Flammability Characteristics of Combustible Gases and Vapor-Bulletin 627 Bureau of Mines

Bulletin 627
BuREu OF MiNS
FLAMMABILITY CHARACTERISTICS
OF COMBUSTIBLE GASES AND VAPORS
By Michael G. Zabetacis
Bulletin 627
BUREAU OF MINES
OF COMBUSTIBLE GASES AND VAPORS
By Michael G. Zabetakis
0
This publication has been cataloged as follows:
Zabetakis, Michael George, 1924-
Flanunability (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. 3. Vapors. 1. Title. II. Title:
Combustible gases. (Series)
TN23.U4 no. 627 622.06173
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 Flammability characteristics-Continued Pape
Abstract -------------------------------------- Aromatic hydrocarbons- Continued
Introduction---------------------------------- I Limits in other atmospheres---------------- 60
Definitions and theory ------------------------- 2 Autoignition ------------------------------ 62
Limits of flammability ----------------------- 2 Burning rate ----------------------------- 62
Ignition ------------------------------------ 3 Alicyclic hydrocarbons ---------------------- 63
Formation of flammiable mixtures -------------- 4 Limits in air ----------------------------- 63
Presentation of data ---------------------- ----- 9 Limits in other atmospheres ---------------- 64
Deflagration and detonation processes..----------- 15 Alcohols----------------------------------- 65
Deflagration ------------------------------- 15 Limits in air ----------------------------- 65
Detonation -------------------------------- 16 Limits in other atmospheres ---------------- 66
Blast pressore ------------------------------ 16 Autoignition ------------------------------ 67
Preventive measures -------------------------- 18 Burning rate ------------------------------ 68
Inerting ------------------------------------ 1 Ethers ------------------------------------- 69
Flame arrestors and relief diaphragms-------- 18 Limits in air ------------------------------ 69
Flammability characteristics ------- ------------ 20 Limits in other atmospheres ----------- -- ---- 69
Paraffin hydrocarbons ------------------------ 20 Autoignition ---- ------------------------- 70
Limits in air----------------------------- 20 Esters ------------------------------------- 70
Limits in other atmospheres ---------------- 27 Aldehydes and ketones ---------------------- 73
Autoignition ----------------------------- 32 Sulfur compounds --------------------------- 74
Burning rate ----------------------------- 42 Fuels and fuel blends ----------------------- 74
Unsaturated hydrocarbons ------------------- 47 aimmonia and related compounds ---------- 74
Limits in air---------------------------- 47 Boron hydrides---------------------------- 82
Limits in other atmospheres ----------------- 50 Gasolines, diesel and jet fuels --------------- 82
Autoignition ----------------------------- 50 Hydrogen ------------------------------- 89
Burning rate ------------------------------ 51 Hydraulic fluids and engin) , oils -------------- 95
Stability --------------------------- -- ---- 51 Miscellaneous ------------------------------ 97
Acetylenic hydrocarbons------- ------------- 653 Acknowledgments-------------------------- --- 106
Limits in air ------------------------------ 3 Bibliography ------------------- -------------- 107
Limits in other attmospheres ------- --------- 55
Autoignition ------------------------------ 0 Appendix A. Siirnmary limits of flammability- 114
Burni~ng rate ----------------------------- 56 pnix.-oihoticom ston---17
Stability-- - - ---------------------------- 57 Appendix C. -11eat contents of gases ----------- 118
Aromictic hydrocarbons.--------------------- 59 Appendix 1). -Definitions of principal symbols- 119
Limrits in air -------------------------- 59 Subject index--------------------------------120
ILLUSTRATONS
Fig. Page
1 . Ignitibility curve and limits of flammiability for methane-air mixtures at atmosphieric pressure and 26* C- 2
2. FfI~tv of tempe-rature onl limits of flinniatdlity of a conmbustibile vapor in air at a constant initial pins-
'i. ini d ilay I aforv ignition of N PN ini air at 1 000)1 pa ig in the tem pira ture range from 1 510* to 21 0* C, . 5
,.1 Logar i ini of time delay bewfore ign itijon of NJi N in air at 1,0001 psig iinitial pressur---------------- ---- 6
.. Simiplified nixer----------------------------------------- ------------------ ------ 7
6. Comnposition of gas in chamlber 2, figure 5 (instantaneous muixing)- - - ---------------------- ------- 7
7, Coiiiposition of gas in chambher 2, figure 5 (delayed mixing) ----------------------------------------- 7
.. Variation in, lower limits oft tlaininatilitv of various comibustibles in air Ps a function of droplet diameter 7
FVnn i in ahi lit 3 di agrain for the systveiIin i(t Ii ate-oxy g(il-nit rogetYi atI at I nospli e pressure and 26' C -
10 n.FlanmiiaI ilitY v (i 5grin for t he syst iiii iii(-ithaoi'(-oxy'geni- nitrogeni at at n osph eric pressure and~ 2110 C f
i. F; icrt o f iuiitia i en I per it uri on liit s of flai iiiability of it coin hust ii d vapor- iii rt-a ir syst lii itt atmnos-
lpheric pr(-&ur-- -- -- ----------- I------- -------------- ------------------ -- ---- - - -----
12. Ictrict oif initial pressure on liimits of' flaiinahility of JP-4 in air at 26' C ------------ -1
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 atinlos-
pherio 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)'Y a detonation
wave rating 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~ 18 i
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.s- raitio 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
1
-nton-rmiuest25Cad
atmospheric pressure ----------------------------------------------------------------------- 32
32. Limits of flammability of various n-pentane-inert gas-air nmixtu- i a tt 250 C and atmospheric pressure- 33
33. Limits of flammability of various n-hexane-inert gas-air mixtur -s ait 250 C anid atmospheric pressure- 34
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.11
2
,+
2
, n2!5) in carbon dioxide-
air 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-nlitrogen-
air, 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 mixtures-
43. 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
a t 26 ' C - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 4
48. Effect of temperature on burning velocities of four paraffin hydrocarbons in air at atmospheric pressure- 49
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 atmos-
pheric 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 atmos-
phieric ressure and 26' C-------- ------------ ---------------------------------------------- 51
.56. Limits of flainmability of inobutylerie-carbori dioxide-air and isobutylene-nitrogenl-air mlixtures lit
5 a ttmnlosp ieric pressurremandl26' C --------------------------------------------------------------
52
57 . Limits of flammnability of isobuitylene-water vapor-oxygen inixtures at I 5)O C and atmospheric pressumre- 53
58. Limits of flaminmibility of bmtene- I-carbon dioxide-air 1111d bUteme- I-nitrogen-air mixtures ait atniospl(briC
pressure and 26* --- ---------------- ---------------------------------------------------- 54
5 9. 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 V
Fig. Prg
60). ,imyits of flatnmabilit 'y of butudlenc-ccirbon dioxide-cur find btitadlene-nitrogon-air mixtures at atmos-
phteric pressure and 260 C - -- -- - -- - - - - - - - - - - - - - - - - - - - - - 55
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 ------------------------------------- 58
64. Mini ccci autoigi iio temperatures of aceetylene-air aind acctylcne-oxygcn mixtures at atmospheric
and elevated pressures----------------------------------------------------------------------- 58
65. Burning velocity of acetylene-air mixtures ait atmospheric pressure and room temperature -------------- 59
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 -------------- ----------------------------------------------------- 59
#17. Ficcal-to-initial pressure ratios4 developed by acetylene with (letonatijn initiation at various points
aloncgcatube--------------------------------------------------------------------- - - 60
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 ----------------- _ - 61
69. Lilits Of flammablttiility Of ll
2
()
2
-C
6
lI
4
.(Cl13)h-ll
2
O ait 1540 C aind 1 atmosphere pressure ---------------- 62
70. Limits of flammnability of 90-weight-perceet llY0
2
-C
6
11
4
.( Clf
3
)
2
-lCOOiI at 154V C and 1 atmosphere
pressure-.---------------------------------------------------------------------------------- 63
71. Nliniinuin autoignition temperatures of aroinatic hydrocarbons in air as a function of correlation
paramieter L --------- ----------------------------------------------- 64
72. Limits of flammllInabili ty of cyclopropan-cacrhon dioxide-air, cyclopropane-nitrogen-air, and cyclopropane-
heliumn-air miixtures ait 250 C aind atmospheric pressure ------------------------------------------ 65
73. Limits of flammi iability of cyclopropatne-hiutni-oxygen aind cyclopropane-nitrous oxide-oxygen mixtures
ait 25' C and atmospheric pressure ------------------------------------------ ------------------ 66
74. Limits of flaninability of cyclopropitne,-he(liumt-niitrotus oxide mixtures at 250 C and atmospheric pressure- 66
75. 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 pressure- 68
79). Limits of flammnability of terf-bcctyl alcohol-water vapor-air mixtures at 1500 C and atmospheric pressure- 68
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 pressure- 69
82. Limits of flamniability of dimethyl ether-carbon dioxide-air aind dimethyl ether-nitrogen-air mixtures at
25' C anid atmnospheric presstire------- ------------------------------------------------------ 69
83. Limits of flammability of dilethyl ether-carbon dioxide-air aind diethyl ether-nitrogen-air mixtures at 250
Cafidatilloqpheric pr'ssccre-------- ------------------------------------------------------ - -69
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 pressure- 70
80i. Limlits of flammnabilit y of mnet hcyl formcvite-cccrbon dioxide,-air aind miethyl formate-iiitrogen-air mixtures- 71
87. Limits of taimicabilit y of isobut'vi forinate-ecarbon dioxide-air aind isobutyl formate-n1itrogen -air mixtures- 72
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
4 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'
C andi cit cmslieric pressure, aid carboni discilfide-water vapor-air ait 1000 C and atmospheric pressure. 79
