid composition onl lower limits of flammability of TIIF-toluene mixtures in air at 30* and
2001 C..---------- ----------- --------------------------------- ------------------------76
9:3. Limits of fliamomcilbili~y of acetomie-carboci dioxide-air and acetone-iiitrogeni-air mixtures ---------------77
94. Limiits of flamumnalilit v of mocthtil Othyl ktocie (NI EK)-chilorobromomecthlace (CBM)-air, MIEK-carbon
dioxide-air acnd NI F'IK-ctitrog(.ci-itir'tiixtiires at 250 C aid atmospheric p~ressure -------------------79
95. Limcit s of launiibilit y of carboci distilfide-etirbon dioxide-air, ccarbon dioxide-nitrogen-air mixtures cit 25'
79
C andi cit cmslieric pressure, aid carboni discilfide-water vapor-air ait 1000 C and atmospheric pressure.
96. Limits of fl Icucictabilit y of liydropemi sclfidvearboci dioxide-air mixtures ait 250 C amid atmnosp~heric
-------------------------------------------79
pressuir--------------------97. Licoits of flit titcatdlit Nof ethiyl moerecptaci-F'-12-air aid ethyl mercaptaic-F-22-air mixtures ait atmos.
71)
-------------------phiiric priesurvandul27' C_----_-----98. 1am its of fil c cI)
1hlil y of ium nioc iii, U I) NIl NI NII, anicd hydrazice cit at mosphieric pressure iccsatcurated
acid ieur-saurited vapor-dir inixtcri--------------------------------0
91)I.Flu iinnable mcix tiure cocinpositioc s of It razici -hept ccc -air cit 1250 C acid approximcatel y atmospheric
81
- -- - - - - - - - - - - - - - - - -- - - - - - . - -.
_
_--_ anieous igncition
100. 'N,pressutre
tiniiui Spout
tcinpurat ores of liquid hydrazine, MINI1, and UI) I I at sil incit ial
ucciprau o
of 250 C ici cocctact wit" N02)*-air mcixtucrus cit 740(10 mt
cin Hg as a funct ion of No,*
coiiecctratioc------------------1-----------------------------------82
101 . N ilci iciucci spoictita olis ign it ioc t ciiipi rcto ris of l iquiiid hcydcraz inc at various initial tecI puwrat ores ill
1
NO 2 *-air mixtures at 740 1 1t) mmi fig as at function of NOJ,* coccntration ---------------------

V1

CONTENTS
P84e

rig.

102. Minimum spontaneous ignition tomperatures of liquid MMH at various initial temperatures in NO,*air mixtures at 740 10 mm Hg as a function of NO?* concentration --------------------------.
103. Minimum spontaneous ignition temperatures of liquid UI)MH at various initial temperatures in
NO,*-air mixtures at 740 10 mm Hg as a function of NO,* concentration ..-------------------104. Minimum spontaneous ignition teirperatures of 0.05 cc of liquid UDMH in tle-OrNO,* atmospheres
at 1 atmosphere for various He/Os ratios-- --------------------------------------------105, Minimum spontaneous ignition temperatures of 0.05 cc of liquid UDMH in NO,e-air mixtures at 15
and 45 pas as a function of NO,* concentratioc .......
106. Minimum spontaneous Ignition temperatures of vaporized UDMH-air mixtures in contact with 100
pet NO,* at 250 C and 740 10 mm Hg as a tunetion of UDMH concentration in air------------107. Limits of flammability of diborane-ethane-air mixtures at laboratory temperatures and 300 mm Hg
initial pressure ------------------------------------------------------------------------------108. ASTM distillation curves for, A aviation gasoline, grade 100/130; B, aviation gasoline, grade 115/145;
C aviation jet fuel, grade JP-I; D, aviation jet fuel, grade JP--3; and, B, aviation jet fuel, grade
...................................
JP-4 .....................................
109. Limits of flammability of aviation gasoline, grades 115/145 vapor-carbon dioxide-air vad 115/145
vapor-nitrogen-air, at 270 C and atmospheric pressure ----------------------------------------110. Limits of flammability of JP-4 vapor-carbon dioxide-air and JP-4 vapor-nitrogen-air mixtures at 270 C
and atmospheric presure --------------------------------------------------------------Ill. Limits of flprnmabi9t" nf hydrogen-carbon dioxide-air and hydrogen-nitrogen-air mixtures at 250 C
and atmospheric pressure -----------.-----------.------------------------------------112. Limits of flammability of IHrNO-NjO at approximately 280 C and I atmosphuee -----------------113. Limits of flammability of HrNO-air at approximately 280 C and I atmosphere -------------------114. Limits of flammability of Hi-NO-air at approximately 280 C and I atmosphere -----.................
115. Rate of vaporisation of liquid hydrogen from paraffin in a 2.8-inch l)ewar flask: Initial liquid depth6.7 inches ------------------------------------------.----------------------------------116. Theoretical liquid regression rates following spillage of liquid hydrogen onto, A, an average soil; B, moist
sandy soil; and C, dry sandy soil --------------------------.-------------------------------117. Theoretical decrease in liquid hydrogen level following spillage onto, A, dry sandy soil; B, moist sandy
soil; and C, an average soil ---------------------------------------------------------------118. Extent of flammable mixtures and height of v(sible cloud formed after rapid s illage of 3 liters of liquid
hydrogen on a dry macadam surface in a quiescent air atmosphere at 15'C---------------------119. Motion picture sequence of visible clouds and flames resulting fron, rapid spi~lage of 7.8 liters of liquid
hydrogen on a gravel surface at 180 C -----------------------------------------------------120. Maximum flame height and width produced by ignition of vapor-air mixtures formed by sudden spil--------------------------------------lage of 2.8 to 89 liters of liquid hydrogen --------121. Burning rates of liquid hydrogen and of liquid methane at the boiling points in 6-inch-Pyrex Dewar
flaks
--------------------------------------------------------------------------122. Variation in minimum autoignition temperature with pressure of commercial phosphate ester and
mineral oil lubricantd in air in r 450-cc-stainless steel bomb ---------------------------------123. Logarithm of initial pressure-AIT ratio of seven fluids in air for various reciprocal temperatures -----124. Variation in TnT, of air with V,/Vf and with Pf/P, in an adiabatic compression process.------------125. Variation in air temperature with P,/Pj in an adiabatic compression process for five initial air temperatures
----------------------------------------------------------------------126. Limits of flammability of carbon monoxide-carbon dioxide-air and carbon monoxide-nitrogen-air
mixtures at atmospheric pressure and 26 C
--------------------------------------------127. Lower limits of flammability of NPN vapor-air mixtures over the pressure range from 0 to 1,000 psig
at 750 1250 1500 and 1700 C -------------------------------------------------------------128. Flammable NPN vapor-air mixtures formed over the pressure range from 0 to 1,000 psig at 500 and
1250 C --------------------------.---------------------.-------------------------------129. Variation of explosion pressure following spontaneous ignition with NPN concentration- -----..
-130. Minimum spontaneous ignition and decomposition temperatures of n-propyl nitrate in air as a function of pressure ------------------------------------------------------------------------131. Flammability of trichloroethylene-air mixtures.--------------------------------------------

84
85
80
87
87
88
88
88
- 88
89
A
91
92
93
93
94
94
95
96
96
98
99
100
101
102
102
103
104
104
105

TABLES
Page
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
II.

Conditions of failure of peak overpressure-sensitive elements ------------------------------------17

Properties of paraffin hydrocarbons ---- -.------------.-------.------------.-----------------21
Upper flammability limits of methane-air mixtures at 15 psig _... ...------------------------24
Lower temperature limits and autoignition temperatures of paraffin hydrocarbons at atmospheric
pressure -----------------.---------------------------------------------------------25
Limits of flammability of methane in chlorine- .
...............---------------------------27
Limits of flammability of ethane in chlorine- ---.--------- ----------------------------------28
Properties of unsaturated hydrocarbons ....
..--------------------------------------------------48
Limits of flammability of unsaturated hydrocarbons at atmospheric pressure and room temperature, in
volume-percent combustible vapor-----------.-------------------------------------------52
Minimum autoignition temperatures of unsaturated hydrocarbons at atmospheric pressure ----------...
52
Heats of formation of unsaturated hydrocarbons at 250 C ---------------------------------------53
Properties of selected aromatic hydrocarbons --------------------------------------------------60

CONT

7N'rS

12. Prop ,rties of aelected alicyclic hydrocarbons ------------------------------------------------------13. Properties of selected simple alcohols ---------------------------------------------------------14. Propertie of selected ethers ---------------------.-----------------------------------------------15. Properties of selected esters --------------------------------------------------------------- -16. Properties of selected aldehydes and ketones ---------------------------------------------------17. Properties of selected sulfur compounds ------------------------------------------------------18. Properties of selected fuels and fuel blends -----------------------------------------------------19. Limits of flammability of ammonia at room temperature and near atmospheric pressure --------------20. Autoignition temperature values of various fuels in air at I atmosphere----------------------------21. Limits of flammability of hydrogen in various oxidants at 250 C and atmospheric pressure .-----------A-I. Summary of limits of flammability, lower temperature limits, and minimum autoignition temperatures
of individual gases and vapors in air at atmospheric preuure --------------------------------

VIU
Pageo
64
67
70
71
73
74
77
78
88
89
114

FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS

Acu IA Zxketakiqi

A bstract

HIS is a summiary of the available limit of flammiability, autoignition,

and burning-rate (lata for more than 200 combustible gases ancd vapors
in air and other oxidants, its well as of empirical rules and graphs that
c'an be used to predict similar dta for thousands of other combustibles unider
a variety of environmental conditions. Specific data are presented on the
paraffinic, unsaturated, aromatic, arid alivNycl ic hydrocarbons, alcohols, ethers,
aldehydes, ketones, and sulfur vomnpoundls, and" an assortment of fuels, fuel
blends, hydraulic fluids, engine oils, and miscellaneous combustible gases and
vapors.

Introduction
Prevention of unwanted fires andl gas4 explosion disasters requirei a
knowledge of flamimability chlaracteristics (limits of flamnimabdity, ignition
and burning rates) of pertinent combustible gases and vapors
Mrequirements,
lky to be enicountered under various conditions oif use (or misuse). Available
data maly not always be adequate for use in at particular application since they
mnay have been obtained at, tt lower temperature and pressure than is encountered
in practice. For example, tile quantity of air that is required to diecrease the
comlbustible vapor concentration to at safe level in in. particular proem"; Carried
out at 200 'Cj should be based onl flammiability data obtained at this temperature.
When these are not, available, suitable approximations can be made to permit a
realistic evaluation of the hazards associated with the process b)eing considered;
such approxiniat ions can serve as the basis for dezsi;7;tng suitable safety devices
for the protection of personnel and equipment.
Tile purpose of this bulletin is to present a general review of the subject
of flammability, and to supply select expe-rimiental data and empirical rules on
the flainiabillty characteristices of various famiilies of combustible gases arid
vapors iii air and other oxidizing atmospheres. It contains what, are believed
to be the latest and molst reliable dlata for more than 200 combustibles of
interest to those concerned with the prevention of dishstrous gas explosions.
In addition, the emipirical rules and graphs presenlted here can be used to
preti ict similar data for other com bustiles tunder a variety of conditions.
This b~ulletin sup plemients Bureau bulletins (40)" andh other pub~lications (158).
Basic knowledge of coimihust ion is (desirable for I- thorough understanding
of thie material, which can be found in numierous publications (69, 19.9, eoe).
Therefore, only t hose aspects requiiredl for anl understanding, of flammability
are considered here; even these are considered from a fairly elemnentary
viewpoint.
lhrii hernlst. project coordinator, Otxi

Explosiwilves Reeh center, numeu of Mines. Pittsburgh, Na

itl
idntumbers in parenthes reer to Items In the bibiloi phy at toand of titl report
Work on manumoript oompleted May 19N.

FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS

DEFINITIONS AND THEORY

LUMil1S OF FLAMM AIIT

combustible gas-air mixture can be burned
over a wile range of concentiations-when
either subjected to elevated temperatures or
exposed to a catalytic surface at ordinary
temperatures. However, homogeneoug cornbustible gas-air mixtures are flammable, that, is,
they can propagate flame freelyv within
~ a
limnlted range of compositionts. F~or examplke,
trace amounts of methane in air can be readily
oxidized on a heated surfaee, but a flame wi
propagate from an ignition source at amirbient
tmetures and pressures only if the surronigmixture contains at least 5 but less
than 15 volume-percent methane. The more
dilute mixture is known as the lower limit, or
combustible-lean, limit, mixture; the more
concentrated mixture is known as the upper
limit, or combustible-rich limit, mixture. In
practice, thle limits of flammability of at particular system of gases aire affected by the
temperature, pressure, direction offan rpgation, gravitational field strength, and surroundings. The limits are obtained experimentally by determining thle limiting mixture
compositions between flammable and nionflammable mixtures (244). That is,
-

LT. 11[C,+C~1,(1)
and
UTT.p=

1/2[(,,+

C1.],

(2)

where L,.P and U7 .P are the lower andl uppe.r

limits of flmmability, respectively, at at specifled temperature and pressure, C,,, and C, are
the greatest and least concentrations of fuel in
oxidant that are nonflammnable, and ('if and
(?gf are the least and greatest concentrations of
fiiel in oxidant that aire flamimable. Tile rate
at which a flamie propagates through it flamnmable mixture depends on at number of factors,
including temperature, pressure, amnd mnixture
composition. It is at minimui ait thle limits of
flunmnuabifity and atmaximumi at near' stoichiometric mixtures (130).
The Bureau of Mlines has adop)ted at st andaird
apparatus for limit -of-flammiability doeteininailtions (40). Originally designed for use ait
atmospheric pre'ssu~re and roo~m t emplera ture,
it, wats later mnodified for use t.t rediuced preggl il
mgasar-a
;tire, 1wIcloa
tile hase, of thme 2-inch, glass, flaine-propagation
tube. T i riodifiCat io1 iintr0otlueVi' I ihCullt r
that

wats

not

inmiiediatelY

apparenlt,

as

thle

spark energ 'v was lill alwalys adiequate for uise ill
F'i'ure
hliit-of 'I* mniiv(etmiutos
, tihle effit oif miixtur'e conmpositionl on
illmusita
hle electrical spark energy reqjuiremlenits fora

'

FILimits

'

of
f lammability

__

E 4>:
I.,g2

rX

W 2Z
W

blit
lmt

X
.8
.6

'n

A
X--

12- 14
10
8
6
METHANE, volume-percent

16

18

Fiouau .- Ignitihility Curve and Limits of Fiamninability for Methane-Air Mixtures at Atmospheric

Prsuead2'C
ignition of meothane-air mixtures (75). For
example, at 0.2-millijoule (mij) spark is inadequate to ignite even a stoichiometric mixture at
atmospheric pressure and 260 C; a 1-mj spark
can ignite mixtures containing between 6 and
11.5 volume-percent methane, etc. Such limitmixture compositions that depend on the ignition source strength may be d~efined ats limits of
ignitibiity or more simply ignitibility limits;
th'ey are thus indicative ot the ignitin'g ability
of the energy source. Limit mixtures that tire
essentially independent of the ignition source
strength and that give a measure of the ability
of at flamie to propagate iaay from the ignition
source mnay be defined ats lim'its of flammability.
Considerably greater spark energies aire required
to establish limits of flammability than tire
required for limits of ignitibility (218); further,
more energy is usually required to establish tile
upper limit thani is requiredl to establish thle
lower limit. !n general, when the sour-ce
strength is adlequate, mixtures just, outside therange of flammnable comp1
1 ositionls Yield flaime

caps when ignitedl. These flaiiie caps prop~agate

on Iv at short, (listaunce fromn the ignitioni source
illitauniifor in iixture. The reason for t his
e seenii i figure 2 which shows (,he effec't of
a
temp~erature oil limits of flaimmnlability at at

As the temperat tire

inlitil pressurem.
is increased, t he lower limit delec(ases and1(tile
upper limiit jecretses, Thus, since at localized

('on1sUta

energy somirc(. elevates' the ternpermit tire of

nlemimby gases, even at nonflaniiale mixture vall
propaigate llaiiie at shorit distance fromin lhe

DiEFINIT'IONS AND THEORY

Saturated vapraurmxtur

Upper
limit
Auto-

Fignition

Mist

Flammable

'

9factory
8

limit

I I
rt

AlT

AIT

TEMPERATUREFiouis 2.--Effect of Temperature on Limits of

Flammability of a Combustible Vapor in Air at a

Constant Initial Pressure.

source. That is, a nonflammable mixture (for

example, com )osition-temperature point A,
fig. 2) may become flammable for a time, if its
temperature is elevated sufficiently (composition-temperature point B).
Flammable mixtures considered in figure 2
fall in one of three regions. The first isleft of
the saturated vapor-air mixtures curve, in the
region labeled "Mist". Such mixtures consist,
of droplets suspended in a vapor-air mixture;
they are discussed in greater detail in the section
on formation of flammable mixtures. The second
lies along the curve for saturated vapor-air
mixtures; the last and most common region lies
to the right of this curve. Compositions in the
second and third regions make up the saturated
and unsaturated flammable mixtures of a
combustible-oxidant system at a specified
pressure.
In practice, complications may arise when
flame propagation and flammability limit determinations are made in small tubes. Since heat
is transferred to the tube walis from the flame
front by radiation, conduction, and convection,
a flame may be quenched by the surrounding
walls. Accordingly, limit determinations must
be made in apparatus of such a size that. wall
quenching is minimized. A 2-inch-ID vertical
tube is suitable for use with the paraffin
hydrocarbons (methane, ethane, etc.) at atmospheric pressure and room temperature.
lowever, such a tube is neither satisfactory
under these conditions for memny halogenated
and other compounds nor for paraffin hydrocarbons at. very low temperatures and pressures
(1,97, 2, /N).
Because of the many difficulties associated
with choosing suitable apparatus, it is not
surprising to find that the very existence of the

limits of flammability has been questioned.

After a thorough study, Linnett and Simpson
concluded that while fundamental limits may
exist there is no experimental evidence to
indicate that such limits have been measured
(18).

In a more recent publication, Mullins

reached the same conclusion (154). Accordingly, the limits of flammability obtained in an
apparatus of suitable sise and with a satisignition source should not be termed
fundamental or absolute limits until the existence of such limits has been established.
However, as long as experimentally determined
limits are obtained under conditions similar to
those found in practice, they may be used to
design installations that are safe and to assess
potential gas-explosion hazards.
Industrially, heterogeneous single-phase (gas)
and multi-phase (gas, liquid, and solid). flaa.
mable mixtures are probably even more important than homogeneous gas mixtures. Un-

fortunately, our knowledge of such mixtures

is rather limited. It is important to recognire,

however, that heterogeneous mixtures can
ignite at concentrations that would normally
be nonflammable if the mixture were homogeneous. For example, I liter of methane can
form a flammable mixture with air near the top
of a 100-liter container, although a nonflammable (1.0 volume-percent) mixture would
result if complete mixing occurred at room
temperature. This is an importa:t concept,
since layering can occur with any combustible
gas or vapor in both stationary and flowing
mixtures. Roberts, Pursall and Sellers (176180) have presented an excelent series of review
articles on the layering and dispersion of
methane in coal mines.
The subject of flammable sprays, mists, and
foams is well-documented (5, 18, , 7, 76,
05, 215, 45). Again, where such heterogeneous mixtures exist, flame propagation can
occur at so-called average concentrations well
below the lower limit of flammability (86);
thus, the term "average" may be meaningless
when used to define mixture composition in
heterogeneous systems.

IGNrON
Lewis and von Elbe (130). Mullins (153,154)
and Belles and Swett (156) have prepareA
excellent reviews of the processes associated
with spark-ignition and spontaneous-ignition
of a flammable mixture. In general, many
flammable mixtures can be ignited by sparks
having a relatively small energy content (1 to
100 mj) but a large power density (greater
than 1 megawatt/cm). However, when the
source energy is diffuse, as in a sheet discharge,
even the total energy requirements for ignition

FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE OASES AND VAPORS

may be extremely large (79, 82, 85, IeS, 181,

28). There is still much to be learned in this
field, however, since electrical discharges are
not normally as well defined in practice as
they are in the laboratory.
When a flammable mixture is heated to an
elevated temperature, a reaction is initiated that
may proceed with sufficient rapidity to ignite
the mixture. The time that elapses between the
instant the mixture temperature is raised and
that in which a flame appears is loosely called
the time lag or time delay before ignition. In
general, this time delay decreases as the temperature increases.
According to Semenov
(193), these quantities are related by the
expression
0.22E
log r=---+B,
(3)
where T is the time delay before ignition in
seconds; E is an apparent activation energy for
the rate controing reaction in calories per
mole; T is the absolute temperature, expressed
in degrees, Kelvin; and B is a constant. Two
types of ignition temperature data are found in
urrent literature. In the first, the effect
temperature on time delay is considered for delays of less than 1 second (127, 158). Such data
are applicable to systems in which the contact
time between the heated surface and a flowing
flammable mixture is very short; they are not
satisfactory when the contact time is indefinite.
de i se
e
of is
Frt hefactr e n (3)contatti
Further,second
it gives only the time delay for a range of temperatures at which autoignition occurs; if the
temperature is reduced sufficiently, ignition does
not occur. From the standpoint of safety, it
is the lowest temperature at which ignition can
occur that is of interest. This is called the
minimum spontaneous-ignition, or autoignition,
temperature (AIT) and is determined in a uniformly heated apparatus that is sufficiently
large to minimize wall quenching effects (194,
Figures 3 and 4 illustrate typical auto287).
ignition-temperature
data. In figure 3 the
minimum autoignition-temperature or AIT
value for n-propyl nitrate is 1700 C at an
(243). Data
pressure
initial
a log inT
to construct
used psig
be 1,000
may of
this figure
I
versus
plot such as that in figure 4. Such

graphs illustrate the applicability of equation

(3) to autoignition temperature data. The
equation of the broken line in figure 4 is
log

12.3
ogr

10

25
-25T..

(
(4)

In 'his specific case, equation (4) is applicable

only in the temperature range from 1700 to

1950 C; another equation must be used for

data at higher temperatures. The solid lines
in figure 4 define an 8 C' band that includes
the experimental points in the temperature
range from 1700 to 1950 C.

FORMATION OF FLAMMABLE
MIXTUES

In practice, heterogeneous mixtures are

always formed when two gases or vapors are
first'brought together. Before discussing the
formation of such mixtures in detail, a simplifled mixer such as that shown in figure 5 will be
considered briefly. This mixer consists of
chambers I and 2 containing gases A and B,
respectively; chamber 2, which contains a
stirrer, is separated from chamber 1 and piston
3 by a partition with a small hole, H. At time
te, a force F applied to piston 3 drives gas A
into chamber 2 at a constant rate. If gas A
is distributed instantaneously throughout chamber 2 as soon as it asses through H, a couposition diagram such as a given in figure 6
results; the (uniform) piston motion starts at
of t. and stops at t,. However, if a time interval
At is required to distribute a samll volume from
chamber 1 throughout chamber 2, then at any
instant between t. and t, + At, a variety of
mixture compositions exists in chamber 2.
This situation is represented schematically in
during which
interval of time
figure 7. The gas
mixtures would exist in the
heterogeneous
case is determined in part by the rate
at which gas A is added to chamber 2, by the
size of the two chambers, and by the efficiency
of the tirrer.
of the stirrer.
In practice, flammable mixtures may form
either by accident, or design. When they are
formed by accident, it is usually desirable to
reduce the combustible coicentration quickly
n conn erta
mirr
nona b
nonflammable mixtures. Under certain conditions, it may be possible to increase the conbustible
concentration
as procedures
to produce area
nonflammable
mixture. soSuch
discussed in greater detail in the following
section.
Fectinb
Flammable mixtures are encountered in
production of many chemicals and in certain
physical operations. These include gasfreeing
ic tank containing a combustible gas (232),
drying plastic-wire coating, and recovering
solvent fromt
solvent-air mixture. When
layering can occur, as in drying operations, it
is not enough to add air at such a rate that the
verall mixture composition is below the lower
limit of flammability (assuming that uniform
mixtures result). Special precautions must, be
taken to assure the rapid formation of nonflammable mixtures (235). When a batch

DEFINITIONS AND THEORY5

1*

4o

Sample

360

vol, cc

32

320-

X
0

28
Q
0- 240

0.50
0.75

1.00
1.50
1.75

2.00

0
A
v
A

2.25

2.50
2.75
300
325

00
w 2000

m.
LLI

Region of
au toignition

160-

0 120I
w
80--

0
150

JAT
160

0
K
1 %

170
180
190
200
TEMPERATURE, OC

210

220

FIOURE 3.-Time l)elay Before Ignition of NPN in Air at 1,000 Psig it,
the Temperature Range From
1500 to 2100 C. (1-33 apparatus; type-347, stainless steel test chamber.)

rocess is involved, an added precaution must

Ce taken; a constituent at a partial pressure
near its vapor pressure value may condense
when it is momentarily compressed by addition
of other gases or vapors. Accordingly, mix-

tures that are initially above the upper limit of

flammability may become flammable. A similar effect must be considered when mixtures are
sampled with equipment that is cooler than
the original sample; if vapor condenses in the

FLAMMABILITY

CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS

TEMPERATURE, OC
600

200

210
1

190

I80

170
|

AWT

400

8Co
l:I/

'02000

80-

--

Region of

outoignition

_
w

60

co

40-

tL

/o
A

U020
I-

20

10

82.05

IIII0
EI
2.2
2.20
2.15
2.10
15r.
TEMPERATURE,
RECIPROCAL

2.0

Fzouits 4,-Logarithm of Time Delay Before Ignition of NPN in Air at 1,000 Paig Initial Pressure.
(Data from figure 3.)

sampling line, the test sample will not yield

accurate data. A flammable mixture sampled
in this manner may appear to be nonflammable
and thus create a hazardous situation (236).
A flammable mixture can also form at ternperatures below the flash point of the liquid
combustible either if the latter i6 sprayed into
the air, or ifa mist or foam forms. With fine

mists and sprays (particle sizes below 10 microns) the combustible concentration at the
lower fimit is about the same as that in uniform
vapor-air mixtures (17, 18, 22, 4, 76, 245).
However, a. the droplet diameter increases, the
lower limit appears to decrease. In studying
this problem, Burgoyne found that coarse droplets tend to fail towards the flame front in an

DEFINITIONS AND THEORY

Chamber I

Chamber 2

100oo-

Gas AGs8

- fl3

Figure 5.-Simplified mixer.

0100

FIGURE 5.-Simplified Mixer.

ELAPSED TIME
FIGURE 7.-Compo ition of Gas in Chamber 2, Figure

Z~ 10

5 (Delayed Mixing).

16
0E

1
0

Qi 5

0 01

100 0

If

10
ELAPSED TIME

FIGURE 6.-Composition of Gas in Chamber 2, Figure

5 (Instantaneous Mixing).

upward propagating flame, and as a result the

concentration at the flame front actually approaches the value found in lower limit mixtures

of fine droplets and vapors (24). With sprays,

the motion of the droplets also affects the limit
composition, so that the resultant behavior is
rather complex. The effect of mist and spray

droplet size on the apparent lower limit isillusS trated in figure 8. Kerosine vapor and mist
data were obtained by Zabetakis and Rosen
(2045); tetralin mist data, by Burgoyne and
Anson
Cohen (24); kerosine spray data, bydata,
by
(5); and the methylene bistearamide
Browning, Tyler, and Krall (18).
Flammable mist-vapor-air mixtures may
on a flammable liquid colthe foam
occur
when ignited, many foams can
lapses. as Thus,
propagate flame. Bartkowiak, Lambiris, and
Zabetaki found that the pressure rise AP pro-

100
-0.07
---- Stoichiometric
B

.L

0 0

U
E

80

60

mixture (decane-air)

17

.06

Kerosine spray

-. 05.aZ

Kerosine vapor
and mist

.
-. 04 E

00
.-

Methylene

bistearamide spray

Z
20.0
-

retaln is
0
FiouRJF 8.-Variatioi

20

40

-Tetralin

100
80
60
DROP'.ET DIAMETER, miictonv

120

mist
140

.01

160

i" Lower Limits of FlanitabilIity of Various Combustibles in Air m~a Function of D~roplIet
Aiameter.

FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS

duced in an enclosure by the complete combustion of a layer of foam of thickness A, is propertional to h, and inversely proportional to hA,
the height of the air space above the liquid
before foaming (7). That is
ha
Pressures in excess of 30 psi were produced by
the ignition of foams in small containers,
Thomas found that an additional hazard
could arise from production of foams by oxygen-

enriched air at reduced pressures (215). Air

can become oxygen-enriched as the pressure is
reduced, because oxygen is more soluble than
nitrogen in most liquids (83). Thus the presence of foams on combustible liquids are a potential explosion hazard.
A flammable foam can also form on nonflammable liquid if the foam is generated bi a flamunable gas mixture instead of air.
urgoyne
and Steel, who studied this problem, found that
the flammability of methane-air mixtures in
water-base foanis was affected by both the wetness of the foam and the bubble size (28).

PRESENTATION OF DATA
Limit-of-flammability data that have been
obtained at a specified temperature and pressure
with a particular combustible-oxidant-inert
system may be presented on either a triangular
or a rectangular plot. For example, figure 9
shows a triangular flammability diagram for
the system methane-oxygen-nitrogen.
This
method of presentation is frequently used
because all mixture components are included
in the diagram. However, as the sum of all
mixture compositions at, any point on the triangular plot is constant (100 pct) the diagram
can be simplified by use of a rectangular plot
(24.). For example, the flammable area of
figure 9 may be presented as illustrated in
figure 10. As noted, the oxygen concentration
at any point is obtained by subtracting the
methane and nitrogen concentrations at the
point of interest from 100 as follows:
Pet 02=100 pet-pct CH 4-pct N 2. (6)

With either type of presentation, addition of

methane, oxygen, or nitrogen to a particular
mixture results in formation of a series of mixtures that fall along the line between the composition point (for example, Mi in figures 9 and
10) and the vertices of the bounding triangle.
For example, addition of methane (+CH,) to
mixture M1 yields initially all mixture cornpositions between Mi and C (100 pct CH 4).
After a homogeneous mixture is produced, a
new mixture composition point, such as M2, is
obtained. Similarly, if oxygen is added (+02)
to the mixture represented by point Mi, all
compositions between M1 and 0 (100 pct O)
are obtained initially; if nitrogen is added, all
compositions between MI and N (100 pct N2 )
are obtained initially. If more than one gas is
added to M1, for example, methane and oxygen, the resultant composition point may be
obtained by considering that the mixing process

00

ioo

MI
-02

+CH4

06

M3~

+N2

Air

Flammable
S

mixtures

//
/O/7

,Min
100
0
FIGURE

90

so

70

02
60

50

40 r1gz::aticol
30C/N

20

0 0'

i0

OXYGEN, volume-percent

9.--Flammability Diagram for the Syatem Methane-Oxygen-Nitrogen at Atmospherilo Pressure and 200 C.

______

10

FLAMLABILITY CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS

100
-

% 0 2 -100%-% CH4 -% N 2

80C

+CH4

02

160
E

-N
-N

N2

zA

44-

! /4
Fla mmaoble

20-

mixtures-

40

Lriticl
0

20

MiN

C/NL

40
60
NITROGEN, volurne-percent

Aso

100

Fioulz 10.-Flammability Diagram for the System Methano-Oxygen- Nitrogen at Atmospheric Pressure and W6 C.
(Data from fig. 9).
occurs in two steps. First,, the methane is added
to Mi and the gases are mixed thoroughly to
give M2. Oxygen is then added to Af2 with
mixing to give a new (flammable) mixture, M3.
If the methane and oxygen were added to a
fixed volume at constant pressure, some of M 1
and then of M2 would escape and mix with the
surrounding atmosphere. In many instances
this is an important consideration because the
resulting mixtures may be flammable.
For
example, even if an inert gas is added to a
constant-volume tank filled with methane,
flamnmable mixtures (-an form outside the tank
as the displaced methane escapes into the
atmosphere. If the inethant, is not dissipated
quickly, a dangerous situation1 can arise.
When a mixttire compoment is removed by
condensation or absorption, the corresponding

composition point (for example, M1 in figures 9 and

10) shifts away from the vertices C, 0, and N
along tile extensions to the lines MI-C, Mi
-O and Mi -N, indicated in figures 9 and 10
by the minus signs. The final composition is
determined by the percentage of each component,
removed from the initial mixture.
Mixtures with constant oxygen-to-nitrogen
ratio (as in air), are obtained in figures 9 and 10
by joining the apex, C, with the appropriate
mixture composition along the baselne, ON.
Thus, the Air line, CA, (fig. 10) is formed by
joining C with the mixture A (21 percent 0
+79 percent N2). Using this latter point, A,
one can readily determine the mixture cornpositions that are formed when mixture M1 is
displaced from an enclosure and mixed with air.
Initially, all mixture compositions between Af I

ie
PRESENTATION OF DATA

and A would form.

Since these would pass

through the flammable mixture zone, a hazardous condition would be created. Similarly, if
pure combustible CH, were dumped into the
atmosphere (air) all mixtures between C and A
would form. These would include the flammable mixtures along CA so that a hazardous
condition would again be created, unless the
c)mbustible were dissipated quickly.
Mixtures with constant oxidant content are
obtained by constructing straight lines parallel
to zero oxidant line- such mixtures also have a
constant combustible-plus-inert content. One
particular constant oxidant line is of special
importance-the minimum constant oxidant
line that is tangent to the flammability diagram
or, in some cases, the one that passes through
the extreme upper-limit-of-flammability value.
This line gives the minimum oxidant (air,
oxygen, chlorine, etc.) concentration needed to
support combustion of a particular combustible
at a specified temperature and pressure. In
figures 9 and 10, the tangent line gives the
minimuin oxygen value (Min 01, 12 volumepercent) required for flame propagation through
methane-oxygen-nitrogen mixtures at 260 C
and 1 atmosphere.
.
Another important construction line is that
which gives the maximum nonflammable combustible-to-inert ratio (critical C/N). Mixtures
along and below this line form nonflammable
mixtures upon addition of oxidant. The critical
C/N ratio is the slope of the tangent line from

the origin (Figs. 9 and 10), 100 percent oxidant,

to the lean side of the flammable mixtures

curve. The reciprocal of this slope gives the

minimum ratio of inert-to-combustible at which
nonflammable mixtures form upon addition of
oxidant. It is of interest in fire extinguishing.
An increase in temperature or pressure
usually widens the flammable range of a
particular combustible-oxidant system. The
effect of temperature is shown in figure 11;
two flammable areas, T, and T,, are defined for
a combustible-inert-oxidant system at constant
presure. The effect of temperature on the
limi!ts of flammability of a combustible in a
specified oxidant was previously shown in
figure 2. This type of graph is especially
useful since it gives the vapor pressure of the
combustible, the lower and upper temperature
limits of flammability (T, and Tv), the Hammable region for a range of ten eratures, and

the autoignition temperature (AlT).