96. Limits of fl Icucictabilit y of liydropemi sclfidvearboci dioxide-air mixtures ait 250 C amid atmnosp~heric
pressuir--------------------- ------------------------------------- -------- 79
97. Licoits of flit titcatdlit Nof ethiyl moerecptaci-F'-12-air aid ethyl mercaptaic-F-22-air mixtures ait atmos.
phiiric priesurvandul27' C_----_------ ---- ------------- ---- -- - - 71)
98. 1 am its of fil c cI) 1hlil y of ium nioc iii, U I) N Il NI NI I, anicd hydrazice cit at mosphieric pressure icc satcurated
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
,pressutre _--_ _ . - -. - - -- - - - - - - - - - - - - - - - -- - - - - - - 81
100. 'N tiniiui Spout anieous igncition tcinpurat ores of liquid hydrazine, MINI1, and U I) 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 spoict it a olis ign it ioc t ciiipi rcto ris of l iquiiid hcydcraz inc at various initial tecI puwrat ores ill
NO
2
*-air mixtures at 740 1 1t) mmi fig as at function of NOJ,* coccntration --------------------- 1
V1
CONTENTS
rig. P84e
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 --------------------------. 84
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 ..-------------------- 85
104. Minimum spontaneous ignition teirperatures of 0.05 cc of liquid UDMH in tle-OrNO,* atmospheres
at 1 atmosphere for various He/Os ratios-- ----- ----------------------------------------- 80
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 ....... 87
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 ------------- 87
107. Limits of flammability of diborane-ethane-air mixtures at laboratory temperatures and 300 mm Hg
initial pressure ------------------------------------------------------------------------------- 88
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 ..................................... ................................... 88
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 ----------------------------------------- 88
110. Limits of flammability of JP-4 vapor-carbon dioxide-air and JP-4 vapor-nitrogen-air mixtures at 270 C
and atmospheric presure --------------------------------------------------------------- - 88
Ill. Limits of flprnmabi9t" nf hydrogen-carbon dioxide-air and hydrogen-nitrogen-air mixtures at 250 C
and atmospheric pressure -----------.-----------.------------------------------------- 89
112. Limits of flammability of IHrNO-NjO at approximately 280 C and I atmosphuee ------------------ A
113. Limits of flammability of HrNO-air at approximately 280 C and I atmosphere -------------------- 91
114. Limits of flammability of Hi-NO-air at approximately 280 C and I atmosphere -----................. 92
115. Rate of vaporisation of liquid hydrogen from paraffin in a 2.8-inch l)ewar flask: Initial liquid depth-
6.7 inches ------------------------------------------.----------------------------------- 93
116. Theoretical liquid regression rates following spillage of liquid hydrogen onto, A, an average soil; B, moist
sandy soil; and C, dry sandy soil --------------------------.-------------------------------- 93
117. Theoretical decrease in liquid hydrogen level following spillage onto, A, dry sandy soil; B, moist sandy
soil; and C, an average soil ---------------------------------------------------------------- 94
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 ---------------------- 94
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 ------------------------------------------------------ 95
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 --------- --------------------------------------- 96
121. Burning rates of liquid hydrogen and of liquid methane at the boiling points in 6-inch-Pyrex Dewar
flaks --------------------------------------------------------------------------- 96
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 ---------------------------------- 98
123. Logarithm of initial pressure-AIT ratio of seven fluids in air for various reciprocal temperatures ------ 99
124. Variation in TnT, of air with V,/Vf and with Pf/P, in an adiabatic compression process .------------- 100
125. Variation in air temperature with P,/Pj in an adiabatic compression process for five initial air tem-
peratures ----------------------------------------------------------------------- 101
126. Limits of flammability of carbon monoxide-carbon dioxide-air and carbon monoxide-nitrogen-air
mixtures at atmospheric pressure and 26 C --------------------------------------------- 102
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 -------------------------------------------------------------- 102
128. Flammable NPN vapor-air mixtures formed over the pressure range from 0 to 1,000 psig at 500 and
1250 C --------------------------.---------------------.-------------------------------- 103
129. Variation of explosion pressure following spontaneous ignition with NPN concentration- -----.. -- 104
130. Minimum spontaneous ignition and decomposition temperatures of n-propyl nitrate in air as a func-
tion of pressure ------------------------------------------------------------------------- 104
131. Flammability of trichloroethylene-air mixtures .-------------------------------------------- 105
TABLES
Page
1. Conditions of failure of peak overpressure-sensitive elements ------------------------------------- 17
2. Properties of paraffin hydrocarbons ---- -.---------- ---.-------.------------.------------------ 21
3. Upper flammability limits of methane-air mixtures at 15 psig _... ...------------------------- 24
4. Lower temperature limits and autoignition temperatures of paraffin hydrocarbons at atmospheric
pressure -----------------.--------------------------- -------------------------------- 25
5. Limits of flammability of methane in chlorine- . ...............---------------------------- 27
6. Limits of flammability of ethane in chlorine- ---.--------- ----------------------------------- 28
7. Properties of unsaturated hydrocarbons .... ..--------------------------------------------------- 48
8. Limits of flammability of unsaturated hydrocarbons at atmospheric pressure and room temperature, in
volume-percent combustible vapor -----------.-------------------------------------------- 52
9. Minimum autoignition temperatures of unsaturated hydrocarbons at atmospheric pressure ----------... 52
10. Heats of formation of unsaturated hydrocarbons at 250 C ---------------------------------------- 53
II. Properties of selected aromatic hydrocarbons --------------------------------------------------- 60
CONT 7N'rS VIU
Pageo
12. Prop ,rties of aelected alicyclic hydrocarbons ------------------------------------------------------- 64
13. Properties of selected simple alcohols ---------------------------------------------------------- 67
14. Propertie of selected ethers ---------------------.------------------------------------------------ 70
15. Properties of selected esters --------------------------------------------------------------- - -- 71
16. Properties of selected aldehydes and ketones ---------------------------------------------------- 73
17. Properties of selected sulfur compounds ------------------------------------------------------- 74
18. Properties of selected fuels and fuel blends ------------------------------------------------------ 77
19. Limits of flammability of ammonia at room temperature and near atmospheric pressure --------------- 78
20. Autoignition temperature values of various fuels in air at I atmosphere ----------------------------- 88
21. Limits of flammability of hydrogen in various oxidants at 250 C and atmospheric pressure .------------ 89
A-I. Summary of limits of flammability, lower temperature limits, and minimum autoignition temperatures
of individual gases and vapors in air at atmospheric preuure -------------------------------- 114
FLAMMABILITY CHARACTERISTICS OF COM-
BUSTIBLE GASES AND VAPORS
Acu I A Zxketakiqi
A bstract
3 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
Mrequirements, and burning rates) of pertinent combustible gases and vapors
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 ~ Explosi wilves 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.
2 FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS
DEFINITIONS AND THEORY
LUMil1S OF FLAMM AIIT I ' ' I I
combustible gas-air mixture can be burned ILimits of __
over a wile range of concentiations-when F f lammability
either subjected to elevated temperatures or
exposed to a catalytic surface at ordinary E 4-
temperatures. However, homogeneoug corn- >:
bustible gas-air mixtures are flammable, that, is, I.,g2 blit
they can propagate flame freelyv within a W 2- r lmt
- ~ Z X
limnlted range of compositionts. F~or examplke, W
trace amounts of methane in air can be readily X
oxidized on a heated surfaee, but a flame wi
propagate from an ignition source at amirbient .8
tmetures and pressures only if the sur- 'n .6
ronigmixture contains at least 5 but less A
than 15 volume-percent methane. The more X--
dilute mixture is known as the lower limit, or
combustible-lean, limit, mixture; the more .
concentrated mixture is known as the upper 2 4 6 8 10 12- 14 16 18
limit, or combustible-rich limit, mixture. In METHANE, volume-percent
practice, thle limits of flammability of at par-
ticular system of gases aire affected by the Fiouau .- Ignitihility Curve and Limits of Fiamn-
temperature, pressure, direction offan rp- inability for Methane-Air Mixtures at Atmospheric
gation, gravitational field strength, and sur- Prsuead2'C
roundings. The limits are obtained experi-
mentally by determining thle limiting mixture ignition of meothane-air mixtures (75). For
compositions between flammable and nion- example, at 0.2-millijoule (mij) spark is inade-
flammable mixtures (244). That is, quate to ignite even a stoichiometric mixture at
atmospheric pressure and 260 C; a 1-mj spark
LT. 11[C,+C~1,(1) can ignite mixtures containing between 6 and
and 11.5 volume-percent methane, etc. Such limit-
UTT.p= 1/2[(,,+ C1.], (2) mixture compositions that depend on the igni-
tion source strength may be d~efined ats limits of
where L,.P and U
7
.P are the lower andl uppe.r ignitibiity or more simply ignitibility limits;
limits of flmmability, respectively, at at speci- th'ey are thus indicative ot the ignitin'g ability
fled temperature and pressure, C,,, and C, are of the energy source. Limit mixtures that tire
the greatest and least concentrations of fuel in essentially independent of the ignition source
oxidant that are nonflammnable, and ('if and strength and that give a measure of the ability
(?gf are the least and greatest concentrations of of at flamie to propagate iaay from the ignition
fiiel in oxidant that aire flamimable. Tile rate source mnay be defined ats lim'its of flammability.
at which a flamie propagates through it flamn- Considerably greater spark energies aire required
mable mixture depends on at number of factors, to establish limits of flammability than tire
including temperature, pressure, amnd mnixture required for limits of ignitibility (218); further,
composition. It is at minimui ait thle limits of more energy is usually required to establish tile
flunmnuabifity and at maximumi at near' stoichio- upper limit thani is requiredl to establish thle
metric mixtures (130). lower limit. !n general, when the sour-ce
The Bureau of Mlines has adop)ted at st andaird strength is adlequate, mixtures just, outside the-
apparatus for limit -of-flammiability doeteininail- range of flammnable comp1
1
ositionls Yield flaime
tions (40). Originally designed for use ait caps when ignitedl. These flaiiie caps prop~agate
atmospheric pre'ssu~re and roo~m t emplera ture, on Iv at short, (listaunce fromn the ignitioni source
it, wats later mnodified for use t.t rediuced preg- illit auniifor in iixture. The reason for t his
;tire, 1wIcloa mgasar-a gl il a e seenii i figure 2 which shows (,he effec't of
tile hase, of thme 2-inch, glass, flaine-propagation temp~erature oil limits of flaimmnlability at at
tube. T i riodifiCat io1 iintr0otlueVi' I ihCullt r ('on1sUta inlitil pressurem. As the temperat tire
that wats not inmiiediatelY apparenlt, as thle is increased, t he lower limit delec(ases and1( tile
spark energ 'v was lill alwalys adiequate for uise ill upper limiit jecretses, Thus, since at localized
hliit-of 'I* mniiv(etmiutos F'i'ure energy somirc(. elevates' the ternpermit tire of
illmusita , tihle effit oif miixtur'e conmpositionl on nlemimby gases, even at nonflaniiale mixture vall
hle electrical spark energy reqjuiremlenits fora propaigate llaiiie at shorit distance fromin lhe
DiEFINIT'IONS AND THEORY 3
Saturated vapr- limits of flammability has been questioned.
aurmxtur Upper After a thorough study, Linnett and Simpson
z limit concluded that while fundamental limits may
exist there is no experimental evidence to
indicate that such limits have been measured
Auto- (18). In a more recent publication, Mullins
i t Fignition
reached the same conclusion (154). Accord-
Mist Flammable
ingly, the limits of flammability obtained in an
apparatus of suitable sise and with a satis-
' 9factory ignition source should not be termed
8 fundamental or absolute limits until the exist-
ence of such limits has been established.
A limit However, as long as experimentally determined
limits are obtained under conditions similar to
those found in practice, they may be used to
I I AlT design installations that are safe and to assess
r
t u
AIT potential gas-explosion hazards.
TEMPERATURE-
Industrially, heterogeneous single-phase (gas)
Fiouis 2.--Effect of Temperature on Limits of and multi-phase (gas, liquid, and solid). flaa.
Flammability of a Combustible Vapor in Air at a mable mixtures are probably even more impor-
Constant Initial Pressure. tant than homogeneous gas mixtures. Un-
fortunately, our knowledge of such mixtures
source. That is, a nonflammable mixture (for is rather limited. It is important to recognire,
example, com )osition-temperature point A, however, that heterogeneous mixtures can
fig. 2) may become flammable for a time, if its ignite at concentrations that would normally
temperature is elevated sufficiently (composi- be nonflammable if the mixture were homoge-
tion-temperature point B). neous. For example, I liter of methane can
Flammable mixtures considered in figure 2 form a flammable mixture with air near the top
fall in one of three regions. The first isleft of of a 100-liter container, although a nonflam-
the saturated vapor-air mixtures curve, in the mable (1.0 volume-percent) mixture would
region labeled "Mist". Such mixtures consist, result if complete mixing occurred at room
of droplets suspended in a vapor-air mixture; temperature. This is an importa:t concept,
they are discussed in greater detail in the section since layering can occur with any combustible
on formation of flammable mixtures. The second gas or vapor in both stationary and flowing
lies along the curve for saturated vapor-air mixtures. Roberts, Pursall and Sellers (176-
mixtures; the last and most common region lies 180) have presented an excelent series of review
to the right of this curve. Compositions in the articles on the layering and dispersion of
second and third regions make up the saturated methane in coal mines.
and unsaturated flammable mixtures of a The subject of flammable sprays, mists, and
combustible-oxidant system at a specified foams is well-documented (5, 18, , 7, 76,
pressure. 05, 215, 45). Again, where such hetero-
In practice, complications may arise when geneous mixtures exist, flame propagation can
flame propagation and flammability limit deter- occur at so-called average concentrations well
minations are made in small tubes. Since heat below the lower limit of flammability (86);
is transferred to the tube walis from the flame thus, the term "average" may be meaningless
front by radiation, conduction, and convection, when used to define mixture composition in
a flame may be quenched by the surrounding heterogeneous systems.
walls. Accordingly, limit determinations must
be made in apparatus of such a size that. wall IGNrON
quenching is minimized. A 2-inch-ID vertical
tube is suitable for use with the paraffin Lewis and von Elbe (130). Mullins (153,154)
hydrocarbons (methane, ethane, etc.) at at- and Belles and Swett (156) have prepareA
mospheric pressure and room temperature. excellent reviews of the processes associated
lowever, such a tube is neither satisfactory with spark-ignition and spontaneous-ignition
under these conditions for memny halogenated of a flammable mixture. In general, many
and other compounds nor for paraffin hydro- flammable mixtures can be ignited by sparks
carbons at. very low temperatures and pressures having a relatively small energy content (1 to
(1,97, 2, /N). 100 mj) but a large power density (greater
Because of the many difficulties associated than 1 megawatt/cm). However, when the
with choosing suitable apparatus, it is not source energy is diffuse, as in a sheet discharge,
surprising to find that the very existence of the even the total energy requirements for ignition
4 FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE OASES AND VAPORS
may be extremely large (79, 82, 85, IeS, 181, 1950 C; another equation must be used for
28). There is still much to be learned in this data at higher temperatures. The solid lines
field, however, since electrical discharges are in figure 4 define an 8 C' band that includes
not normally as well defined in practice as the experimental points in the temperature
they are in the laboratory. range from 1700 to 1950 C.
When a flammable mixture is heated to an
elevated temperature, a reaction is initiated that FORMATION OF FLAMMABLE
may proceed with sufficient rapidity to ignite MIXTUES
the mixture. The time that elapses between the
instant the mixture temperature is raised and In practice, heterogeneous mixtures are
that in which a flame appears is loosely called always formed when two gases or vapors are
the time lag or time delay before ignition. In first'brought together. Before discussing the
general, this time delay decreases as the tem- formation of such mixtures in detail, a simpli-
perature increases. According to Semenov fled mixer such as that shown in figure 5 will be
(193), these quantities are related by the considered briefly. This mixer consists of
expression
chambers I and 2 containing gases A and B,
0.22E respectively; chamber 2, which contains a
log r=---+B, (3) stirrer, is separated from chamber 1 and piston
3 by a partition with a small hole, H. At time
where T is the time delay before ignition in te, a force F applied to piston 3 drives gas A
seconds; E is an apparent activation energy for into chamber 2 at a constant rate. If gas A
the rate controing reaction in calories per is distributed instantaneously throughout cham-
mole; T is the absolute temperature, expressed ber 2 as soon as it asses through H, a coupo-
in degrees, Kelvin; and B is a constant. Two sition diagram such as a given in figure 6
types of ignition temperature data are found in results; the (uniform) piston motion starts at
urrent literature. In the first, the effect of t. and stops at t,. However, if a time interval
temperature on time delay is considered for de- At is required to distribute a samll volume from
lays of less than 1 second (127, 158). Such data chamber 1 throughout chamber 2, then at any
are applicable to systems in which the contact instant between t. and t, + At, a variety of
time between the heated surface and a flowing mixture compositions exists in chamber 2.
flammable mixture is very short; they are not This situation is represented schematically in
satisfactory when the contact time is indefinite. figure 7. The interval of time during which
Frt hefactr e n (3)contatti e is of de i se heterogeneous gas mixtures would exist in the
Further,second
case is determined in part by the rate
it gives only the time delay for a range of tem- at which gas A is added to chamber 2, by the
peratures at which autoignition occurs; if the size of the two chambers, and by the efficiency
temperature is reduced sufficiently, ignition does of the tirrer.
not occur. From the standpoint of safety, it of the stirrer.
is the lowest temperature at which ignition can In practice, flammable mixtures may form
occur that is of interest. This is called the either by accident, or design. When they are
minimum spontaneous-ignition, or autoignition, formed by accident, it is usually desirable to
temperature (AIT) and is determined in a uni- reduce the combustible coicentration quickly
formly heated apparatus that is sufficiently nona b mirr n erta n con-
large to minimize wall quenching effects (194, nonflammable mixtures. Under certain con-
287). Figures 3 and 4 illustrate typical auto- ditions, it may be possible to increase the con-
ignition-temperature data. In figure 3 the bustible concentration so as to produce a
nonflammable mixture. Such procedures are
minimum autoignition-temperature or AIT discussed in greater detail in the following
value for n-propyl nitrate is 1700 C at an section.