Nearly

20 of these graphs were presented by Van

Dolah and coworkers for a group of cornbustibles used in flight vehicles (218).
The lower temperature limit, TL, is essentially
the flash point of a combustible in which upward propagation of flame is use4 ; in general, it
is somewhat lower than the flash point, in which

11

%oir 100

% combustible vapor-%inert
r

i
INERT, volume-Percent
FIouRm ll.-Effect of Initial Temperature on Limit.
of Flammability of a Combustible Vapor-Inert-Air
System at Atmospheric Pressure.
9
-

%air

100 % % J P4 vapor
V

1E
7
0

a
>

/
4-

Flammable
mixtures

.r

a
-

2 iL
0

200

400

600

800

INITIAL PRESSURE, mm Hg

Frouaz 12.-Effect of Initial Presure on Limita of

Flammability of JP-4 (Jet Fuel Vapor) in Air at

269 C.
downward propagation
T, is the intersection
vapor-pressure curves,
developed between Tl,,

of flame is used. Since

of the lower-limit and
a relationship can be
or the flash point, and

the constants defining the vapor pressure of a

combustible liquid. An excellent summary of

such relationships has been presented by M ullins
for simple fuels and fuel blends (154).
At constant temperature, the flammable
range of a combustible in a specified oxidant can
be represented as in figure 12. Here the flammable range of JP-4 vapor-air mixturm is given

12

FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS

-~
L"
rL1

II

--

--

- _IT 2

Pvapor hp
Fiouns 13.-Effect of Temperature and Pressure on Limits of Flammability of a Combustible Vapor in a Specified
Oxidant.

as a function of pressure (241). A more

generalized flammability diagram of a particular
combustible-oxidant system can be presented
in a three dimensional plot of temperature, pressure, and combustible content-as illustrated
in figure 13 (244). Here, composition is given
as the ratio of partial pressure of the combustible
vapor,pVAPOR, to the total pressure P. For any
value of P, the limitis of flammabiity ar given
as a function of the temperature. For example,
at I atmosphere (P= 1), the flammable range is
bounded by the lower limit curve L4LL", and
the upper limit curve UU2; all mixtures along
the vapor pressure curve L4 U,' U are flammable.

The flammable range is the same as that depicted in figure 2. At constant temperature
(for example, T), the flammable range is
bounded by the lower limit curve LIPLI and the
upper limit curve U1Pc,; the broken curve
PLIPUI represents the low pressure (quenched)
limit. The flammable range is the same as
that depicted in figure 12. A similar range is
defined at temperatures T,, T3, and T# which
are less than T,. However, at T3 and T, the
upper limit curves intersect the vapor pressure
curves, so that, no upper limits are found above
U. and U,. In other words, all compositions
along U.U. and U.L4 are flamuable. The curve

13

PRESENTATION OF DATA

-T

28

A
24
X air

=100

% gasoline vapor - %water vapor

20

Nonflammablemmixture

10

0B
70 100
I

20

120
I

30

140
I

150
I

40
50
60
WATER VAPOR, volumtu-percent
160

..

]70
=i

70

180

190

80

90

200

100
210 212-

IL

CORRESPONDING AIR-SATURAT!ON TEMPERATURE. "F.

Fionw

14.- Flammability Diagram for the System Gasoline Vapor-Water Vapor-Air at 700 F (2i
2120 F (iO0 C) and At :u spheric Pressure.

C) and at

L 4 'LUJ UZU defines the range of limit mixtures

which are saturated with fuel vapor. Further,
since L4 is the saturated lower limit mixture at~
one atmosphere, TWis the flash point,
Some of the points considered in this and the
prex ious ,ectioni are illustrated in figure 14
(A73).
This is the flammability diagram for
the system
gasoline v-apor-wWterr vapor-air at
700 F(2 10 () and 2120F (100 C) and atnospheric pres.ure. The air saturation temperature, that is, the temperature at which saturated
air contains the quantity of water given on the
water vapor axis, is t1lsincluded. For precise
work, a much larger graph or an enlargement
of the region from 0 to 8 percent gasoline vapor
and from 0 to 30 percent water vapor ould
be used. However, figure 14 is adequate here.
If water vapor is added to a particular mixture
A, all mixture compositions between
andt

percent-water-vapor point. If water vapor is

removed by condensation or absorbtion, the
composition point will move along the extension
to the line drawn from A to the 100-percentwater-vapor point. The same applies to the
other components, air and gasoline, as indicated
.Moreover,
more than one component
isearlier.
involved,
the finalif composition
point can be
found by considering the effect of each corponent separately.
po
Figure 14 is of special interest since it can be
used to evaluate the hazards associated with a
gas-freeing operation. For example, mixture
represents a saturated gasoline vapor-airwater vapor mixture at 700 F. A more volatile
gasoline than the one used here would give a
saturated mixture with more gasoline vapor
and less air in a closed tank, a less volatile
gasoline would give less gasoline vapor and

pure water vapor will form as noted (if the

temperature is at least 2120 F), and the cornposition point will shift towards the 100-

more air. In any event, if a continuous supply

of air saturated with water vapor is added to a
tank containing mixture A, all compositions

L.A

14

FLAMMABILIT1

CHARACTERISTICS

between A and B (air plus water vapor) will be

formed until all the gasoline vapor is flushed
from the tank, and mixturv B alone remains.
If steam is used to flush mixture A from the
tank, all compositions between A and C will
form until all the gasoline vapor has beer
flushed from the tank and only steam remains
(at 2120 F or higher). If the tank is permitted
to cool, the steam will condense and air will be
drawn into the tank giving mixtures along
C-B. At 700 F, only air plus a small amount
of water vapor will remain.
If hot water and water vapor at 1750 F are
used to flush mixture A from the tank, the
mixture composition can only shift along AC to
E. Mixtures between A andE that are flushed
from the tank mix with air to give mixtures

OF COMBUSTIBLE

GASES AND

VAPORS

between points along AE and B. Again, as

the water vapor in these mixtures condens i
outside the tank, the composition of the resultant mixtures will shift away from the 100percent-water-vapor point, C. The mixture in
the tank will remain at E unless air is used to
flush the tank, in which case mixture compositons between E and B will form. Again, if
the water vapor within the tank condenses, the
mixture composition will shift away from C.
In any event, at this temperature (175 F), the
addition of air to mixture E will lead to formation of flammable mixtures. Thus, mixture A
cannot be flushed from a tank without form ing
flammable mixtures, anless steam or some other
inert vapor or gas is used.

DEFLAGRATION AND DETONATION PROCESSES

Once a flammable mixture is ignited, the
resulting flame, if not extinguished, will either
attach itself to the ignition source or propagate
tra)m it. If it propagates from the source, the
propagation rate will be either subsonic (deilagration) or supersonic (detonation) relative
to the unburned gas. If it is subsonic, the pressure will equalize at the speed of sound throughout the enclosure in which combustion is taking
place so that the pressure drop across the flame
(reaction) front will be relatively small. If the
rate is supersonic, the rate of pressure equalization will be less than the propagation rate and
,hire will be an appreciable pressure drop across
the flame front. Moreover, with most conbutible-air mixtures, at ordinary temperatures,
the ratio of the peak-to-initial pressure within
the enclosure will seldom exceed about 8:1 in
the former, but may be more than 40:1 in the
latter case. The pressure buildup is especially
great when detonation follows a large pressure
rise due to deflagration. The distance required
for a deflagration to transit to a detonation
depends on the flammable mixture, temperature,
pessure, the enclosure, and the ignition source.
ith a sufficiently powerful ignition sourbe,
detonation may occur immediately upon ignition, even in the open. However, the ignition
energy required to initiate a detonation is
usually many orders of magnitude greater than
that required to initiate a deflagration (3, 249).

weight, of the burned gases, and T is the final

(16, ',mttic) temperature of the products. With
otle 1 eCloisurem, or with noncentral ignition,
the flame front is disturbed by the walls before
,orihuntion is completed, so that calculated
pressure cannot be expected to approximate
actual pressure. Even with spherical enclosures,
the flame front is not actually spherical, so that
the walls tend to disturb the flame before cornhustion is complete (118, 130). A graph of the
pressure developed by the combustion of a
stoichiometric methane-air mixture (central
ignition) in a 19.7 cm diameter, 9-liter cylinder
is given in figure 15. The calculated pressure
for a 9-liter sphere is included for comparison;
K in equation (7) was evaluated from the
experimental curve at 70 milliseconds. The
calculated curve follows the experimental curve
closely about 75 milliseconds, when the latter
curve has a break. This suggests that the
flame front was affected by tbe cylinder walls
in such a way that the rate of pressure rise
decreased, and the experimental curve fell below
the calculated curve. Further, since the combustion gases were being cooled, the maximum
00

80

Calculated
I
(9-liter sphre)--, 11
II Experimental

DEFLAGRATION

Where a deflagration occurs in a spherical

enclosuire of volume V with central ignition, the
approximate pressure rise AP at aLv instant t
itter ignition is given by the expressions:

(9-liter cylinder)

L60
ci)

&
W
c/n40-

APA7

_]P=

(7)

Wu)
0.

and
1" = A-

_.'-

(I)

where K is a constant. S. is the burning velocity,

', is the initial pressure, 1'm is the maximum
pressure, '1 is the initial temperlture, it, is the
number of inoles of gas in the initial mixture,
n, is the nU'nl)er of moles of gas in the hurned
gases, Al7 is the average molecular weight of the
initial mixture, -Ifb is the average molecular

20

40
ELAPSED

80
TIME,

[
120
milliseconds

160

Fiuar
15.---Pr(wssure
Produced Mixture
by Ignition
a 9.6
Volum(",Percent
Methane-Air
in Hof9-Liter
Cylinder (E-xperimental).

15

16

FLAMMABILITY CHARAC*TERISTICS

pressure fell below the calculated value. The

minimum elapsed time (in milliseconds) required to reach the maximum pressure appears
to be about 75 iV for the paraffin hydrocarbons
and fuel blends such as gasoline; V is the
volume in cubic feet in this case.

DETONATION
Wolfson and Dunn (52, 230) have expressed
the pressure ratio P2/P1 across a detonation
front as
P2

(,,M, 2+ 1),

(9)

where %,is the specific heat ratio of the burned

gases, y is the specific heat ratio of the initial
mixture, and
is the Mach ntunber of the
diretatondwv ithe respct tomber the
detonation wave with respect to the initial
mixture. M, is given in terms of the temperatures T and molecular weights W of the initial
and final mixtures by the expression:
( 1M'+l)' (ya)TW
"n 1'
'Y2T,W
7
2

(10)

OF COMBUSTIBLE GASES AND VAPORS

Wolfson and Dunn have developed generalized

charts that simplify the operations involved in
obtaining the pressure ratio as well as the density and temperature/molecular weight ratios
across the detonation wave and the energy
release in the detonation wave.
Many investigators have measured and calculated detonation and reflected pressures
resulting from detonation waves (54 57, 204).
Figure 16 from the data of Stoner and Bleakney
(204) gives the detonation velocity, the static
or detonation pressure, and the reflected pressure developed by a detonation wave propagating through hydrogen-oxy en mixtures at
atmospheric pressure and 180 C.

BLAST PRESSURE
The pressures produced by a deflagration or
a detonation are often sufficient to demolish an
enclosure (reactor, building, etc.). As noted, a
deflagration can produce pressure rises in excess
of 8:1, and pressure rises of 40:1 (reflected
pressure) can accompany a detonation. As
ordinary structures can be demolished by pressure differentials of 2 or 3 psi, it is not surprising

3,500

50

P ( theoretical)

45
40

35

30

25

2,500
E

Ps (experimental)0
-20
15

2,000
10
5
1,500
20

I
30

1
40

1
I
50
60
H2 , volume - percent

I
70

I
80

0
90

FIoUsZ 1.Detonation Velocity, V; Static Presure P.; and Reflected Pressure, P,, Developed by a Detonation
Wave Propagating Through Hydrogen-Oxygen Miziures in a Cylindrical TuIbe at Atmospheric Pressure and

180 C.

DEFLAGRATION AND

that even reinforced concrete structures have

been completely demolished by explosions of
near-limit, flammable mixtures.
Jacobs and coworkers have studied the damage potential of detonation waves in great detail
(91, 170). They have considered the principlcs
involved in rupturing of pipes and vessels by
detonations and the relevance of engineering
and metallurgical data to explosions. More
recently, Randall and Ginsburg (171) have investigated bursting of tubular specimens at
ordinary and reduced temperatures. They
found that the detonation pressure required to
burst such specimens was, in general, slightly
higher than the corresponding static-bursting
pressure. Ductility of the test specimen appeared to have little effect on the bursting
pressure, but ductility increased the strength
of pipes containing notches or other stress
raisers.
When a detonation causes an enclosure to

must be taken to protect the personnel and

equipment from blast and missiles. Browne,
Hileman, and Weger (16) have reviewed the
design criteria for suitable barricades. Other
authors have considered the design of suitable
laboratories and structures to prevent fragment damage to surrounding ar-9,s (44, 174,
203, 20).
TABLE

1.-Conditions of failure of peak overpressure-sensitive dements (217)

Approx-

iniate

determined

by

characteristics

of

the

medium through which it is transmitted, and

the available energy. hi the shock velocity, ,
is known, the resulting overpressure, (P-P,),
is given by the expression (20.1)

PP~l~

(11)a

where, is the ratio of specific heats, and a is the

velocity of sound in the medium through which
the shock wave passes. The approximate

damage potential can be assessed from the data

in table 1 (217).
In conducting experiments in which blast
pressures may be generated, special precautions

Failure

Structural element

incident

blast
pressure
(psi)

Glass windows, large

and small.

Usually shattering,
occasional frame

Corrugated Asbestos

Sh ittering.

1.0-2. 0

Corrigattd steel or
aluninumrr panel-

Conneclion failure,
followed by buck-

1.0-2. 0

fail, a shock wave may propagate outward at a

rate

17

DETONATION PROCESSES

Aidiug.
ing.

Wood siding panels,

standard house
construction.
Concrete or cinder-

block wall panels,

8 or 12 inches
thick (not reinforced).
Brick wall panel, 8
or 12 irches thick
(not reinforced).

failure.

Iih

Usually failure occurs at main connections, allowing

whole panel to
be blown in.
Shattering of the

0. 5-1.0

1.0-2. 0

2. 0-3.0

wall.

Shearing and flexure

failures.

7. 0-8.0

PREVENTIVE MEASURES
INERTING1
In principle, a gas explosion hazard can be
eliminated by removing either all flammable
mixtures or all ignition sources (23, 240).
However this is not always practical, as many
industrial operations require the vresence of
flammable mixtures, and actual or potential
ignition sources. Accordingly special precautions must be taken to minimize the damage
that would result if an accidental ignition were
to occur. One such precaution involves the
use of explosive actuators which attempt to
add inert, material at such a rate that an
d before structural
explosive reaction is quenohi
damage occurs (70, 72). Figure 17 shows how
the pressure varies with and without such
protection. In the latter case, the pressure
rise is approximately a cubic function of time,
as noted earlier. In the former case, inert is
added when the pressure or the rate of pressure
rise exceeds a predetermined value. This
occurs at the time t, in figure 17 when the
explosive actuators function to add the inert.
As noted, the pressure increases momentarily
aboe the value found in the unprotected
case and then falls rapidly as the combustion
reaction is quenched by the inert.
FLAME ARRESTORS AND RELIEF

DIAPHRAGMS

Inert atmospheres must be used when not

even a small explosive reaction can be tolerated.
However, when the ignition of a flammable
mixture would create little hazard if the burning
mixture were vented, flame arrestors and relief
diaphragms could be used effectively. The
design of such systems is determined by the
size and strength of the confining vessels, ducts,
etc.
In recent studies of the efficiency of wire
gauze and perforated block arrestors (161, 162),
almer found the velocity of approach of the
flame to be the major factor in determining
whether flame passed through an arrestor. For
these two types of arrestors, lie found the
critical approach velocity to be
S1.75k(2-T.),

01,(12)

and

andT
V9"6kA"(T-T),
dQ/13)
18

(3

Unprotected

C
Co

W
a.

Protected

ti
ELAPSED TIME
1-Pressure Variation Following Ignition of
a Flammable Mixture in Unprotected and Protected

FIGURE

Enclosures.

where k is the thermal conductivity of the gas;

m is the mesh width; T is the mean bulk ternperature of the flame gases through the arrestor;
T. is the initial temperature of the arrestor; Q is
the heat lost by unit area of flame; x, is the
thickness of the flame propagating at the burning velocity, S; d is the diameter of an aperture;
A is the area of a hole in unit area of the
arrestor face; and t is the arrestor thickness.
Equations (12) and (13) can be used to
determine the mesh width or aperture diameter needed to stop a flame having a particulur
approach velocity. In practice, application of
these equations assumes a knowledge of the
flame speed in the system of interest. Some
useful data have been made available by
Palmer and Rasbash and Rogowski (172, 173),
as well as by Jost (118) and Lewis and von Elbe
(130).
Tube bundles also may be used in place of
wire scraens. SC3tt found that these permit
increased aperture diametera for a given approach velocity (192).
In practice, it may be desirable to install
pressure relief vents tu imit damage to duct
systems where flime may propafate. Rasbash
and Rogowski (173) found that with propaneand pentane-air mixtures, the maximum pressure PM (pounds per square inch) developed in
an open-ended duct, having a cross section of
1 ft- is:

19

PREVENTIVE MEASURES

L
PM--O.7 ,and6<
where

<48,

(14)

is the ratio of duct length to diameter.

However, the presence of an obstacle (bend,

constriction, etc.) in the path of escaping

and it is thus proportional to K.

values of K it, was found that

For small

PS=K.
As with ducts, larger pressures wvr6 obtained
whea obstructions were placed in the oven.

gases increased the pressure due to resistance

to fluid flow by the obstacle. Location of a

relief vent near the ignition source decreased
the maximum pressure as well as the flame
speed. For values of K (cross-section area
of duct/area of vent) greater than 1, these
authors found

O.8K<P, _i.8K,

P2
4

(15)

L
where 2_5K<32, and 6 <5T__.30.
To keep the
pressure at a minimum either many small
vents or a continuous slot was recommended
rather than a few large vents.

P1
0W
c

In addition,

vents should be located at positions where

ignition is likely to occur and should open

ELAPSED TIME-

before the flame has traveled more than 2 feet.

When possible, relief vents should be used

with flame arrestors. The vents tend not only
to reduce the pressure within a system following
ignition but also to reduce the flame speed,
thus making all arrestors more effective. Unfortunately, in certain large applications (for
example, drying ovens), it is difficult to use
flame arrestors effectively. In such cases,
greater reliance minst Ie placed on the proper
fue
of
,tioning
relief vents. Siesmonds and
Cubbage (42, 43, 195) have investigated the
design of affective vents for industrial ovens,
They found two peaks in the pressure re-ords
obtained during the vnting of cubical ovens
(fig. 18). The first peak, Pi; the oven volume,
I"; the factor, K; and the weight per unit
area (lb/ft) of relief, w, were related as follows
for -t 25 percent town gas -air mixture:

More generally,
Po(O.3Kw+0.4),

(17)

where S, is the burning velocity of the mixture

tit the oven temperature.
The first, pressure pulse was ascribed to the
release and mIotion o tAe relief vent following
igniton; the sec('ond pulse, to (ontitue(d jurning at an inrcased rate. 'Phe secord pulse
represents thip pressure drop across the vent,

Town USepetmane;pproxalnely
,OWnogien, IS pet i ,thane; the
i ,Uali ;

52
i

the
hyroon
o"

nr

17 ICt cprtn
3 pet1

iouE18--Pressure Produced by

Ignition of a
Fiammable Mixture in a Vented Oven.

In designing explosion reliefs for ovens, Simmonds

ubbage pointcd out that (1) the
reliefs should be c,.astrueted in such a way that
they do not form dangerous missiles if an explosion occurs; (2) the weight of the relief must bc
small so that it, opens before the pressure builds
up to a dangerous level: (3) the areas and positions of relief openings must be such that the
explosion pressure is not excessive; (4) sufficient
free space must be utilized around the oven to
pterrmit satisfactory operation of the relief and
minimize risk of burns to personnel; and (5)
oven doors should be fastened securely so that
they do not open in the event of an explosion.
Burgoyne and Wilson have presented the
results of an experimental study of pentane
vapor-air explosions in vessels of 60- and 200cubic-foot volume (30). They found the rates
of pressure rise greater than could be predicted
from laminar burning velocity data, so that the
effect of a relief area in lowering the peak
pressure was less than expected. All experiments were conducted at an initial pressure of
I atmosphere. Vent data for use at higher
initial press,.res are summarized in an article
by Block (10); a code for designing pressure
relief systems has been proposed in this article.
Other authors have considered the effects of
temperature and characteristics of the flaremable mixture on vent requirements
8ydrc4u5I 46ns,

3845,46,134 14.,
18, 21)

Otrot~i mmpet;ca~on ioaiieS pt; nd o~en

(14, 35,

FLAMMABILITY CHARACTERISTICS
The flammability data (limits of flammability, flash point, ignition temperature and
burning velocity) of the various chemical farnilies exhibit many similarities. Accordingly,
the data presented here are grouped under the
various commercially important families, blends,
and miscellaneous combustibles.

PARAFFIN HYDROCARBONS
(C.H
Rn2 2 )
Limits in Air
Lower and upper limits of flammability at
250 C (or at the temperature noted) and 1
atmosphere (L25 and U25) for many members of
the paraffin hydrocarbon series are given in
table 2, together with the molecular weight, M,
vapor specific gravity, sp gr, stoichiometrict[
composition in air, C., (appendix B) and heat
of combustion, AH, (188). At room temperature and atmospheric or reduced pressure, the
lower limits of flammability of most of this
series fall in the range from 45 to 50 mg com-

i50mg/I
.4

45 mg/I

2240-

bustible vapor per liter of air at standard conditions, that is, 00 C and 760 mm Hg (0.045 to
0.050 oz combustible vapor per cubic foot of
air) (247). This is illustrated in figure 19 in
which some lower limits of flammability are
plotted against molecular weight; except for
methane, ethane, and propane all limit values
fall in a band between concentrations of approximately 45 and 50 mg/r.
The following expression may be used to
convert from a lower lirrit L in volume-percent
of vapor in the vapor-air mixture to one in
milligrams of combustible, per liter of air at
standard conditions:
lmg\
L (vol pct)
L(volpct)
0
L (mg)
1
1
volmg
specific volume being volume of combustible
vapor per milligram of combustible. At standard conditions (00 C and 760 mm Hg) this is
about 22.414/1,OOOM, where M is the molecular

FLAMMABILITY

2.-Propertiesof parafin hydrocarbons

TABLE

Combustible

Formula

Pr
(A -1)

I.n

(n pr
(vol pot)

Net AH.
(W a
ol
/

9.48
8.65
4.02
3.12
2.55
2.16
1.87
1.65

191.8
341.3
488. 5
635.4
782.0
928.9
107.8
1222.8

5.0
3.0
2.A
1.8
1.4
1.2
1.05
.96

n-Decane -- _----------- Colin --------- 142.28

C ---...........
1 .30
n- Undecane ----------..----_---- 170.33
Cn-Dodecane ....... n-Tridecane------Ciallsa,.........184.36
n-Tetradecane ............ Cills0 . . . . . . . . . .. 198.38
n.1'entadecane --------- C::la............212 41

4.91
5.40
5.88
6.37
7.8
7:33

1.33
1.22
1.12
1.04
97
90

1516.6
1663.6
1810.5
1957.4
2104.3
2231.

'.75
.68
.60
.85
b.0
.4

Cll, .--------- . 1. 28

147

443

n-llexadecane----------C 11 - - - - - - - - - 22644

85

7 82

169.7

2398.

)(vol
p(ot) ,

0.65
1.04
1.52
2.01
2. 49
2.96
3.46
3.94

n-No,,ane ----------.---

Upper limit in air

Lower limit i air

16.04
CH,----------CaH .---------- 30.07
CsH .--------- 44.09
C 4H0--------88,12
C all- - - - - - - - - - 72.15
C---- ........... - 88.17
C,Ha ........... 10020
Call, --------- 114.23

Methane ...............
Ethane --------------Propane .................
n-Butane...----.-----n-Pentane -----------.
n-Hexane .............
n-Heptane ................
n-Octane ----.----------

21

CHARACTERISTICS

0.
3
.53
.52
.58
.85
.56
.W
.58

.6

.6
.6
.84
.3
.62
5.1

Rf

N Ur

t)vl)
pot)

g)

R
Ref.

8
1
42
48
4
47
47
49

126
40
1.0
1.6
4
12.4
2.2
190
2.4
210
(116)
9.6
2.7
240
(11)
84
J40
7.8
3 1
270
7. 4
8.4
810
(546
(546
6.7
8.6
820
(56 .......... ..................

48

(4)
(4

....

48 ,146)
49.(546)
46
40
44

40

51

(Vol

ef

44

4.2
'5.6
__
(4
(').........................----)
'--1(---

(40)

4,

(41
41

(40)

401

880.

(I

4 Calculated value extrapolated to 25" C at Explosives Re. Center,

Federal Bureau of Mlnes.

1t-43' C.
Uj.53 C.
t-86 C.

weight of the combustible. Since L (vol pct)

of most members of this series is much less than
100 percent, the lower limit can be expressed
as
(for

-0.45ML

(vol pet).

(20)

At any specified temperature, the ratio of

the lower limit to the amount of combustible
needed for complete combustion, C,,, also is
approximately constant. This was first noted
by Jones (95) and later by Lloyd (138), who
found that for paraffin hydrocarbons at about
250 C,
(21)
L 21. ru0.55C,,.
For the complete combustion of the paraffin
hydrocarbons, we have:
CaH 2 .+2 + (1.5n + 0.5)O--*nCO2+ (n-+ 1)H 20,

so that in air
50

(22).

C,=I+4.73(.5n
100

vo pet,
0.5 vo
pAs

(23)

1+4.773(1.5n+0.5)

where 4.773 is the reciprocal of 0.2095, the

molar concentration of oxygen in dry air. The
values of C,, (appendix B) are included in table
2. By weight these become
(

1,000[12.01n+ 1.008(2n2)) ing

122.414X4.773(1.5n0.5)

(24)

or
1

g.

(,9.34 1 14.03n+2.02
l
_.n+0.5 J 1

(25)

Thus,
C,,-87 mg/l,

n>4.

(26)

Combining this equation with equation (21),

we have
(27)
L 2 o(mg/1) -48 mg/i,
paraffin hydrocarbons, except methane,
ethane, and propane. Substitution of this
value into equation (20) gives
107
L2olO

(28)

The following expression may be used to

convert a lower limit value in volume-percent
to a fuel-air (weight) ratio:

L (Vol pet)
.96/A)0_0-L (volpt)j

L(F
The reciprocal expression
gives the air-fuel
(weight) ratio:
7NF--

00

--~*

(30)
(30

LL (vol pct) j
(Al
noted, the lower limits given in figure 19
were determined at room temperature and atmospheric or reduced pressure. Lower limits
vary with temperature as shown for methane in
figure 20. The limit values obtained with upward propagation of flame (R1) fall fairly close
to a straight line that passes through the lower
limit value at 250 C and the flame temperature
(12250 C). This is in accordance with the
White criterion that the flame temperature is
constant at' the lower limit (RO2). The data
obtained by White with downward propagation
of flame fall along a line parallel to the line
through the limit values obtained with upward
propagation. Taking the value 1,300' C as

22

FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS

air

100%-% methane

5-

Flammable mixtures
4

-- Vapor pressure
curve

Downward propagation of flame

E
r

AIT

Upward propagation of flame

qc

-200

200

400

600

TEMPERATURE,
Fiouim

800

1,000

1,200

1,400

20.-Effect of Temperature on Lower Limit of Flammability of Methane in Air at Atmospheric Pressure.

the approximate flame temperature for the

plot of L,/L 25. against the temperature (fig. 23,
paraffin hydrocarbon series (5), and using the
solid line).
lower limit values at room temperature in table
These data are also correlated fairly well with
2, the limits of the first 10 paraffin hydrocarthe modified Burgess-Wheeler Law suggested
bons are represented as in figures 21 and 22.
by Zabetakis, Lambiris, and Scott (.42):
Figure 21 ives the lower limits in volume-per-07
cent and figure 22 in milligrams per liter. By
0"75 (t-25'),
(33)
weight, the lower limits of most members of
this series again fall in a fairly narrow band
("higher hydrocarbons" region). Individual
where t is the temperature in 'C and AM, is the
net heat of combustion in kilocalories per mole.
adiabatic flame temperatures can be determined
for lower limit mixtures using the data in table
Then,
2 and appendix C (55).
L, =
0.75
The by:
straight lines of figures 21 and 22 are
L 2 So(34)
given
L2 o t (t-25).
L
Substituting the value 1,040 for
L 25.AH, ob0 ),
Li
2& (1,3000--250) - (t-25
(31)
tained by Spakowski (R01), we have
or
L
(35)
L 2 *-- 1-0.000721(t-250),
(32)
L,- 1-0.000784(t-25*).
They are described in more general terms by a

which is also given in figure 23 for a limited

temperature range with the broken line.

23

FLAMMABILITY CHARACTERISTICS

% air = 100%-% combustible

5

Flammable mixtures
MetPrpn

4
9.

AIT

Ethane

0>
C, 3 L"
j
Propane
DButane

AIT-

022CD)
Pentane

Hexane.

-'"

1 Heptane
Octane
,,
Deane

-200

AIT

200

400
600
TEMPERATURE,

800
C

1,000

1,200

1,400

FIGURE 21.-Effect of Temperature on Lower Limits of Flammabilty of 10 Paraffin Hydrocarbons in Air at

Atmospheric Pressure.

Only the lower limit at 250 C and atmospheric

pressure is needed to use figure 23. For exampie, assuming a constant flame temperature, the
ratio L 23tL. at 6000 C is 0.55. The calculated
lower limit of methane at 6000 C therefore is
5.0X0.55, or 2.75 volume-percent. The same
value can be obtained directly from figure 21.
From the modified Burgess-Wheeler Law curve,
L/L 25.=0.585 at 6000 C, so that L4o.=2.92
volume-percent.
Limit-of-flammability measurements are cornplicated by surface and vapor-phase reactions
that occur at temperatures above the auto-

ignition temperature. For example, Burgoyne

and Hirsch (25) have shown that methane'air
mixtures containing up to 5 percent methane
burn readily at 1,000' C. E'xperinments were
conducted with mixtures containing as lit le as
0.5 percent methane; figure 20 predicts that a
flame would not propagate through such a
mixture,
Flammability experiments at elevated tenperatures indicate that in the absence of cool

flames (87, 88), the upper limit also increases

linearly with temperature.
The effect of
temperature appears to be fairly well correlated
by the modified Burgess-Wheeler law:
0.75

+ y- (t-250 ).

U-

(36)

If we assume that the heat release at the upper

limit is equal to that at the lower limit, then
U

- 1+0.000721(t-25).

(37)

A plot of Ui Un. against temperature fig. 24)

was used to corn are recent experimental values
of Rolingson and coworkers (18.e) for methaneair mixtures at 15 psig with those predicted bY
the modified Burgess-Wheeler law. The expen-r
mental and calculated upper limits are givenx in
table 3 together with tlie difference U,,U..r, In each case, the difference is iess than

24

FLAMMABILITY

CHARACTERISTICS OF COMBUSTIBLE aASES AND VAPORS

60

50

Higher
hydrocarbons

40-

Propane
Ethane

Methane

I3O
20-

10

-200

400

200

600

TEMPERATURE,

800

1,000

1,200

1,400

Fouau 22.-Effect of Temperature on Lower Limits of Flammability of 10 Paraffin Hydrocarbons in Air at

Atmospheric Pressure by Weight.

4 percent of the experimental value, which is

approximately within the limit of experimental
error. Earlier experiments of White (222) at
temperatures to 4000 C, with downward flame
propagation, also are represented quite adequately by equation (37). For example, White
found that the upper limit of pentane in air
(downward propagation) increased linearly from
4.50 volume-percent at about 170 C to 5.35
volume-percent at 300' C.

The ratio of 5.35:

4.50 is 1.17, which compares

UW./U&.

quite

point. The lower temperature limits of paraffin

hydrocarbon at atmospheric pressure are given
in table 4.
TABLE

3.-Upper flammability limits, U, of

methane-air mixtures at 15 psig

Temperature
(C)

(vol
perceLt)

U,.p,,

U.,1. (vol
percent)

Uo.I -Uo. .
(vol percent)

well with

=l.20 obtained from figure 24.

Given the vapor pressure curve and the lower

limit of flammability, the low " temperature
limit or approximate lash point of a combustible

25 ----------

100 -------200 -------30.

15.5
16. 3

15.5
16. 4

17. 9

18. 6

17.0

17. 5

0
.1

.5

.7

can be calculated from either equation (32) or

(35) (.018).
Approximate flash points were
obtained previously, using only the vapor
pressure curve and the lower linit at ordinary
or elevated temperatures (1,54). The values
obtained with this procedure are somewhat
low because the lower limit at any temperature
above the flash point is less than at the flash

(J8I.

Moderate changes in pressure do not ordinarily affect the limits of flammability of the
paraffins in air, as shown in figure 25 for pentane, hexane, and heptane in air (241) in a
range from 75 to 760 mm Hg. The lower limits

25

FLAMMABILITY CHARACTERISTICS
TABLE

4.-Lower temperature limits and autoignltiontemperatures oJ paraffln hAdrocarbonw at

atmospheric pressure
Autoignition temperature
Lower temperature limit
In air
In air
C

Methane ----------------187
Ethane ------------------ 130
Propane -----------------102
n-Butane -----------------72
Isobutane-----------------81
n-Pentane- ----.--------48
n-Hexane ----------------26
n-Heptane --------------4
n-Octane ---------------13
n-Nonane ---------------31
n-Decane ---------------46
n-l)odecane -------------74
n-1(exadecane ------------126
Caculated value.

1.2

oF

Ref.

-305
-202
-152
-96
-114
-54
-15
25
56
88
115
165
259

C
537
515
466
405
462
258
223
223
220
206
208
204
205

(1)
(1)
(1)
(1)
(1)
(1)
(159)
(169)
(159)
(159)
(159)
(159)
(1)

0F
999
959
871
761
864
496
433
433
428
403
406
399
401

In oxygen
Ref.

oC

Ref.

(158) -------...........
(937)
506
943
(94)
(158)
----................
(2,17)
283
542
(191)
(158)
319
606
(94)
(194)
258
496
(144)
(194)
225
437
(94)
(237)
209
408
(94)
(*37)
208
406
(191)
(2,37) -------(237)
202
396
(94)
(237) ........................
(237) .........................

N2

.8

-N

Modified Burgess-Wheeler Low

"

.6

-N

.4

.4

Constant flame temperature

.2

01
-200

1
0

200

400

600

800

1,000

1,200

1,400

TEMPERATURE, -C
Fiounz 23.-Effect of Temperature on L,/LNo Ratio of Paraffin Hydrocarbons in Air at Atmospheric Pressure.

26

FLAMMABILITY

CHARACTERISTICS

OF' COMBUSTIBLE

GASES AND

VAPORS

Neither expression is applicable when cool

flames are obtained. Substitution of equation
(21) for Lw. into equation (39) gives

1.4

U.=4.8

1.3

(40)

The limits of flammability of natural gas

(85-95 pct methane and 15-5 pct ethane)
have been determined over an extended pressure range by Jones and coworkers (78, 105).
They are given in figure 26 for pressures from
1 to 680 atmnos heres (10,000 psig). An
analysis of these Sata shows tile limits vary
linearly with the logarithm of the initial

1.2 -

100

10

200

1%
300

,
300

400

pressure.