initial pressure of 1,000 psig (243). Data in Fectinb
this figure may be used to construct a log T Flammable mixtures are encountered in
I production of many chemicals and in certain
versus , plot such as that in figure 4. Such physical operations. These include gasfreeing
ic tank containing a combustible gas (232),
graphs illustrate the applicability of equation drying plastic-wire coating, and recovering
(3) to autoignition temperature data. The solvent fromt solvent-air mixture. When
equation of the broken line in figure 4 is layering can occur, as in drying operations, it
is not enough to add air at such a rate that the
log 12.3 10 25 ( verall mixture composition is below the lower
ogr -25T. . (4) limit of flammability (assuming that uniform
mixtures result). Special precautions must, be
In 'his specific case, equation (4) is applicable taken to assure the rapid formation of non-
only in the temperature range from 1700 to flammable mixtures (235). When a batch
DEFINITIONS AND THEORY5
4o 1* 1 I I i
360 Sample
A vol, cc
y 0.50
32 0.75
320-
1.00
X 1.50
0 1.75
C
0 2.00
28
0 2.25
A 2.50
v 2.75
Q 240 -
A 300
0-
0 325
0 0
w 2000
m. Region of
160-
au toignition
LLI
0 120I
w
80--
K 0
0 JAT I 1 %
150 160 170 180 190 200 210 220
TEMPERATURE, OC
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 tures that are initially above the upper limit of
Ce taken; a constituent at a partial pressure flammability may become flammable. A simi-
near its vapor pressure value may condense lar effect must be considered when mixtures are
when it is momentarily compressed by addition sampled with equipment that is cooler than
of other gases or vapors. Accordingly, mix- the original sample; if vapor condenses in the
TEMPERATURE, OC
210 200 190 I80 170
600 1
|
AWT
400 V
l:I/
8Co
'0200-
0
80- Region of
-- outoignition
w 60
_ 0
tL
co 40-
/o
U020 A
I- 20
A
10 0
8-
EI IIII0
2.05 2.10 2.15 2.20 2.2 2.0
RECIPROCAL
TEMPERATURE,
15r.
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 mists and sprays (particle sizes below 10 mi-
accurate data. A flammable mixture sampled crons) the combustible concentration at the
in this manner may appear to be nonflammable lower fimit is about the same as that in uniform
and thus create a hazardous situation (236). vapor-air mixtures (17, 18, 22, 4, 76, 245).
A flammable mixture can also form at tern- However, a. the droplet diameter increases, the
peratures below the flash point of the liquid lower limit appears to decrease. In studying
combustible either if the latter i6 sprayed into this problem, Burgoyne found that coarse drop-
the air, or if a mist or foam forms. With fine lets tend to fail towards the flame front in an
DEFINITIONS AND THEORY 7
Chamber I Chamber 2 100oo-
- fl3 Gas AGs8
Figure 5.-Simplified mixer.
1
0100
FIGURE 5.-Simplified Mixer. ELAPSED TIME
Z~ 10 - FIGURE 7.-Compo ition of Gas in Chamber 2, Figure
5 (Delayed Mixing).
16 of fine droplets and vapors (24). With sprays,
1 0E the motion of the droplets also affects the limit
0 composition, so that the resultant behavior is
rather complex. The effect of mist and spray
Qi 5 7 droplet size on the apparent lower limit isillus-
S trated in figure 8. Kerosine vapor and mist
0 0- 1 100 0 data were obtained by Zabetakis and Rosen
10 If (2045); tetralin mist data, by Burgoyne and
ELAPSED TIME Cohen (24); kerosine spray data, by Anson
(5); and the methylene bistearamide data, by
FIGURE 6.-Composition of Gas in Chamber 2, Figure Browning, Tyler, and Krall (18).
5 (Instantaneous Mixing). Flammable mist-vapor-air mixtures may
occur as the foam on a flammable
liquid col-
upward propagating flame, and as a result the lapses. Thus, when ignited, many foams can
concentration at the flame front actually ap- propagate flame. Bartkowiak, Lambiris, and
proaches the value found in lower limit mixtures Zabetaki found that the pressure rise AP pro-
100
-0.07
- ---- Stoichiometric
B .L 80 - mixture (decane-air)
17 - .06
Kerosine spray
0 0 -. 05.aZ
U 60 Kerosine vapor
E and mist
.
-. 04 E
0 0
00
.- Methylene
Z bistearamide spray
20.0
o
-
retaln is -Tetralin mist .01 8
0 20 40 60 80 100 120 140 160
DROP'.ET DIAMETER, miictonv
FiouRJF 8.-Variatioi i" Lower Limits of FlanitabilIity of Various Combustibles in Air m~ a Function of D~roplIet
Aiameter.
duced in an enclosure by the complete combus- enriched air at reduced pressures (215). Air
tion of a layer of foam of thickness A, is proper- can become oxygen-enriched as the pressure is
tional to h, and inversely proportional to hA, reduced, because oxygen is more soluble than
the height of the air space above the liquid nitrogen in most liquids (83). Thus the pres-
before foaming (7). That is ence of foams on combustible liquids are a po-
tential explosion hazard.
A flammable foam can also form on nonflam-
ha mable liquid if the foam is generated bi a flam-
unable gas mixture instead of air. urgoyne
Pressures in excess of 30 psi were produced by and Steel, who studied this problem, found that
the ignition of foams in small containers, the flammability of methane-air mixtures in
Thomas found that an additional hazard water-base foanis was affected by both the wet-
could arise from production of foams by oxygen- ness of the foam and the bubble size (28).
PRESENTATION OF DATA
Limit-of-flammability data that have been With either type of presentation, addition of
obtained at a specified temperature and pressure methane, oxygen, or nitrogen to a particular
with a particular combustible-oxidant-inert mixture results in formation of a series of mix-
system may be presented on either a triangular tures that fall along the line between the com-
or a rectangular plot. For example, figure 9 position point (for example, Mi in figures 9 and
shows a triangular flammability diagram for 10) and the vertices of the bounding triangle.
the system methane-oxygen-nitrogen. This For example, addition of methane (+CH,) to
method of presentation is frequently used mixture M1 yields initially all mixture corn-
because all mixture components are included positions between Mi and C (100 pct CH
4
).
in the diagram. However, as the sum of all After a homogeneous mixture is produced, a
mixture compositions at, any point on the tri- new mixture composition point, such as M2, is
angular plot is constant (100 pct) the diagram obtained. Similarly, if oxygen is added (+02)
can be simplified by use of a rectangular plot to the mixture represented by point Mi, all
(24.). For example, the flammable area of compositions between M1 and 0 (100 pct O)
figure 9 may be presented as illustrated in are obtained initially; if nitrogen is added, all
figure 10. As noted, the oxygen concentration compositions between MI and N (100 pct N
2
)
at any point is obtained by subtracting the are obtained initially. If more than one gas is
methane and nitrogen concentrations at the added to M1, for example, methane and oxy-
point of interest from 100 as follows: gen, the resultant composition point may be
Pet 02=100 pet-pct CH
4
-pct N
2
. (6) obtained by considering that the mixing process
00
+ +CH
4
06
io o MI -02
J
4
M3~
+N
2
Air
/ -
Flammable 0
S mixtures
//
/O /7
,Min 02
r1gz::aticol C/N 0'
100 90 so 70 60 50 40 30 2 0 i0 0
0 OXYGEN, volume-percent
FIGURE 9.--Flammability Diagram for the Syatem Methane-Oxygen-Nitrogen at Atmospherilo Pressure and 200 C.
9
L ______
10 FLAMLABILITY CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS
100
- L
% 0
2
-100%-%
CH
4
-% N
2
80-
C
160 02 +CH
4
E
-N
-N 1 N 2
zA
I
40 6
44- ! /4
Fla mmaoble
20-
mixtures-
Lriticl
C/NL
MiN
0 20 40 60 Aso 100
NITROGEN, volurne-percent
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 composition point (for example, M1 in figures 9 and
to Mi and the gases are mixed thoroughly to 10) shifts away from the vertices C, 0, and N
give M2. Oxygen is then added to Af2 with along tile extensions to the lines MI-C, Mi
mixing to give a new (flammable) mixture, M3. -O and Mi -N, indicated in figures 9 and 10
If the methane and oxygen were added to a by the minus signs. The final composition is
fixed volume at constant pressure, some of M 1 determined by the percentage of each component,
and then of M2 would escape and mix with the removed from the initial mixture.
surrounding atmosphere. In many instances Mixtures with constant oxygen-to-nitrogen
this is an important consideration because the ratio (as in air), are obtained in figures 9 and 10
resulting mixtures may be flammable. For by joining the apex, C, with the appropriate
example, even if an inert gas is added to a mixture composition along the baselne, ON.
constant-volume tank filled with methane, Thus, the Air line, CA, (fig. 10) is formed by
flamnmable mixtures (-an form outside the tank joining C with the mixture A (21 percent 0
as the displaced methane escapes into the +79 percent N2). Using this latter point, A,
atmosphere. If the inethant, is not dissipated one can readily determine the mixture cornposi-
quickly, a dangerous situation
1
can arise. tions that are formed when mixture M1 is
When a mixttire compoment is removed by displaced from an enclosure and mixed with air.
condensation or absorption, the corresponding Initially, all mixture compositions between Af I
ie
PRESENTATION OF DATA 11
and A would form. Since these would pass %oir 100 % combustible vapor-% inert
through the flammable mixture zone, a hazard- r
ous 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 flam-
mable 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 i
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, INERT, volume-Percent
oxygen, chlorine, etc.) concentration needed to FIouRm ll.-Effect of Initial Temperature on Limit.
support combustion of a particular combustible of Flammability of a Combustible Vapor-Inert-Air
at a specified temperature and pressure. In System at Atmospheric Pressure.
figures 9 and 10, the tangent line gives the 9 -
minimuin oxygen value (Min 01, 12 volume- % air 100 % % J P4 vapor
percent) required for flame propagation through 8 V
methane-oxygen-nitrogen mixtures at 260 C 1E
and 1 atmosphere. . 7
Another important construction line is that
which gives the maximum nonflammable com- 0
bustible-to-inert ratio (critical C/N). Mixtures *
along and below this line form nonflammable 2
mixtures upon addition of oxidant. The critical / Flammable
C/N ratio is the slope of the tangent line from mixtures
the origin (Figs. 9 and 10), 100 percent oxidant, 4-
to the lean side of the flammable mixtures a
curve. The reciprocal of this slope gives the > 3
minimum ratio of inert-to-combustible at which .r
nonflammable mixtures form upon addition of a 2 -
oxidant. It is of interest in fire extinguishing. -
An increase in temperature or pressure iL
usually widens the flammable range of a
particular combustible-oxidant system. The
I
effect of temperature is shown in figure 11; 0 200 400 600 800
two flammable areas, T, and T,, are defined for
a combustible-inert-oxidant system at constant INITIAL PRESSURE, mm Hg
presure. The effect of temperature on the Frouaz 12.-Effect of Initial Presure on Limita of
limi!ts of flammability of a combustible in a Flammability of JP-4 (Jet Fuel Vapor) in Air at
specified oxidant was previously shown in 269 C.
figure 2. This type of graph is especially
useful since it gives the vapor pressure of the downward propagation of flame is used. Since
combustible, the lower and upper temperature T, is the intersection of the lower-limit and
limits of flammability (T, and Tv), the Ham- vapor-pressure curves, a relationship can be
mable region for a range of ten eratures, and developed between Tl,, or the flash point, and
the autoignition temperature (AlT). Nearly the constants defining the vapor pressure of a
20 of these graphs were presented by Van combustible liquid. An excellent summary of
Dolah and coworkers for a group of corn- such relationships has been presented by M ullins
bustibles used in flight vehicles (218). for simple fuels and fuel blends (154).
The lower temperature limit, TL, is essentially At constant temperature, the flammable
the flash point of a combustible in which up- range of a combustible in a specified oxidant can
ward propagation of flame is use
4
; in general, it be represented as in figure 12. Here the flam-
is somewhat lower than the flash point, in which mable range of JP-4 vapor-air mixturm is given
rL1
-~ L"
II
_ p
S
-- --
- _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 The flammable range is the same as that de-
generalized flammability diagram of a particular picted in figure 2. At constant temperature
combustible-oxidant system can be presented (for example, T), the flammable range is
in a three dimensional plot of temperature, pres- bounded by the lower limit curve LIPLI and the
sure, and combustible content-as illustrated upper limit curve U
1
Pc,; the broken curve
in figure 13 (244). Here, composition is given PLIPUI represents the low pressure (quenched)
as the ratio of partial pressure of the combustible limit. The flammable range is the same as
vapor, pVAPOR, to the total pressure P. For any that depicted in figure 12. A similar range is
value of P, the limitis of flammabiity ar given defined at temperatures T,, T3, and T# which
as a function of the temperature. For example, are less than T,. However, at T3 and T, the
at I atmosphere (P= 1), the flammable range is upper limit curves intersect the vapor pressure
bounded by the lower limit curve L4LL", and curves, so that, no upper limits are found above
the upper limit curve UU2; all mixtures along U. and U,. In other words, all compositions
the vapor pressure curve L4 U,' U are flammable. along U.U. and U.L4 are flamuable. The curve
PRESENTATION OF DATA 13
28
-T
A
24
X air =100 - % gasoline vapor - %water vapor
20
C
4 Nonflammablemmixture
0B 10 20 30 40 50 60 70 80 90 100
WATER VAPOR, volumtu-percent
70 100 120 140 150 160 ]70 180 190 200 210 212-
I I I I I .. I = i I I IL
CORRESPONDING AIR-SATURAT!ON TEMPERATURE. "F.
Fionw 14.- Flammability Diagram for the System Gasoline Vapor-Water Vapor-Air at 700 F (2i

C) and at
2120 F (iO0

C) and At :u spheric Pressure.
L
4
'LUJ UZU defines the range of limit mixtures percent-water-vapor point. If water vapor is
which are saturated with fuel vapor. Further, removed by condensation or absorbtion, the
since L
4
is the saturated lower limit mixture at~ composition point will move along the extension
one atmosphere, TW is the flash point, to the line drawn from A to the 100-percent-
Some of the points considered in this and the water-vapor point. The same applies to the
prex ious ,ectioni are illustrated in figure 14 other components, air and gasoline, as indicated
(A73). This is the flammability diagram for earlier. .Moreover, if more than one component
the system gasoline v-apor-wWterr vapor-air at is involved, the final composition point can be
700 F(2 10 () and 2120F (100 C) and atnos- found by considering the effect of each cor-
pheric pres.ure. The air saturation tempera- ponent separately. po
ture, that is, the temperature at which saturated Figure 14 is of special interest since it can be
air contains the quantity of water given on the used to evaluate the hazards associated with a
water vapor axis, is t1ls included. For precise gas-freeing operation. For example, mixture
work, a much larger graph or an enlargement represents a saturated gasoline vapor-air-
of the region from 0 to 8 percent gasoline vapor water vapor mixture at 700 F. A more volatile
and from 0 to 30 percent water vapor ould gasoline than the one used here would give a
be used. However, figure 14 is adequate here. saturated mixture with more gasoline vapor
If water vapor is added to a particular mixture and less air in a closed tank, a less volatile
A, all mixture compositions between t and gasoline would give less gasoline vapor and
pure water vapor will form as noted (if the more air. In any event, if a continuous supply
temperature is at least 2120 F), and the corn- of air saturated with water vapor is added to a
position point will shift towards the 100- tank containing mixture A, all compositions
14 FLAMMABILIT1 CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS
between A and B (air plus water vapor) will be between points along AE and B. Again, as
formed until all the gasoline vapor is flushed the water vapor in these mixtures condens i
from the tank, and mixturv B alone remains. outside the tank, the composition of the result-
If steam is used to flush mixture A from the ant mixtures will shift away from the 100-
tank, all compositions between A and C will percent-water-vapor point, C. The mixture in
form until all the gasoline vapor has beer the tank will remain at E unless air is used to
flushed from the tank and only steam remains flush the tank, in which case mixture composi-
(at 2120 F or higher). If the tank is permitted tons between E and B will form. Again, if
to cool, the steam will condense and air will be the water vapor within the tank condenses, the
drawn into the tank giving mixtures along mixture composition will shift away from C.
C-B. At 700 F, only air plus a small amount In any event, at this temperature (175

F), the
of water vapor will remain.
If hot water and water vapor at 1750 F are addition of air to mixture E will lead to forma-
used to flush mixture A from the tank, the tion of flammable mixtures. Thus, mixture A
mixture composition can only shift along AC to cannot be flushed from a tank without form ing
E. Mixtures between A andE that are flushed flammable mixtures, anless steam or some other
from the tank mix with air to give mixtures inert vapor or gas is used.
L.A
DEFLAGRATION AND DETONATION PROCESSES
Once a flammable mixture is ignited, the weight, of the burned gases, and T is the final
resulting flame, if not extinguished, will either (16, ',mttic) temperature of the products. With
attach itself to the ignition source or propagate otle 1 eCloisurem, or with noncentral ignition,
tra)m it. If it propagates from the source, the the flame front is disturbed by the walls before
propagation rate will be either subsonic (de- ,orihuntion is completed, so that calculated
ilagration) or supersonic (detonation) relative pressure cannot be expected to approximate
to the unburned gas. If it is subsonic, the pres- actual pressure. Even with spherical enclosures,
sure will equalize at the speed of sound through- the flame front is not actually spherical, so that
out the enclosure in which combustion is taking the walls tend to disturb the flame before corn-
place so that the pressure drop across the flame hustion is complete (118, 130). A graph of the
(reaction) front will be relatively small. If the pressure developed by the combustion of a
rate is supersonic, the rate of pressure equaliza- stoichiometric methane-air mixture (central
tion will be less than the propagation rate and ignition) in a 19.7 cm diameter, 9-liter cylinder
,hire will be an appreciable pressure drop across is given in figure 15. The calculated pressure
the flame front. Moreover, with most con- for a 9-liter sphere is included for comparison;
butible-air mixtures, at ordinary temperatures, K in equation (7) was evaluated from the
the ratio of the peak-to-initial pressure within experimental curve at 70 milliseconds. The
the enclosure will seldom exceed about 8:1 in calculated curve follows the experimental curve
the former, but may be more than 40:1 in the closely about 75 milliseconds, when the latter
latter case. The pressure buildup is especially curve has a break. This suggests that the
great when detonation follows a large pressure flame front was affected by tbe cylinder walls
rise due to deflagration. The distance required in such a way that the rate of pressure rise
for a deflagration to transit to a detonation decreased, and the experimental curve fell below
depends on the flammable mixture, temperature, the calculated curve. Further, since the com-
pessure, the enclosure, and the ignition source. bustion gases were being cooled, the maximum
ith a sufficiently powerful ignition sourbe,
detonation may occur immediately upon igni- 00
tion, even in the open. However, the ignition
energy required to initiate a detonation is Calculated I
usually many orders of magnitude greater than (9-liter sphre)--, 11
that required to initiate a deflagration (3, 249). 80 I I Experimental
DEFLAGRATION
t (9-liter cylinder)
Where a deflagration occurs in a spherical
L 60
enclosuire of volume V with central ignition, the ci)
approximate pressure rise AP at aLv instant t &
itter ignition is given by the expressions: W
c/n 40-
APA7 _]P= (7) Wu)
and
0.
1" = A- _.'- (I) 20
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 0 40 80 120 160
number of inoles of gas in the initial mixture, ELAPSED TIME, milliseconds
n, is the nU'nl)er of moles of gas in the hurned
gases, Al7 is the average molecular weight of the Fiuar 15.---Pr(wssure Produced by Ignition of a 9.6
Volum(",Percent Methane-Air Mixture in H 9-Liter
initial mixture, -Ifb is the average molecular Cylinder (E-xperimental).