TEMPERATURE,'C

That is,

L (vol pet) =4.9-0.71 log I' (atm),

(41)

U (vol pet) =14.1 +20.4 log P (atm),

(42)

Fioum 24.-Effect of Temperature on U,/U.

Ratio
of Paraffin Hydrocarbons in Air at Atmospheric
Pressure in the Absence of Cool Flames.

and

coincide, but the upper limits, by weight,

increase with increasing molecular weight.
Be volume, at atmospheric pressure and 250
C, Spakowski (201) found that the upper and
lower limits were related by the exprcs~sion:

with a standard error of estimate of 0.53 vol

pet for L and 1.51 vol pet, for U.
Although the limits of flammability are not
taffected significantly by moderate changes in
pressure, the temperature limits are pressure
dependent. As the total pressure is lowered,
the partial pressure of the combustible must
also be lowered to maintain a constant cornbustible concentration. The effect of pressure
on the lower temperature limit of the normal
paraffins pentane, hexane, heptane, and octane
in air, for pressures from 0.2 to 2 atmospheres,

U 26. =-7.1L5'.

(38)

However, the data presented here are correlated

more precisely by a somewhat simpler expression:
U26.=6.5 421n.
(39)
400

~Heptane
z
0

300

z
Uj.

Hexane

0
0-,",
W

o0

200

Pentane

Flammable mixtures

100

100

200

300

400

500

600

700

800

INITIAL PRESSURE, mm Hg
FIuu'aE 25.-Effect of Presure on Limits of Flammability of Pentare, Ilexane, and lieptane in Air at 26' C.

FLAMMABILITY

27

CHARACTERISTICS

60

% air = 100%-% natural gas

50
C

40

.2

Flammable mixtures

9 30
20
z
10

100

200

300

400

500

800

700

600

INITIAL PRESSURE, atmospheres

FJGuRE 26-Effect of Pressure on Limits of Flammability of Natural Gas in Air at 280 C.
is shown in figure 27. '[ire tepn erature limits
were calculated from the L,,. values, the vapor
pressure curves, and the data of figure 23.

TABLE 5.-Limits of flammability of methane in

chcrine
(volume-pecnt)

Limits in Other Atmospheres

Temperature,
Prevmre,
p sig

Limits
L5_100

Liim its of fla

aininbilityof soine paraffin ydrocarbots hav-e been determined in oxygen,
25
100
200
c h,lorin e , a n d o x id e s o f n itr og e n ,
.'w e ll 'a s in
.
. . ..
.
m ixtures of air id various inerts. The l wer'
fLowr
5.63
0.6
li ,its ill o xy g e n a l ( in a w id e v a r iet y o f
t
. [. U p pe r ---- 70
66
-.-- 0 .Ox g n-imtrogen
iixtures are essentially the
100 ... .
. Lower.------ ---.
2.4
6
sliw its those ill air at the smniiie temperatire
tUppcr 72
"76
77
---- - - - - - - -..-2 0(0
.. . . .-L o w ,r . ..
.. a b ilit y
a n d p re s s u r e (fig . 10 ) . Li mii -oi-I ttlan
75
72
73
pjwr
Iileasurements by Bartkowirik and Zabetaki.;
for mrthiane aii eliaic iii clilrinte at 1, 7.8,
widi 4.6 atio spheres, riuiiiiig from 2 5 to 200
nre
i
miniliarized
,
in tab vs 5 ad 6( (S).
atiiiosphere with
wich tie combustible is
('oard
ad Joles
,
(,;0) have Iresiit vd
lixed. ''hie cimrrposit ion of i poitnt oi such a
diagrani, exc pt one that represents only conlgi'allhicall v t e liimiof fla inahbilit vof the first
six INVIIiii*'s of lie paralnfihi series in air conbustible a)d air, cannot be read directly.
tainig various ii rts, based mi a repivse nita- I list
ead, one mnust determinie he co miposition
tion foiund useful ill som 111i1iig applitations
of the atillosphere, add the combustible conaid treating inert gas or vapor as part oif the
tent, and then compute the total mixture coin-

28

FLAMMAL4ITY C1-L.IACTERISTICS OF COMBUST'IBLE GASES AND VAPORS

40

20-

0~n.
Octane

:3

Heptanereportad

Unfortunately, the methane-methyl bromideair data were obtained in a 17-inch tube.

Although satsfactory for methane and other
hydrocarbons,, th.3 tube is apparently not
satisfactory for miany of the halogenated ydro
carbons. Thus a recent industrial explosion
involvitig methvi b~romide prompted Hill to
reconsider the f i-immabiity of methyl bromide
itL air (84), He found that methyl bromide was
not ,nly iiammable in air but that, it formed
flananable mixtures 4t 1 atmosphere wits a
wider variety of eoncentrations than Jones had
(96). This would sug,-e&, that, there
the assumption that
is no justification
Jones'
flammabii r for
data for methyl bromide
were influenced bsy the presence of mercury

aire included in figure '8 amid are used

to form the approximate, brokeon, flammability
curves for the methane-methyl bromide-air
system.
Data of Moran. and Bertschy for pentane-40prnoropropane-air, pentane-sulfur hexafluo~
rie-air and peintane-perfiuoromethiane-air mixPentan
ture aeicuded in figure 32 (147). Data by
and Williams-Leir for hexane-methyl
IBurgoyne
-60
and hexane-Freon-12 I (F-12;
1bromnide-air
-60 - 71
2
CF2 Cl2)-air mixtures have been included in
1
0.4
0.6
0.2
figure 33. These data were all obtained in
PRESSURE, atmospheres
1'%-inch-diameter tubes. An investigation of
flamm~biity of hexane-methyl bromide-air
FIGURE 27.-Effect of Pressure on Lower Temperature
Limits of Flammability of Pentane, Ilexane, lleptane,
mixtures in a 4-inch tube indicated that an inand
ir.crease
ctan in
in tube size (from 17%-inclies to 4-inchesID) resulted in a narrowing of the flammable
range; the uipper limit decreased from 7.5 to
TABLE 6.-Limits of flammability of ethane in
5.7 volume-percent. n-hexane vapor in air while
ch.,o ine
the lower linmit remained constant. The
amount of methyl bromide required for extinc(volume-percent)
tion decreased from 7.05 volume-percent in the
tube to ti.0 volume-percent in the 4Temperature, C13a'-inch
Prsur,Liis
inch tube. However, again this is not in line
Liis____
Pssure
with the results obtained by Hill with meth vI
200
100
25
0Hexanepressure

______

mixtures (84).

____bromide-air

2.5
2. 5
6. 1
9------------ {9wer--- - 58
58
Lppe
---1. 0
1.0
3.5
100 --------- JLowr-82
75
Ulpper_ __ 63
200 --------- Lower.------------- ------- ----------~Upper~.-- (6
73
76
______________________________

--

position. This 'oas been done for methane

through hexane (figs. 28-33). C onmpositionis
aire determined directly fromi the abscissas (inert
conicent ration) amnd orintes (comnbust ible eonlcentration-); the air in tany mixture is thle differemice between~ 100 percent and the sum of inert
Data of 13urgoyne amid
and coinbuitible.
XWiIliainr-. Leir for inethane-miethmyl bromide
(.MeBr)-air an~d niethane-carbori tetrachllorideatir mixtures aire included in figure 28 (29).

Accordingly, winkl

2-inch
in approximately
data obtained
the
Hill tubes
data,
'
iue3,the
ocnsc
eeue
obtained in *t larger apparatus, tire also used to
form the approximate, broken, flammability
curves for the hiexane-inethyl bromide-air
system.
The limits of flammability diagrams for the

systemi n-hieptane-w.ater vapor-air tit 100' and

2000 C (fig. 34) show the effects of temperature
on it systemi that, pro~iuces both nornial anid
InCool flu~nes at atm~osphieric pressure (192).
o xygen reterestinigly enough, the mininima
quirernent for flaine propagation (Mii 002 t
200- C is thc samie for the (coo1 and normnal
flame regions in this instance. Further, the
decrease in zninimnuni oxygen requirements
11 Trade names are Used for leniificatiol (only; this does not imply
endorseinent by the Bfureau of Wines.

29

FLAMMABILITY CHAP ACTERISTICS

16

-1-

--

%air =100%--%

1
methane.-% inert

14

12

MeBr
U~10

CCI4
C02

Lj

H0H

Flammable

10

20
30
40
ADDED INERT, volume-percent

FioUnt 28. -Limits of Flammability of Various Methane-Irer,

Pressure.

(fromn 1:3.50.3 vourne-percent tt 1000 C to

12.80.3 volutre-pereent kit, 200' C) is wit' in
the range predicted by the miodified BurgessWheeler law (equation 35 and fig. 231), HIowever, the a~'iiable data ve14)'
to mear-r ait
present to permit at realistic evaluation of the
vaitidity of this latw,
N'Spection of the liinit-of-flaniuability curves
in figures 28 to 33 reveals that c cept for
miethatn( and ethane, Clio miinium amounts Of
carbon dioxide and nitrogen required for flame

50

'*ts.Air Mixii rs at 250 C and Atmospheric

extinction (peak values) at 250 C and atmospheric pressure tire about 28 and 42 volurnepercent, respectively. Ti. 7utio of these values
is appro:, ,dtely inversel y proportional to the
ratio of tfieii nieat capacities at the temnperature
ait which co .bustion
occurs. Accordingly,
genieralized flammability diagramns of the type
given in figure 35 can be constructed for the
higher Itydr -arbons, ignoring Lhe presence of
cool flamies. 31uch diagralms do not appear to
be applicable to the Maogenated hydrocabons

30

FLAMMABILITY CHARACTERISTICS

OF COMBUSTIBLE

GASES AND VAPORS

14

%air =100%-% ethane-% inert

12

10-

Flammable
N2

La
z

4-

2-

10

20
30
40
ADDED INERT, volume-percent

50

FicUE 29.-Limits of Flammability of Ethane-Carbon Dioxide-Air and Ethane-Nitrogen-Air Mixtures at 25* C

and Atmospheric Pres8ire.

since these materials tend to decompose even

in flames of limnit-mixture composition and, ats
noted, may themselves propagate flamne. Coleman (37) hats found that time ratios of the peak
values of a hialogenated hydrocarbon tire not
constant but are proportional to the heats of
combustion of the combustibles to which the
halogenated ht'ydrocarbon is added.
Few data aire available for the effects of
pressure on the limits of flammability of coinb ustible-inert-air mixtures. One such set of
data is sumnmairized in figur 36, which gives
the limits of flammability of natural gas
(85 pct nethane+15 pet ethane) nitrogen-air
at 260 C and 0, 500, 1,000 and 2,000 psig (106).

Similar dtai atre given for ethane-carbon

dioxide-atir (fig. :37) and ethie-nitrogen-atir
(fig. 318) (121), andl for propane-carbon dlioxideCair (fig. :19) and propaine-nitrogen-air (fig. 40)
(122). Miiii
oxygen reqluiremuents for
flame propagation (inin 02) through natural
gas-nitrogen-air, ethane-nitrogen-alir, and proJpane-nitrogen-itir att atmospheric and elevated
pressures and 260 C are summarized in figure 4 1.
[he inininmum 02 values in v'oluie-Vpi-rcent
are related to pressure ats follows:
for natural gas:
Miil.

02= 13.98-1.68 log P;,

(4:3)

FLAMMABILITY CHARACTERISTICS

31

10
% air = 100%-% propane-% inert

8
4,-

a)

Flammable

) 6-

E =

N2

mixtures

CL
0

2-

II

10

20
30
ADDED INERT, volume-percent

40

50

FIouRE 30.-Limits of Flammability of Propane-Carbon Dioxide-Air and Propane-Nitrogen-Air Mixtures at 250 C

and Atmospheric Pressure.

for ethane:
Min.(=12,60-.36
for propane:

log P; and

(44)

Min.O=13.29-1.52 log P;
(45)
paia.
in
pressure
initial
the
where I' is
The lower limit of flammability of any
mixture of the paraffin hydrocarbons can be
calculated by Le Chatelier's law (40, 12.9, 235):
300
L . _I

",

100
X-,

(46)

100
5 5
80
5.0+3.0 - 2.1

-,
where C,and L, are the percentage composition
and lower limit, respectively, of the -tbcom-

For example,

Liquid mixtures can be treated in the same way

if tie relative escaping tendencies of the various
components are known. Since the paraffin
hydrocarbons obey Raoult's law (143), the
partial pressure

bustible in the mixture.

mixture containing 80 volume-percent methane,

15 volume-percent ethane and 5 volume-percent
propane has a lower limit in air at 250 C and
atmospheric pressure of:

of each

calculated as follows:
p=paNj

component can be

(48)
'

where p, is the vapor pressure of the i com-

32

FLAMMABILITY

10

CHARACTERISTICS OF COMBUSTIBLE

GASES AND VAPORS

% air = 100%-% butane-% inert

8

4-.

6-

E
>
z

,N2

Flammable
mixtures

4-

/Cst

C02

2-

SI

10

20
30
ADDED INERT, volume-percent

40

50

FIGURE 31.-Limits of Flammability of Butane-Carbon Dioxide-Air and Butane-Nitrogen-Air Mixtures at 250 C

and Atmospheric Pressure.

ponent in the blend, po is the vapor pressure

of the pure com ponent and N, is its mole
fraction in the solution. This procedure has
been used to calculate the lower temperature
limits of decane-dodecane blends in air (fig. 42).
The vapor pressures of decane and dodecane
and the calculated low temperature limits are
given by solid lines and four experimental
values by circles,

Autoignition
Two types (,f autoignition data are obtained
depending upon whether the objective is to
cause or to prevent the ignition of a combustible
in air. The first type are usually obtained at
high temperatures, where the ignition delay is
relatively short. Typical of these are the data
of Mullins (153), Brokaw and Jackson (15, 90),

Ashman and Biichler (6), and Kuchta, Lambiris, and Zabetakis (127). These are not
normally used for safety purposes, unless there
is some assurance that the contact time of
combustible and air is less than the ignition
delay at the temperature of the hot zone. The
minimum autoignition temperature (AIT) is
usually the quantity of interest in safety work,
especially when combustible and air can remain
in contact for an indefinite period.
Some AIT values for paraffin hydrocarbons in
air obtained by Setchkin in a 1-liter spherical
Pyrex flask (194) and by Zabetakis, Furno, and
Jones in a 200 cc Pyrex Erlenmeyer flask
(237) are given in table 4. Interestingly
enough, experiments conducted in these and
other flasks generally indicate that flask shape
and size are important in determining the AIT.
The AIT data obtained in the 200 ce flask may

FLAMMABILITY

33

CHARACTERISTICS

% air =100%-% n-pentane-%00 inert

7

6-

4-

3--N

zL&J

10

20
30
40
ADDED INERT, volume-percent

50

FIGURE 32.-Limits of Flammability of Various n-Pentanc-Inert Gas-Air Mixtures at 250 C and Atmospheric
Pressure.

34

FLAMMABILITY CHARACTERISTICS

OF COMBUSTIBLE

GASES AND VAPORS

8-11

% air =100%-% n-hexane-% inert

7

6
4-'

E
MeBr

zj

F-12
C02

32N

117

0
FIOURE

10

20
30
40
ADDED INERT, volume-percent

33.-Limits of Flammability of Various n-I Iexane-Iiiert (ias-Air

Pressure.

Mixtures at 25

50
C and Atmospheric

FLAMMABILITY

35

CHARACTERISTICS

30

%air =100%-% n- heptane-% water

25--

~20

\200'

E~c

Cool flame

5-

Normal flame
1000 CCs

10

20
30
WATER VAPOR, volume-percent

40

50

FtouiE 34.-Limits of Flammability of n-llcptane-Water Vnpor-Air Mixtumres at 1000 and 2000 C and Atmospheric
Pressu re.

36

FLAMMABILITY

CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS

I
1
1
% air = 100%-% combustible-% inert

-,

E
.2_3
0

46
C
0

Flammable
IJmixtures

N2

Cst

0
C-,

L
0

10

20
30
ADDED INERT, volume-percent

40

FIGuRE 35.-Approximate Limits of Flammability of Higher Paraffin Hydrocarbons (C.H 2 .+3,

Dioxide-Air and Nitrogen-Air Mixtures at 230 C and Atmospheric Pressure.

50
n>5) in Carbon

FLAMMABILITY

37

CH{ARACTERISTICS

%air =100%-% nitrogen-% natural gas

56

w 4

2,000 psig

32 -100pi
U
24
24
:D
!ZC
Z 16-

500 psig
Flammable
mixtures
Atm ospheric

8-

0
Fi' tiE

16
24
32
40
48
ADDED NITROGEN, volume-percent

56

64

36.-Effect of Pressure on Limits of Flammability of Natural Gans-Nitrogen-Air Mixtures at 260 C.

38

FLAMMIABILITY

CHARACTERISTICS

OF COMBUSTIBLE

GASES AND VAPORS

56-

go air

=100%0-%0

ethane-%00 O2

48-

40
900 psig
~32

500 psig

R
Ld
z 24-

250 psig

16-

8-

0
IIG(LkL

16
24
32
40
CARBON DIOXIDE, volume-percent

48

56

Ig.-L(1ect of IPrcsiiri oil Ljimit- of Ihirnriinality of Ethancj-('nrbon Jioxio-Air Nhytire'. at 26' C

FLAMMABILITY

39

CH{ARACTERISTICS

561

%0air

=100%7-10% ethane-%07

N2

48

40
900 psig

a)

>24
z
w 16Atmospheric
8

0
Fmumn.

3s".- iI-rof

16
24
32
40
ADDED NITROGEN, volume-percent

48

56

I'russire on Limits of FIaimability of Ethaict-Nitrogen-Air Mixtures at 26 ' C.

40

FLAMMABILITY CHARACTERISTICS

40

OF COMBUSTIBLE

GASES AND

VAPORS

% air = 100%-% propane-% C02

32
C
0)

9-244)
E

200 psig

>
Ld

zg 160

100 psig

..,,,,,,.,.

At mos phe ric

lb

24

32

40

CARBON DIOXIDE, volume-percent

FIGuRE 39.-Effect of Pressu.-c on Limits of Flammability of Propane-Carbon Dioxide-Air Mixtures.

48

41

FLAMMABILITY CHARACTERISTICS

4U

% air = i00%-%propane-% N2
32L 24-

d24
E
0

,/200psig

100 psig

S16
0

,,

16
24
32
40
ADDED NITROGEN, volume-percent

48

56

FIOURE 40.-Effect of Pressure on Limits of Flammability of Propane-Nitrogen-Air Mixtures.

where g, is the number of possible chains each

containing N, carbon atoms and 31 is the tIumher of methyl (--('113) groups. For example,
n-nonane and 2,2,3,3-tetraniethyl pent e each
have 9 carbon atoms, but the former has 2
methyl groups and the latter ha 6. The former
has only one chain of 9 carbon atoms with a
methyl group on each eml, and the latter has

length as abscissa (fig. 43). The data fall into

two regions-a high-temperature region in
which the AIT is greater than 4000 Cand a
low temperature region in which the AIT is less
than 3000 C. These regions coincide with those
of Mtilcahy who found that oxidation proceeds
by one of two different mechanisms (162), and
by Frank, Blackham, and Swarts (60). The
AIT values of combustibles in the first, region
are normally much more sensitive to the oxygen concentration of the oxidizing atmosphere
and to the spray injection pressure than are the
combustibles in the second region. Unfortunately, the available consistent AIT data about
the effec's of oxygen concentration and injection pressure are too meager to permit a

maximnuni of 4 chains with : carblon at oms, 8

chains witi 4 carbon atoms, and 3 chains with 5
carbon at oms. Thus, n-nomanc has an average
and 2,2,3,3-tei ramnethvl
chain length of
pentame has am average of 3.9. 'The more highly
branched e combustible is, the higher its
ignition temperature will be. .ininium autoignition temperatures of 20 paraflins were
plotted as ordinate against the average chain

detailed comparison.
The physical processes (206) and reactions
that lead "to autoignition are of interest in any
detailed st uidy of this ignition process. Salooja
(18.J), Terao (207), Affens, Johnson and Carhart
(1, 2), and others have studied the autoignition
of various hydrocarbons in an effort to determine the mechanisms that lead to the ignition
reaction.

be correlated with molecular structure by

p lotting them against the average carbon chain
length defined as
La~

Lay.-

LI

gjiN,

4('-(4))

(49)

42

FLAMMABILITY

CHARACTERISTICS OF COMBUSTIBLE

GASES AND VAPORS

4,000

2,000

1,000
800-600
400-

La
1A
L

U'

U)
LiJ
in

200 -

0Natural gas

100 80-80

Propane

60Ethane

40

20-

10
6

12
10
OXYGEN, volume-percent

14

FIoURE 41.--Effect of Pressure on Minimum Oxygen Requirements for Flame Propagation Through Natural Gas-

Nitrogen-Air, Ethane-Nitrogen-Air, and Propane.Nitrogen-Air Nlixtures at 26' C.

An increase in pressure generally decreases

the AlT of a .n)If ustible in a given oxidant.
For example, the AIT of a nat undl ga-; il air
decreased front 530 (C at I atmosphere to 240'
(' at 610 atmospheres (9,000 psig) (7S). The
AIT's of several hydrocarbons were found to
obey Semnenoiv's eq uation over a limited pressure
range (248):

P A"
log /

A +B

(50)

where T is the AIT at in initial pressure P, and

A and B are constants. Accordingly, the &IT
v'almes obtained at atmospheric pressure should
not he used to assess ignition hazards at high
pressures.
The burning velocities, S., of various hydrocarbons have
' been measured by numerous investigators in air and other oxidants (68, 131).

At one atmosphere and 26'

C, the burning

-P

43

FLAMMABILITY CHARACXERISTIC13

32

68

TEMPERATURE,
104
140

0F

176
I

212 248
I

t'O 101.32

CL

1.05 6

7_Flammable

E
E

Calculated,..

.79

W.,

E
_

.39 0

0-

Decane

.26
C

.50

20

40
60
TEMPERATURE, 0C

80

100

120

FIGURE 42.-Low-Temperature Limit of Flammability of Decane-Air, Dodecane-Air and Decane-Dodecane-Air

Mixtures (Experimental Points 0).

velocities of paraffin hydrocarbons in air range

from a few centimeters a second near the limits
to about 45 cm/sec near the stoichiomietric
mixture composition; much higher values are
obtained with paraffin hydrocarbon-oxygen miixtures. Figure 44 gives results obtained by
Gtibbs and Calcote for four paraffin hydrocarbon-air mixtures at atmospheric pressure and
roomi iemperature (68). The datta are expressed in t.?ris of the stoichio)letric composilion. C,,; burning velocities aire given for the
composition range front 0.7 to 1.4 (',,. These
nut hors hanve presented1 similar dtai for comnbiistibles ait 25' and 100' C. Figure 45 gives
results ob~tained by Singer, Giuner, and Cook
for three paraffin hydroearbon-oxygen mnixt ures
ait at mospheric p1 essure and roolin temperatuire
'in thle range from 0.3i to 1.4 (",, (198) . Buirning
x'elecities range front !t low of 125 ('il/sec to at
high of 425 i/s&e; th~ese vluies aire coInsiderably greater thait those obtainmed in akir. A
chllge in eithber temperatuare or pre11suret will
ailter S,, for at particulari
t
For. exam ple,
Pie

from 0.2 to 2 atmospheres (fig. 47). The effect

of temperature is more consistent. For a given
pressure and mixture composition, an increase
in temperature raises S.. In general:
(51)BT,
where A and B are constants, T is the temperature and n is; a constant for a particular mixture
composition.
Dugger, Heimel, and Weast
(50, 51, 81) obtained a value of 2.0 for n for
some of the paraffin hydrocarbons (fig. 48).
The burning velocity of the stoichionietric
inethane-air and mietthane-oxygen miixtures given
in figures 44 and 45 (10 not, agree with the values
given in figures- 46 to 48 but, in each catse, the
burning velocity data are internally consistent.
The actualil flamle speed relative to at fixed
observer maty be much greater than S. since
the burned gases, if not vented, will expand and
impart it inot ion to~ thle flamne zone. If detonat ion occurs, thle reacetioni speed increases nmarkedly.

For example, figure 40 gives t hi Kogarko

A~gnew aind ( iaifi (3) found t hat an inicrease in

Jpressure caus~es S,, of si oichiioietri n nlt hane-air
andl propatne-atir mixtuares to~ decrease in thle
pr.isim range from 0.5 to 20 atimospheres (fig.
46l)) S, of stoichioniet vie nmetillne-uxygeii mix-

data oil velocities; wit li which at dot onattiomi wave

tunes, however, increasedi in the pressure range

pressuires with natural gas-air mixtures (67).

piropagat es t hroumgh various miet hane-air inixt ares ait atmnosphieric pressure iii a 310.5 CIIdiamieter pipe (12;5). Similar results hatve been
obtained b y (en:t cim, (Ct arlson, and Hill t low

44

FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS

550

-CH4

C2 H6

500-

.- .

C3 H

8
, o ---C-C-C

C-C-C-C-C

6
m 400-

I-.

C-C-C-C

z 350-

96
C-C-C-C.C
C

/~~- tC

n-C4 H1 0 1

C
300z

n-C 5 H12

n-C

250n

n-C6 H1 4 n-CH

2001'
1

/n-C10H22

7.C8 H1 8

n-CI 2 H2 6

n-C16H34

nC14H30

1
1
5
7
9
11
13
AVERAGE CARBON CHAIN I ENGTH, Lovg

15

1
17

FIGURE 43.-Minimum Autoignition I rqnperaturc, of Pi "9flin Ifydrocart, ijq ii Air as a Function of Average
Carbon Chin oingth,

In each case, powerful initiators were required

to obtain a detonation in relat,velv large ip'-.
Theenergyrequiremanausforignitioii
srere
uce,
if oxygen is used as the oxidant in place of air.
Further, the detonation velocity incre ,s as

is s,. reait t'mt pre., rq ,vaves are net sent ott

ahea of the :lctnati,,n frwit
Thus, pressure
detect j- that are 'sef 1 -1 e.\plosion prevention witi

de 'fnatioj

loflagrati

i i'ovi

ire useless with

the oxygan content of the atmosphere

inWith liqi i fuels,, t
bthriiing rote depends
creased.
Detonation velocities
,,tained k
,
r),rt ,i tI
eto
P *r zktiol ,id on the
Morrison for methane, ethane, propa;.i, I,'itaie,
poI size [3(;rges Stia. er itnd ("runer (20)
and hexane in oxygen are given in Ifi.
1 50
,
.'0 siowi that tho liqu,
.. rcision ate ' Ls
(150); similar data obtained by Wayint,
tid
gi,
by
Potter are given in figure 51 for n-hepLau.ov=v=(!-e ',
(52)
nitrogen-white fuming nitric acid . ipors (219).
Of principal interest ere is the ii gnitude of
wh.'r, i is the vdue of v _,l iargr pour,
IT is
the detonation velocity; even in air, ti is velocity
a ca Aa.tt, and d is the pool d;auetter 'iery

FLAMMABILITY

45

CHARACTERISTICS

r-r" .Ethane
40 -

,-/
n-Heptane"Propane
/*'Methane

E 30-

o/

. \

20

10

0.6

0.8
1.0
1.2
1.4
COMBUSTIBLE, fraction of stoichiometric

FIGuRE 44.--Burning Velocities of

1.6

Miethane-, Ethane-, Propane-, and n-fleptane Vapor-Air Mixtures at Atimospheric Pressure and Room Temperature.

46

CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS

FLAMMABIUTY

5 00 - -

-T

I'

450-

400

N" 350
E

rpn

0 300CD

250

200

150

100 1I

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

COMBUSTIBLE CONCENTRATION, fraction of stoichiometric

J"'unIE

45.-Burning Velocitfi

of N ethane-, E'tha ,-,aniid Propntrie-Oxygen Nfixtur.. tt Atmo t

anOd Room "l'ipIeraturtv.

vhric 1Prvssurr

mp

FLAMMABILITY

50

-T - I

47

CHARACTERISTICS

'

4o -

E
30

Propane

020
zMethane-

106

10

0.2

FIGURE

0.4

0.6

1
2
4
6
PRESSURE, atmospheres

46.-Variation in Burning Velocity of Stoichiometric

10

20

40

Methane-Air and Propane-Air Mixtures With

Pressure at 26" C.
expressed v_ as:
0 0076 ( net heat of combustion, AIh"
- sensible heat of vaporization, Aif!
em/mai.

(53)

lower limits of flammabilit

of the olefins
((Iv,) excluding ethylene fall in the range
from 46 to 48 ng combustible vapor per liter
of air (0.046 to 0.048 oz combustible vapor per
cubic foot of air).
The effect of temperature on the lower limit

Figure 52 gives a summary of the r,, values for

it number of cojubustibles, including several
p~araffin hydlroarbos (21).
Of special igiificalce here is tlat Al J.All is niearliv cipnsti
t
(about 100) for the paraffin liydrovarbons, s
tliat
their linar bitrnlinl[ rate,' t lre
. l
are tir
l
i per ininrate

of flammability of ethvlene in air at atmospieric

prsure. assunilng a (onstant limit flame
temperature,
is sh own ofbyflane"
(he curve
labeled
"U
pwirdpropagation
in figure
53.
1 ifirtunatlel,
ml downward Ilate pro pagation dta art, available over an extended ternperat"ure range (2,22); these are included in
figure 53. As in the case of similar data ob-

UNSATURATED HYDROCARBONS

tained with inellane, tliese define a straight

line parilhl tip t ll' "(',,istant flame t:emipera,,,
)ur,
.
pward pro Ipagation of flari)'" line.
Again, the nodifiel Burgess-Wiheler law,

Limits

in Air

The iniecilar weight, .pecific gravity, iiid

1the.- properties of tile 3I"rmlr'aimouin, cosidered here ire inluded in' table 7.
At roonm
peniperat ure and atmospheric pressure, tit

equation (33), give., a variation in lower limit

with temperature that Is ('lose tip t iot given I)y
flauin temiperature" line. so that
( 'ntnt
t he
either
u il he eI
lit temllp)erat Uires below tile
"
AlT (of ethylere (-|ttf)' C)as
('.
.I*,:,The
,
tile
lilnit

Hlati'

te nperatniras of ohclins are no t toot

48

FLAMMABILITY

CHARACTERISTICS

TABLE

OF COMBUSTIBLE GASES AND VAPORS

7.-Propertiesof unsaturated hydrocarbons

Lower limit In air

Combustible

Formula

A4

(Air

Ethylene... .
............
C-----------28.05
Propylene--....-- .
Csla ............
42.08
Butene.l -------- -------- Coils .---- .---56.
ite-Butene-2-------------Cdl,------------'6.10
lobutylene .............. lC,- .........
56.10
3-M ethyl-butene-I ... .. . l---- ..
...-------70.13

adiene............--

-40.06

1,3-Nutadiene............--C if............

54.09

0.97
1.45
11.194
1.94
1.94
2.42

In air
(vol pct)

/e

L,

\till)

(
pet)

6.53
4.45
3.37
3.37
3.37
2.72

316.2
460.4
17.7
(a6,0
(04. i
752.3

2.7
2.4
1.7
!.8
1.8
1.5

1.3

4.97

443.7

1.87

3.67

576.3

Upper limit In air

L
Ref.

-(Vol
C

0.41
.54
.50
.i
.53
.5,5 1

35
46
44
46
46
48

2.6

53

48

10

.54

(115)
(102)
()
(40)
(40)
(40)

ICalculated value.

800

700
41)

Ethylene

-J

E 500 0

4 00

0.2

0.4

0.6

PRESSURE, atmospheres
IIOUFtE

47.-Variation in

Burning

Velocity

of

Stoi-

chiomntric Methane- and Etltylcne-Oxygen Mixtures

With Presaure at 26C.

36
II
9.7
9.7
9.6
9.1

ef.
e----

,
5.5
2. f
2.9
2.9
2.8
3.3

700
210
270
270
260
310

(26)
(40)
(1)
(40)
(26)
(40)

3.3

320

())

(2)---

491 (10P)

I Figures compiled at Explosive Res. Center, Federal Bureau of Mines.

(vol
pet)

12e

49

FLAM3ABILITY CHARACTERISTICS

200

0
*
o
A

150-

KEY
Methane
Propane
n
-eptane
iso-octane

0 100o

0A
>

-,10 + 0.000342 r

z
z a=50-0

ca

0
400

300

200

600
500
TEMPERATURE, a K

800

700

FGuRz. 48.-Effect of Temperature on Burning Velocities of Four Paraffin Hydrocarbons in Air at Atmospheric
Pressure.

,000

3.000

1,500

2.500

0
01

EE

00

L 1,000
z
0

: 2,000
o

z
500-

-i

1,00
KEY
Hexane
A Butane
03 Propane
*0 Ethane
Methane

0A

c1

10
12
METHANE, votume-percent

F'ww rip; 49 -- letoratiolt

Velocjtis of

14

),ttiume-kir

Mixtres at At
liospheric I'ressuire.

grams of armitol exlloive.

(Initintor: 50 70
Pipe diiietcr 30.5 er.)

different froin those of p[araflili hNI(II'(W1L1)orIs,

he generalized pralph fir IL,,'L
(fig. 23) (an 14used for these un iaturated hydfocalbOmls.

1,000-

500
0

10

20

30

40

COMBUSTIBLE, volume percent

')etoyjti
Vejociiies of \letrharl-,
Ethanet*-, l'rolpar e-, Butane-, ald Ilexrie-()xgr'l
Nlixture- at .itmospheric PtI.-.i.ure.

50

FLAMMABILITY

CIIARAC'rERISr01CS OF COMBUSTIBLE
T

".001-

GASER AND) VAPORIS

I

II

proplagationl
flame

-Downward

9,400of

E
0

z~aUpward
Constant flame temperature-

ui 2.000 -

WFNA N2

z(Mole

fraction N12=0.5)

t~1,500--

Modified Burge'ss
Wheeler Law

*WFNA

0_
0

oTEMPERATURE,

400

800

600

1,000

i1200

1,000Flammability
I
lOOC
5
10
15
n-HEPTANE, mole-percent

?l'0

propagation
of flame

"

20

FIGURE 51.-Detonation Velocities of n-Heptane Vaporin WFNA (White Fuming Nitric Acid)-Nitrogen
Gas Mixtures at Atmospheric P'ressure and 400' K.

FIGURE 53.-Effect of Temperature on Lower Limit of

of Ethylene in Air at Atmospheric
Pressure.
40
-----%air =100%-%
ethylene-% inert

30

1.42

1.0z

C41-11

S.8

C6111-O

\1

.4

C8 1-10 -0

FIGURE 54.-Limits of Flamm~bility, ef -Hthylenie-

-Cg 6 ,,

1)ioxide-Air anid Ethylene-Nitrogen-Air

Carbon
Mixtures at Atmnospheric Pressure and 26' C.

UDMHO

.2

-i

CT
C C 0
Cf130H

50'

100

150

200

250

300

He /N Hthe
Firo;i

50

LNG

.6

40
30
20
10
ADDED INERT, volume-percent

52-Relation

Between

Litrnid-Butrning Rate

(LarVr- Pool Diameter) and Rtatio of Net Heat of

Comb -ltion to Sensible Heat of Vaporization.