15
16 FLAMMABILITY CHARAC*TERISTICS OF COMBUSTIBLE GASES AND VAPORS
pressure fell below the calculated value. The Wolfson and Dunn have developed generalized
minimum elapsed time (in milliseconds) re- charts that simplify the operations involved in
quired to reach the maximum pressure appears obtaining the pressure ratio as well as the den-
to be about 75 iV for the paraffin hydrocarbons sity and temperature/molecular weight ratios
and fuel blends such as gasoline; V is the across the detonation wave and the energy
volume in cubic feet in this case. release in the detonation wave.
Many investigators have measured and cal-
culated detonation and reflected pressures
DETONATION
resulting from detonation waves (54 57, 204).
Figure 16 from the data of Stoner and Bleakney
Wolfson and Dunn (52, 230) have expressed (204) gives the detonation velocity, the static
the pressure ratio P2/P
1
across a detonation or detonation pressure, and the reflected pres-
front as sure developed by a detonation wave propa-
P
2
I gating through hydrogen-oxy en mixtures at
(,,M,
2
+ 1), (9) atmospheric pressure and 180 C.
where %, is the specific heat ratio of the burned BLAST PRESSURE
gases, y is the specific heat ratio of the initial
mixture, and is the Mach ntunber of the
diretatond wv ithe respct tomber the The pressures produced by a deflagration or
detonation wave with respect to the initial a detonation are often sufficient to demolish an
mixture. M, is given in terms of the tempera- enclosure (reactor, building, etc.). As noted, a
tures T and molecular weights W of the initial deflagration can produce pressure rises in excess
and final mixtures by the expression: of 8:1, and pressure rises of 40:1 (reflected
pressure) can accompany a detonation. As
(
1
M'+l)' (ya)TW (10) ordinary structures can be demolished by pres-
"n
1
'
7
'Y2T,W
2
sure differentials of 2 or 3 psi, it is not surprising
3,500 50
P ( theoretical) 45
40
/ 35
30
2,500 25 E
E Ps (experimental)0
-20
15
2,000
10
5
1,500 I 1 1 I I I 0
20 30 40 50 60 70 80 90
H
2
, volume - percent
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 DETONATION PROCESSES 17
that even reinforced concrete structures have must be taken to protect the personnel and
been completely demolished by explosions of equipment from blast and missiles. Browne,
near-limit, flammable mixtures. Hileman, and Weger (16) have reviewed the
Jacobs and coworkers have studied the dam- design criteria for suitable barricades. Other
age potential of detonation waves in great detail authors have considered the design of suitable
(91, 170). They have considered the principlcs laboratories and structures to prevent frag-
involved in rupturing of pipes and vessels by ment damage to surrounding ar-9,s (44, 174,
detonations and the relevance of engineering 203, 20).
and metallurgical data to explosions. More
recently, Randall and Ginsburg (171) have in- TABLE 1.-Conditions of failure of peak over-
vestigated bursting of tubular specimens at pressure-sensitive dements (217)
ordinary and reduced temperatures. They
found that the detonation pressure required to Approx-
burst such specimens was, in general, slightly iniate
higher than the corresponding static-bursting
incident
pressure. Ductility of the test specimen ap- Structural element Failure blast
peared to have little effect on the bursting pressure
pressure, but ductility increased the strength (psi)
of pipes containing notches or other stress
raisers.
Glass windows, large Usually shattering, 0. 5-1.0
When a detonation causes an enclosure to and small. occasional frame
fail, a shock wave may propagate outward at a failure.
rate determined by characteristics of the Corrugated Asbestos Sh ittering. 1.0-2. 0
medium through which it is transmitted, and Aidiug.
the available energy. hi the shock velocity, , Corrigattd steel or Conneclion failure, 1.0-2. 0
aluninumrr panel- followed by buck-
is known, the resulting overpressure, (P-P,), ing. Iih I
is given by the expression (20.1) Wood siding panels, Usually failure oc- 1.0-2. 0
standard house curs at main con-
construction. nections, allowing
PP~l~ (11)a whole panel to
be blown in.
Concrete or cinder- Shattering of the 2. 0-3.0
where, is the ratio of specific heats, and a is the block wall panels, wall.
velocity of sound in the medium through which 8 or 12 inches
the shock wave passes. The approximate thick (not rein-
damage potential can be assessed from the data forced).
Brick wall panel, 8 Shearing and flexure 7. 0-8.0
in table 1 (217).
or 12 irches thick failures.
In conducting experiments in which blast (not reinforced).
pressures may be generated, special precautions
K
PREVENTIVE MEASURES
INERTING1
In principle, a gas explosion hazard can be
eliminated by removing either all flammable
mixtures or all ignition sources (23, 240). Unprotected
However this is not always practical, as many
industrial operations require the vresence of
flammable mixtures, and actual or potential
ignition sources. Accordingly special pre- C
cautions must be taken to minimize the damage
that would result if an accidental ignition were Co
to occur. One such precaution involves the W
use of explosive actuators which attempt to a.
add inert, material at such a rate that an Protected
explosive reaction is quenohi d before structural
damage occurs (70, 72). Figure 17 shows how
the pressure varies with and without such
protection. In the latter case, the pressure ti
rise is approximately a cubic function of time, ELAPSED TIME
as noted earlier. In the former case, inert is FIGURE 1-Pressure Variation Following Ignition of
added when the pressure or the rate of pressure a Flammable Mixture in Unprotected and Protected
rise exceeds a predetermined value. This Enclosures.
occurs at the time t, in figure 17 when the
explosive actuators function to add the inert.
As noted, the pressure increases momentarily where k is the thermal conductivity of the gas;
aboe the value found in the unprotected m is the mesh width; T is the mean bulk tern-
case and then falls rapidly as the combustion perature of the flame gases through the arrestor;
reaction is quenched by the inert. T. is the initial temperature of the arrestor; Q is
the heat lost by unit area of flame; x, is the
FLAME ARRESTORS AND RELIEF thickness of the flame propagating at the burn-
DIAPHRAGMS ing velocity, S; d is the diameter of an aperture;
A is the area of a hole in unit area of the
Inert atmospheres must be used when not arrestor face; and t is the arrestor thickness.
even a small explosive reaction can be tolerated. Equations (12) and (13) can be used to
However, when the ignition of a flammable determine the mesh width or aperture diam-
mixture would create little hazard if the burning eter needed to stop a flame having a particulur
mixture were vented, flame arrestors and relief approach velocity. In practice, application of
diaphragms could be used effectively. The these equations assumes a knowledge of the
design of such systems is determined by the flame speed in the system of interest. Some
size and strength of the confining vessels, ducts, useful data have been made available by
etc. Palmer and Rasbash and Rogowski (172, 173),
In recent studies of the efficiency of wire as well as by Jost (118) and Lewis and von Elbe
gauze and perforated block arrestors (161, 162), (130).
almer found the velocity of approach of the Tube bundles also may be used in place of
flame to be the major factor in determining wire scraens. SC3tt found that these permit
whether flame passed through an arrestor. For increased aperture diametera for a given ap-
these two types of arrestors, lie found the proach velocity (192).
critical approach velocity to be In practice, it may be desirable to install
pressure relief vents tu imit damage to duct
S1.75k(2-T.), systems where fli me may propafate. Rasbash
0
1,(12) and Rogowski (173) found that with propane-
and
and pentane-air mixtures, the maximum pres-
andT sure PM (pounds per square inch) developed in
V9"6kA"(T-T), (3 an open-ended duct, having a cross section of
dQ/13)
1 ft- is:
18
p
PREVENTIVE MEASURES
19
L L and it is thus proportional to K. For small
PM--O.7 ,and6< <48, (14) values of K it, was found that
where is the ratio of duct length to diameter.
PS=K.
D
As with ducts, larger pressures wvr6 obtained
However, the presence of an obstacle (bend, whea obstructions were placed in the oven.
constriction, etc.) in the path of escaping
gases increased the pressure due to resistance
to fluid flow by the obstacle. Location of a
relief vent near the ignition source decreased
P
2
the maximum pressure as well as the flame
speed. For values of K (cross-section area 4
of duct/area of vent) greater than 1, these I
authors found
O.8K<P, _i.8K, (15) P
1
L
0W
where 2_5K<32, and
6
<5T__.30. To keep the c
pressure at a minimum either many small
vents or a continuous slot was recommended
rather than a few large vents. 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 F iouE 18--Pressure Produced by Ignition of a
with flame arrestors. The vents tend not only Fiammable Mixture in a Vented Oven.
to reduce the pressure within a system following
ignition but also to reduce the flame speed, In designing explosion reliefs for ovens, Sim-
thus making all arrestors more effective. Un- monds ubbage pointcd out that (1) the
fortunately, in certain large applications (for reliefs should be c,.astrueted in such a way that
example, drying ovens), it is difficult to use they do not form dangerous missiles if an explo-
flame arrestors effectively. In such cases, sion occurs; (2) the weight of the relief must bc
greater reliance minst Ie placed on the proper small so that it, opens before the pressure builds
fue ,tioning of relief vents. Siesmonds and up to a dangerous level: (3) the areas and posi-
Cubbage (42, 43, 195) have investigated the tions of relief openings must be such that the
design of affective vents for industrial ovens, explosion pressure is not excessive; (4) sufficient
They found two peaks in the pressure re-ords free space must be utilized around the oven to
obtained during the vnting of cubical ovens pterrmit satisfactory operation of the relief and
(fig. 18). The first peak, Pi; the oven volume, minimize risk of burns to personnel; and (5)
I"; the factor, K; and the weight per unit oven doors should be fastened securely so that
area (lb/ft) of relief, w, were related as follows they do not open in the event of an explosion.