Limiis in Other Atmospheres

Th~e limits of flammability (if ethylene, propylene, isobutylene, but ene- I, :3 methyl butene-1I,
and butadienie in various inert-air atniosphleres
hii've been determined by Jones and coworkers

(100, 1101, 103), (figs. 154-60). The first two

figures are modifications of the limit-offlainniability diagramns given in (.40); the third
is essentilly the same ITs that viven in the earlier
Publication hut include., the experimental
The oither curves were constructed1
points.
Irom originail, unpublished data obtained t
Explosives Res. Center, Federal Bureau of
Mines.
Other

liniit-of-flarnm-ability determinations

have been made in oxygen and nitrous oxide.

These data are included in table 8 (40, 100,1007).
Autoignition
There have been few determinations of AIT's
of the unsat orated liyplrocarbonus in air or other

oxidants; the available data (9./j, 116, 191) are

summarized in table 9.

FLAMMABILITY CHARACTERISTIC435

12

-1-

%air =100%-% propylene-% Inert

10

-%

Flammable
mixtures

>6

LAS

zW

N2

-j

a>, IctCO

0.42

2-

10

20
30
ADDED INERT, volume-percent

40

50

FI"ouRE 55-Lrnits of Flammability of Propylene-Carbon IDioxide-Air and Propylene-Nitrogen.

Atmospheric Pressure and 26' C.
fill?-ina rliiz,

The burning velocity of ethylene has been

(leterinined in air, oxygen), and o)xygen-nitrogen
atmiospheres by numerous investi.gators (8, 7,
P/, O'S, 131). In generatl, it is higher than the
b
rning velocities of the paraffin hydrocurbons
under
the samne comiditionls (fig. 47).
Simmnilar
results tire to Ibe expectedl for other unisaturatedl
hydrocarbonis, although thie available datat are
rather mneager.

Stability
Many unmsaturated hydrocarbon vapors can
propagate flame in the absence of air at, elevatedl
temperatures and pressures; that is, they have

110

'

I itk

'-f

9i

Air

MixeCat
itla

lbustib e,; have positive heUL, of formiation,

AJI, (table 10) iunri Would therefore it~erat-a
heat if (iecomiposed to thle elements carbon and
hydrogen. Even miore heat would be liberateol if gases with it negative heat of fornation -~for example, inetane-form froin thle
elenments. In practice, at mixture of products
results ulpon decoinposition of such conibustibles.
F~or examlple, at propagating decomposition reaction can be initiated -ill pure ethylene
in at 2-inch-iD tube at 230 C an dlpressures as

low as 750 psig, using 2 gramso guncottoll.

A reaction can lbe initiated at 2 1 'C and pro;;sures ats low as 975 psig with I grain of
guncotton. 'IFie decomuposition products are

52

FLAMMAB.LI'Y CHARACTEREISTICS

OF COMBUSTIBLE

GASES AND VAPORS

80

N2

.4-

02

C02

Ljd
Uj

Flammable
mixtures

4-

10

20

40

ZG

50

ADDED INERT, volume-percent

FIGURE 56.--Imits of Flammability of Iobutylfne-Carbon Dioxide-Air and Irobutylen -Nitrogon-Afr
Amosphcrio Prewure and 26* C.

8.---Limit qfflammability of unsaturate']

hydrocarbons at atmosphericpre sure and room
temperature, in 2olume-percent combustible

TABLE

vapor

0.-M.finimum autoignition temperatures

oj unsaturated hydrocarbons at atmospheric
prtssure

TAimL

L
.......
In ai:

Autoignition temperature

In oxygen

SL
Ethylere ------Fropylene ---Butene-i_-.----Butene-2- -----

In nitrous

oxide

CombustibleI
1

2. 7
2. 0
1.6
1.7

UIL
36
2. 9
11
2. 1
10
1.7
9.7 1.71

Mixturre at

IU

L IU

80 1.9
53 1.4
58
i
----55
i

.................

Combustible

In W'r
oC 0

40
29
..

Ethylene --------Propylene ------Butene-l -------1,2Jutadiene

prinarily carbon, methane, and hydrogen:

approximately 30 Kcal are reieased per iwole of
ethylene decmposed. Propylene yielded si ilar products followig explosive decimposition
during compression to 4,860 atmospheres (34).

In
.. oaygen
.

~ F Ref.
~f

490 914 (116)

458 156
(9)
394
723
(I)
'3261Butene5
(1 )
418
784 (19

I Figures oompiled by Explosives

Mte.

'C
0
CO

0FRf

485
423
310

9
793
590

33

Ref.

(116)
(1)
(1)

35" ( 91)

es.Canter, Federal Bureau ox

Propadiene and buiadiene also decompose

readily under the action of powerful igijitors.
Propadiene vapor has beon decomposed in a

FLAMMAI3ILITY CHARiACTERIBTICS

53

60

% oxygen

100% -% isobutylene -% water vapor

50

02
16%

2~Min

(1)40
E
-5
030

a-

Flammable
m~ixtures
w

0
CC)

024060

80

100

WATER VAPOR, volume-percent

FIGURE

57.-Limits of Flammability of Isobutylene-Water Vapor-Oxygen Mixture at

Pressure.

~-,,wh ;1be at

120'

C an('

0 psig using a

piatir'umn wire ignitor. Decomposition of butadiene in an industrial accidJent resulted in a

itpopcorn" polymer; the reaction was a pparently
initiated by an unstable peroxide (.4).Lnt
TAHLE

lO.-Heats ol formation (Kcal/miole)

unsaturated hydrocarbons at 25' C.

Combustible:
Acetylene -----------------------------

of

I Refs. (114,18P),

ACETENNihl~hQCARBONS
(

R
i

Af
i

Acetylene forms flammuble mixtures in air

at atmospheric pressure and 250 C, in a range

from 2.5 to 100 volume-percent

all/

~54.

Propadvne
-_-----------_-45. 9
1-3, laetadjene.- --------------4,3
1-, thyene-------------------------- 6.
Propylene -------------------------- --- ~ 4.

1-Butce -----------------------------.

150* C and Atmosperie

acety'lene.

Quenched and apparatus limited upper limits

have been obtained in 1-, and 2-, and 3-inch-

diameter tubes (40), but pure acetylene can

propagate flame at atmospheric pressure in

tubes with diameters of at least 5 inches.
Sargent has summarized availablo data on
initial pressure requirements for deflagration and

54

FLAMMABIITY CHARACTERISTICS

10(

air

OF COMBUSTIBLE

detonation through acetylene in horizontal

tubes of about .02 to 6 inches ID at 600 F. (89,
185). His curves are given in figure 61, which
also includes an experimental point from the
data of Jones and coworkers obtained in a
2-inch-diameter tube. The existence
of this point, at a pressure below that given by
Sargent's curve for a 2-inch tube, indicates that
this curve should be used only for horizontal
systems. The point labeled "Industrial explosion" was reported by Miller and Penny (144)

100%-% butene-I-% Iner,

.vertical
N2
E

SFlar.am

C02
bl

and presumably refers to a deflagration.

W 4

..j
to

The

third experimental point is discussed, along

with the detonation curve, in the section on

2-

stability.

21

GASES AND VAPORS

Iflame

10

20
30
40
50
ADDED INERT, volume-percent
Fiouaz. 58.-Limits of Flammability of Butene-lCarbon Dioxide-Air and Butene-l-.Nitrogen-Air
Mixtures at Atmospheric Pressure and 260 C.

The effect of temperature on the lower limit

of flammability was determined by White in a
2.5-cm tube with downward propagation of
(2).
Although the actual limit values
tire not satisfactory for our purposes, they can
be used to check the applicability of the fL-/'2 5
ratio
presented
ratio data
of lower
limits inatfigure
3000 23.
and The
200 White
C. is
2.19/2.90=0.76; the corresponding ratio from

10

% air

l00%-% 3 methyl butene.l-% inert

8
43
0.

_6--N

E
FiGuRE 59.-Limits of Flammability of 3 Methyl Butene-1Carbon
Dioxide-Air and 3
Methyl-Butene-l-Nitrogen-Air
Mixtures at Atmospheric Pre.
sure and 260 C.

N2
"

L-

M
01

4-

Flammable
mixtures

-2

10

30
20
ADDED INERT, volume.percent

40

50

55

FLAMMABILiTY CHARACTERISTICS

12

1
% air = 100%-% butadiene -% inert

10I

FGuRE 60.-Limits of Flamma-

bility of Butadiene-Carbon
Dioxide-Air and ButadieneNitrogen-Air Mixtures at Atmospheric Pressure and 260 C.

E
> 6-

Flammble

z
W

NZ

mixtures

C0 2

24

SI

10

20

I
30

I
40

50

ADDED INERT, volurtie-percent

"Constant flame temperature" curve in figure
23 is 0.78. Accordingly,, this figure should be
satisfactory for use wit i acetylene at temperatures in the range from 20' to 3006 C.
The lower limit of flammability of methylacetylene (propyne) in air at' atmospheric
pressure is 1.7 volume-percent, equal to 0.34 C,,
which compares favorably with the value for
acetylene (0.32 0,,). Upper limit investigations have been conducted bv Fitzgerald (59)
in a 2-inch tube at 20' and 1200 C to determine
the low-pressure limits or lowest pressures at
which a flame will propagate through methylacetylene vapor at these temperatures. He
fouwd these to be 50 and 30 psig at 20' and
120' C, respectively. In a 4-inch tube, Hall
and Straker (77) obtained a low-pressure limit
of 43 psig at. 20' C. This indicates that the
upper limit of flammability of methylacetylene
in air is probably less than 100 percent at 200 C
and 1 atmosphere.

The quantities of propylene required to

prevent flame propagation through methylacetylene-propadiene-propylene
mixtures at
120' C and 50 and 100 psig have been determined in 1-, 2-, 4-, and 12-inch tubes (fig. 62),
and at 120' C and 100 psig in a 24-inch sphere.
As noted, the propylene requirements are
strongly affected by temperature, pressure, and
container size. As the tube diameter increases,
the quantity of propylene required to prevent
flame propagation increases; this effec, is less
pronounced in the larger vessels (diameter
greater than 4 inches) than in the smaller
vessels (diameter less than 4 inches). The
results obtained in the 24-inch sphere were
similar to those in the 12-inch tube.

Limits in Other Atmospheres

Gliwitzky (71), and Jones and coworkers
determined the effects of carbon dio.-ide and

56

FLAMMABILTY CHARACTERISTICS OF COMBUSTIBLE GASEE AND VAPORS

400

----

11I

200 -Deflagration

10080
C,,
CLJ

60

40

20

Sargent
Miller and Penny (Extrapolated)

Industrial explosion

Jones and others

100.02

NN
0.04 0.06

0.1

0.2
0.4 0.6
DIAMETER, inches

10

FiouRI 61.-Effect of Tube Diameter on Initial Pressure Requirements for Propagation of Deflagration and
Detonation Through Acetylene Gas.

nitrogen, on the limits of acetylene in air at

atmospheric pressure and room temperature.
Unfortunately, all measurements were made in
tubes that were too narrow to give actual upper
limit data.
Nevertheless,
the
resulting
quenched-limit data are summarized in figure
63, because they show the relative effects of
adding two inert diluents to- acetylene-air
mixtures in a 2-inch-ID tube.

gel, or charcoal lowered the pipe temperature

required for ignition to a 280 to 300' C range.
The presence of 1 gram of potassium hydroxide
lowered tile pipe temperature still further to
170' C. The impact of a 0.25-inch steel ball
falling from a height of 15 inches against a
fragment of copper acetylide produced a hot
spot that ignited the surrounding gaseous acetylene at room temperature and 3 atmospheres.

Autoignition

Burning Rate

A summary of available autoignition temperature data for acetylene, acetylene-air, and

acetylene-oxygen mixtures in clean systems is
given in figure 64. They are based on measurements by Jones and Miller (110), by Jones and
Kennedy in quartz tubes (99), and by Miller
and Penny in a 0.5-inch steel pipe, 15 inches
long (14). Jones and Miller found minimum
autoignition temperatures of 3050 and 2960 C
for a variety of acetylene-air and acetyleneoxygen mixtures, respectively, at atmospheric
pressure. Miller and Penny report little wariation in the autoignition temperature of acetylene in a clean pipe at 4 to 26 atmospheres initial
pressure. However, the presence of I gram of
powdered rust, scale, kieselguhr, alumina, silica

The burning velocity data for acetylene in

air obtained by Manton and Milliken at 1
atmosphere and room temperature are given in
figure 65 (158). The burning velocity ranges
from a low of a few centimeters per second near
the lower limit to a high of about 160 cm/sec
on the rich side of the stoichiometric composition. Parker and Wolfhard (164) have found
considerable variation in the burning velocity
of acetylene in various oxidants. The burning
velocities in stoichionetric mixtures with oxygen, nitrous oxide, nitric oxide, and nitrogen
tetroxide were found to be 900, 160, 87, and 135
cm/sec, respectively; for comparison, the burning velocity in a stoichiometric acetylene-air
mixture (fig. 65) is 130 cm/sec.

57

C'I IAltA(Tl.Ei1STICS

FLAMNMAIILTTY

'000

,Z

\Flammable mixtures

12-inch-I D bomb,l0O psi

2-inch-I D bomb,IO0psig

~~0

00

90

'\

I~~-inch-ID bomb,IO0psig

80

60

70

50

\-"2-inch~-i D

00

\obs~i

PROPYLENE, volume- percent

FIGURE 62.-Itange of Flamnmable Mixtures for Mc(thy-lacety.lene-Propadienc-Propylenie System at 1200 C and at
50 an~d 100 Psig.
The burning velocities of acetylene-air m1ixlures were found to ibe indlependcit, of pressure
b~et ween 0.1 and 1.0 atmnosphlere (138). Sint'raiffl (3) and Parker andi~
ibrly, A 'new andt(
WVofhard (164~) found U'h, 1urninq, velocities
of stoicliioietric, acetylene-oxygen and1( acetylene-nitrous oxide inixt tires wereo independent (of
p)ressure bet ween approxiimately 0,5 and 2
atmuospheires and~ 0.03 and I atniospliere, respectively. Th'le b~urning velocities (if st ojchioInetric 1cctylene-mitiic ox'ide and( acetyliene11i rogen let rt xide iiixtures incrca:~ed slightly
o vern thiis pressurme range 0.03 tot I at mospier'e
(1 ((.4).

Stabfitytanlce

Staili~r

As noted, iicetyleiie canil propagatte fltiie

the absence

(if

air (39,

165).

inl

The pressures

required for propagation ait subsonic (deflagration) and supersonic rotes (detonation) into
the unhurijod gats tire giveni for ai range of pipe
D~eflagration is
(I.
-41er.s i!, ''',ure 61 (185).
LIscussed briefly under Liniits of Flan-iniability;
dletonatio 1s : dfiscussed in this section.
The cuirse labeled ''Detonation'' in figure
61 gives thle iniimui pressure required for
propagation (of it (detonaltion, once initiated, inl
tuibes of 0.3 to 1(0 inches (liv ieter. In iprawlive, at (detonat ion inay be initiated directl
front it defla grittion t hat hias lpropaglited throu l
at rat,her ill -definied distance, know itsiIts
pedletInait) 0n or run-up) distanimce. This
itemneritutre, pressure. tuhbe'
depends ontc
Ijittiieter, conidition iof tube watls, and onl
igilit ion-s( urce streligtbI.
Fori exampiJle, using
it fulsed p~itiiui wir-e ignit(Ir, Miller anid P~enny

(us-

58

FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS

(144) found the predetonation distance for

100
%air

acetylene in a 1-inch tube to be t1 feet at 51.4

psia, 22 feet at 55.9 psia, 12 feet ot 73.5 psia,
and 2.8 to 3.2 feet at 294 psia initial pressure.
Extrapolation of these data yields the point
in figure 61 for a very large predetonation
distance. This point (44 psia and1-inch diameter) lies fairly close to the detonation curve
established by Sargent (185). The maximum
lenth-to-diameter ratios (LID) given by Sargent
for establishing detonation in acetylene is
against intial pressure in figure 66.
In tubes, Fa vingta diameter greater than those
given along the top of the figure and having
powerful ignitors, the LID ratio will be less than
that given by the curve. Nevertheless, this
figure should be of use in giving the outer
of LID and the approximate quenching
diameter; a better value for the quenching
diameter can be obtained directly from figure

100%-% acetylene-% Inert

80

A,
9plotted
Z
40 -

mixtures

20

C02 -

N2bound

~61.

est

FIUnt 63.-Quenched Limits of Flammability of

Dioxide-Air and AcetyleneAcetylene-Carbon

Although predetonation distances are difficult to measure and experimental data often
exhibit much scatter, they are of interest in
safety work because they can be used to evaluate the maximum pressures likely to occur in
a system due to cascading or pressure piling.

Nitrogen-Air Mix~'rcs at Atmospheric Pressure and

-'bis phenomenon presents a sp..-:-ial problem

20

80

40

ADDED INERT, voiurre-percent

26' C, Obtained in a 2-Inch Tube.

because the final pressure achieved in a detona1

1
I
KEY
Oxidant
Pressure
Tube
* Air
1 atm
131 cc quartz
0 Air
1 atm
200 cc quartz
Air
2 atrm
200 cc quartz
0 Oxygen
1 atm
131 cc quartz
None
4-26 atm !-inch steel pipe

700

.L 600-

500FiGURa

64-Minimumn Autoigni-

tion Temperatures

of Acety-

lene-Air and Acetylene-oxygen

mixtures at atmospheric and

elevated pressures.

z
9
Z 4 00

Region of autoigntion

300I-

200
0

20

40
60
ACETYLENE, volume-percent

80

100

59

FLAMMABILITY CHARACTERISiTICS

2001g

00 150-

to be expected from a detonAtion is about

50 times the initial pressure. As the pre-sure
equalizes at the speed of sound in a deflrgration, the maximum initial pre3sure to be expected upon tranisiticn from deflagration to a
detonation is approximately 1i times the fraction of acetylene that has been burned times
the initial precombustion pressure. Fifty times
this pressure is -.ho ap'proximate maximum
pressure that rould be o ;ained when a detonation occur-. '.Lo illustrate this, Sargent has
the final-to-initial pressure ratio (P,/Pj)
the predetonation distance-to -tube
length for acetylene. A siniliar graph is given
in figure 67. To use this graph, the maximum
redetonation distance to be expected must

N.

E
U

3 100 r-plotted
>
z/

~against

W
z

be deemndfo

-s

figure 66. Tb.-n'z

maximum final-to-initial pressure ratio.

____

____

____

2.

____(C.H

5
10
ACETYLEJE, volume-percent

1s

,)

LiMitS inaAir
The combustibles considered in this section
are listed in table 11, with pertinent properties.
At atmospheric pressure and room temperature,
the lower limits of flariimabilit ofte aromatic
hdoabn arap
oately 502 mg/l
(0.050 0.002 oz combtustible vapor per cubic
foot of air).
The lower limit of toluene was determined
by Zabetakis and coworkers in air at 300,

Fso.-s, 65.-Burning VnIocity of Acetylcnc-Air Nfx

tures at Atmospl.cric k'ressurc and Room Temperature.

tion depends on the initial pressure at the onset

of detonation. F, r example, the maximum
pressure to be expected from the deflagration
of Lcetylene at moderatc pressures is about 11
times the initial pressure (144); the maximum

QUENCHING DIAMETER, inches

0.5

421
0128

LID ratio
Rea uired for Transition of a
Deflgration to a Detonation
in Acetylene Vapor at '*01 F
and from 10 to 70 Psia.

FIOURE 66.-Mlaxiimum

.S
*:. 40C
.

10

20

30

40
50
INITIAL PRESSURE. psia

60

70

60

FLAMMABILITY CHARACTERISTICS
TABLE

('ombustihlm

OF COMBUSTIBLE GASES AND VAPORS

11.-Properties o selected aromatic hydrocarbons

Formula

Sp gr

C, in
air (vol

net Ali

/Kcal
Wr pt(volle
)

Lower limit in air

.....
-

'

1 mj00(L
II..
o

110
PCtI

Blzeee
('1,1
"IhUe(_(
l711,
(...
IE'thl ihmnzene C
(!e
omI-X'vn.
.....
(l10
rn-Xvmmmle
----- cjl
p-Xl.n_-C---(IIinmI----------C 1 2
p-Cym--en--.....--Co11, 4

78. 11
92. 13
116. 16
106.t 16
106. 16
106. 16
120. 19
134.21

2.,69)
3. is
63.17
. 7
:3.67
3. 67
4. 15
4.63

2. 72
2.27
1.96
1.96
1, 96
1.96
1. 72
1. 53

757. 5
101. 5
104s. 5
1045., 9
1045. 5
1145. 7
111,.2
1341.8

1, 31
1.2
1. 1)
1. 1
1.- 1
1 1

[Ii

pet)
0. 48
. 53
51
56
.56

56
.1
56

.8,8

Upper limit in air I

85

47
50
48
53
53
53
4S
51

7. 9
7. 1
6. 7
6. 4
6. 4
6. 6
6 .5
t.5

2. 9
3. 1
3. 4
3. 3
3. 31
.4
3. 8
3.6

300
310
341)
320
321)
340
3170
350

IRe. (147).
400

--

---.--------...

.......

300

FiorRaE 67.--Final-lo-Initial Pressunr Ratios Decvvopied y Acetyeime With I),olitiol l 1litimtion at Various Points Along a
Tube.

200

100 ,--

1000, and 200' (i (235, 247); the varintion in

lower limit with tonipertlikre is given by eqauitions (31) and (33') derived for parafflin h 'drocarbons, aid the vorresponding curves of filgure
23. For example, jImp, rIL.3, ,.vwits folund to he
1.07/1.24 or 0.86; the ratio predicted by the
curve in figtire 23 is 0.87.
irminiics (iin.idered
Ihe u )p(er litijts of tie
here it 1000 ( nire inchded in t able 11 (270.
These were otlaiiied it ntnisl)lierii' fpreslr
iii it 2-incl-diwnietr Itihe, oiin
ait line eid.
Blier nind W~elbb 4lobtiL
Ined uppier iliii n miatit
R mtmilinrciil grade m'iieriv (9;.1 prt riiiet-e)
;ii nir tit elevated tenimer ires
anm iiimmmtheic
milld 'el'vtted pressures Ii it chim1ed b11111 (I).

0.2
0.4
0.6
0.8
PREDETONATION DISTANCE/ TUBE LENGTH

10

Their values rmiuge f'rin 8.8 percent (ctiinieiie

(80' (' aid a) tii pherie pres,.re) (if 10.8 per(,ett ctiiniiei (I4i' (' kiind 11) psig pressutire).

Limits in Other Atmospheres

The !iniit ,,if flhininititilitl
(;29) mrid lhv r.,i1

g(li.

miirl)lml

di~xhNle-iir

and

,dtgiiumed hv
ir.
iur zlmc'l(.t[)) f
eli? 'mi.-iitrmigeu-nuli

mixilt tires at tit Iiimmli'n jtreslilre nllml

a
25 (' mie
glixen in igtre WS, ; simiillir dall mire :ivlii fir
ithe last two Ililiires t 1it
n111, m1hwric pes~olrt
1i11ml I 1
('
The iiertint rpqtltrm'liieit tit 2i
t ire liprixhlihitek lile silmie 1 tihfse if ItIlexine (fig. 33). Agnili, it sloi le
hi IIl!

FLAMMABILiTY CHARACTERXSTJCO

. ......

10.

%air =100%-97o benzene - qV inert

8
150

6,

25

>Ee~

z 4
Zi

r-W

30

20

10

40

50

ADDED INERT, volume-percent

Fioiunw 6S.'--Limila of Flarnmabilitv of Benzene-Methyl Bromide-Air Mixttures at 250 C and Benzene.-Carbon
Dioxide-Air and Bnzene-Ntrogen-Air Mixtures at 250 and 1500 C and Atmospheric Pressure.

that the methyl lbromide datta aire not consistent

with those obtained by Hlill (rompare figs. 28
an3), Tjhese lattter (lain (80) were used to,

expressed in mole-percent as in the ori~ia

presentation. 'Plur system has no lower mit
mixtures, as a flamie can be initiated in hydrogen
peroxide vapors (186). As a 90-weight-percent,
hydrog en peroxide was actually used to obtain
these flawinability data, all compositions were
cailculated to) yield values based on a 10-cercent,
hydrogen per(')xidle co nten t. This co~uld be done
here because only three cemiponients are considPred. Where four components aire considered,
the flumnahiiity 6ata can be presented in a
plot ; if two of the cornpo tiiree-itnenginn
mient 11ppear in fixed proportions, at triangular
plot (,an Ce used wit It the two compnets (for
exaniple, 90-weight. Iercemit hydrogen peroxide)
C40mnsid ered ats a sinigle c~npinemlt. Such a
plIot is presented in figure 70 for 00-weightpercent hydroigen 1)eroxidle-4 rthoxyvilenie-forinic
acid (HMUMO~) at 1540 C and I 'atmnosphere.
rhit; was considered to) he at plane in a regular
tetrahedIron in the original article and is there-

construct. thle approxitnate (broken) flaninmahility curves for the benzene-iriethyl bromideitir system,.
Tlhe decrease in the minimium oxyNgen requiremnents for flaine p~ropatgationi (fronti 14.2+0.3
vohiinw-percent ait 250' C to 1:3 1013 volumve[)ere~ont ait 150t' in it carbon dioxidle-air atnmrsphere; fromt ! 1.4 0.3 voluine-jiercent at 250
C to 10.1 -f.0.3 v'ohiine-percemit fit I 50, in) at
initri pgcm-air tttJ11iO~jpher'e) iS withilin(fhe Irange
predic ted lv (flie miodified ilurgess4-Whepeler
lakw (equialion (05),fig. 23).
Tlhe limlits of 1f1ilnifilalitY of ort Iioxvknle
(( df11 (('i,) 2)-water-h' dogemi peroxide huIwres were dri crmin ed tit I 54' C and I titimu14l'ohere
rs'weby
Matrt iiidill, Lang, atid
(lait tire pretiented iii
4itbem skis (1T).hle
it triangular plot. in figure t19; emflposiionS are

.--.

-.-

---

,-......

......

62

FLAMMABMI1TY CHARACTERISTICS ul, COMBUSTIBLE GASES AND VAPOUIS

100

80

20

Composition line formed with

82.6 mole % (go wt %) H2 02

600
g

dFlammbble
mixtures

co
aoe

200

100

so

eseo

60

40

20

H202, mole-percent

FimuRi 69.--Limits of Fladsmabity of HiOrCH4 (CH3)rHO at 154i C and I

Atmosphere Prature.

upean
hepeoxideloers
Decmpsitonof
fore not
a regular triangle.
As before,th onl~y
upper limit curve is given because 90-weightpercent hydrogen peroxide is flammable. In
addition, a calculated curve based on Le Chatelier's rule is given, as is the upper liait curve
obtained with decomposed hydrogen peroxide
Decomposition of the
ide lowers the upper
limit
ields a system
has a appreciably
lower limit ane
ofo flammability
(not wLch
determined in this study).

epciey.T'
eaadpr-oitos
-CHa
group (24 1). When the benzene ring
contains two side groups, L, is determined
first for the side roup that yieds the largest
average value andto this
d is added l, , or
of the average chain length of the second side
p,
group; (a,
and
correspond to the ortho-,
meta-, and para-positions, respectively). Tdata again
regions
(fig. fal
43).into high- and low-temperature

Autoignition

Burning Rate

The minimum autoignition temperatures of

a series of aromatic hydrocarbons in air at
atmospheric pressure are given in figure 71 as
a fntion oF the correlation parameter L ...
This parameter was determined by use of
equation (49), treating the benzene ring as a

Burning rates and detonation velocities of

benzene in air and oxygen appear to be approximately the same as those of the higher
paraffin hydrocarbons. For example, the results of Golovina and lFyodorov (211) show
that the maximum burning velocities of benzene
in nitrogen-oxygen mixtures range from about

6Ao

FLAMMABILITY CHARACTERISTICS
100

80

20

.60

00

Oxtdant; ecompose
0
100

VaV100
so

60
40
90 weight-percent H202. mole-percent

Fioun. 70-Limitaof Flammability of 90-Weight-Paeent IIOrCH# .(CH3)rlICOOH

Pressure.

295 cm/sec in oxygen to 45 cm/sec in air; the

maximum burning velocities of haxane in
various nitrogen-oxygen mixtures range from
abouit 260 cm/sec in oxygen to 40 cm/sec in
air. Similarly, Fraser (0!) found the maximum
detonation velocities of benzene and n-octane
iii oxygen to be 2,510 and 2,540 rn/see,
respectively,

ALICYCLIC HYDROCARBONS
(CA.,,)
Limita in Air
A summary of the pertinent properti&; of
some of the members of the series is given in

20

at 1540 C and I Atmnosphere

table 12. The lower limits of flammability in

air at atmospheric press ire and room temperature fall in the range from 48 3mg/i (.048
.003 oz combustible per cubic foot of air).
By volume, this is equivalent to approximately
0.55 02,,, which is the same as for paraffini
hydrocarbons. The ratio of the upper limit
to C,, appears to increase with molecular
weight.

According to Jones (40), the lower limit of

cyclohexane in air at atmospheric pressure and

260 C determined in a 2.0-inch tube is 1.26

voluine-percent. Under thea same conditions,
Burgoyne and Neale (26) found the lower limit
to be 1.34 volume-percent, using a 2.5-inch
tube. Matson and Dufour (141) found the

64

FlAML4DIITY CHARACTER18TICS OF COMBUSTiBLE GAGES AND VAPORS

57-

-1
52

~~CH

CHH-H

ICH

a-wH

3 CCH3

02475 -

0H

F-

CH3 -CH-CH3

S425
CH3-H
37

2H

3-H3-C 2

CH
375

C2H5
3
Lavg

1
12

Fiaunu 71.-Minimum Autoignition Temperatures of Aromatic Hydrocarbons in Air as a Function of Correlation

Parameter L.,..
TABLE

Combustible

C corpn------Cy lb(ae-----C eoAnse_.----- C coeae-----Eflif1eycobutane----

Formula

Cas..
11. --. ----lo --_I... (:11-----lhg.

12.-Properties;of selected alicyclic hydrocarbons

S9 !r,
(Au)

4208
.10
70.13
84.16
84. 10

lower limit to be 1.12 volume-percent,

1.48
A'94
2 42
2.91
2. l

C.0
inair
(Vol pet)

4.45
3.37
2.72
2.27
'2.27

tit 21' C
in a 12-inch diamieter chamber about 15 inches
long: however, there is evidence that they did
not use the same criteria of flammability am did
the other authors; only one observation window
was provided at the to p of a rather squatty
chamber, whereas with the glas's tubes used by
Jones and by Burgoyne and Neole the flame
could be observed along the entire tube. Ac-

LI

A J.......
Net
k.0l
mole )
L.
(Vol

465
1'600
740.8
81. 7
MW)

2,4
1,8
1.'5

1.

1.2

limit In air
LM
*

pe)
1

L
~(mg)
T

0.54
.5
.M
.6
:7
.53

46
46

48
49
41

Upper limit in air

Ref.

U,,
(vol
pot)

(107)
10.4
(1) ----

U
Un
C.,

mg)

2.3

220

- ----

-- -

Rat,

(107)
-i

(I)6

(40)
(40)

-7.8
7. 7

3.4
3.4

32
310

(40

cordingly, the data of Jones and of Burgoyne

and Neale are used here.

Limits in Other Atmospheres

The limits of flammability of cyclopropanecarbon dioxide-air, cyclopropaiie-nitrogen-air,
and cyclopropanc-helium-air mixtures at 250 C~
and atmospheric pressure are given in figure

FLAW&ADILITY CHARACTERISTICS

% air

100O%-% cyclopropane-% inert

10-

E
FiGUaRE 72.-Liits of Flammability of Cy clopropane- Carbon
IDioxide-Air, Cyclopropane-Nitrugen-Air, and Cyclopropane1Iihum-Air Mixturcs at 250
and Atniospheric Pressurc

Flmae

U36

Flmal
mixtures

01020

&

30
ADDED INERT, volume-percent

40

50

ALICOHOLS (05 H2.+ 1 0H)

72 (106). The first two curves are similar to
those obtained with naraffin hydrocarbons (fig.
35).LiisiAr
~~~Thp
limits of flainmability of cyclopropane-LiisiAr
The alcohols considered here are listed in
heliumn-oxygen and cyclopropane-nitrous oxideoxygen mixtuires at 25' C and atmospheric prestable 13 together with L~s. and U26.. The
sare are given in figure 731 (106). The latter
ratios Lzso/C., are approximately 0,5. Howclurvn diffctrs from the former, as both additives
ever, the L (mg/i) values decrease with increase
in molecular weight. If L* is taken to be the
are oxidants (oxygen andl nitrous oxide).
weight of combustible material (exclusive of the
The limits o! flammability of cyclopro paneoxygen in the molecule) per liter of air, then for
lielirnt-ii~itrons oxide initires at 25' C and
the simple alcohols:
atinospherie. pressure are giren in figure 74 (106).
Hlere the minimum oxidant, concentration
*LM- 16
(4
(nitrous oxide) required for flame propagation
L*~
M.(4
is approximately twice the corresponding concentration of oxygen in the systems cycloThis eqkuation gives the value,; listed in parentheses in the mg/I coluimn; these are in fair
propane.-heliumi-air (fig. 7-2) and ('yclopropaneagreement with the values obtained for the
helium-oxygen (fig. 73).

66

FLAMMABILITY CHARACTERISTICS

--on

p
100c-%
-

oxygen

He, or N20)

measured value is 3.3 volume-porcent.

iN 2 0

50

The lower limits of methyl alcohol have been

determined by Scott and coworkars at 25', 100',
and 2000 C (192). The values at these three
temperatures
are 6.7,rhe
6.5, and 5.9 volume-percent,
respectively.
calculated values obfrom the modified Burgess-Wheeler law

40
4tained

(fig. 23) at 1000 and 2000 C are 6.4 and 5.8

volme-percent, respectively.

He

Flammable
mxtue

I3

VAPORS

corresponding L*. from figure 19 for ethyl

alcohol (M=-46) is 2.2 volume-percent. Then,
from equation (54), L is 3.4 volume-percent; the

eo2

lopropne-(

OF COMBUSTIBLE GASES AND

Limits in Other Atmospheres

The limits of flammability of methyl alcohol-

C5 1 (in 02 + N20)

20-

cal

(in

02

IS

20

40 20

40 606o

loo

carbon dioxide-air and metnyl alcohol-nitrogenair mixtures at atmospheric pressure and 25'
in figure 75; flammability
50' C are given
and
determinations
on mixtures
containing more
than 15 percent methyl alcohol vapor were
conducted at 50 C. The maximum amounts
required
to
of
carbonflame
dioxide
and nitrogen
prevent
propagation
in these
inixtures

NITROGEN OR NITROUS OXIDE, volume-percent

40

FIGuRa 73.-Limits of Flammability of CyclopropaneHelium-Oxygen and Cyclopropane-Nitrous Oxide-

%]

X air

100%-% methyl alcohol-% inert

Oxygen Mixtures at 250 C and Atmospheric Pressure.

40

I35

% N2 0 = 100%-% cyclopropane-% He
3030

\k

E2

Min N20

6= 25-\

21\

uz 20> 20\

Flammable

o
10

z
10!

i
smixturesS
Flammable
\

XSaturated at
25' C and 1 atm.

mixtures

s.CO
C02

20
40
60
HELIUM, volume-percent

80

FiGURE 74.-Limits of Flammability of C clo ropaneflelium-Nitrous Oxide Mixtures at 250 JandAtmos-

10-

pherio Pressure.

saturated hydrocarbons. Approximate L (mg/

I) values can be obtained from the higher
hydrocarbon values given in figure 22 by
multiplying these by the ratio M/(M-16).
Further, figure 19 can be used to obtain L* and
values in volume-percent.

250 C, L" is about 47

For example, at

mg/1 from figure 22; the

0
DE10 20

30

40

50

ADDED INERT, voiume-percent

FIGURE 75.-Limits of Flammability of Methyl

Alcohol-

Carbon Dioxide-Air and Methyl Alcohol-NitrogenAir Mixtures at 25* C and Atmospheric Pressure.
(Broken curve at 500 C and atmospheric pressure.)

67

FLAMMABILITY CHARACTERISTICS

TABLE 13.-Propertesoj 8elected simple akohols

Formula

Al

(AirI

in ai
(Vol pct)

jj

Upper limit In air

Lower limit In air

NetalHe
Combustible

uLu,
(vol

pet)

U
.

,g

C.,

Ref.

(Vol

Ref

pct)

Methyl alcohol-----

oH
S.......
_--

82.04

1.11

12.25

IN1

8.7

0.65

1103

(40)

'31

2.0

Ethyl alcohol .............

CH OH ........

46.07

1.59

6.58

306

3.3

.5

70

(40)

'11

n-Propylalcohol ........

CHF O- ........

60.09

2.07

4.48

448

'2.2

.49

1460

(40)

814

2.9
3.2

n-Butyi alcohol ---------

CiHoOH........

74.12

2. M

3.37

41.7

.50

87

pri-n-Amyl alcohol -... C&IIIsOH ----- 83.15

n.-..exyl alcohol.------102.17

3.04

2.72

742

'1.4

.51

3.53

2.27

888

VO

412 --------------

()

10 .................

(6)

.53

1.2

1 )(086)
420 j (4

............

e
t-100 C.

. M*Fgures
t L-L..
it-60'.saturation temperature.
At

compied by Explosivu Re. Center, Federal Bureau of

Min
I Calculatedo.value.

were compared with the corresponding maxima

60

for paraffin hydrocarbons (figs. 28-35); it was

found that appreciably more inert is required to

make mixtures containing methyl alcohol nonflammable. Conversely, methyl alcohol requires less oxygen to form flammable mixtures,
at a given temperature and pressure, than paraffin hydrocarboni do. This may be due in part
to the oxygen of the alcohol molecule. For the
simple alcohols, we have:
C.H,,OH+ 1.5nO2 --*nCO3 + (n + I )H 20.

I (S)

f5

T
air -100%-% methyl alcohol-% wa

so
400 C
40

2W C
30

(55)
20 -

Thus, the ratio of oxygen required for complete

Flamrmable

mixtures

combustion of an alcohol to that for complete

combustion of the corresponding paraffin,
equation (22), is:

rz 10

(56)

20

30

40

5O

60

VAPOR,
volume.percent
WATER

When n-- 1, this ratio is 0.75. The corresponding ratios of the experimental minimum oxygen
values from figures 75 and 28 are 0.82 with
carbon dioxide and 0.85 with nitrogen as inert.
The limits of flammability of methyl alcoholwater vapor-air were obtained by Scott (192)
in a 2-inch-ID cylindrical tube at 1000 and
200' C and in a '4.9-liter cylindrical bomb at
4000 C and I atmosphere (fig. 76). Similar
data were obtained by Dvorak and Reiser in a
2.2-liter apparatus at 1000 C (58).
The limits of flammability of ethyi alcoholcarbon dioxide-air and ethyl alcohol.nitrogenair mixtures were obtained at 25' C and
atmospheric, or one-half atmosphere, pressure as
noted (fig. 77). Additional flammability data,
obtained for ethyl alcohol at 100' C 'and I
atmosphere are given in figure 78. Flammabil-

FIGURE 76.-Limits of Flammability of Methyl AlcoholWater Vapor-Air Mixtures at 1000, 2000, and 4000 C

and Atmospheric Pressure.

ity data for the systems tert-butyl alcoholcarbon dioxide-oxygen and 2-ethylbutanolnitrogen-oxygen are given in figures 79-81.

Autoignition
The minimum autoignition temperatures in
air and oxygen of a number of alcohols at
atmospheric pressure are given in appendix A.
Comparison of these values with those of the
corresponding paraffins (methyl alcohol and
methane; ethyl alcohol and ethane, etc.),
shows that the AlT values of the alcohols are
generally lower.

68

FLAMMABILITY

CHARACTrERISTICS OF COMBUSTIBLE GIASES AND VAPORS

air an l00%-% alcohol-% water vapor

air m100%-% ethyl alcohcl-% Inr

15It

'13.8%

vkq"210-

Flammable8

Flammable
mixtures

C02

10

20
30L
ADDED INERT, volume-percent

40

so0

Fiounia 77.-Limits of Flammability of Ethyl AlcoholCarbon Dioxide-Air and Ethyl Alcohol-Nitrogen-Air

Mixtures at 250 C and Atmospheric Pressure.
(Broken curves at one-half atmosphere.)
251

% air

-100%-%

Cs,

8
_

0
24

III
ethyl alcohol-% water

*20

10
20
30
WATER VAPOR, volume-percent

40

Fioumz 79.-Limits of Flammability of ter-Butyl

Alcohol-Water Vapor-Air Mixtures at 1500 C and
Atmospheric Pressure.

iO
15Mi
2.3

601
%

100% -% 1\alcohol-% C02

oxygen

50-

Flammable

nmlbe

400

WaX Vao-i Mixure at100CadAmop2i

5r sre

and
a rnge
Cacoteo ormixtue comositios

Alchol-Cros

Dixd-xge

itrs

t10

apC;-the mxmmturni
00 n veloispwereinctoshrcPrsue
ate
5
fosutre 5.
n 14c/e 1 rsetvl

rinvesotiaos
(8.Thes

otland th

burning velocities of methyl and n-propyl alco-

Lik

hlt

00

the
CRO

were 72.
aximumves
IDE

and 64.8 cm/sec, respectively.

These values

FLAMMtABILU/Y

60

40

----IXygsk'plt a

lei

89

CHARCTERISTICS
T

tenoI-.% n

"
% air

Cool

100%-% ether-% Inert

flames

400
40-

.1mixtures

20
oble

FlammF
9.3%9

0
8

2
t o\

30
i

o N2Ner
D m h

920C-st

ADDED INERT, volume-percent

10-

FiauaE 82.-imxits of Flammability of Dimethyl EtherCarbon Dioxide-Air and Dimethyl Ether-NitrogenMixtures at 250 C and Atmospheric Pressure.

*Air
0

20

40

60

80

100

40 [

NITROGEN, volume-percent

FiOuRs 81.-Limits of Flammability of 2-Ethylbutanol-Nitrogen-Oxygen Mixtures at 1500 C and

Atmospheric Pressure.

K
4 30

are in fair agreement with the corresponding

values of the paraffin hydrocarbons.
The methyl alcohol liquid-burning rate obtained from equation (53) is in fair agreement
with that obtained experimentalir (fig. 52).
The relatively low AHeILJJ.ratios .or the alcohols indicates that they should be characterized
by low-burning rates in large pools.

Q:

ETHOS (CUH,.,.OCAj)

Liitsn

The properties of a few common ethers are

listed in table 14. Unfortunately, the limits

data show appreciable scatter, so it is difficult

to establish any general rules with the given

data. However, as a first approximation, the
L/C,,
is about 0.5 for the simple ethers.
Limits in Other Atmosphereo
Because of the importance of ethers as anesthetics, limits of flammability were determined
in several atmospheres. The limits of the systems dimethyl ether-Freon-12 (CCI2 F2)-air
dimethyl ether-carbon dioxide-air, and dimethyl
ether-nitrogen-air obtained by Jones and coworkers are given in figure 82 (114); the
limits of the systems diethyl ether-carbon dioxide-air and diethyl ether-nitrogen-air are
given in figure 83 (26, 166, 108), Cool flames
exist above the upper limit as noted; the upper

1
air - 100%-% ether-% inrt

Cool flames

20-

a
FlammbIe
mixtures

N2

0C02

0iit 1n0i

20

30

40

ADDED INERT, volume-percent

50

FIGURE 83.--Limits of Flammability of Diethyl EtherCarbon Dioxide-Air and Diethyl Ether-Nitrogen-Air

Mixtures at 250 C and Atmospheric Pressure.

limit of the cool flame region in air is 48.4 volume-percent, according to Burgoyne and Neale
(26). The limits of the systems diethyl etherhelium-oxygen and diethyl ether-nitrous oxideoxygen are given in figure 84 and the limits of
diethyl ether-helium-nitrous oxide are given in
figure 85 (106). Again, as with the alcohols,
more inert is needed to assure the formation of
nonflammable mixtures than is needed for the
corresponding paraffin hydrocarbons. Also,
cool flames are encountered at lower temperatures and pressures.
Comparison of curves in figures 84 and 85
shows that the minimum oxidant requirement
for the formation of flammable diethyl etherhelium-oxidant mixtures is approximately twice

70

FLAMMABILITY

CHARACTERISTICS
TABLE

OF COMBUSTIBLE

limit in aW

- -Lower

is

(Vol pct)

moe

Ls
C.

(vol
pet)

1. 50

6. 83

0.16

3.4

0.562

74. 12

2. N6

3.37

608

1.9

. 56

.8&15
88.

3. 28

2. 72

5 760

1.7

.62

Dl-t-propyi ether-....C~I1,OCI,?--102.17

3.53

2.27

'900

1.4

.87

... 70.00

2.42

4. 02

31,770

1.7

.42

C~igOCH .... 4&. 07

Dimetllyl ether.........
Dletliyl ether----------CilsEth~yl propyl ether----

CiHsOCa,,

Dlvtnyl ether----------...CillOCifla
IVLM-16

10%-

Upper limit ill air

/,\

{
(

elf.

Tin
(vol
pet)

Us

K)ig Ref.
0

4
68

(40)

g36

11

(114)
(40)

(3.)

1501 (40)
54

760
1,880

4.1

7 1 1

11)

7.9

3.
6. 7

M0

(8)

291)

(40)

1,160

(97)

I Calculated value.

'cool fiames: Ua.'>16 vol pot.

IRef. (165).

V---

'Cool flsmes: tVag-53 vol pot.

100

AND VAPORS

14.-Properties Of 8elected ethers

orml,

Comba~lbe
Fomula

GASES

dity ete-%H

30

2)3

lhe- 1 % e o
% 02= 10%-%diehyl

N20

100%-% diethy! ether-% He

',

20
E 0

Flammable

Min N20

wmixtures22

401
5

~N20
Csf~n 02+ N0)
H
Csj
2 ,, in

HELUMvolume-percent

2)

FioTTasE 85.-Limits of Flammability of Diethyl EtherNitrous Oxide-Helium Mixtures at 250 C and At-

20
40
60
80
HELIUM OR NITROUS OXIDE, volume-percent

100

Fzouaai 84.-imits of Flammability of Diethyl EtherHelium-Oxygen and Diethyl Ether-Nitrou's OxideOxygen Mixtures at 25' C and Atmospheric Pressure,

as great with nitrous oxide as with oxygen.ES

However, if .1 mole of nitrous oxide furnishes
one-half mole of oxygen during combustion,
then the minimum oxygen contents in the two
cases are otearly equa.
Unfortunately, the
available data are too meager to permit a more
detailed comparison,
Autclinitioper

AuFistetdo

In genere.l, ethers are readily ignited by hot

surfaces. These combustibles usually hlave a
lower ignition temperature in air and in oxygen
than do the corresponding paraffin,; and
alcohols. The available at'toigraion temiperature data are included in app-ndix A.

mospheric Pressure.

Since the ethers tend to formn peroxides under

a -variety of conditions, they inay appear to be

unstable at room temperature (238).
RS(n n_0 CH.I
The properties of several esters are listed in
table 15. The ratio of the lower limit at 25' C
to the stoichiometric concentration is about 0.55
for many of these compounds. This is tile
same ratio as in equation (21) for paraffin
hydrocarbons. The lower limit values expressed in terms of the weight of combustible
liter of air (see section about alcohols) are
in parei.these,3 under L(mng/1). These ore
larger than thle corresponding values for the
hydrocarbons and alcohols. The inert requirenients and minimum oxygen requirements for
the firs,.t member of the series, methyl formate,
tire neI4 rly the same as for mnethyl alcohol and
diniethyl' ether (figs. 76, 82, 86). This is not

71

FLAMMABILrITY CHARACTERISTICS
TABLE

15.-Properties of selected esters

Lower limit in air

(omlunstibh"

Formula

Methyl formate-...... II('OOCJI ...

Ethyl foruate. .........

Sp. gr.
(Air-1)

60.05

....74.08

2.07

C.,
Net ll,
in air
(Kcal
L2 &
(vol pct) \i0
)(vol
pet)
9,48

2. b0

5,65

n-Buty1 forniate ......... COOCI,n..... 102.13

3.53

3.12

Methyl acetoe-.........

|COO(',ii

219

5.0

L
( g
.TI.
0.53

307

2.8

.50

2650

1.7

.M

CIICOOCIh, ..

74.08

2,50

L.65

358

3.2

.57

Ethyl acetate ......... CICOOC11,..

n-Propyl acetato ...... CII3COOCsII?..

88.10
102.13

3.04
3.53

4.02
3.12

504
1650

2.2
1.6

.55
.58

n-Butyl acetate .........

('1COOC4lt,..

116.16

4.01

2.55

...........

'14

.55

n-Amyl acetate ......... CIICOOC,1j .

130,18

2.16 ---4.02 ........

1.0
2.4

.51
.60

3.12

1.8

.58

Methyl proplonate ......CHCOOCIIs..

88.10

4.50
3.04

Ethyl propionate .......

102.13

3 53

C 11COOC,21.

L- LM -32
ML-Calculated value.

2650

Upper limit inair

142

{
1

(ng\

Ref.

\I
2.4

800

t111)

(40) 16.0

2.8

630

(40)

(40)

8.2

2.6

410

(40)

(146
40)

16.0

2.8

630

(40)

(40) 11.0
(40)
8.0

2.6

510
400

(176)
(40)

(')

450

(6)

IM
57

(,,,)

U.,
(vol
pet)
23.0

{73

Re.

'8.0

3.1

1 40 5 )
7 (0)

' 7.1
13.0

3.3
'5.2

(40)

11.0

3.5

440
(')
580 (40)
510

(4())

4 1=100 C.
a Figures eompled by Explosives Res. Center, Federal Bureau of Mines.
6 P-0.5 atm.

t=90' C.

true of the othei' members for which data

compiled at the Explosives Research Center are
avaialable--.isobutyl formate and methyl acetate
(figs. 87, 88). Accordingly, it is rather difficult
to make additional generalizations for this series,

25

The autoignition temperatures of many esters

in air and oxygen at atmospheric pressure are
given in appendix A. In general, the AIT
values of the esters are lower than are those of
the corresponding paraffins.

-n1--5%air

100%-% methyl formate-% inert

20

FIGURE 86.-Limits of Flamma-

bility of Methyl Formate-Carbon

Dioxide-Air and Methyl FormateNitrogen-Air Mixtures.

F
F
mixtures

0
W

5-

10

20

30

ADDED INERT, volume-percent

40

50

FLAMMABWLITY

niiRACTXHISTIC3

or

COMBUSTIBLE GAOVI AND

VAPORA

10T

air m 100%-% isobutyl formate

aH
81
C02
Fioun. 87.--LUmite of Flimrabfl-

ity of Isobutyl Formato'-Carbon

Dioldde-Air and lonbutyl Foria 4eNltrogn-.AIr Mixtures.

4&
mixtures

C
a
0

10

air

Nitrogen-Air Mixture.

U
t
t
!

10-

30
20
ADDED INERT, volume-percent

Flammable

50

100%,-% methyl acetate-% inert

M2

mixtures

-j

40

""I

20T

Fsolua 88.-ALmlit o! FlamnmabilIty of Methyl Aoetate-Carbon

Dioxide-Air and Methyl Aoetate-

N2

Flammable

tj

10

C0

20
30
ADDED INERT, volume-percent

40

50

IP

FLAMMABILITY

20~
-n- ~

I~- --

73

CHIARACTERISTICS

-------

r~

Flammable mixtures

____

70.5 mole

MEK + 29.5 mole

%utoene

0
C')

AtmospericiPessure

Fgive i tablEe 1.Thto Teprte

of

Lower Limits

airO
E timi
the s1ici0n-ri
KEO E
atDHY
250

(C.

on,
Famity

sown
M -tat he sytues
Ccpsto
aosen
ahd THFo

is approximately 0.5.

Zabe takis, Cooper, and Furno found that the

lower limits of wethyl ethyl ketone (MEK) and
MEK-toluene mixtures vary linearly with
temperature between room temperature and
20 0 C (36.
A summary of these data is
given in figure 89; broken curves in this figure
were obtained from the modified BurgessWheeler law, equation (33), taking the lower

MnEKa

en oe vlueChitler

law, equation (46). Calculated and experimental values for the preceding systems in air
are iven in figures 91 and 92.
Te limitsoth systems acetone-carboD
dioxide-air, acetone-nitrogen-air, MEK-chlorcbromomethane (CBM) -air, MEK-carbon dioxide-air, and MEK-nitrogen-air are given in
figures 93 and 94. The data in these ftgurcs
were obtained by Jones and coworkers (2588).

TABLE I 6.-Propertim of 8e.ected aldehydes and kcet ones

Combustible

Aretaldehyde..........
Pmopionuidehyde.
.1'mraidehy~de
.....
Acetone
Niethyl ethyl ketone.
hiethyl prcpyl ketone
Nfethyl butyl ketone

Formula

Ai

.I1aCIIO. .
44.051
CS1tCHO.
.
&S.08
(CIIiCHO)s,_.132.16
(lC
I,
8.08
C 113CC . ,c72.10
C~I
M.sC
813
a(011CCVI
PA.13
CII,3COC,1it
100.16

ICool flameL: U-f0 Vol pet.

' Cool Barnes: Via-17 vol pot.
I CalculatA~ t'Clue.
*f-60 C.
I-100 C.

(Ag

- 1)

L.62
2.01
4.%8
2.01
2,49
2.97
2.'J
3 4A

inAai

(Volpet)

7.73
497
2.72
4.97
3 67
2.90
2 90
2,40

mole)

264
409
..

403
648
692
592
840

Upper limit In air

Lower limit lo air

NLA.

14

(Vol
pet)

4
40
2.9
1.3
2.6
1.9
1.6
I'6
'1. 4

LIDU
4

IL
( !E/g\)

Ref.

0.52
.69
.49
.52
.52
.55
.65
.58

82
7
78
70
62

63

63

64

U
C,,
U

(voi
pet).

'kJ

(M9) ' 36
(9)

(98)
(U3)

(40)
(1)
(40)

4.7
2.8

*14
j
Ii
10
8.2

(40)_
-

'8.0

Rof.

/f-g\

k.

1,100
420
_i

(961)
(96)

2.7
2.8

360
340

(19#3

3.3

390

(40)

2.6

(40,

BS
S VI ND VA ?O
r,G X~
L
USSTI
CO

1 I S MS
A ~ ~ cR CVT~

74 A 1

Flammable Mixt'Ures

2.0
THE
GD

1.8
70.5 mote-%

'14

35.6 mol%

HE+ 29.5 mo~e% toluen~e

~l-lV

* 6

.4me%toluenle

00
204

40

20
1.2U

T h eeci
de
aatigpOiS

60IA

va i uSfi
atiTe r r Per t e s of

und
inad.
teme rtrelowes anof endIO
those
ln
a5ueaeg~e
n

~ ~ ~
aldehy
r
vralues are low
at os hei
us.
para
'h
r-1
of

at

topetthe
veontp r e
t~~

L S AND

EO

nE mL

'kili
d
Fuis used for
t ee e t~f5 r nIaae

i
u no coonrd
eed
not
here(tble1

OP

n ,(

A m o iy

sulfu copud
of
havei
theytyl
pCflb0 4 ,I7
nd
T h eM
theoyi
give
tapo
aegniA)ti
infu
arerie
enes I ppae
7 1 , g l i , ,l o carb o n
water
A8
anedr
an
a n
r n e
lv
ltab~t
i O -.
v n fr carboan
d a r' en aon
am~%
r a uerp
tel
;5) d
td~m
diskwide
( ft 9 an
4dair
bo
diodfor in
car
n s e- 4with nl
vicarbo
ar
g*an
(lor
7)fi
m
7)
Fl
(fg.
(17
,,
chorl
roge
d] meeapanwit
chlo
with
not
it shows
anineth tcar11bon
disulfd e
j
lO%
,Eich
qguof oet
fcr.ie
flarnt
th 'a2.

uenMlitureB in Air at

of T Fo

.
TEMP~ailt

I ) ~ .' a

adusnlren

This

rzin
mNle
e
edi(N2')
I ' moSn
zse N,9
s
ixtuire
flammable
tr ia
iM i a v r .I o fe coflcen and
rformCS)S
an o h
Vht
f,
n
ti o
(
a n i ncae
ase xi at s in .
widn
o
~
N
re
19
,(1)
ben, us
ano ra a noted. in tdoaar crbo
mton
ar,1 iens
Fue s
hy
..
that
in
iniia
r
~temt fa Fl rt er axrre
ne b e raige.
ethe
trie 1m
thet rfa
inar
ifoun
wth er
n press
t a h In ce us
essentially

l rang

teperature.
of inert requr
guatj:e
s ntjflr v n ~ nd
T A1L t 1 7 . - P r OPe' " 6 oJ .etecte d

p e ot i
P

-3

0213

231

75

FLAMMABILM' Y' CIHARACTERISTICS

2.0-r-------

---

0
1.8

Experimental points
Calculated
0

9.

300C

Flammable mixtures

~1.60

CL

LU

0
FioUREI

20

08
4
MEK, mole-percent

91.-Effect of Liquid Composition on Lower Limits of Flammability of MIEK-Toluene Mixture-s in Air

at 300 and 2000 C.

76

FLAMMABILITY

CHARACTERISTICS

2.0

OF COMBUSTIBLE GASES AND VAPORS

0
-

Experimental points
Calculated

Flammable mixtures
E0
~1.60
U0

~1.4C,,

1.0
0

20

60
40
THF, mole-percent

Fioug, 92.-Effect of Liquid Composition on Lower Limits of Flammability of THF-Toluexte Mixtures in Air
at 300 and 2000 C.

77

FLAMMABILY CLARACTERISTICS

14

aair - 100%-% acetone-% inert

12

10

aE
.-

Flammable
mixtures

Fiovas 9&.-Limita of Flammability of Aoetone-Carbon Dioxide-

N2

Air

ti

and

Mixtures.

Cs,,

Aeetone-Nitrogen-Air

C02

4-

10

20

30

40

50

ADDED INERT, volume-percent

TABLE

18.-Propertiesof selected fue. andfuel blend.

limit In air

Not Aem
Combustible

Ammonia ------------.-.--

Hydrasine ...............

?eonomtyl b draem
Monmtylyn
ln..
Unspunmetrl

Ddioa...

Formula

--..-

N-.-'".NuCi.::
N E
a....4
NH*(CHs)s.

..........
D ......

AV

46.07
0
60.10

.27.09

Tetra
..........
.....
.
Pentaborane............
B ...........
17
Deosorae........Da.u
..... ...... .12.:
Aviation S .............
lP... Be U.............................

Aviation let
fuel .1P-I ........................
Aviation
etfuelJ
Aviation jet
tuel JP-4....
P-4.........................-.---..-............,......
Aydron .............

Calculated value.
't-30 0.

Ht ............

(22i)

17.08
7..

2 06

---2.0

0.0

1.:80
.0i
2%OR

...

1 4

2,18
4.2
............

/ AH
(oPa)(Vol

.,
iNCS

.8a

Pet)

21.58 ..........

17.32- .........
7.73------4
??
.....
4.07.....

88

4.7
.2

478

&67
8
308
0
7..--------...........
.1.2
298

87.3
I-u100. 0.

.8
.

4
2.

(Lu-U
-MOWG

C
0.0

134

.27

70

.82
.40

--

-a

(o
pot)19'"
2

(16,

10-

so

(18)_!----5'.
mn
.65

(
1.8

.3

j\

Ia

800

(181)

-88 .

(...

........
10.1....

.12

10
(11 8.
1..I ........ 16)
.---1........10---.12
12
............
.11 . ........
It
I
........
.....
........
(141)....38

1.4............."1
.........
4.--

IS

Upper limit In air

.
8.7

(40)

871
7

... ..
.84

.
270.

78

FLAMMABILITY

CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS

12

, air = 100%-% methyl ethyl ketone-% inert

10

E
N2
Fiovaa 94.-Limits of Flammabilit
of Methyl Ethyl Ketone
(E
K) - Chlorobromemethane
(CBM)-Air, MEK-Carbon Dioxide Dioxide-Air and MEK-Nitrooen- Mr Mixtures at 250 C and
Atmospheric Pressure.

CBM

6
Flammable
mixtures

"
-.

C02 /

-j 4XI
IT

,Cst

2q

10

TABLE 19.-Limits of flammability of ammonia

at room temperature and near atmospheric

pressure
C.o

Oxidant

Ref.

21.8
57. 1
40. 0

15
15
2. 2

28
79
72

(167,(18)
$25)
(109)

Hydrazine vapor burns in the absence of an

oxidizer, so that it has no upper limit and can
therefore be used as a monopropellant. The
deomposition flame yields hydrogen, nitrogen,
and ammonia (64, 78). However, hydrazine
vapor can be rendered nonflammable by addition of stable diluents or inhibitors. The
amount of diluent required at any temperature
and pressure appears to be governed in part by
thA ignition source strength. With a 0.25-inch
spark gap and a 15,000-volt, 60-ma-luminoustube transformer as the energy source, Furno,
Martindill, and Zabetakis (68) found that the

i-

40

50

following quantities of hydrocarbon vapor were

needed to inhibit flame propagation in a
lY-inch glass tube ' at 1250 C and atmospheric
pressure: 39.8 pct benzene; 35.0 pct toluene;
27.3 pct m-xylene; 23.8 pct cumene; 21.0 pct
n-heptane.

Air
O-e------------.
Oxygen
---------------Nitrous oxide --------

20
30
ADDED INERT, volume-percent

On this same basis, 95.3 pct air is

needed to prevent flame propa ation (188); this

corresponds to a lower limit of flammability of
4.7 pct hydrazine vapor. The flammable range
in air at atmospheric pressure is presented

raphically in figure 98, which also gives the

fammable ranges of monomethylhydrazine,
unsymmetrical dimethylhydrazine, and ammonia for comparison (218). The flammability
diagram for the system hydrazine-n-heptaneair at 125 C and atmospheric pressure is given
in figure 99. These data were also obtained
in a 0l4-inch glass tube.
A summary of the autoignition temperature
data obtained by Perlee, lmhof, and Zabetakis
(166) for hydrazine, MMH, and UDMH in air
and nitrogen dioxide (actually, the equilibrium
I Comparble results were partialy obtained ina 2-nch tube.

Fp

FLAMMABILITY

CHARACTERISTICS

507

20air - 100%-% carbon disulfide-% Inert

40 SF-22

79
1

air = 100%-% ethyl mcrcaptan-% inert

1
(CH CI 172)

..

CHcCl 172)

30

\o
Flammable
mixtures

I-

Flammable

M 0

mixtures

min 02

10-

C02
00

20
40
60
ADDED INERT, volume.percent

80

FiouRE 95.-Limits of Flammability of Carbon Disul-

fide-Carbon Dioxide-Air, Carbon Dioxide-Nitrogen-

Air Mixtures at 250 C and Atmospheric Pressure, and

Carbon Disulfide-Water Vapor-Air at 1000 C and

Atmospheric Pressure.

50
1009-% hydrogen sulfid.

-%

C02

Fioumm 97.-Limits of Flammability of Ethyl Mereaptan-F-12-Air and Ethyl Mercaptan-F-22-Air Mixtures

at Atmospheric Pressure and 270 C.

mixture NO 2 *-NO2 NO 4 ) is given in figure

100; short horizontal lines indicate th uncertainty in N0 2 * concentrations. These materials may ignite spontaneously at room

ignites in N02*-air atmospheres that contain

more than about 8 volume-percent NOa*; MMH

and hydrazine ignite in atmospheres that

contain more than about 11 and 14 volume-

40-

30-Flammable

Flmmatue

u' 20

mixtures

Zanomal*
0=

0
S10-

S
10
CARBON

20
30
DIOXIDE, volumepercent

40

FIwRE 96.--Limits of Flammability of Hydrogen Sulfide-Carbon I)ioxide-Air Mixtures at 25' C and

Atmospheric Pressure.

percent NO 2 *, respectively.

In

general, even

smaller concentrations of N0 2 * produce spontaneous ignition of these combustibles at

higher initial combustible liquid temperatures.
The effect of the hydrazine liquid temperature
on the spontaneous ignition temperature in
NO2 *-air atmospheres is illustrated in figure 101.
Similar data are given in figures 102 and 103
for MMH and UDMH; there is an apparent
in the
36' 55 , and
67' data
C. obtained with ivi1il at

Mi 02
11.6%
,

*
0_J

20

temperature with relatively small NO2 * concentrations in the air; at 250 C, liquid UDMH

1
% air

5
10
15
ADDED INERT, volume-percent

The use of various helium-oxygen atmospheres in place of air results in the spontaneous
Igniton temperature curves given in figure 104
for UDMH.
Comparison of curve B of this set
with curve A of figure 100 indicates that the
spontaneous ignition temperature of UDMH in
NO 2 *-He-O. atmospheres is the same as that
obtained in N 2 -air atmospheres.
Ignition temperature data obtained with
tTDMH
in NO 2 *-air mixtures at 15 and 45 psia
are summarized in figure 105. These indicate
that although the spontaneous ignition tem-

perature of UDMII in air is not affected ap-

80

FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS

760
1
1
600 -Ammonia
400-

100
Upper -78.9
~limit

-DH52.6
.

E
E 200 -FlammableCs,

26.3 E
mixtures

-d

Flovitz 9S.-ljznits of FlamInat 7 ofandAmmonia

MMIH,
HydrazineUD
at MH,
AtniOSPheric Presaure in Saturated
and Near-Saturated vapor.Akr

Mixtures.

CO

100:

1.

CO0.
W8
so
cr

0.

60

C51

40-

Cst

-7.9 >
w

Lower

-5.
-

-limit

20-

Hydrazine

-2.6

MMH
10L
1.3
150O -100 -50
0 50 100 150 200
TEMPERATURE, OC

Jt

I~

81

FLAMMABILITY CHARACTERISTICS
100

10

90

20
0

30

%30

4000

50

70

00

mixtures

60o

&

mFlammable

50

016

4!

0KEY

60

X
70

30

0
80

~0

KEY
Flammable

HEPTANE-VAPOR, volume-percent
F

URN 99.-oFlammable Mixture Compositions of

Approximately Atmospheric Pressure.

at 125* C and
20ydrazine-Heptane-Air

82

FLAMMABILITY CHARACTP.RISTICS OF COMBUSTIBLE GASES AN)

300

VAPORS

Boron Hydrides

This series includes diborane (B2H,), tetraborane (B4Ho), pentaborane (B '), and deca-

a UOMH
b MMH

borane (B1 oH 4).

c Hydrazine

250

However, reliable tipper and

lower limit data are available only on the first

member of this series at the present time.
These were obtained by Parker and Wclfhard

(168) who determined the limits of flammability

200

of diborane in air in a 5-cm-diameter tube at an

initial pressure of 300 mm Hg; this combustible
forms flammable mixtures in air in the range
from 0.8 to 87.5 volume-percent. A pale blue
propagated throughout the tube at, the
upper limit; luminous iltmes were not visible
above 79 volume-perccnt. Limit of flammability curves for the system diborrnie-ethane-air
are presented in rectangular coordinates in figure
107. Except for the slight dip to the ethineaxis (zero diborane) in the area in which ethane