for -t 25 percent town gas -air mixture: Burgoyne and Wilson have presented the
results of an experimental study of pentane
vapor-air explosions in vessels of 60- and 200-
More generally,
cubic-foot volume (30). They found the rates
of pressure rise greater than could be predicted
Po(O.3Kw+0.4), (17) from laminar burning velocity data, so that the
effect of a relief area in lowering the peak
where S, is the burning velocity of the mixture pressure was less than expected. All experi-
tit the oven temperature.
ments were conducted at an initial pressure of
The first, pressure pulse was ascribed to the I atmosphere. Vent data for use at higher
release and mIotion o tAe relief vent following initial press,.res are summarized in an article
igniton; the sec('ond pulse, to (ontitue(d jurn- by Block (10); a code for designing pressure
ing at an inrcased rate. 'Phe secord pulse relief systems has been proposed in this article.
represents thip pressure drop across the vent, Other authors have considered the effects of
temperature and characteristics of the flare-
, Town US epetmane; pproxalnely 52 the hyroon 17 ICt cprtn mable mixture on vent requirements (14, 35,
,OWnogien, IS pet i ,thane; the i ,Uali ; i o" nr 8ydrc4u5I 46ns, 3 pet1
Otrot~i mmpet;ca~on ioaiieS pt; nd o~en 38 45,46,134 14., 18, 21)
The flammability data (limits of flamma- bustible vapor per liter of air at standard con-
bility, flash point, ignition temperature and ditions, that is, 00 C and 760 mm Hg (0.045 to
burning velocity) of the various chemical farn- 0.050 oz combustible vapor per cubic foot of
ilies exhibit many similarities. Accordingly, air) (247). This is illustrated in figure 19 in
the data presented here are grouped under the which some lower limits of flammability are
various commercially important families, blends, plotted against molecular weight; except for
and miscellaneous combustibles. methane, ethane, and propane all limit values
fall in a band between concentrations of approx-
PARAFFIN HYDROCARBONS imately 45 and 50 mg/r.
(C.H The following expression may be used to
R
2
n
2
) convert from a lower lirrit L in volume-percent
Limits in Air of vapor in the vapor-air mixture to one in
Lower and upper limits of flammability at milligrams of combustible, per liter of air at
250 C (or at the temperature noted) and 1 standard conditions:
atmosphere (L
25
and U25) for many members of lmg\ L (vol pct)
the paraffin hydrocarbon series are given in L (mg) 0 L(volpct)
table 2, together with the molecular weight, M, 1 1
vapor specific gravity, sp gr, stoichiometrict[ volmg
composition in air, C., (appendix B) and heat
of combustion, AH, (188). At room tempera- specific volume being volume of combustible
ture and atmospheric or reduced pressure, the vapor per milligram of combustible. At stand-
lower limits of flammability of most of this ard conditions (00 C and 760 mm Hg) this is
series fall in the range from 45 to 50 mg com- about 22.414/1,OOOM, where M is the molecular
6
5 X
i50mg/I
.4
L
45 mg/I
0
2240-
0
FLAMMABILITY CHARACTERISTICS 21
TABLE 2.-Properties of parafin hydrocarbons
Lower limit i air Upper limit in air
Net AH.
Pr I.n (W a U N Ur
Combustible Formula M (A -1) (n pr ol Rf (Vol g) R
p( ot) , pot) (
(vol pot) / )(vol ( ef t)vl) Ref.
Methane ............... CH, ----------- 16.04 0.65 9.48 191.8 5.0 0. 3 8 40 1.0 1.6 126 (40)
Ethane --------------- CaH .---------- 30.07 1.04 8.65 341.3 3.0 .53 1 4 12.4 2.2 190 4,
Propane ................. CsH .--------- 44.09 1.52 4.02 488. 5 2. A .52 42 (116) 9.6 2.4 210 (41
n-Butane...----.------ C
4
H0 --------- 88,12 2.01 3.12 635.4 1.8 .58 48 (11) 84 2.7 240 41
n-Pentane ------------ C all
- - - - - - - - - -
72.15 2. 49 2.55 782.0 1.4 .85 4 J40 7.8 3 1 270 (40)
n-Hexane ............. . --- C-- - ........... 88.17 2.96 2.16 928.9 1.2 .56 47 (546 7. 4 8.4 810 401
n-Heptane ................ C,Ha ........... 10020 3.46 1.87 107.8 1.05 . W 47 (546 6.7 8.6 820
n-Octane ----.---------- Call, --------- 114.23 3.94 1.65 1222.8 .96 .58 49 (56 .......... - ..................
n-No,,ane ----------.--- Cll, .--------- 1. . 28 443 147 169.7 . .6 48 ,146) .... 49.(546)
n-Decane -- _----------- Colin --------- 142.28 4.91 1.33 1516.6 '.75 .6 48 (4) '5.6 4.2 880.
n- Undecane ----------- --- C - ........... 1 .30 5.40 1.22 1663.6 .68 .6 8 (4 __
n-Dodecane ....... C- - ..---- _---- 170.33 5. 88 1.12 1810.5 .60 .84 46 (4 - -
n-Tridecane------Ciallsa,.........184.36 6.37 1.04 1957.4 .85 .3 40 (').........................-----
n-Tetradecane ............ Cills
0 . . . . . . . . .
.. 198.38 7.8 97 2104.3 b. 0 .62 44 )
n.1'entadecane --------- C::la............212 41 7:33 90 2231. .4 5.1 40 1( --- '---
n-llexadecane----------C 11
- - - - - - - - -
22644 7 82 85 2398. 51 44 (I
1 t-43' C. 4 Calculated value extrapolated to 25" C at Explosives Re. Center,
Uj.53 C. Federal Bureau of Mlnes.
t-86 C.
weight of the combustible. Since L (vol pct) Combining this equation with equation (21),
of most members of this series is much less than we have
100 percent, the lower limit can be expressed L
2
o(mg/1) -48 mg/i, (27)
as (for
paraffin hydrocarbons,
except methane,
L -0.45ML (vol pet). (20) ethane, and propane. Substitution of this
value into equation
(20) gives
At any specified temperature, the ratio of 107
the lower limit to the amount of combustible L2olO t (28)
needed for complete combustion, C,,, also is
approximately constant. This was first noted
by Jones (95) and later by Lloyd (138), who The following expression may be used to
found that for paraffin hydrocarbons at about convert a lower limit value in volume-percent
250 C,
to a fuel-air (weight) ratio:
L
21
. ru0.55C,,. (21) ! L (Vol pet)
For the complete combustion of the paraffin L(F .96/A)0_0-L (vol pt)j
hydrocarbons, we have:
The
reciprocal
expression
gives
the air-fuel
CaH
2
.+
2
+ (1.5n + 0.5)O--*nCO
2
+ (n-+ 1)H
2
0, (weight) ratio:
so that in air (22). 7NF-- -- (30)
50 * 00 -~* (30
100 vo
(Al LL (vol pct) j
C,=I+4.73(.5n 0.5 vo pet, (23)
1+4.773(1.5n+0.5) pAs noted, the lower limits given in figure 19
were determined at room temperature and at-
where 4.773 is the reciprocal of 0.2095, the mospheric or reduced pressure. Lower limits
molar concentration of oxygen in dry air. The vary with temperature as shown for methane in
values of C,, (appendix B) are included in table figure 20. The limit values obtained with up-
2. By weight these become ward propagation of flame (R1) fall fairly close
to a straight line that passes through the lower
1,000[12.01n+ 1.008(2n2)) ing limit value at 250 C and the flame temperature
( 22.414X4.773(1.5n0.5) 1- (24) (12250 C). This is in accordance with the
or White criterion that the flame temperature is
14.03n+2.02
1
g. constant at' the lower limit (RO2). The data
(,9.34 1 l _.n+0.5 J 1 (25) obtained by White with downward propagation
of flame fall along a line parallel to the line
Thus, through the limit values obtained with upward
C,,-87 mg/l, n>4. (26) propagation. Taking the value 1,300' C as
air 100%-% methane
5-
Flammable mixtures
-- Vapor pressure
4 curve Downward propagation of flame
E
r AIT
z
qc Upward propagation of flame
1 -
-200 0 200 400 600 800 1,000 1,200 1,400
TEMPERATURE,

C
Fiouim 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 hydrocar- the 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
adiabatic flame temperatures can be determined net heat of combustion in kilocalories per mole.
for lower limit mixtures using the data in table Then,
2 and appendix C (55). L, = 0.75
The straight lines of figures 21 and 22 are L
2
- So- (t-25). (34) given by: L
2
o t
L
Substituting
the value 1,040 for L
25
.AH, ob-
Li 2& - (t-25
0
), (31) tained by Spakowski (R01), we have (1,3000--250)
or L
L,- 1-0.000784(t-25*). (32) L
2
*-- 1-0.000721(t-250), (35)
which is also given in figure 23 for a limited
They are described in more general terms by a temperature range with the broken line.
23
6 f I
% air = 100%-% combustible
5
Flammable mixtures
-
4
MetPrpn
C,
9.
0> Ethane AIT
L" 3 -
j Propane
DButane
CD)
022- AIT-
Pentane
Hexane. -'" .