forms flammable mixtures in air, these curves
are rather similar to those obtained with other
combustible-oxidant-inert systems. Burning
velocities in excess of 500 cm/sec were measured
in this same study for fuel-rich diborane-air
mixtures.
Berl and Renich have prepared a summary
report about boron hydrides (9). It includes
obtained by these and other authors; they
found the lower limit of pentaborane in air to
be 0.42 volume-percent.
The autoignition temperature of diborane in
air is apparently quite low. Price obtained a
value of 135' C at 16.1 mm Hg (169); that of
pentaborane is 30' C at about 8 mm Hg (9).

Region of spontaneous ignition

egogflame

S150

E
100.

50 -data
h

25* C

Dew point line of NO*

10

is

20

25

30

Gasolines, Diesel and Jet Fuels

NOI CONCENTRATION, volume-percent

FicVRu

100.-Minimum Spontaneous Ignition Tern-

peratures of Liquid Hydrazine, MMH, and UDMH

at an Initirl Temperature of 25* C in Contact With

NO,*-Air Mixtures at 740 10 mm Hg as a Function

of NO,* Concentration.

preciably by this pressure change, it is affected

in a range of NO,*-air mixtures.
The data presented in figures 100 to 105 were
obtained with liquid fuel in contact with aporized NO* ;n air. Similar data obtained with
vaporized UDMH-air in contact with NO*
are given in figure 106. This figure indicates
that LTDMH-air mixtures that contain more
than 9 volume-percent UDMH will ignite spontaneously on contact with NO*; UDMH-air
mixtures that contain more than approximately
2 volume-percent UDMH can be ignited by an
ignition source under the same conditions (166).

Fuels considered in this section are blends

that contain a wide variety of hydrocarbons
and additives. Accordingly, their flammability
characteristics arc governed by the method used

to extract a vapor sample as well as by the

history of the liquid. For example, since the

lower limit of flammability, expressed in
volume-percent, is inversely proportional to
the molecular weight of the combustible vap(,r,
equation (28), the first vapors to come from a
blend, such as gasoline, give a higher lower
limit value than the completely vaporit.sd
sample. Conversely, the heavy fractions or
residue give a smaller lower linit value. For
this reason, there is some disagreement aboutI
the limits of flammability of blends such as
gasoline and the diesel and jet fuels. These
fuels are, in general, characterized by a wide
distillation range; the ASTM distillation curves

FLAMMABILITY

83

CHARACTERISTICS~

300

200

Lj

Region of spontaneous ignition

000

10036*
770

670

I
x

15

20

NO CONCENTRATION, volume-percent
FiGuRE

101.-Miniiui

Spontaneous Ignition Temperatures of Liquid Il:3drazine at Vafious Initial Temperatures

lg as a Fuikction of N0 2 * Concentration.

in NO,*-Air Mixtures at 740 10 mmn

84

FLAMMABILITY

CHARACTERISTICS OF

COMBUSTIBLE

GASES AND

VAPORS

200 .................

,.*

C100

/ 67"

"36

Region of spontaneous ignition

0o

-1

05

10

15

25

20

NO* CONCENTRATION, volume-percent

FhG'RE 102.-

a :t trius Initil] "

Miiniml 111 Spontneous lgniitioii Tiperaturv of Liqih' \IN1\
otionof N02* 'onceittratioth.
iil N( ) -Air M[ixtizrtus at 740 10 min lig as a Iwt

tih-ir trci

85

FLAMMABILITY CHARACTERISTICS

200

SRegion

of spontaneous ignition

w
D

36* and 55*

"

10

15

20

NO* CONCENTRATiON, volume-percent

FIGURE 103.-Minimum Spontaneous

lgtition Temperatures of Liquid UDMlf at Various Initial Temperatures

in N)3*-Air Mixtures at 740:_ 10 mm lig as a Function of N0* Concentration.

86

FLAMMABILITY CHARACTERISTICS
400

OF COMBUSTIBLE

GASES

AND VAPORS

Curve
a

He/0 2
0.0/100

100/25

100/6.50
100/1.70
100/0.30
100/0.00

d
300

V
we

-200

Region of spontaneous ignition

cc

FIGURE 104.-Minimum Spontaneous Ignition Temperatures

Ratios.
of 0.05 cc of Liquid UD MNHin
Atmosphere for Various He/O 2

100

'i

--

ob
5

__

-a

line of N* 2
10

15

NO* CONCENTRATION, volume-percent

22

~ .
20

25

87

FLAMMABILrTY CHARACTERISTI( 5
300 .

250 ---T-T

-T-----T-- iF

a 15 psia
b 45 psia

200

200Region of spontaneous ignition

Region of spontaneous ;gnition

150

IJ

100

100

Lower limit of flammability

of UDMH in air
]
]
5
10
15
NO* CONCENTRATION, volume-percent

50I

FiouRx 105.-Minimum Spontaneous

20

Dew point line

Ignition Tern-

peraturep of 0.05 cc of Linuid UDNIH in NO,*-Air

Mixtures at 15 and 45 Psia as a Function of NO,*
Concentration.
of two gasolines and three jet fuels considered
here are given in figure 108. Unfortunately,
such curves give only an approximate measure
of the volatile constituents in the liquid blend.
Even relatively nonvolatile high-flashpoint, oils
may liberate flammable vapors at such a slow
rate that the closed vapor space above the
liquid may be made flammable at reduced
temperatures. Gasolines can produce flammable saturated vapor-air mixture at temperatures below -65'
C (241), although the flash
points of such fuels are considered to be about
-45' C (158). An apparent discrepancy thus
exists if flashpoint data are used to predict
the lowest temperature at which flammable
mixtures can be formed in a closed vapor space
above a blend in long-term storage.
As noted earlier, the limits of flammability of
hydrocarbon fuels are not strongly dependent
on molecular weight when the limits are expressed by weight. However, since results
measured by a volume are perhaps more widely
used than those measured by weight, typical
flammability curves are presented by volume
for the light fractions from aviation' gasoline,
grade 115/145 (fig. 109), and aviation jet fuel,

""

I
4

I
8

I
12
16
UDMH CONCENTRATION, volume-percent

20

FIGURE 106.-Minimum Spontaneous Ignition Temperatures of Vaporized UDMH-Air Mixtures in Contact With 100 pct NO; at 250 C and 740 10 mm
Hg as a Iunction of UDMH Concentration in Air.
grade JP-4 (fig. 110). Combustible vapor-aircarbon dioxide and vapor-air-nitrogen mixtures
at about 25' C and atmospheric pressure are
considered for each. Similar data are given in
figure 14 for the gasoline vapor-air-water vapor
system at 21' and 100' C; the effect of pressure
on limits of flammability of volatile constituents
of JP-4 vapor in air are discussed in connection
with figure 12.
Minimum autoignition temperatures of gasolines and jet fuels considered here are given in
compilations by Zabetakis, Kuchta, and coworkers (126, 237). These data are included
in table 20.
Setchkin (194) determined the AIT values of
four diesel fuels with cetane numbers of 41, 55,
60 and 68. These data are included in table 20.
Johnson, Crellin, and Carhart (92, 93) obtained
values that. were larger than those obtained by
Setchkin, using a smaller apparatus.

88

FLAMMAI3ILIT

CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS

100

air

S air

100 -% diban@-X ethane

100X- X psolIne- S inert

lammable

lmF

wimm~

Luminous

(cltio\\a

flame

20-

mixtures

,I

to 20

40

3
i

ADDED INERT. volume-percent

40
60
ETHANE. volume-percent

20

1W.

so

109.-Limit. of Flammability of Aviation

Fzoaui
Gasoline Grades 115/145 Vapor-Carbon Dioxide-Air
and 115/145 Vapor-Nitrogen-Air, at 27" C and Atmospherlc Pressure.

Fnouzz 107.-Limits of Flammability of DiboraneEthane-Air Mixtures at Laboratory Temperatures

and 300 mm Hg Initial Pressure.

10

460-

420

ir00%-%

JP4-

inert

I8

-/

!"

6-

380-

N2

//

/4-

340

Flammable
CL

3407

mixture

It

C02"

02

S260-

,"

l'-

220-

30

-Mixtures
,

20

40

50

TABLE

"

40
60
DISTILLED, percent

of

JP-4 Vapor-

Carbon Dioxide-Air and JP-4 Vapor-Nitrogen-Air

at 270 C and Atmospheric Pressure.

140

20

ADDED INERT,. volume-percent

Fiouaz 110.-Limits of Flammability

180-/

I00

10

80

100

FJouaz 108.-ASTM Distillation Curves for, A, Avistion Gasoline, Grade 100/130; B, Aviation Gasoline,
Grade 115/145; C, Aviation Jet Fuel, Grade JP-I;
D, Aviation Jet Fuel, Grade JP-3; and F, Aviation
Jet Fuel, Grade JP-4.

20.-Autoignition temperature ialues of

various fuels in air at 1 atmosphere

Fuel:
AlT, -c
Aviation gasoline:
440
100/130-------------------------471
115/145 -------------------------Aviation jet fuel:
228
JP-1 ---------------------------238
JP-3-------------------------JP-4---------------------------242
232
JS-6 n----------------------.-----)iesel fuel:
233
41 eetane ----------- -----------230
55 cetane-----------------------225
00 cetane-----------------226
68 cetane -------- _----------------

89

FLAMMABILITY CHARACTERISTICS

Burning velocities of the fuels considered

here are in the same range as those of the
hydrocarbons considered earlier. Values for
various fuels have been tabulated by Barnett
and Hibbard (156).

Hydroqen

80
ir= 1bo%-% hydrogen-% inert
Mn 02

o -%

Numerous
flammability
characteristics
studies have been conducted with hydrogen in
recent years. Drell and Belles have prepared
an excellent survey of these characteristics (48).
This survey includes all but the most recent
work of interest.
The low pressure limits of flame propagation
for stnichiometric hydrogen-air mixtures are

somewhat lower than those for stoichiometric

ethylene-air mixtures (197) in cylindrical tubes.
In the range from 6 to 130 mm Hg, the limit
for stoichiometric hydrogen-air mixtureS is

22
0

,
Cs5

.
20

Famab_mixtres

C02

I
0

60
40
20
ADDED INERT, volume-p.rnent

80

given by the expression:

log P=3.19-1.19 log D,
(57)
where P is the low-pressure limit inmillimeters

Fiuaz III.-Limits of Flammability of Hydrogen.

Carbon Dioxide-Air and Hydrogen-Nitrogen-Air
Mixtures at 250 C and Atmospheric Pressure.

of hydrogen
mmability
5laa an od
oen
invarious o)xidants at 25'C and atmosp~ric
pressure

curves were found to deviate from the results

obtained from the Le Chatelier law, broken
curves; additional data are given in the original
article.
The burning velocity of hydrogen in air at
25' C and one atmosphere range from a low
of a few centimeters per second to 325 cm/sec
(68). When liquefied, it, vaporizes and burns
in air at a rate that is determined by the rate
at which heat enters the liquid. Heat is
abstracted from the surroundings and, where a

of Hg, and D is the tube diameter in millimeters.

Hydrogen forms flammable mixtures at
ambient temperatures and pressures with oxygen, air, chlorine, and the oxides of nitrogen,
Limits of flammability in these oxidants at
approximately 250 C and I atmosphere are
listed in table 21.
21 -Limits ofa
TABLE
T i variouoiatfs

Oxidant

L3

(t

Ref.

.liquid

hydrogen from paraffin cast in a Dewar

Air
-----------------.
.
Oxygen
--------

4.flask;
0
75

(40)

Chlorine--------------

4. 1

89

(em, ike)

S---------------------3.

NO -------------------

0
6.8

84
66

flame exists, from the flame itself. Figure 115

gives the results obtained from vaporizing

(189)

(189)

Flammability diagrams of the syatems hydrogen-air-carbon dioxide and hydrogen-air-niitrogen obtained by Jones and Perrott (112) are
given in figure 111. Lines that establish
minimum oxygen values for each system are
also included. Note that although the minimum value occurs near the "nose" of the
hydrogen-air-nitrogen curve, the corresponding
value occurs atr
the upper limit of the hydrogenair-carbon dioxide curve.
Flammability diagrams obtained by Scott,
Van Dolah, and Zabetakis for the systems
hydrogen-nitric oxide-nitrous oxide, hydrogennitrous oxide-air, and hydrogen-nitric oxide-air
aregivenin figures 112-114 (189). Upperlimit

points wereThe
obtained
from
epe
ental
gas evolto
measurements.
solid curve
exper5imental
(theoretical) was obtained by Zabetakis and
Burgess by assuming the heat influx rate to be
conduction limited (234); the initial flash
vaporization rates are probably film- and
nucleate boiling-limited. The theoretical liquid
regression rates following spillage of liquid
hydrogen onto three soils are presented in
figure 116, the corresponding decrease in liquid
level is given in figure 117. Because of its
low temperature, the vaporized hydrogen
forms a vapor trail as it. leaves the liquid.
However, the position of this trail or visible
cloud does not necessarily coincide with that
of the flammable zones formed above the liqui,
pool. This is illustrated in figure 118, in which
the positions of the flammable zones and visible
clouds are defined in a height-elapsed time
graph. Two flammable zones are defined here.
These are also seen in the motion picture
sequence (fig. 119) of the visible clou 6 and

g0

FLAMMABILITY

CHARACTERISTICS

100

KEY
* Flammable mixture
0 Nonflammable mixture

40

OF COMBUSTIBLE

OASES AND

VAPORS

so

20

NO,

mleecen

Fiouiaz 112.-Limits of Flammability of HrNt).';2

at Approximately 280 C ane I Atmosphere,

A..AMMABILITY

100

CHARACTERISTICS

91

KEY
A

Flammable mixture
Nonflammable mixture
Coward and Jones,
Bureau of Mines

o3

Smith and Linnett,

o*

80

20

JCS (London),

1953, pp. 37-43

20

0
100

80

80

60
40
N2 0, mole-percent

20

FIGURE 113.-Limits of Flammaubility of Ilr-N20-Air at Approximately 280 C and 1 Atmosphere.

100
0

92

FLAMIMABILIT

CHARACTERISTICS

100

KEY
* Flammable mixture
* Nonflammable mixture
A Coward and Jones,
Bureau of Mines
Bull. 503

OF COMBUSTIBLE

GASES AND

VAPOR$

80

20

60

40 1

00

0
10

80

60
40
AIR, mole-percent

-100
20

FIOL'Rz 114.-Limits of Flammability Of HrNO..Air at Approximately 280 C and I Atmosphere.

FLAM"MABILITY

93

CHARACTERISTICS

Start of liquid transfer to Dewar

1----T - -T - T -

10

'

a.

(Film and nucleate boiling limited)

.-

I:

Theoretical

(conduction limited)

IAI
2

Region i
_of vilent
boiling F--1- Quiet vaporization

0 1I
-20

1
0

20

1
40

I1

1I

I 1

60
80
ELAPSED TIME, seconds

100

120

140

160

FxoUiuE 115.-Rate of Vaporization of Liquid Hydrogen From Parafin in a 2.8-Inch Dewar Flask: Initial Liquid
Depth-6.7 Inches.

0.4

.3

040

60

80

100

120

140

1'60

ELAPSED TIME, seconds

FiOURs 116.-Theoretical Liquid Regression Rates Following Spillage of Liquid Hydrogen Onto, A, an A\'trage
,oil; B, Moist Sandy Soil (8 Pet. Moisture); and C, Dry Sandy Soil,

94

FLAMMABILITY

CWARMcIERISTICS OF CO)MBUSTIBLE~ GASES AND VAPORS

4-

20

40

60

8
0
ELAPSED TIME, seconds

Fzonn 17.TheretcalDeceas inLiquid Hydrogen Level Folowing Spillage Onto, A, Dry Sandy Soil; B,
Fioitz117-Thoreica Merist San Sol (S Pet. Moisture); and C, and Average Soil.
14KEY

0 Loer-limit mixture

12 Nonflammable

10
FIGURE I I.-Extent of Flammable Mixtures and Height of
Visible Cloud Formed After
Rapid Spillage of 3 Liters of
Liquid Hydrogen on a Dry Mac-~
adam Surface in a Quiescent
Air Atznoephere at 150 C.

Nonflammable

8of visible cloud

-Height

6-

""N
4LPE

T-E sNod

FLAMMABILITY CHARACTERISTICS

95

flames that resulted following spillage of 7.8

liters of liquid hydrogen and subsequent
ignition of vapors above the spill area. The
height and width of fireballs that resulted from
ignition of vapors produced by rapid vaporization of about 3 to 90 liters o? liquid hydrogen
are given in figure 120. The data are represented fairly well by the equation
Hm.= Wym,= 7./)V feet= 17.8V!M feet, (56)
where H.. and W. are the maximum flame
height and width, respectively, V1 is the volume
of liquid hydrogen in liters, and M is the mass
of this volume in pounds.
The burning rate of a 6-inch pool of liquid
hydrogen in air is given as the regression of the
liquid level in figure 121; burning rate data for
liquid methane are included for comparison.
An extrapolated value of burning rate for large
pools of liquid hydrogen is included in figure 52.
Approximate quantity-distance relationships
can be established for the storage of liquid hy&-ogen near inhabited buildings and other storage sites f certain assumptions are made (83,
160, ,34). Additional work is required to
establish such distances for very large quantities
of liquid.
The detonation velocity and the static and
reflected pressures developed by a detonation
wave propagating through hydrogen-oxygen
mixtures are given in figure i6. The predetonation distance in horizontal pipes is reportedly
proportional to the square root of the pipe
diameter (229); this is presamably applicable
to results obtained with a mild ignition source,
since a shock front can establish a detonation

.375

2o0-

1510- W
3 .

V)
0-1

.3

'161).

at essentially zero runup distance. Numerous

investigators have examined this and related
problems in recent years (11--8, 65, 155-137,

HYDRAULIC FLUIDS AND ENGINE

OILS
Both mineral oil derivad and synthetic hydraulic fluids and engine oils are presently in
common use (148). These materials are often
used at elevated temperatures and pressures
and contain additives designed to improve qtability, viscosity, load-bearing characteristics,
etc. Such additives affect flammability characteristics of the base fluid. However, the base

.364
2

Floun ll.-Motion Picture Sequence (16 Frames per

Second) of Visible Clouds and Flames Resulting
From Rapid Spillage of 7.8 Liters of Liquid Hydrogen
on a Gravel Surface at 180 C. Ignition Source: 20
Inches Above Gravel.

96

FLAMMABILITY

CHARACTERISTICS OF COMBUSTIBLE GASE4' AND VAPOJ%3

100-r-T--r-F--F-r

60- I-

,1F-

i1I

Flame height
Flame width

ME0

20

2
FiounE

120.-Maimurn

riane

height
pitcd-c'd
by
mixtures0
vapor-air
U widtk.
Ignitioniand
formed by sudden spillage of

10

II

2.8 to 89 liters of liquid hydrogen (VI).

I I I IL

8 10

20

40

60

80 100

VI, liters

5U

.4-

00

Hydrogen

Methane

0
FG URE 121.-Burning rates of
liquid hydrogun %nd of liquid
methane at the boiling points in
6-inch-Pyrex Dear flasks.

w
0
W

1i

10

20
30
40
ELAPSED TIME, minutes

50

60

FLAMMABILiTY CHARACrERISTIL"S

fluid generally plays a predominant role iii deternining limits of flammability and ignition
tAmperaturo of a particular fluid. For exampie, many of the oil-based fluids have lover
limits of flammability that fall in the ranges
given in figure 22 for paraffin hydrocarbons.
Further, those that have minimumn autoignition
temperatures in the lower temperature ranges
considered in fiugres 43 and 71 are not affected
appreciably by oxygen concentration of the
atmotsphere and by ambient and fluid-injec'ion
pressures; those that, have minimum autoignition temperatures in the higher temperature
ranges do not follow these generblizat ions (287).
Since these fluids are designed for use at elevated temperatures and pressures, they are nor-

mally made up of high -molecular weight matetials. Accordingly, they are flammable at
ordinary temperatures and ressures as mists
and foams. Burgoyne and his coworkers (27)
found that, lubricating-oi mists were flrmmable in air but not in carbon dioxide-air mixture,: that contained about 28 ,volume-percent
carbon dioxide (fig. 1i5). At elevated temperOtnre4, the ,A!, vapors cracked Rnd produced
acetylene and hydrogen, which affected the

flarmmability of the resultant mixture; the vapors are often unstable at elevated temperatures. Chiantella, Affens. and Johnson have
determined the effect of elevated temperatures
on the stability and ignition properties of three
commercial triaryl phosphate fluids (36).
Zabetakis, Scott, and Kennedy have determined the effect of pressure on the autoignition
temperatures of commercial lubricants (248).
Figure 122 gives the minimunm autoignition
temperatures for four commercial phosphate
ester-base fluids (curves 1-4) and three
mineral oils (curves 5-7). In each case, the
minimum autoignition temperature was found
to decrease with increase in pressure over most
of the pressure range considered. A plot of the
logarithm of the initial pressure to temperature
ratio versus the reciprocal of the temperature
is given for curves 1 to 7 in figure 123. The
resultant curves are linear over P limited ternperature range.
The ratio of the final temperature attained by
air in an adiabatic compression process to the
initial temperature is given in figure 124 as a
function of both the final-to-initial pressure
ratio and initial-to-final volume ratio. If a
lubricating oil is exposed to high temperatures
during a compression process, autoignition may
occur if the residence or contact time is adequate. Such high temperatures do occur in
practice and have been kLown to cause disastrous explosions (68, 146, 149, 27, 2 1). The
curves ii ligure 125 show that in the compression
pressure range 1 to 10 atmospheres (initial
praesure=l atmosphere), a wide range of

97

ambient temperatures can lead to the autoignition oi ,t mineral oil lubricant (curve 5) if
sufficient vapo' or mist is in the system. In the
same pressure range, only elevated initial
temperatures could lead to the autoignition of a
phosphate ester (curve 4). If the initial pressure
is increased to 10 atmospheres, autoignition
cin oo-ur at, lower air-intake temperatures in
every case (248).
M

C]

OUS

The flammability characteristics of a number

of miscellaneous combustibles not considered
elsewhere, are discussed in this section. These
include carbon monoxide, n-propyl nitrate, and

the halogenated hydrocarbons. The properties

of these and a geat variety of other materials
are included in Appendix A.
The limits of flammability of the systems carbon monoxide-carbon dioxide-air and carbon
monoxide-nitrogen-air are presented in figure
126. These curves were constructed from the
flammability data obtained by Jones in a 2-inch
vertical glass tube with upward flame propaga-

tion (11); other representations may be found

in the original reference and in the compilation

prepared by Coward and Jones (40).
Materials that are oxidized or decomposed
readily may yield erratic flammability data
under certain conditions. This effect i illustrated in figure 127 which summarizes the
lower-limits data obtained by Zabetakis, Mason
and Van Dolah with n-propyl nitrate (NPN) in
air at various temperatures and pressures (248).
An increase in temperature from 750 to 1250 C
is accompanied by a decrease in the lower-limit
values; a further increase in temperature to
1500 C results in a further lowering of the lower
limit at pressures below 100 psig, but not at the
higher pressures. An increase in the temperature to 1700 C results in an apparent increase in
the lower-limit value because of the slow oxidation of NPN. A complete flammability diagram has been constructed for the NPN vapor
system in figure 128; a single lower limit curve
and two upper limit curves are given here tc
show the effect of pressure on the flammable
range of a vapor-air system.
The spontaneous ignition of NPN in air was
considered earlier at 1,000 psig (figs. 3, 4). The
explosion pressures obtained at this initial pressure in air and in a 10 volume-percent oxygen
+90-volume-percent nitrogen atmosphere at
various NPN concentrations are presented in
figure 129. A summary of the minimum spontaneous ignition and decomposition temperatures obtained with NPN in air and nitrogen
respectively are given in figure 130. The data
given in this figure exhibit a behavior that is
typical of that found with other combustibles

98

FLAMMABILITY

6.50

CHARACTIEISTICS OF COMBUSTIBLE. GASES AND) tAPORS

-T-- -

.T.. ............

-T-T
T

-TT

-1

00

C0
autignti1

0:500

IV~

80

0.

FIUR

12.Vrai4i0i0umAtintoiTmeaur
viiurcnsi a2 Miea

20
INT2450SSR,
i

416810
t

ihPesr
na40-cSaiesSellonj

t(omnrh

hsht

0
s

FLAMMABILrrY CHARACTERISTICS

650

TEMPERATURE, -C
300
450 400 350

550

.6

Phosphate
esters0

.4
-X

Regioo of
outoignition
.10
.08
0D6
FIGUIC~ 123.-togarithm of Ini-

tial Prpe~ura-AIT Ratio of

Seven Fluids in Air for Various
Reciproca~lTemperatureb. Data.
from Figure 122.

200

250

be .04I-,
E
-

.02-

.0i.008.006.004

V11

.002

I.

.40I

VI

1.8

M nera l
ol

175

100

FLAMMABILITY CHARACTERISTICS

OF COMBUSTIBLE GASES AND VAPORS

2.4

2.2V,

2.0-

v-

1.8Pf
FiouUm 124.-Variation in T,/T,
of Air With V4 /Vt and With

PIPi in an Adiabatic Cornpreaion Procen.

-i

1.6-

1.4

1.2

vi Pf

vf P,

LAs

10

FLAMM4ABILITY

Otm

500500-

Fiouaa 125.-Variation In Air

rIemperature With P,/P, in an
Adiabatic Compnression Proces3
for Five Initial Air Tepea
Tepr
tures (00, 250, 5O*, 750, and
1000 C). Regions of autoignltion for lubricants TV and Vat
P,/P, Between 1 and 10 Atmosphere and P, of Between 1 and
10 Atmospheres.

101

CHARACTERISTICS

Re(!ion of
autoignition

11A;
30

<~~0P

-/I-t

MAIT

0.

CL
2
W

20

-P-1

P,,i100

102

FLAMMABILITY

CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS

at elevated pressures; the minimum spontaneous

ignition temperature first decreases with initial increase in pressure and then increases as
the pressure is increased still further (120,

80

air- 1009-

carbon monoxide-

Inert

60

248).

I20
id

0 40-

Flammable
mixtures
_,,
'st C02/

o0

N2Stable

z
cc
5Although

20
40
60
ADDED INERT, volume-percent

80

Frounn 126.-Limits of Flammability of Carbon Monovide-Carbon Dioxide-Air and Carbon MonoxideNitrogen-Air Mixtures at Atmospheric Pressure and
2W' C.

Burning velocities were found to range from

cm/sec to 110 cm/sec in NPN-air mixtures
containing 3.0 to 7.2 volume-percent NPN.
Detonations were obtained in saturated NPN
vapor-air mixtures from 300 to 650 C and 1
atmosphere pressure; the detonation velocit
was from 1,500 to 2,000 meters per second
detonations were obtained with liquid
NPN at 900 C; the detonation velocity was
from 4,700 to 5,100 meters per second.
many of the halogenated hydrocarbons are known to be flammable (40) still
others such as methyl bromide, methylene
chloride, and trichloroethylene (TCE) have
been considered to be nonflammable or essentially nonflammable in air. As noted in connection
witb the methyl bromide data given in figure
28 Hill found methyl bromide to be flammable
. H
in air at 1 atmosphere pressure (84); the reported limits of flammability were from 10 to

Flammable mixtures
0

0 2 --

1700C (3 hr

>

/75C

0z

- 1.500C

100

200

/170C (2 hr
- -

- -

I
300

.1250C

heating time)

heating time)
-

400
500
600
PRESSURE, psig

700

800

900

1,000

Mixtures river the l'r,ssijrv Range I.-roi

0 t
FIGUaz 127.-Lower Linitq of Flammability of NPN Vapor-Air
o
1,000 Psig at 75', 125', 150 , and 170" C.

FLAMMABILrrY CHARACTERISTICS

15 volume-percent methyl bromide. At an

initial pressure of 100 psig, the flammable range
was found to extend from 6 to 25 volume-percent. Similarly, methylene chloride and trichloroethane were found to be flammable in air
at ambient temperatures although the flammable ranges were not determined. In general,
much higher source energies are required with
these combustibles than are required to ignite

100
90

--

so Impossible

103

vapor-air

methane-air mixtures.

mixtures at T &I25 "C

70

An approximate flammability diagram was

prepared by Scott for trich oroethylene-air
mixtures (190); a modification is reproduced in
.figure 131. The lower limit data were obtained

60
60

in a vertical 7-inch-diameter flammabil~ty tube

0

and the upper limit data in an 8-inch-diameter

glass sphere with upward propagation of flame.
lammable mixtures of TCE and air were also
obtained between 10.5 and 41 volume-percent
TCE at, I atmosphere and 1000 C in an 8-inchdiameter glass sphere. Under the same conditions, flammable mixtures of TCE and
oxygen were obtained between 7.5 and 90
volume-percent TCE. However, additional
work must be conducted with this and the
other halogenated hydrocarbons to determine

50-

a40
>
Z
z
30
20

the effect of vessel size, ignition source strength,

Saturated vapor-oir

mixtures T 1250C

1o
T-50o6C
.. Flammable

" ,
200

400

,(40,
600
800

1,000

PRESSURE, psig
128.-Flammable NPN Vapor-Air Mixtures
Formed Over
the l'ressure Range From 0 to 1,000
Psig at 50 and 1250 C.

1"1OURE

temperature and pressure on their flammability

characteristics.
Other useful flammability data may be found
for various miscellaneous combustibles in many
of the publications listed in the bibliography
154, 200, 208-214, 118). These include
data on the gases produced when metals react
with water (56) and sulfur reacts with various
hydrocarbons (62). Still other references consider the hazards associated with the production
of unstable peroxides (142, 157, 187, 238) ,and
other reactive materials (66, 74, 80, 139).

,.S

104

FLAMMABILITY CHARACTERISTICS

OF COMBUSTIBLE GASES AND VAPORS

5,000-In

ct 4,000-

o3,000a-

z 2,0000

Q. 1,000-0

Ai

~0-10%

0.3

0.6

0.9

NPN VAPOR,

1.2

02 + 90% N2

1.5

1.8

2.1

volume-percent

FIOURZ 129.-Variation of Explosion Pressure Following Spontaneous Ignition With NPN Concentration, Initial
Pressure 1,000 Psig.
24 0C

_ T

11T

Regions of spontaneous ignition and

spontaneous decomposition

220-

Dcoposition

400

800

in N2

1,200
1,600
2,000 2,400
INITIAL PRESSURE, psig

2,800

3,200

3,600

4,000

FIGURE 130.-Minimum Spontaneous Ignition and Decomposition Temporatures of n-Propyl Nitrate in Air as a

Function ofPressure, Type 347)Stainless Steel Test Chamber,

105

FLAMMABILITY CHARACTERISTICS
TEMPERATURE. "C

1,o000

10

20,

30
r

40,

50
,

70

60
I

80

90T 100
-F..

800

.
-- 1O

-90

600

L80

- 60/
400

5
30

300 -

Upper limit

4
-440

"

Impossible mixtures
200

Flammable mixtures

i,

i0ower limit

__-e,/,r

420

60u

40-10
Nonflammable mixtures

30-

10

I
0

50

0 >

100
TEMPERATURE, "F

I,
150

FIouRE 131.-Flammability of Trichloroethylene-Air Mixtures.

200

0
250

ACKNOWLEDGMENTS
Many of the unpublished data reported here
were obtained by the predecessor of the author,
the late G. W. Jones, former chief of the gas
explosions branch. Other data were obtained
by the author and his coworkers, particularly
Messrs. George S. Scott, Joseph M. Kuchta,
Aldo L. Furno and Henry E. Perlee. In
addition, the author is indebted to Drs. David
106

Burgess 6 and Robert W. Van Dolah for many

fruitful discussions of the material contained in
the sections on Definitions and Theory, Deflagration and Detonation Processes, and Preventive Measures.
IPresently

with Reaction Motors Division, Thiokol Chemical corpo-

ration, Denville, New Jersey.

BIBLIOGRAPHY
1. Affens, W. A, J. F. Johnson, and H1.WV.Carhart.
Effect of hernical Structure on Spontanleous
Ignition of Hydrocarbons. J.ChRn., Eng.
Data, v. 6, 1961, pp. 613-619.
2. .
Ignition Studies, Part V, Study of
the Processes Occurring D)uring the Spontaneous
Ignition of the Hexane Isomers. N111 Rept,
5437, January 1960, 15 pp.
3. Agnew, J. TI., and L. 13. Graiff. 'file Pressure
D~ependence of Laminair Burrning Velocity bly
the Spherical lotrib Method. Comnbustion an d
Flame, v. 5, 1961, pp, 2M~J-219.
4. Alexander 1) 8
Explosions in Butadiene Syf.tents.
nd. and Eng. Chemn., v. 51, 1959, pp.
733- 7318.
5. Anson, 1). Influence of the Quality of Atoinization onl the Stability of Comnbustion of Liquid
Fuel Sprays. Fuel, v. .32, 1953,_p p. 39-51.
6. Ashmnan, L. E., and A. l3tichler. The Ignition of
Gases by Electrically Hfeated Wires. Combustion and Flame, v. 5, 1961, pp. 113-121.
7. Bartkowiak, Alphonse, Sotirios Lambiris, and
Michael G. Zahetakis. Flame Propagation
Through Kerosine Foamns. Combustion and
Flamei, v, 3, 1959, pp. 347-353.
8. Bartkowiak, Alphonse, and Michael G. Zabe-takis.
Flammability Limits of Methane anid Ethrane in)
Chlorine at Ambient and Elevated Temperatures and Pressure.. Bu~lines Rept. of Inv.
5610, 1960, 6 PP.
9. Bert, W. G., and W. lienich. The Combustion
of Boron Hydrides. CNI-942, Johns Hopkins
Unliv., Silver Spring, Md., 1958, 53 pp.
10. Block, Benjamin. Emergency Venting for Tanks
and Reactors. Chein. Eiug., January 1962,
pp. 111- 118.
11. Ilollinger, Lorenr E., and Rudolph Edse. Therrmodynramric Calcuilatioris of Hydmrogew-Oxygen
I )(tuuation Parimtvrs for 'Various Initial
Pressirris. ARS J., v. :31, 1961, pp. 251-256.
12. Bollinger, Lorrr, E., Mficliael G. Fong, and
Measurrvrnents
lise. 'xpvririrntaI
If idr'llul
and lhr114orrtiei Analysis of D~etonartion Inuihctioni
ARS J., 1961, lpp. 5S.-594.
lDistatices.
,oellE.,JaiivsA.Laulin,
13.Bolingr,
ad
rog
loitriolandIdliction irrtlei It
Iricti,., irrl
)it~rrce
IirlictoriI
inIlvrrr~rrDautai,
Nitroris Oxidi Mixtres. AitS J., v.:32, I 962,
PPI.1%A1,2
14. Blritish Ctnrricrl Enigirneering.
Vse of l1'rt.inr
I ises ait Iliglri Terhiiroires. D ee,'inberr 1957,
Ii. 677
I.5. Blrokaw, Vioiiard S.,
ranl .Iosih 1-... aick~rr.
1:ffiret of I ,rr
rt.,
Iressiur, arid Courmpostjdonir oni Ignitrionr Dc)lnivs for l'irltiri 110 inws.
501~' ip
u
lilt'l
tCrillhi:tiourll, tiiiioldl
Pubil. C orp. Now Nirk, 195~5, lpp .563 569,
16i. Brorwrre, IlowarrI C., lI:rr,,ld Jliknianr,
anil Lo\ell
C. Weger.
Ki:rriend,, for I ligi I'ressilrri Heseaciri.h I arnd Erg. Chclirrr, v, 53, N61il,
pp.) 52A-58A.
17. Browning, J. A., aind W. G. Errill. Fffcet of Fuivl
lDrolvts onl Flaril Staluilit.N, Flaiir, VelurcitY,
and IruflarurnabilitY L~itmits . 5thr Symrp. (Inernat.) onl Combustion, Rteinhloldl Putr.
Corp.,
New York, 1955, lip. 159-163.

18. Browning, J.A., T. L. Tyler, and W. G. Krall.

Effect of Particle Size on Combustion of Uniform Suspensions. 'Id. and Eng. Cher'., v. 49,
1957, pp. 142-148.
19. Buckley, William L., and Howard WV. liusa.
Combustion Properties of Ammonia. Chern.
Eng. Prog., v. 58, 1962, pp. 81-84.
20. Burgess 1)., A. Strasser, and J. Grunter.
lDiffusive turniing* of l.!Xiuid Fuels in Open Trays.
Fire Res. Abs. and Rev., v. 3, 1961, pp. 177-102,
21. Burgess, D~avid, and Michael (s. Zabetgkis. Fire
and Explosion Hazards Associated WAith Liqu,!!fled Natural Gas. BuMines Rept. of Inv. 0099,
190,2, 34p.
22. Burgoye,JT.H.
Mist and Spray Explosions.
Chem11i.Eng. Frog., v. 53, 1957, pp. 121-M124- M.
23.
.
Principles of Explosion Prevention.
Chem. anid Process Eng., April 1961, p p. 1-4.
24. Blurgoyne, J. If., and L. Cohen. The Effect of
Drop Size on Flame Propagation in Liquid
Aerosols. Roy. Soc. (London), Proc. v. 225,
1954, pp. 37a-392.
25. Burgoyne, J. If., andl 11. Hirsch. Trhe Combustion
of Methane at High Temperatures.
Roy. Soc.
(London), Proc. v. 227, 1954, pp. 73-93.
26. Burgoyne, J. H., anid R. F, Neale. Some New
Measurements of Inflammabilit) Ranges in Air.
Fuel, v. 32, 1953, pp. 5-16.
27. Burgoyne, J. H., and J. F. Richardsonr. The
Inflammability of Oil Mists. Fuel, v. 28, 1949,
pp. 2 -6.
28. Burgoyne, J. H., and A. J. Steel. Flammability
of Mlethane-Air Mixtures in Water-Base Foams.
Fire lRes. Abs. and Rev., v. 4, Nos. I and 2,
1962, pp. 67-75.
29. Burgoyne, J. if., aind G. Williams-Leir. The Influence of Incombustible Vapours onl tire Limits
of Inflammnab~ility of Gases and Vapours in Air.
Roy. Soc. (London) Proc., \-. 193, 1948, pp.
525-539.
30. B~urgoynie, J. 11I and M. J. (3. Wilson. The Relief
of Penitane %apour-Air Explosions in Vessels.
l'roc. Syrup , orr ('hreur. P rocess llazards, lInt.
:1.ButIler, JIudson (U., arnd Willian '. W Ibt
ppI r
)Ixposvr( Limrits of ( urriie. (Pier
v. 2, 19.57, lpp. 42-461.
32, (ussutt, Lrorn If. Lxp,rirriral Irivesligatirri of
Detonation ill Irieoriiried ( ascous llvrrrgri(hygiri-Nitrogeri Mixtures.
Alt' J., 1961, pp.
11 22-Il128.
313. ( asnitt, L. If., F. E. M addocks, ririrl W. A.
Siruv-er. A '-rudlv of ltheIHazirdus in tir, Storagv
andi'Ilarrilirig (if liquid llYulrogeru. Adelvc
iii (r .N.geic Eng., vd, hY K. I). Tilirrvirus.
l'lerrijrrr Press, Inc., New York, v. 5, 196t0,p.
5.5 61.
341. ('lirnilicrl aii 1Eriginvriirg Nr,%\s. Explosie IDccorripositiori of l'ropylzi-. V, 30i, 1952, p.1 239.
35. Cheimrical Frigirruriug. Plle Relievers~ crirt
plosivye I opoel.. -Jan. 22,11962, 1)1) 7r 72.
36. (riaritria, A. J., NNV.
A. Al~ens, anl T...
uruoi
'Il
Effi-ct of High Tlripratures onl th Slithirlity sridl Ignition l'ropertics of I onircial
Triaryl Ph'losphrate FlIuids..N IL It ipt. 58319,
1962, 15 pp.
107

108

FLAMMABILITY

CHARACTERISTICS

37, Coleman, F. H1. Effects 4) Fluorinated Hlydrocarbons oii the Inflammability Limits of Cornhustible Vapours. Fuel, v. 31, 1953, pp. 445447.
38. Conison, Joseph. How to D~esign a Pressure
Relief System. Chem. Eng., 1960), pp. 109--i14.
39. Copeland, N. A., and M. A. Y'ouker. German
Techniques for Handling Acetylenq- in Chemical
FT kT Finial Rept. No. 720, JanuOperations
ary 1946 130 pp.
40. Coward, It. F., nnd G. W. Jones. Limits of
Flammahility of Cases and Vapors. BuMines
Bull. 503, 1952 155 pp
nes, C. G. Dunkle, and
V.
41. Coward, H. F,
B. E. Hess. Tfhe Explosibility of Mebhane and
Natural Gas. Carnegie Inst. of Technol., Min.
and Met. Inv., Coop. Bull. 30, 1926, 40 pp.
42. Cubbage, P. A., and W. A. Simmonds. An investigation of Explosion Reliefs for Industrial
Drying Ovens. Gas Council, Rtes. Comniunication GC23 (London), 1955, 46 pp.
Explosion RenIvsiainof
~
43.
licfs for Industrial Drying Ovens. Gas Council,
Res. Communication GC43 (London), 1957, 41
PP.
George B. Huber, and
44. Davenport, Donald B
evataininent, of Fragments
Norman R. Zabel.
From Runaway Nulear Reactors. Progress in
Nuclear Energy, v, 4, Pergarnon Press, New
York, 1961, pp. 484-503.
45. DavisD S. Emerg3ncy Vent Size for Tanks
Cnainn&s Flarmable Liquids. British Chem.
Eng. Nomogram No. 62, v. 6, 1961, p. 644.
46. Dias, E., H. Karam, and C. Jones. Practical Way
to Size Safety Disks. Chem. Eng., 1961, pp.
187-190.
47. Dixon-Lewis G. and G. L. Thles. Limits of
Flammabijity." 7th Symip. (Internat.) on Cornbustion, Butterworths Scientific Pub. (London),
1959 pp. 475-483.
48. Drell, Isadore L., and Frank E. Belles. Survey
of Hydrogen Combustion Properties. Nat.
Advisory Conmmittee for Aeronau'*Ics Rept.
1383, 1958, 34 p?.
., and Dorothy D. Graab.
49. Dugger, Gordon
alme Velocities of Propane- and EthyleneOxygen-Nitrogen Mixtures.
Nat. Advisory
Committee for Aeronautics RM E52J24, January 153, 2 pp.Suppression
and Sheldon Heimel. Flame
50. DugrGrnL.
t c~sofMehane-Air, Propane-Air, and
E~tylne-irMitures at Low Initial Ternm eratures. Nat. Advisory Committee for Ae'ro
nauties TN 2624, February 1952, 25 pp.
51. Dugger, Gordon L., Robert C. Wcast, and Sheldon
HeimeI. Effect of Preflame Reaction on Flame
Velocity of Propane-Air Mixtures. 5th Sym p.
(Internat.) on Combustion, Reinhold Pu.
Corp., New York, 1955, p. 589-595.
52. 1)'iz.n, Robert G., and lierna- T. Wolfson.
Single C ',neralized Chart of D~etonation Parameters; for Gaseous Mixtures. J. Chetn. and
Eng. Data, v. 4, 1959, pp. 124-127.
53. Dvrk Karel, and Arnost Reiser. Influence of
Water Vapor on the Flame Extinction of
Methanol in Air. Chem. Listy, v. 49, 1955,
pp. 467-472.
54. Edwards, D0.H, G T Williams, and J. 1). Breeze.
Pressure and {~elocity Measurements on D~etonation Waves in flydrogen-Oxygen Mixtures. J.
Fluid Mech., November 1959, pp. 497-517.,
55. Egerton, Sir Alfred C. Limits of Inflammability,
4th Symp. (Internat.) on Combustion, Williams
& Wilkins kCo., Baltimore, Md., 1953, pp. 4 13.
50. Epstein, Leo F'. Correlation and Prediction of
Explosive Metal-Water Reaction Temperatures.

6.

OF COMBUSTIBLE

57.
59.
59.
60.

61.

62.

63.
64.

65.

66.
67.

68.
69.
70.
71.

72.
73.

74.
75.

76.
77,

78.

GASES

AND 'VAPORS

Nuclear Sci. and Eng., v. 10, July 1961, pp.

247--253.
Evons, Marjorie W and C. MI. Ablow. Theories
(Chem. Rev., v. 129, 1961,
of D~etonation.
pp. 129-178.
1).
F. White. Ignition of
Faeth, G. M., and
Hydraulic I luids by Rapid Compr~ession, Ami.
Soc. Naval Eng. J., v. 73, 1961, p~p.467-475.
Fitzgerald,' F. D)ecomposition of Methylacetylene.
Nature 1960) p. 387.
Frank, dharles E., and Angus U. Blackhiam.
Investigation of Hydrocarbon Ignition. Nat.
Advisory Committee for Aeronautics TN 2549,
1952, 33 p p
Fra'ser, R.P. Detonation Velocities in Liquid
I uel Vapours With Air or Oxygen at 100" C and
rinterrnat.)
Atmnosphieric Pressure. 7th Symp.
Pub.
Sci.
Butterworths
or) Combustion,
(London), 1958, pp. 783-788.
Furno, Aldo L., George H1.Martindill, and Michael
G. Zahetakis. Gas Explosion Hazards Associated With the Bulk Storage of Molten Sulfur.
Bu Mines Rt.it of Inv. 6185, 1903, 11 p p.
.Lmits of Flammability of Hydrazine-Hydrocarhon Vapor Mixtures. J. Chem.
Eng. D~ata, July 1962 pp. 375-376.
CGaydon, A. G., andH.0 Wolfhard. Flames,
Their Structure, Radiation and Temperature.
Chapman & Hall, Ltd. (London), 2d ed.. 1960,
383 Topp.
Sui
. hrhll
eoa
DenGealeroyLadtutW.Crcil
tion Characteristics of Hydrogen-Oxygen Mixtures at High Initial Pressures. AICh1E, v. 6,
September 1960, pp. 501-505.
Gerstein, M. A S-tudy of Alkylsilane Flamnes.
7th Symp. (Internat.) on Combustion. Butterworths Sci. Pub. (London), 1959, pp. 903-905.
Gerstein, Melvin, Edward R. Carlson, and Francis
U. Hill. Natural Gas-Air Explosions st Reduced Pressure. Ind, and Eng. Chem., v. 46,
1954, p p. 2558-2562.
Glibbs, G. J., and H. F.Calcote. Efffk~t of Molecular Structure on Burning Velocity. ,J. Chem.
Eng. Data, v. 5, 1959, pp. 226-237.
Glasstone, Samuel. Thermodynamics f'or Chemists. 1). Van Nostrand Co., Inc., New York,
1946, 522 p!).
(ileiidinning, W4. G., and A. M. MacLennan.
of Fuel-Air Explosiond. Nat. Fire
Protect. Assoc. Quart.. v. 45, July 1951, p. 61.
Gliwit~ky, W. Prevention of Acetylene-Air Explosions by Addition of Carbon Dioxide arid
Nitrogen. Autogene Metalbearheit, v. 33,
1940, pp. 2-5.
Industrial Explosion Protection.
Grabowski G -J
J. Am. 6i1 ChePm. Soc., v. 36, 1959, pp. 57-59.
Gray, P., anid J. C. Lee. Recent Studies of the
Oxidation and Decomposition Flames of Hydrazine. 7th Symp. (Internat.) on Combustion,
Butterworths Sci. Pub. (London), 1959, p. 61.
0 reenlee, Konneth. Butadiene-Crotonaldehyde
Explosion. C'hem. and Eng. News, v. 26, 19,
p. 1985.
Guest, P'. G., V. W. Sikora, and Bernard Lewis.
Static Electricity in Ilospital Operating Suites;
D)irect and Related Hazards and Pertinent
Remedif-s. BuMines Rept. of Inv. 4833, 1952,
64 pp.
Ilaher, F., andl i1. Wolff. Mist Explosions.
Zeit, angew. Chem., v, 36, 1923, p. 373.
Hall, A. It., and It. A. M. Straker. The Methylapetylene (Propyne) D~ecompositionl Flame at
l'ressures of I 0, 20 and 41) Atmospheres.
Rocket Pr~opulsion Establishment (Weatcott),
TN 192, 1960, p. 11.
Haara, N. E., M, G. Zabetakis, Rt. W, Van Dolah,

i.

BIBLIOGRAPHY

79.

80.
81.

82.

83.
84.
85.

86.
87.

88.

89.
90.

9.

92.

93.

94.

9A.

and G. H. Damon. Potential Ignition Hazards

Associated With Compressed-Air Blasting Using
a Compressor Underground. BuMines Rept.
of Inv. 5223, 1956, 33 pp.
Harris, D. N., Glenn Karel, and A. L. Ludwig.
Electrostatic Discharges in Aircraft Fuel Systems. 41st Ann. API Meeting Preprint, 1961,
10 p.
Heck, W. B., Jr., and R. L. Johnson. Aluminum
Alkyls. Ind. and Eng. Chem., v. 54, December
1962, pp. 35-38.
Heimel, Sheldon, and Robert C. Weast. Effect
of Initial Mixture Temperature on the Burning
Velocity of Benzene-Air, n-Heptane-Air, and
Isooctane-Air Mixtures. 6th Symp. (Internat.)
on Combustion, Reinhold Publishing Corp.,
New York 1957, pp. 296-302.
Herzog, R. K., E. & Ballard, and H. A. Hartung.
Evaluating Electrostatic Hazard During the
Loading of Tank Trucks. 41st Ann. API
Meeting Preprint, 1961, 7 pp.
Hildebrand, Joel H., and Robert L Scott. The
Solubility of Nonelectrolytes. Reinhold Pub.
Corp., New York, 3d ed 1950 p. 243.
Hill Howard W. Methyl Bromie-Air Explosion.
Chem. Eng. Prog., v. 58, August 1962, pp.
46-49.
Holdsworth, M. P., J. L. vander Minne, and S. J.
Vellenga. Electrostatic Charging During the
White Oil Loading of Tankers. 41st Ann. API
Meeting Preprint, 1961, 30 pp.
Holtz, John C., L. B. Berger, M. A. Elliott, and
H. H. Schrenk. Diesel Engines Underground.
BuMines Rept. of Inv. 3508, 1940, 48 pp.
Hsieh, M. S., and D. T. A. Townsend. An Examination of the Mechanism by Which "Cool"
Flames May Give Rise to "Normal" Flames.
Part I. The Inflamrpable Ranges of Ether-Air
Mixtures in Closed I Vessels. J. Chem. Soc.
(London), 1939, pp. 337-340.
Whc
. An Examiriation of the Mechanism by
Which "Cool" Flames May Give Rise to "Normal" Flames Part II.
The Inflammable
Ranges of Higher Paraffin Hydrocarbons in
Air: The Establishment of "Cool" Flame
Ranges at Ordinary Temperatures and High
Pressures. J. Chem. Soc. (London), 1939, pp.
341-345.
International Acetylene Association. Acetylene.
Transmission for Chemical Synthesis. Internat.
Acetylena Assoc., New York (no date), 40 pp.
Jackson, J. L., and R. S. Brokaw. Variation of
Spontaneous Ignition Delays With Temperature
and Composition for Propane-Oxygen-Nitrogen
Mixturee at Atmospheric Pressure. Nat. Advisory Committee for Aeronautics Res. Memo.
E541319, 1954 29pp.
Jacobs, R. B., W. L. Bulkley, J. C. Rhodes, and
T. L. Speer. Destruct'on of a Large Refining
Unit by Gaseous Detonation. Chem. Eng.
Prog., v. 53, December 1957, pp. 565-573.
Johnson J. Enoch, John W. Crellin, and Homer
W.
arhart. A Study of the Autoignition
Properties of Certain Diesel Fuels. Naval Res.
Laboratory Rept. 3859, 1951, 29 pp.
.
Ignition Studies. Part I1--The
Spontaneous Ignition Properties of Some Diesel
Fuels and Pure Hydrocarbons. NRL Rept.
4202, 1953, 14 pp.
Jones, G. W. Fire and Explosion Hazards of
Combustible Gases and Vapors. Ind. Hygiene
and Toxicology, ed. by !'rank A. Patty. Intersci. Pub., Inc., New York, v. 1, ch. 13, 2d rev.
ed., 1958, pp. 511-548.
-. Inflammation Limits and Their
1'ractical Application in 11azardous Industrial

96.
97.
98.
99.

100.
101.

102.
103.

104.

105.

106.
107.
108.
109.
110.

I 1.

112.

113.

114.
115.

116.
117.

109

Operations. Chem. Rev., v. 22, February 1938,

pp. 1-26.
. The Inflammability of Refrigerants.
Ind. Eng. Chem., v. 20, 1928, pp. 367-370.
Jones, G. W., and B. B. Beattie. Explosive Propertice of Divinyl Ether. Ind. and Eng. Chem.,
v. 26, 1934, pp. 557-560.
Jones, G. W., E. S. Harris, and W. E. Miller.
Explosive I roperties of Acetone-Air Mixtures.
BuMines Tech. Paper 544, 1933, 26 pp.
Jones, G. W., and R. E. Kennedy. Effect of
Pressure on Ignition Temperature of Acetylene
and Acetylene-Air Mixtures. BuMines Rept.
of Inv. 3809, 1945, 7 pp.
. Extinction of Ethylene Flames by
Carbon Dioxide and Nitrogen. Anesthesia and
Analgesia, v. 9, 1930, pp. 6-10.
. Extinction of Propylene Flames by
Diluting With Nitrogen and Carbon Dioxide
and Some Observations on the Explosive Properties of Propylene. BuMines Rept. of Inv.
3395, 1938, 14 pp.
.
Limits of Inflammability of Butadiene in Air. BuMines Rept. of Inv. 3565,
1941, 4 pp.
. Prevention of Butadiene-Air Explosions by Addition of Nitrogen and Carbon
Dioxide. BuMines Rept. of Inv. 3691, 1943,
11 pp
Jones, 6. W., R. E. Kennedy, and W. E. Miller.
Limits of Inflammability and Ignition Temperature of Ethyl Mercaptan in Air. BuMines
Rept. of Inv' 3648 1942, 6 pp.
Jones, G. W., R. h. Kennedy, and I. Spolan.
Effect of High Pressures on the Flammability of
Natural Gas-Air-Nitrogen Mixtures. BuMines
Rept. of Inv. 4557, 1949, 16 pp.
Jones, G. W. it E Kennedy, and G. J. Thomas.
Explosion Hazards of Combustible Anesthetics.
BuMines Tech Paper 653, 1943, 47 pp.
.
Explosive Properties of Cyclopropane. BuMinesRept. of Inv. 3511, 1940, 17 pp.
. Inflammability of Ether-OxygenHelium Mixtures. BuMines Rept. of Inv.
3589 1941, 15
Jones, E., and J. C. Kerr. Inflammability Limits
of Ammonia, Nitrous Oxide, and Air. J. Soc.
Chem. Ind., .v. 68, 1949, pp. 31-34.
'ones, G. W., and W. IE. MiUer. Ignition Temperatures of Acetylene-Air and Acetylene-Oxygen
Mixtures. BuMines Itept. of Inv. 3567, 1951,
5 pp.
Jon-s, G. W., W. E. Miller, and H. Seaman.
Explosive Pro erties of Methyl-Formate-Air
Mixtures. Ind. and Eng. Chem., v. 25, 1933,
pp. 694-696.
Jones, G. W., and G. St. J. Perrott. Oxygen
Required for the Propagation of Hydrogen,
Carbon Monoxide, and Methane Flames. Ind.
and Eng. Chem., v. 19 1927, pp. 985-989.
Jnes, G. W., and F. k. Scott. Extinction of
Propane and Butane Flames by Dichlorodifluoromethane. BuMines Rept. of Inv. 3908,
1946, 8 pp.
Inflammability of Dirnethyl EtherMixtures.
Dichlorodifluoromethane-Air
Bu.Mines Rept. of Inrv. 412.5, 1947, 4 pp.
Jones, G. W., W. P. Yant, W. E. Miller, and R. E.
Kennedy. Limits of Inflammability of )iethyl
Ether and Ethylene in Air and Oxygen.
BuAlines Rlept. of Inv. 3278, 1935, 5 pp.
.
The Ignition Temperatures of
Dielhyl Ether and Ethylene in Air and Oxygen.
BuMines Itept. of Inv. 3284, 1935, 6 pp.
Jones, (,. W., M. G. Zahttakis, and G. S. Scott.
Elimination of Ethyl Mercaptan Vapor-Air

110

FLANLMABILITY

CHARACTERISTICS

OF COMBUSTIBLE

Explosions
in Stench
Warning Systems.
Bu.Mines Rept. of Inv. 5090 1954 8 p.
118. Jost, Wilhelm. Explosion and Comliustio'n Proceases in Chases. McGraw-Hill Book Co., New
York, 1948, 621 p p.
119, Kharasch, M S. Heats of Comhustion of Organic
C'ompounds, NBS J. Res., v. 2, 1929, pp.
359.-430.
12. ennedy, It. E., G. S. Scott and M. (7l. Zahetakis.
1 . 1"hiirntility' Liints of hydrocarhons at Hi1gh
'l'l'rlturt
s and Pressures. Chern. Eog.
l'rog., v, 53, l05?74 pp. 125 126.
121, K,'nnedy, II.
ipolan,
S.
W. K. Mork, oind C,. S.
Seottr. Eiect 'of F] igh Pressures on the~ Ex po0sittility of Mixt ures of Ettne, Air, aind Carl toni
D~ioxide, and Ethane, Air, atid
N it rogeni.
Ito Mint's Retpt of Inv'. 4751l, 11;50, 11 pp.
122. Kennedy, 1t, IC, . spolan, finti G. S. Scott.
E'xpIlosihiiv, of M ix tnrt's of l1ropa nv, Air, andt
Carhon I)ioxide anti of Propaine, Air, ando
N it rogenr
at Elevateld
P'ressures. ]it Mint's
lIept. of I if%.-18 12, 1951, 9t pp.
123. Klinkenherg, A., and J . L. vanit'r M mone. Eleetrostatics in ttie lpetroleumn Indoust iv. Elsevier
Pulising Co,, New York, 19)58, 191 p.142.
12., Kobv, Kenneth A., and Ernest (.1. Long. Thvrniochemistry for the' Petrochemical Intdustry.
P'art %11. Acetylenes and I iolefins. Pe-trol.
Refiner, v. 28, 1949, p. 13:3.
125. Kogarko, S. M. D~etonation of M(taeArhold
Mixtures and the D~etonation Limits of Hlydrocarhori-Air Mixtures inl a Larg('-Iiameter Pip~e.
Soviet physics Tech. Phys.. v. 3, 195S, pp.
1904-1916. (1Transl. 'of J. Tech. Phys., USSRi,
v. 28, pp. 2072-2078.)
126. Kuph ta, Joseph M., Alphonse Bartkowiak, Irving
SPOlanI, and IXIichael G. Zabetakis. Flammiability ('laraicterist ics of High-Temiperature
Ilvdrocartor FuIs. Wright Air Devtelopmeit.
D)iv ision Techt. 11ept . 61- -89, 1961, 29 pp.
127. Kudit I, Joseph XM., Sot irios 1,811) ins, andi
Aicift'tael
GA, '/,atet uk is.
Flat muaIfb iiit'
afind
Aito ign itiott of Hyd(Irocarb on Fuels Unde(1r
Stat it asti
i.Nrtarnic ('oiidttioris.
Itt1iliut's
Rept). (if lrt)%. 5992, 11062, 21 pp.
128. Kuio, TI. I,, iand V. 1. Serdlir kov, Imits and
leiinwittuirts tof I ;\llo-ionr
of IlydrogiriChtloriteo.
\IiNtiir(s Ii llvttrog, nI ( Iihtidt-.
1.121

1-130,

it

(.t

od
A a I

r'l

III

luit

Livit

tlow, Ni-tv
pp
\1":;ti

k. 1,-

lv

lo

, to.1i (P
iur

It.-

12,1 lirir

Detonation Wavcs. J. Chem. Eng. Data, v. 4,

1959d,p p. 133-135.
137. Luker, James A., Paul L. McGill, and Leonard B.
Adler. Knallgas and Knaligas-Steam Mixtures at HIPl Initial Temperature and Pressure.
J. Chem. Eng. Data, v. 4, 1951), pp. 136-142.
138. Mantn J., and B. B. Milliken. Study of Pressue
ependence of Burning Velocity by the
Spherical Vessel Method. Gas DynamicsSymp.
on Aerotlierroochein. Proc., 1955, pp. 151-17.
139. Mlarsel,J.., and L. D~ramner, Spontaneous Ignition
Properties of Metal Alkyls. 7th Sympt. (Internat.) on Combustion, lAutterwort hs Sci. Pub.
(London), 1959, p. 906.
1410. Mlartindill, G. If., F. W. Lang, an( 1M. G.
Zahetakis
Flammability Characteristics oft lie
Vapor System lfidrogen
Peroxide- XyleneFormic Acid-Water.' J. Chemn. Eng. Data, v.
5, I 960, pp. 355-358,
141. Miatsot,, A. F., and Itl. IE. Dufotir. Limits of
Flammtabilit y of Methb v I Et hyl Ketone Vapor
in Air ait Initial Twmperatures of 1100', 1500 and
200'. 1T'nderwrit ers Laboratory
Bull, lRes.
39, 1947, PP. 5-18,.
Mci~onald, J. S., and J. IE. Owens. Investigation
of Tetralin ExNplosion. Atomics tinterriat. Ilvt'I.
NAA-SR-4803, Cianoga Park, Calif., 1960, 58
PP.
14:3. Mfellai, Ibert. Industrial Solvents. 2d ed. RleiniPub. Corp., New York, 1950, 758 pp.
144. Miller, S. A., and EC.PI 'v. Hazards in llantduing Ace-tylIene in Chemical Processtes, Particularlv Unde:r Pressre
Proc. Symp. on Chiem.
Process flazards, Inst. of Chenm.'Eng. (London),
1960, p. 87.
1415. Mfiissen, It. WV. Pressure D~rop in Vapor-Relief
S , stems;. Chem. Eng., I1162, pp. 101-102,
1.I46. Moore, It. IL. Fire s an(l Explosionisi i Uopre sed
Air Systemis. Canadian Mfil. and( Met. Boll.
No. (10)9 . 56S, 1963, pp. 18-19.117.,\Morani, Ii. 7.,.Jr.,
arid A. XW.Ittrtselly. Flamtnahilit v I.ito its for lixt tiresof 11;, rociromti~ti s,
Air,' and( HIalogeni ( oin ou rids. N IHL Itept.
.112 1, 153, 12 pp.
I-1S. Mor'to,
1). 11. Iteviitw oif Synthectic L.trbricirnts.
lubricat ion Eng~., 19j54, pp. 6.5-73.
I Il. Monrganr, N. 1). Tilt linlioie of tLbricanits ott
EC~pdtsioit, in Comripressed Air Sestetis. ('aria150).

731 pp

Mtftrrioti, lhctivrt
ti

Bol

1,91

,X

of

t-,

o of

Mlich
,

GASES AND VAPORS

1-1t

\I

l,

Nh

)Srk
152.

Dert ot
P.,

ivan,IltIt.
Mrtoni

Bltvtl

A Shlock-lTittt Itivesti

I ihir
-9,15,.

%i l.r
2

Po., RitiTr Nt.

I'.tu iv

p
Mo, rin,

Iiil
Iti[061b ppit,) 92-94i.
N1."FIt,

lip;

inofLw

ote

rVral

Told82

BIBLIOGRAPHY11
1,58. National Fire Protection Asoociation. Fire-Hazard
Properties of Flammable Liquids, Gas". and
NFPA 325, 60 Battery inatrch
Volatile Solids.
St., Boston 10, Mass., 1960, 126 pp.
1591. Nuckolls, A. H. U nderwriters' Laboratory Method
for the Classification of the Hlazards of Liquids.
National Board of Fire Underwriters, Chicago,
Ill1 1921) 20 pp
160. Ordna*nce dorps, U1j.S.D~epartment of the Army.
Ordnance Safety Manuial, ORI)M 7-224, 1951;
Sec. 17, May 15, 1958, 68 lPp.
The Quenchinjg of Flame by
161. Palmer, K. N.
Perforated Sheeting and Block F lame Arrestors.
Proc. Srnp. onl Chemical Process Hazards,
Inst. Chem. Eng. (London), 1960, p. 51.
The Quenching of Flame by Wire
---.
162,
Gsauzes. 7th Svinp. (Internat,) on Combustion,
Brittcrworths Sci. Pub. (L.ondon), 1959, pp.
497-503.
163. Parker, W. G., and H., G. Wolfhard. Properties
of Diborane Flames. Fuel, v. 35, 1956, pp.
323-331.
Characteristics of Flames
.Some
164. - --Supported by NO and NO 2 . 4th Symp. (Internat.) on Corn~usion, Williams & Wilkins
Co., Baltimore, Md l 953, pp. 420-428.
165. Penny, E. The Velocity, U Detonation in) Comnpressed Acetylene. Varaday So'> Ditc., No. 22,
1956, p p. 157-161.
166. Perlee H~enry E., Agnes C: Imhof, find Michael
G. iabetakis. Flanimability Chaoract eristics )f
llvdrazine Fuels i n Nitro'gen Tetroxide Atinosliheres. J. Ch'em. Eng. Data, 1962, pp.
:377-379.
167. Pieters, HI. A. J., J. W. Hlovers, anti B. J. Rietvelr.
D~eterminat ion of the Explosion Limits of Gases.
Fuel, v~. 26, 1947, pp. 80-81L
164. Porte-r, It. L. Unuisual Pressure Relief D~evices.
Ind. find Eng. Chem., v. 54, January 1962, pp.
2-1-27.
109. Prie, F'raser P. First and Second Liii.s of Explosin of I iboranie-Oxygen IMixtures. J. Am.
Chou)n. Soc., v. 72, 1956, PP). 5361-5:365.
17t0. Rlandall, P. N., J. Bland, W. NM.l)udle. and It. B.
J'acobs. Effects of G-aseous D)et onations U~poni
Vesisels aiid Piping. J. Client. Eng. Prog., v. 5:3,
1)levernber 1957, pp. 574-580.
71. Rtandall, P'. N., slid 1. Ginsburgh. Bursting of
Tuhular Specinwins 1)- Gaseous D)etonat ion.
AS ME, Trans., Paper No. 60-WA-12, 1960,
9 pP).
172. lftsashl, It. J1., and] Z. W. Itogowski. Gaseous
E:xi dos lors in Ve,..ted Durct s. Cornibt st ion aind
I ecenter 1960, pp. 301 -312.
.4,
Iouni,
I73
R7..Ielief of E~xplosionis inl Duct Systeris. Proc. S'yrup, onl Chern . Process P azarils,
ern. Erg. I .on1don ), 11160. l). 58i
lost. ,
17-1. Rebei.torf. MIelviri A. I )esigning a It igh Presled, arid Eng. ('lit-rn, v. 15:3,
sort, Laburator.
4
WI1,il)lr). 4t0A - 4 2A.
I!5
Explosive
15Richiard soni, E . C ., and C. It . Stilton.
Propt rt it of I acqji r-Sotlv cut Vsapors.- Iin. I
('hem., v-. 20, 19289, pp. 197-- 190.
T"o I1rig.
A-., B3. It. Ptirsall, drid J1. B3. Sellers.
7l;. Itobvrts,
NIt t ioit Lav t ririg ii M in e Airwa vs. (Coil,
Guiard., v . 205, ( )t'tober ')62, pp.53-4
Mlelhant la,ring in Milne Air177
avi.(ol
liryo
1 h
MovsPr
('~
ofBa'Iig
t stiai., v.tr205, 1ii
0591jIto
92,
'- Pl) 59 53
ayvtrin g in MIin e AirMethlarne
Id.
Ulits. Part Ill. Thet Theorv otf Layering
('ouitintd t. C'oll. ( uard., v. 205, 1962, jpp
':10-636.
layering in Mint Air.Methasne'
I 79.
Wavs ., Part IV, Sr iii -itg La~ein ig Pheniomenai
('oIl. Gurard. , v-. 205,
i a it i~t ory NIotlel.
1962, pp. 723 -732.

and J1. 13. Sellers.

180. Roberts, A., B. R. Prill
Methane Layering in Mine Airways. Part, V,
Studying Layering Phenomena in at Laboratory
Model. C2i, Guard., v. 205, 1962, pp. 756-763.
Engineer181. Rogers, D. T., and C. E. Schleckser.
ing and Theoretical Studies of Static Electricity
in Fuel%. Proc. 5th World Petrol. Cong., New
York, sec. 8, paper 10, 1959, pp. 103-121.
182. Rolingson, W. R., John MacPherson, P. D. Montgomery, and B. L. Williams. Effect of Ternperature on the Upper Flammable Limit of
Methane, Ammonia, and Air Mixtures, J.
Chem. Eng. Data, v. 5, 1960, pp. 349--351.
183. Rossini, F. D). and others. Selected Values of
Properties of Hydrocarbons. NBS Ciro. C461,
1947, 483 p p.
184. Salooja, K. C. Studies of Combustion Processes
Leading to Ignition in Hydrocarbons. Cornbustion anid Flame, v. 4, 1960, pp. 117-136.
185. Sargent, H. B. How to Design a Hazard-Free
System to Handle Acetylene. Chem. Eng.,
February 1957 pp 250-254.
186. Schumb, W.yC., 6. N. Sit-terfield, and R. L. Wentworth. Hiydrogen Peroxide. Reinhold Pub.
Co., New York, 1955, 750 pp.
D. A. Hazards With Butadiene and its
Scott,
187.
Properties. Am. Chem. Soc., v. 18, 1940, p.
404.
188. Fcott, F. E., J. J1.Burns, and B. Lewis. Explosive
Properties of Hydrazine. BuMines Rept. of
Inv. 4460, 1949, 18 pp.
181.. Scott, F. E., R. W. Van Dolah, and M. G. Zabetakis. The Flammability Characteristics of the
System HrNO-N2O-Air. 6th Symp. (Internat.)
on Combustion. Rein hold Pub. Co., New
York 1957, pp. 540-545.
190. Scott, 6. S. Flammability of Trichloroethylene.
BuMines Rept. of Inv. 6190, 1963, 5 pp.
191. Scott, G. S., G. WN.Jones, and F. E. Scott. Determination of Ignition Temperatures of Corn.
bustible Liqu~ids and Gae.Modification of
the Drop Met hod. Anal. Chem., v. 20, 1948,
pp. 238-241.
192. :uc;ott, George S., Henry E. Perlee, George H.
Martindill, and Michael G. Zahetakis. Review
of Fire aind Explosion Hazards of Flighit Vehicle
Conustjhles. Aeronautical Systems Division
T.-ch. Rvpt. 61-278, supp. 1, 19 62, 43 pp.
193
~DSC nnov, N. N. Sonme Problems in Chemical
Kinetics and Iteactivitv. Princeton Univ.
Press, Princeton, N.J., v. 2, 1959, 331 pp.
'0.
tehkin, Nicholas P'. self-Ignition Temnperatures
of Combustible, Liquids. J. Iles. NBS, v. 53,
1954, Ites. Paper 2516, pp. 49-613.
l ,
inlmmouds, W. A., and P., A. Cibag.
The
D esign of Explosion tReiefs for Industrial Dryrcs
iip
nCer
vns
'o.S
60,es
n~ 1he.
on
Eng
Shevni.
iIg Ovrde nst P.
90
n.(ono)
lvll
69.
lizrs
1
h nlr
viniI.0 ofad
).ios
69.
tu
(I'on lfham. Th 'fan
a~U If Gur
fN R. 1', nd
196 Simos
ts
.51 ,rid1955 p. 1ra211
lneohieth .
1 95 ) 21
FrdvSvv
197. Sireo'r, I )orothl M ., Frank I Belle~s, andl Adolph
E. SpI tktwski . Ir vtsigi oniiand Initerlrtt atimu tof i ll(, Fl:mrir iiailit 'v Region ftor Somt Letarn
II vdrocarun-Air MNtuirts. 4th Srnv. (Intcrlint.)A oil (itribisitin, Williamrus & W'ilkins Co.,
ltnimore, Md., 1953, Ill. 1241-1314.
I104. Sinitger, J. M. , J,ose phi rutnvr, anrd IE. 11, Cook.
Buni~~i-I Inrn r
h
by
Burrnin g ',,eloc itis hv
Method. 1. 11 vearbori-Oxvygtri Mixtures at
I ii,
Atinoie~tre. 11.11 v.Ndroca rm-nAi r \f ix'uitrinospheric l'ressiires. Proc.
lit
ttiriNip., 1955,
Ai-rtt it nocht -in. (;Its I ) -nil- is
pp. 1:19-- 150.
199. Sutill., Marion L., and Karl W.- St inson.- Fuels;

112

FLAMMABILITY

CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS

and Combustion. McGraw-Hill Book Co.,

New York, 1952, 340 pp.
200. Solov'ev, N. V., and A. N. Baratov. Dependence
of the Lower Limit of Flammability on Molecular Structure. Russian J. Phys. Chem. (Zhur.
Fiz. Khim.), v. 34, 1960, pp. 1661-1670.
201. Spakowski, A. E. Pressure Limit of Flame Propagation of Pure Hydrocarbon-Air Mixtures at
Reduced Pressures. Not. Advisory Committee
for Aeronautics Res. Memo. E52H15, 1952,
33 pp.
202. Spalding, I). B. Some Fundamentals of Combustion. Butterworths Sct. Pub. (London), 1955,
250 pp.
203. Stenberg, John F., and Edward G. Coffey. Designing a High-Pressure Laboratory. Chem.
Eng., 1962, pp. 115-118.
204. Stoner, R. G., and W. Bleakney. The Attenuation of Spherical Shock Waves in Air. J. Appl.
Phys., v. 19, 1948, pp. 670--678.
205. Sullivan, M. V., J. K. Wolfe, and W. A. Zisman.
Flammability of the Higher-Boiling Liquids and
Their Mists. Ind. and Eng. Chem., v. 39, 1947,
p. 1607.
206. Tamura, Z., and Y. Tanasawa. Evaporation and
Combustion of Drop Contacting With a Hot
Surface. 7th Symp. (Internat.) on Combustion, Butterworths Sci. Pub. (London), 1959,
pp. 509-522.
207. Terao, Kunio. Selbstzunung von Kohlenwasserstoff-Luftgemischen in Stoss'ellen. J. Phys.
Soc. of Japan, v. 15, 1960, pp. 2086-2092.
208. The Combustion Institute. Combustion and
Flame. Butterworths Sci. Pub. (London), v.
1-7, 1957-63.
209.
. 4th Symposium (International) on
Combustion. The Williams & Wilkins Co.,
Baltimore, Md., 1953, 926 pp.
210.
.
5th Symposium (International) on
Combustion. Reinhold Pub. Corp., New York,
1955, 802 pp.
211.
.
6th Symposium (International) on
Combustion. Reiphold Pub. Corp., New York,
1957, 943 pp.
212. .
7th Symposium (International) on
Combustion. Butterworths Sci. Pub. (London),
1959, 959 pp.
213.
.
8th Symposium (International) on
Combustion. TheWilliam
& Wilkins Co.,
Baltimore, Md., 1962, 1164 pp.
214. The Institution of Chemical Engineers. Proceedings of the Symposium on Chemical
Process Hazards. Inst. Chem. Eng. (London),
1960, 117 pp.
215. Thomas, A. Flame Propagation Through AirFuel Foams. 6th Symp. (Internat.) on Co mbustion, Reinhold Pub. Corp., New York, 1957,
pp. 701-707.
216. Umland, A. W. Explosive Limits of HydrogeniChlorine
1lo 1954, Mixtures.
pp. 626-631.J. Electrochem. "See,, v,

235. Zabetakis, M. G., J. C. Cooper, and A. L. Furno.

Flammability of Solvet Mixtures Containing
Methyl Ethyl Ketone and Tetrahydrofuran in
Air.
BuMines
of 11.
Inv.Engel.
6048, 1962, 14 pp.
236. Zabetakis,
M. G., Rept.
and II.
I'laminable

217. U.S. Atomic Energy Commission. The Effects of

Nuclear Weapons. Ed. "by Samuel Glasstone,
April 1962, p. 163,
218. Van Dolah, Robert W., Michael G. Zabetakis,
David S. Burgess, and George S. Scott. Revie'. of Fire and Explosion 1lazards of Flight
Vehicle Combustibles. BuMines Inf. Circ.
8137, 1962, 8 pp.
219. Wayman, D. H1., and R. L, Potter. Detonations
in Gaseous Fuming Nitric Acid-Hydrocarbon
Mixtures. Combustion and Flame, Butterworth. Sol. Pub. (London), 1957, v. 1, pp.
321-329.

Materials:
A i ectre De00onstration.
BuMines Int. Cir. 8005, 1961, 17 ip.
2t7. Zabetakis, N. G., A. L. Farno, and G. I. Jones.
Minimum Spontancous I fition Temperatures
of Combustibles in Air. fnd. and Eng. Chem.,
v. 46, 1954, pp. 2173-2179.
238. Zabetakis, M. G., P. M, (ossey, and G. S. Scott.
Limits Of Fla ouinability of Methyl Ethyl Ketone
nd Methyl Isobutyl Ketone in Broniochloromethane-Air Mixtures. BuMines Rept. of Inv.
5680 1960, 12 pp.
239. Zabetakis, M. G., and G. W. Jones. Flammability
of Carbon Disulfide in Mixtures of Air and

220. Weber, J. P., J. Savitt, and K. Krc. Detonation

Tets lvaluate lligh Pressure Cells. Ind. and
Eng. Chem., v. 53, 1961, pp. 128A-131A.
221. Well, N. A. Rupture Characteristics of Safety
Diaphragms. J. Appl. Phys., 1959, pp. 621624.
222. White, A. G. Limits for the Propagation of
Flame in Inflammable Gas-Air Mixtures.
I1. The Effect of Temperature on the Limits.
J. Chem. Soe., v. 127, 1925, pp. 672-68.
223.
.
imits for the Propagatiol of Flame
in Vapor-Air Mixtures. Part 1. Mixtures of
Air and One Vapour at the Ordinary Temperature and Pressure. J. Chem. Soc., v. 121, 1922,
pp. 1244-1270.
224.
. Limits for the Propagation of Flame
in Inflammable Gas-Air Mixtures. Part 1.
Mixtures of Air and One Gas at the Ordinary
Temperature and Pressure. J. Chem. Soc., v.
125, 1924, pp. 2387-2396.
225.
. Limitg for the Propagation of Flame
at Various Temperatures in Mixtures of Ammonia With Air and Oxygen. J. Chem. Soc.,
v. 121, 1922, pp. 1688-1695.
226. White, A. G., and T. W. Price. The Ignition of
Ether-Alcohol-Air and Acetone-Air Mixtures in
Contact With Heated Surfaces. J. Chem. Soc.,
v. 115. 1919, pp. 1462-1505.
227. White, Douglas F. The Unintentional Ignition
of Hydraulic Fluids Inside High Pressure
Pneumatic Systems. ASNE J., 1960, pp. 405413.
228. Winter, E. F. The Electrostatic Problem in
Aircraft Fueling. J. Royal Aeronautical Soc.,
v. 66, 1962, pp. 429-446.
229. Wolfson, Bernard T. Harnessing Explosions.
Office of Aerospace Res. Rept. No. 17, 1962,
pp. 3-4.
230. Wolfson, Bernard T., and Robert G. Dunn.
GCineralized Charts of Detonation Parameters
for Gaseous Mixtures. J. Chem. Eng. Data,
v. 1, 1956 pp. 77-82.
231. Zabetakis, Nfichael G. Explosion of Dephliegmator
at Cities Service Oil Company Refinery, Ponca
City, Okla., 1959. BuMines Rept. of Inv. 5645,
1960, 16 pp.
232.
.
Gasfreeing of Cargo Tanks. BuMines Inf. Circ. 7994, 1961, 10 pp.
233. Zabetakis, M. J., M. P. Benoy, and 1. M. Gussey.
Explosion Hazards of Diethyl Ether. BuMines
Rept. of Inv. 6051, 1962, 16 pp.
234. Zabetakis M. G., and D. S. Burgess. Research
on the hazards Associated With the Production
and Handling of Liquid Hlydrogen.
BuMines
Rept. of Inv. 5707, 1961. 50 pp.

BIBLIOGRAPHY

240.
241.

242.
243.

244.

Water Vapor. Ind. and Eng. Chem., v. 45,

1953, pp. 2079-2080.
- . The Prevention of Industrial Gas
Explosion Disasters. Chem. Eng. Prog., v.
51, 1955, pp. 411-414.
Zabetakis, Michael G., George W. Jones, George
S. Soctt, and Aldo L. Furno. Research on the
Flammability Characteristics of Aircraft Fuels.
Wright Air Development Center, Tech. Rept.
52-35, supp. 4, 1956, 85 pp.
Zabetakis, M. G., S. Lambiris, and G. S. Scott.
Flame Temperatures of Limit Mixtures. 7th
Symip. (Internat.) on Combustion, ilutterworths
Sci. Publ. (London), 1959, pp. 484-487.
Zebatakia, M. G., C. M. Mason, anid It. W. Van
Dolah. The Safety Characteristics of Normal
Propyl Nitrate. BuMies Rept. of Inv. 6058,
1962, 26 pp.
Zabetakis, M. C., and J. K. Richmond. The
Determination and Graphic Representation of
the Limits of Flammability of Complex Hydro-

245.
246.

247.
248.
249.

113
carbon F~uels at Low Temperatures and Pressures.
4th Symp. (internat.) on Combustion. Williams
& Wilkins Co., Baltimore, Md., 1953, pp. 121126.
Zabetakis, M. G., arid B. H1.Rosen. Considerations Involved in Handling Kerosine. Proc.
Am. Petrol. Inst., sec. 3 v. 37, 1957, p. 296.
Zabetakis, M. G., G. S. 9cott, and G. W. Jones.
Limits of Flammabilityr of Paraffin Hydrocarbans in Air. Ind. and Eng. Chem., v. 43, 1951,
pp. 2120-2124.
The Flammability Characteristics
-.
of the C,.H2.-s Aromatic Series. BuMines
Rept. of Inv. 4824, 1951, 9 pp.
Zabetakis, M. G., G. S. Scott, and R. E. Kennedy.
Autoignition of Lubricants at Elevated Pressures. Bu Mines Rept. of Inv. 6112, 1962, 10 pp.
Zeldovich, Ia. B., S. M. Koarko, and N. N.
Simonov. Ali ExperimntalI Investigation of
Spherical Detonation of Gases. Zhurnal Tekh.
Fiziki (J. Tech. Phys. (USSR)), v. 26,1956, p. 1744.

APPENDIX A
A-I. Summary o limits offlammability,
lower temperature limits (TL), aml miniMm
autoignition temperatures (AiT) of inditidual
gases and vapors in air at atmospheric pressure

TALILE

T 1,
(0 C)

_.

Combustible

AIT
(0 C)

1 0..77
ler-Butyl benzene ---- 1 .77
2. 5
n-Butyl bromide-- ---Butyl cellosolve ------ 8 1. 1
,ec-Butyl benzene --

n-Butyl chloride -----

37
230
10
1.6
Acetal --------------175
60
------.
0
Acetaldehyde --------- -.
465
40
2 5.4 ----Acetic acid ---------Acetic anhydride-----2 2. 7
8 10
47
390
545
1.0 ..............
Acetanilide ---------465
.
2.6 I 13
Acetone --------------------------. 570
1. 1
Acetophenone ------Acetylacetone .......
1.7 ---....-----340
390
-------- ------ --.5. 0
Acetyl chloride ...
305
5
100
2.
-------Acetylene--235
31
---2.8
Acrolein..-.-......
-6
3. 0 ------- Acrylonitrile -------------- ----2. 2
12
Acetone Cyanohydrin.
420
-------Adipic acid ---------- -1. 6
250
'2.0
-------Aldol- .-------------22
--2.5
18
Allyl alcohol ----------375
22
2. 2
Allyl amine ---------295
2. 7 -----------.
Allyl bromHe --------485
2. 9-......... -32
Allyl chlorid ---------4. 1 I--------450
66
...
o-?kminodiphenyl
--- -28
15
Ammonia ----------36
1 7. 1 I 25
1.0
n-Amyl acetate00)
r
4
1
10
-----1
1.
n-Arnyl alcohol
tert-Amyl
alcohol __._ 1.4 ---------------38
*135
n-Ainyl chloride..-

..

ten-Amyl chloride.

-..

Amyl nitrite_

n-Amyl propionaeAnylene----------Aniline- .---------Anthracene ---------n,-Amyl nitrate- ...

Benzene ------------ Benzyl benzoate_.. .
Benzvl chloride-------'
Bicyclohe-xyl----------

1. 4

.
..
.
.
7
.... ... - J
4*
1.2 ,..
5. 1
65

70 --8
1. 6
2, 0

See tootnotem at end of table.

1--

12

'

12
9.8
9. 0
8. 9
1 5.8

. .
.
I
21
1I

_--

.;3-0inethy. .
im-I

,h.

, :,.

40

----

1.
25

"
4)5
4SO
3s0 N
.110

420
450
265

10 - --------- 245

1.8

1 10

2. 1

1 10

1. 8

by)

'

y7
hy] (,t(hr-

CIO

42o

8.4 I

1"
0 "
,79.
8.

.4

I 5. 8-------- ---------

425
6.5 ...
6.6 ------Cyanogen -----------6
.7....
.
1. 1
Cycloheptane. ------ -245
.
7. 8
1.3
Cyclohexane --------- 300
----1. 2
Cyclohexanol ---------1.2
Cyclohexene- -------33"
1.0
-.
Cyclohexyl acetate _
50 0
10.
2. 4
Cyclopropane- -------415
)5
.
85
..
Cyniene....
2
.D,,aborate-------25i
57
- --- 74 1 1 .1.
Decalin- ........
-16 [
210
3 5.
-1 2 75
n----n---ecane-............
75
4. 1
).iutrium ---------.8 "2,
.
88
-l)iborat
Dies fuel-.-----.--..
(6)ce ahz)
_
.. [
I
.
8
-.l)icth I :,ri.130
- 8 _
t1
,,
Al34l5vl
- 1430
75
1
y yll
0'

-lyl
..

. '7

.,

to i,I

.
1-'20

....

I 2

-11)
_.1

ie

hIe-

24160

290
450

.-------

l)s,, ,utyl ki'-.

2-4, 1 ,.eyvit,
l)uisop , xx 1h.r,,
l)wthyi
*ln2
)i't-hc

24,5

I 110

.
Crotonaldehyde
Cumene ------------

l)h.0 p3li)eot
1)
I), 'hy' 1 ,"_
c) .i,,ol__
Di , ,ht

5,10
!)5
5l'
4Si

5.

8. 2
1. 7
n-Butyl formate ----,
35
-----.
n-Butyl stearate ----450
----......-.
2. 1
Butyric acid --------a-Butryolactone -------- 2.00----------------_
__ 90
50
Carbon disulfide ...-...1.3
...
74
12. 5
Carbon monoxide .211
Chlorolhnzn ---------- 1.4 --------rn-Crosol- _.--.--1.1 ......
..
-..

xI2

275
615

.....
.

1.1
1.3

1-(

_-

7)ie
7
.3

7 2
4.65

1.8
1,3-Butandiol- ---------- 1 9
1. 6
Butene-I ....... ...I
Butene-2 ----- -- ....
5
4
n-Butyl acetate .......
1. 7
n-Butyl alcohol .......
1. 7
-.
see-Butyl alcohol
' 1. 9
tert-Butyl alcohol
1. 7
tert-Butyl amine
82
n-Butyl benze! -----.
114

260

1 0
0.

Bilihenyl-------- -----.

d4.
2fiielini
Promobnzen --------Butadiene (1,3) ... .
n-Butae-- -----------

1 8. 6

1. 6

'1. 570

AIT

Ti.

Us&

Lis

Limits of flammability (volume-1

percent)

Combustible

Limits of flammtibility (vohnmepercent)

2: 15

iWO..

2,3-1)
2, 2-,D31
l), t

s
1..
1.1
.

i !all,v
Ipro),iI l

a a liule .
I1-ulfoxid
- -.
. ..
,
.
,
.
I)tei.la,,ii.

)imt
J)ioxi
1
l)i

35)

3.

,1-r
iii
.. 1hy
p ,
1
)irn(lhvi or.t-

.-.

.
1
.5
' 7

.135
:35
151

:05

0
-

6. 1

.,)
7

115

APPENDIX A

Limits of flam(volumeTL
percent)
(00C)

Imability

Combustible

Los

AIT
(0 C)

Limits of flaminability (volumepeicent)

Combustible

_- (_ (0

Ulf

Lot

TL I__AIT
) (0 C)

C)(

U.

Dip henyl ether .......

40.8
.........
620
Methyl chloride ------47
----------Diphenyl methane
.
7---------------- 485
Methyl cyclohexane_
1. 1
6.7 ------250
DiN~ yl ether --------1.7
27---------Methyl cyclopentan-Do( ecane ---------.
.60---------74
205
diene -------------1.1..3 1
7.6
49
445
Ethan --------------30
12.4 -130
515
Methyl ethyl ketone.
1.9
10
.............
Ethyl acetate --------2
11 -----------Methyl ethyl ketone
Ethyl alcohol --------3. 3 1119
..
365
peroxide ----------------------- 40
390
Ethyl amine ---------3.5.--------------385
Methyl formate ......
5.0
23 -----465
Ethyl benzene -----'1. 0
1 6. 7 -----430
Methyl cyclohexanok_
' 1.0 -------- -----295
Ethyl 12hloride ------3. 8 ----------- " ----Methyl isobutyl carEthyl cyclobatane --1. 2
7. 7.--------210
binol------------ -1. 2-------440 Ethyi yclohexane_.
142. 0
146. 6 -----260
Methyl isopropenyl
E thyl cyclopertane_.
1. 1
6.7 ..--260
ketone ------------1.8
'9. 0 ----------Ethyl formate-------2.8
16
-----455
Methyl lactate --------- 1 2. 2 ----------Ethyl lactate- --------- 1.5 ---------.
400
a-Methyl naphthalee
'.8 -......-.....-530
Ethyl met captan ....
2. 8
18
I--..
300
2, Methyl pentane_--_
41.2 ------------------Ethyl nitrate ---------4 0 ---------I
Methyl propionate.--2. 4
13
----------Elhyl nitrite-..
3.
50
---------Methyl propyl ketone-,
1.6 -------8-2
---------Ethyl propionate - 1.80
11
...
440
Methyl .tyrene ------41.0
/
49
495
Ethyl propyl ether - 1 7
9
----Methyl vinyl ether. __
2. 6
39
-----Ethylele ......---2. 7
36
490
Methylene chloride--- -------- --------- -----615
Ethyleneimine --------3. 6
46
-- .320
Monoisopropyl bicyEthylene glycol- .
3.5 -------------400
clohexy,52
" 4. 1
124
230
.2hylene oxide ------3. 6
100
----- ----2-Monoisopropyl
Furfural alcohol-----, -1.8
in 16
72
390
biphenyl --------1) 53
3. 2
141
435
GasolineMonoinethylhydra100/130------------1.3
7. 1
------. 440
zinc-----------------115/145 --------1. 2
7. 1
------. 470
Naphthalene ------1 88
20 5.9
lycei.------- ---- -------- -------------- -- 370
Nicotine --------------1,751
--..
"
----------n-itcIptane --------1.05
6. 7
-- 4
215
Nitroethaie -----------3. 4 --------30
7-1leXIlecalI-- ----- . 43
-----126
205
Nitro nethane -----------. 3 --------- 33 -llexatle -----------1.2
7.4
-26
225
1-Nitropropane ----2. 2 --34
n-llexvI alcohol ---. -I
1. 2
..............
2-Nitropropane ------- 2. 5--27
,-ll
l ether .
.
.6
.4.
185
n-,oan --21. 5 ----------.
3
205
1llyhazie. .4.
4:----------7
100
n-Octane -----------0. 95 --------- 13
220
l
,drogil........
4. 0
5
400
l'araldehyde ------------ 1. 3
--- --....
-llvdrogen cyaii(ie___
5.6
46
--Pentahorane -.......
42 -----....... .4
4-....
...
--- -- .-1.4
7. 8
-A8
260
'entaon.tilene
I- I
1. 1
1 7. 1
25
360
lsa-It
anl
(ti't
lsoialn
ii(tl]I
,.
I .I
350
eol-.....-------335
lolta.
,..
-- 81
401
Plitlalic aiodridc
.
2
2
Is(ohilvi llvolol .
1. 7
'11
.........3-Picoline ------------ 4 1.4---------------- 5t0
[SlAt vl hiW llo( -6
9,
- - .i43 0
l.l.allt -- ------------------ 23 . 74
23 7. 2
Iulit vi fu-lia,
2. 0
S. 9
'ropadicniw,
.
12. 16
Isb vi',
.
,
1. 8
1.
. . .
.. .
l'ro
_ ...
... . . .
2. 1
.,5
1 )2
450
lsfn-r,I. 4
.
.
.
.
1,2-1'ropanditl I '2.5 . - .
410
--- -- .---..
.. .. -U. .
l /-}'ropiolaetoie
2. ii
4,, 7.
.I
r
i tlhhyd.
2. 9
17
:dd l
.
2
..
.t-I
yl acetiate._
1
1.
I,. 'pr()o 'l tdhilil iyl
4. j
..
. .
t
It
1 -Prop~y ,l' h l _l
1.22. '2 ' 1.1
- ' w o.1
.vI

fi l:

ii

6ii
.

Ki .,si

l'rp

i.:

-230

M' ,1.ii i
\h-!110 v,.All

44_
3.

15
1f;

1. I . '

.,ithi IthYl ,th.r

s,,

iii

I/tntes

1. 7

2. 2

ti t end of table.

_
2111

187

U..,~
Nio 'li
v,',' Ir.
l.
III
t
N11"
ChIA
0 NA t1. 2
McI11tIi :ii 1111w
41!
.N(l'
t(-----._I~ I ..
t 1
12 5 ,
,I
3M ,vIIt- vli -i I)[ on
1. , %1l' ,ut kelm w),
l 2
1.
0
, c jj,'i )1\,,
' 7 2. 5
"2( ...
,.L 'I vIo )"
).l
l ',v
i

210

-..

..

E{(

.-

.
I

46
------.

rou;

Ou

-2

.
.

54 0

.'ri,,
,h0 ;N-1'

.
3"'11

It ttiine

l'rj, yl ,hlori,ic-_
t-Kj,'l nitratei'r,+ l!1h11
.

I.1],

hi

nl
,.u

i.Ityol

l',
i'..-

-i

,.

"

1
I

21
.4

175
460

3. 1
.

,11\,1h',,filralc
%
.

rait...........

100

: 2. 4i
1
12
'1 .0
;7
.
. .
22. 17
.. . ..
. . .
2" 111'. (I........
I.
53.5
l '2. 0
2.17
M) ;
. ...
,
:
*.5
. _.
2

I
Q it rtii
, 'p1v I,.-t]L-IV
St
,
I . -lc-)ht... .
S.1illfi,"
,-T ,.orl~I ,\I v.I. _
.
it, kt -tr
ll.,.
l''

2. 4_
I. 8
.

2 (0

...

5. o

71

315

116

OF COMBUSTIBLE GASES AND VAPORS

FLAMMABILITY CHARACTERISTICS

A-I. Summary of limits of flammability, lower temperature limits (TL) and

minimum autoignition temperatures (AIT) of
individualgaves and vapors rn airat atmospheric

TABLE

pressure- Contiaued

Limits of flammability (volumepercent)

Combusible

L,..

,
U,__

T,
(0C)

AIT
( 0 C)

,2,3,3-Tetrmnethyl
430
0. 8 --------------pentane ----------Tetramethylene gly390
-------------col ...
480
'.7.1 ------1.2
Toluene -----------500
Trichloro~thane ------ ---------I ----------420
30
26 40
Trichlo=oethylene -_-- 2412
8. 0 ....-1.2
Triethyl amine -----2 9.2 -----------.9
Triethylene glycol.
2,2,3-Trimethyl bu420
1.0 -------------tane ...-----------12
----------2. 0
Trimeth;yl amine ....
2,2,4-Trimethyl pen415
.95 -------------tane -------------400
1.7 -------------Trimethylene glycol ----3.2
--------------Trioxane -----------'.7 ............
Turpentine ------..
Unsymmetrical di----------2. 0
95
methylhydrazine_2. 6
------------------Vinyl acetate -------..----......
33
&6
Viniyl chloride ------3.4 ------- 530
1.1
m-Xylene -----------

o-Xyene------------

11.1

16.4------

465

p-Xylene -----------

' 1.1

'6.6 -------

530

1t:100* C,

1:1-0: C.:

i-47* C.

12g.-530

4 Calclated.
t-60* C.
4 t-850 C.
1- 140.0 C.

1 1-72*oC.
Is t-117 C.
9T
- 125o0 C.

8 tm75* C.

'1-160OC.
t-110. C.
"t-17*6 C.

C.
C.
(-

t-:43* C.
o C.
Ug195*
t~m60
1
C.

. t-130 C.

24-96

"t-200 C.
"-78o C.
t-122* C.

"-0
C.
C.
'-203
1

C.
Ist70O C.
C.
U 9-29
o
C .- 247 C.

APPENDIX B
STOICHIOMETRIC COMPOSITION
N,

The stoichiometric composition (C,,) of a

combustible vapor CnH.O\Fk in air may be
obtained from the equation

CH OxFFk+
.+ - A

m k2X14

O--CCO 2

rn-k

Thus, C,,=

H 2O+kHF.

100
- 1_ - A.73
jn -k-2X') volume-per-

1+4.773

cent, where 4,773 is the reciprocal of 0.2095,

the
concentration
The molar
following
table lists of
theoxygen
values inof dry
C,,air.
for
a range of (
m-k-2X) values from 0.5 to

1. 87
1. 72
1.59

0.25
1. 83
1. 68
1,56

18 --------------

1. 38
1.29
1. 22
1. 15

1.36
1.27
1.20
1. 13

0.50
1. 79
1. 65
1.53
1.42
1.33
1.25
1.18
1.12

20 ------------21-------------.
22-------------.
23 -------------.
24
25 -------------.
-------------

1.04
99
94
90
87
83

1.02
.98
.93
.89
.86
.82

1.01
.97
.92
.88
.85
.81

1.00
. 95
.91
.87
.84
.81

26--------------.
27 ------------28 -----------.
29
30 -------------.
-------------

80
.77
74
. 72
69

.79
.76

.78
.76

.78
75
72
.70
68

-----------12------------13
--------------15-----16 ------------17-------------

1. 09

1. 08

0.75
1. 75
1.62
1.50
1.40
1. 31
1. 24
1.17
1. 10

1. 06

1. 05

.73

.74

.71
.69

m-k-2
4

1,45

1. 47

19....------------

1 N-n+

30.75:

..

.71
.68

; where n, m, X,and k are the

number of carbon, hydrogen, oxygen, and halogen atoms,

N1

0.25

0.50

respectively, inthe combustible.

-For
29.53 121.83
12. 25
10. 69

position of acetyl chloride (C 2H 3 0CI) in air

___--

-----------------1--------------17. 32

2-------------9.48
3-------------6.53
4-------------4.97
5-------------4.02
6-------------3. 37
7-------------2. 90
8-------------2.55
9--------------2. 27
10.------------2. 05

14. 35

8.52
6.05
4. 70
3.84
3. 24
2. 81
2. 48
2. 21
2. 00

7. 73
5.65
4.45
3.67
3.12
2. 72
2.40
2. 16
1.96

7.08
5.29
4.22
3.51
3.01
2. 63
2. 34
2. 10
1.91

example, the stoichiometric mixture commay be found by noting that

n m -k-2X
N=n+.

3-1-2
2=4

20

The entry for N=2.0 in the preceding table is

9.48 volume-percent, which is the value of C,,
for this combustible in air.
117

Ihe

APPENDIX C
HEAT CONTENTS OF GASES
(Kcalimole I)

T, - K
298. 16
300
400
500
600
700
800
900
1,000
1,100
1,200
1,300
1.400
1,500
1,600
1,700
1,800
1,900
2,000
2,100
2,200
2,300
2. 400
2.500

CO,

H,O

.017
.941
1.986
3. 085
4. 244
5. 452
6.700
7. 983
9.293
10.630
11.987
lM 360
14.749
16. 150
17. 563
1& 985
20. 416
21. 855
23. 301
24. 753
26.210
27. 672
29. 140

.014
.823
1.653
2. 508
3. 389
4. 298
. 238
6. 208
7.208
8 238
9.297
10. 382
11.494
12.627
13. 785
14. 962
16. 157
17. 372
18. 600
19. 843
21. 101
22. 371
23. 652

O,
0
.013
.723
1.4541
2. 2094
2. 9873
3. 7849
4.5990
5. 4265
6.265
7. 114
7.970
& 834
9.705
10.582
11.464
12. 353
13. 248
14. 148
15. 053
15. 965
16. 881
17. 803
18. 731

N,
0
.013
.709
1.412
2. 125
2,852
3. 595
4.354
5. 129
5.917
6.717
7.529
8. 349
9. 178
10.014
10. 857
11. 705
12. 559
13. 417
14. 278
15. 144
16.012
16. 884
17. 758

I Gordon, J. S. Thermodynamics of High Temperature Gas Mixtuuan-d Application to Combustion Problemn. WADC Technical
Report 57-33, 3anuary 1967, 172 pp.

118

APPENDIX D
DEFINITIONS OF PRINCIPAL
SYMBOLS
Symbol:

Definition

*A--------Constant.
*'--------Avea.
a ---------- Velocity of sound.

B--------C., ------K --------k-------L --------

Constant.

tStoichiometric composition.
-H------Heat
of combustion.
Ratio of duct area to vent area.S----T hermal conductivity.
Lower limit of flammability.
-*-----Modified
lower limit value.
LA-------Average carbon chain
length for
paraffin hydrocarbons arnd correlation parameter for aromatic hydrocarbons.
----Lowe(r
- limit of flammability at io C.
/ID------ Length to diameter ratio.

Symbol:

eigtiUof
filcua

M-----Mach number.
No,--,----Equilibrium mixture
NO at a specified
and pressure.
n---------- Number of moles.

of

NO 2 and
temperature

P----lresmire.
P --------- Maximum pressure.

n~P-------Pressurerise.
p ---------- Partial pressure.
Burning velocity.
T-------- Absolute temperature.
t----------T- emperature.
r- -- -- - -- Tme delay before ignition.
U -------- Upper limit of flammability.
U -------- Upper limit of flammability at P0 C.
V -------- Volume.
V'--------Critical approach velocity.
v---------- Liquid regression rate.
------Specific heat ratio.
119

SUBJECT INDEX

PaeHPg

Acetaldehyde --------------------------73
AkaietIIIV hydrocarbons -----------------------53
Airf1'1!_ ratio--------------------------------21
Alcohols----------------------------------6(5
Aldehydes ----------------------------------73
Ammonia-----------------------------------77
n-Ainyl alcohol ------------------------------67
Aromatic hydrocarbons-----------------------511
Autoignitlon-----------------------------4,32,41

Barrcades----------------------------------17
Blast pressure --------- ----------------------16
Burgess-Wheeler law ------------------ -------22
Burnling velocity.--------------- -- - - -4), 45
Butadiwne --------------------------------48,53
n-Butane ------------------------------21, 25, 32
Butene-1-------------------------------48,50,52
n-Butyl alcohol ------------------------------671
tert-Butyl alcohol ----------------------------68

o
Carbon chain---------------------------------

Carbon monoxide ----------------------------

41
97

Combustion equations-------------------- 21, 117

Contact time_---------------------------------4
Cool flames ---------- -----------------------28
Copper acetylide -----------------------------56
Critical CIN----------------------------------11
Cyclopropane --------------------------------64

n-Decane---------------------------------21,25
Decane-dodecane blends --------------------32, 43
Deco.nposition-------------------------------5A
Deflagration --------------------------------15
Detonation -------------------------------16, 57
Dimethyl ether ------------------------------70
n-Dodccane ------------------------------21,25

EJE

Enigine oils ----------------------------------95

Esters - - -----------------------------------70
Ethane -------------------------------21, 25, 28
Ethers-------------------------------------69
67
Eth' alcohol --------------------------------2-Ethyl butanol -----------------------------67
Ethylene----------------------------------48, 52

Flame arrestors ------------------------------18

Flame caps ----------------------------------2
Flame extinction ------------- _----------------29
Flammability characteristics ------------------20
Foam --------- ------------------------------Formic acid ------------ ---------------------61
Freon-12-----------------------------------69
Fuel-air ratio --------------------------------21
Fuel blends ---------------------------------74

Gas freeing--------------------------------Gas mixtures --------------------------------Gasoline ---------------------------------120

13
3
13, 82

Hlalogenated hydrocarbons -------------102

He~at of formation-_ - ------------------51
Pi-lleptane -----------------------------21.25, 35
Heterogeneous mixtures---------- ------------3

n-llexadecanm-------------------------------21,

25

Yi-llexano ------------------------------21, 25.,34

n-ll&'Xy.l
floo------------------7
Hydraulic fluids --------------------------9
Hiydrogen ---------------------------------77, 89)
Hydrogen peroxide.---------------------------1
1
Ignition ---------------------------------Ignition. temperature -------------- -----------4
Ignitihility limits ------------------------------Inertial
is------------------1
Isobutylene----------------------------------48
JP-4 -------------------------------------

K
Kerosine --------------------------------------

Ketones-------------------------------------

11,88
7
73

Layering ------- -----------------------------3

Le Chatelier's law ----------------------------31
Limits of flammability ------------------------2
Liquid mixtures ------------------------------31
Lower limit ---------------------------------2
Low pressure limits ------------------------12,89

Methane ------------- ---------------------9,21

Methyl acetylene --- _--------------------------5)
Methyl alcohol --------------------------6i)7
Methyl bromide --------------------------- 21N,61
3-Methyl butene-1 ---------------------------48
Mehyl formate -----------------------------71
Methylene bistearamide -----------------------7
Mlethylene chloride-------------------------102
Minimum oxygen value-------_.- --.- -- -----1
Mists -------------------------------------3, 6
MIixer-------------------------------------4,7
Natural gas-------------

-------------------

n-Nonane ---------------------------------

27, 30
21, 25

n-Octane ----------------------------------

21, 25

Paraffin hydrocarbons ----------------------2(0, 3

n-Pentadecane ---------- ---------------------21
?entane-----------------------------------24
n-Pentane -----------------------------21, 25, 33
Perfluo-ometha--- -------------------------28
Perfluoropropane ----------------------------28
Peroxides------------------------------53, 70, 103
Predetonation distance---------------------57
Pressure piling - - - ---------------------------58
Propadiene -------------- -------------------48

121

SUBJECT INDEX
Page

Propane ..........................
Isopropyl alcohol
----------........

------21,

..........
n-irropyl alcohiol ----------------------------n-Propyl nitrate-------.--------------------Propylene ----------.------------------------

25, 31

115
67
97
48,51

Q
Quantity-distance relationships ---------------

95

R
Raoult's law -----------.-------------------Rectangular diagra -----------------------Rc.gression rate- -..------.-------------------Relief diaphragms --------------------------

31
9
44
18

S
Shock wave ------------------------------Spark-energy requirements ------------------Spontaneous ignition -------------------------Spray injection ----------------------------Sprays ..--------------------------------

17
3
3
97
6

Page

Sulfw compounds -----.

Sulfur hexafluoride -------......................

. . . .

74
28

T
Temperature limit --------------------------11
n-Tctradecane ----------------------....---21
7
Tetralin -----------------------------------Time delay- ........
..-------4
Town gas--------------.-----------------19
Triangular diagram -------------------------9
Trlchloroethylene ----------------------------102
n-Tridecane--------------------------------21
Tube diameter ------------------------3,53,57
U
n- Undecane -----------------------------21
Unsaturated hydrocarbons ...--------------47
2, 23, 26
Upper limit--------------------------W
Wall quenching ----------------------------3
X
o-Xylene -----------------------------------

U.S. GOVERNMLNTPRINTING OFICE. 1965

O-761 .-

60