1 Heptane
Octane ,,
Deane
AIT
-200 0 200 400 600 800 1,000 1,200 1,400
TEMPERATURE, C
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 flames (87, 88), the upper limit also increases
pressure is needed to use figure 23. For exam- linearly with temperature. The effect of
pie, assuming a constant flame temperature, the temperature appears to be fairly well correlated
ratio L tL
23
. at 6000 C is 0.55. The calculated by the modified Burgess-Wheeler law:
lower limit of methane at 6000 C therefore is
5.0X0.55, or 2.75 volume-percent. The same 0.75
value can be obtained directly from figure 21. U- + y- (t-25
0
). (36)
From the modified Burgess-Wheeler Law curve,
L/L
25
.=0.585 at 6000 C, so that L4o.=2.92 If we assume that the heat release at the upper
volume-percent.
limit is equal to that at the lower limit, th en
Limit-of-flammability measurements are corn-
plicated by surface and vapor-phase reactions
that occur at temperatures above the auto- U = 0 0 ( )
ignition temperature. For example, Burgoyne - 1+0.000721(t-25). (37)
and Hirsch (25) have shown that methane'air
mixtures containing up to 5 percent methane A plot of Ui Un. against temperature fig. 24)
burn readily at 1,000' C. E'xperinments were was used to corn are recent experimental values
conducted with mixtures containing as lit le as of Rolingson and coworkers (18.e) for methane-
0.5 percent methane; figure 20 predicts that a air mixtures at 15 psig with those predicted bY
flame would not propagate through such a the modified Burgess-Wheeler law. The expen-r
mixture,
mental and calculated upper limits are givenx in
Flammability experiments at elevated ten- table 3 together with tlie difference U,,-
peratures indicate that in the absence of cool U..r, In each case, the difference is iess than
24 FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE aASES AND VAPORS
60
50 Higher
hydro-
carbons
Propane
40- Ethane
0 Methane
I3O
20-
I
10
-200 0 200 400 600 800 1,000 1,200 1,400
TEMPERATURE,

C
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 point. The lower temperature limits of paraffin
approximately within the limit of experimental hydrocarbon at atmospheric pressure are given
error. Earlier experiments of White (222) at in table 4.
temperatures to 4000 C, with downward flame
propagation, also are represented quite ade- TABLE 3.-Upper flammability limits, U, of
quately by equation (37). For example, White methane-air mixtures at 15 psig
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 Temperature U,.p,, (vol U.,1. (vol Uo.I -Uo. .
volume-percent at 300' C. The ratio of 5.35: (C) perceLt) percent) (vol percent)
4.50 is 1.17, which compares quite well with
UW./U&. =l.20 obtained from figure 24. 25 ---------- 15.5 15.5 0
Given the vapor pressure curve and the lower 100 -------- 16. 3 16. 4 .1
limit of flammability, the low " temperature 200 -------- 17.0 17. 5 .5
limit or approximate lash point of a combustible 30. 17. 9 18. 6 .7
can be calculated from either equation (32) or
(35) (.018). Approximate flash points were (J8I.
obtained previously, using only the vapor
pressure curve and the lower linit at ordinary Moderate changes in pressure do not ordi-
or elevated temperatures (1,54). The values narily affect the limits of flammability of the
obtained with this procedure are somewhat paraffins in air, as shown in figure 25 for pen-
low because the lower limit at any temperature tane, hexane, and heptane in air (241) in a
above the flash point is less than at the flash range from 75 to 760 mm Hg. The lower limits
TABLE 4.-Lower temperature limits and autoignltion temperatures oJ paraffln hAdrocarbonw at
atmospheric pressure
Autoignition temperature
Lower temperature limit
In air
In air In oxygen
C oF Ref. C 0 F Ref. o C F Ref.
Methane ----------------- 187 -305 (1) 537 999 (158) -------- ...........
Ethane ------------------ 130 -202 (1) 515 959 (937) 506 943 (94)
Propane ----------------- -102 -152 (1) 466 871 (158) ----................
n-Butane ------------------ 72 -96 (1) 405 761 (2,17) 283 542 (191)
Isobutane-----------------81 -114 (1) 462 864 (158) 319 606 (94)
n-Pentane- ----.-------- -48 -54 (1) 258 496 (194) 258 496 (144)
n-Hexane ----------------- 26 -15 (159) 223 433 (194) 225 437 (94)
n-Heptane --------------- 4 25 (169) 223 433 (237) 209 408 (94)
n-Octane ---------------- 13 56 (159) 220 428 (*37) 208 406 (191)
n-Nonane ---------------- 31 88 (159) 206 403 (2,37) - - --------
n-Decane ---------------- 46 115 (159) 208 406 (237) 202 396 (94)
n-l)odecane -------------- 74 165 (159) 204 399 (237) ........................
n-1(exadecane ------------- 126 259 (1) 205 401 (237) .........................
Caculated value.
1.2 7 7 p 7 I
N2
.8 -N
Modified Burgess-Wheeler Low
" .6 -N
.4
.4 -
Constant flame temperature
.2
01 1
-200 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
1.4 Neither expression is applicable when cool
flames are obtained. Substitution of equation
(21) for Lw. into equation (39) gives
1.3 U.=4.8 (40)
The limits of flammability of natural gas
1.2 - (85-95 pct methane and 15-5 pct ethane)
have been determined over an extended pres-
sure 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% , pressure. That is,
1
0
100 200 300 400 300
TEMPERATURE,'C L (vol pet) =4.9-0.71 log I' (atm), (41)
Fioum 24.-Effect of Temperature on U,/U. Ratio and
of Paraffin Hydrocarbons in Air at Atmospheric
Pressure in the Absence of Cool Flames.
U (vol pet) =14.1 +20.4 log P (atm), (42)
coincide, but the upper limits, by weight, with a standard error of estimate of 0.53 vol
increase with increasing molecular weight. pet for L and 1.51 vol pet, for U.
Be volume, at atmospheric pressure and 250 Although the limits of flammability are not
C, Spakowski (201) found that the upper and taffected significantly by moderate changes in
lower limits were related by the exprcs~sion: pressure, the temperature limits are pressure
dependent. As the total pressure is lowered,
U
26
. =-7.1L5'. (38) the partial pressure of the combustible must
also be lowered to maintain a constant corn-
However, the data presented here are correlated bustible concentration. The effect of pressure
more precisely by a somewhat simpler expres- on the lower temperature limit of the normal
sion: paraffins pentane, hexane, heptane, and octane
U
2
6.=6.5 421n. (39) in air, for pressures from 0.2 to 2 atmospheres,
400
~Heptane
z
0
! 300
z Hexane
Uj. Pentane
0 200
0-,",
Flammable mixtures
W W
= 100
o0
0 100 200 300 400 500 600 700 800
INITIAL PRESSURE, mm Hg
FIuu'aE 25.-Effect of Presure on Limits of Flammability of Pentare, Ilexane, and lieptane in Air at 26' C.
60
% air = 100%-% natural gas
50
C
40
E
.2 Flammable mixtures
9 30
20
z
10
0 100 200 300 400 500 600 700 800
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 TABLE 5.-Limits of flammability of methane in
were calculated from the L,,. values, the vapor chcrine
pressure curves, and the data of figure 23. (volume-pecnt)
Limits in Other Atmospheres Temperature, 0 C
Prevmre, Limits
Liim its of fla aininbility of soine paraffin y- p sig L5_100
drocarbots hav-e been determined in oxygen, 25 100 200
c h ,lo rin e , a n d o x id e s o f n itr o g 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 x y g e n a l ( in a w id e v a r ie t y o f t [. . U p p e r -- -- 7 0 6 6 -. -- 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
a n d p r e s s u r e (fig . 1 0 ) . L i m ii -o i-I ttlan .. a b ilit y 2 0(0 .. . . .- L o w ,r . .. ..-- - - - - - - - - - - - -
Iileasurements by Bartkowirik and Zabetaki.; pjwr 73 72 75
for mrthiane aii eliaic iii clilrinte at 1, 7.8,
-
wid i 4.6 atio spheres, riuiiiiig from
2
5 to 200
i nre , 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
gi'allhicall v t e liimi of fla inahbilit vof the first diagrani, exc pt one that represents only conl-
six INVIIiii*'s of lie paralnfihi series in air con- bustible 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 con-
aid 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 - Unfortunately, the methane-methyl bromide-
air 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
20-
carbons. Thus a recent industrial explosion
0~n. involvitig methvi b~romide prompted Hill to
Octane 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
:3 flananable mixtures 4t 1 atmosphere wits a
wider variety of eoncentrations than Jones had
Heptanereportad (96). This would sug,-e&, that, there
is no justification for the assumption that
Jones'
flammabii
r data
for methyl
bromide
were influenced bsy the presence of mercury
0Hexanepressure aire included in figure '8 amid are used
to form the approximate, brokeon, flammability
curves for the methane-methyl bromide-air
system.
-40- Data of Moran. and Bertschy for pentane-
prnoropropane-air, pentane-sulfur hexafluo-
Pentan ~ rie-air and peintane-perfiuoromethiane-air mix-
ture aeicuded in figure 32 (147). Data by
-60 IBurgoyne and Williams-Leir for hexane-methyl
-60 - 71 1bromnide-air and hexane-Freon-12 I (F-12;
0.2 0.4 0.6 1 2 CF
2
Cl
2
)-air mixtures have been included in
PRESSURE, atmospheres figure 33. These data were all obtained in
1'%-inch-diameter tubes. An investigation of
FIGURE 27.-Effect of Pressure on Lower Temperature flamm~biity of hexane-methyl bromide-air
Limits of Flammability of Pentane, Ilexane, lleptane, mixtures in a 4-inch tube indicated that an in-
and ctan in ir.crease in tube size (from 17 %-inclies to 4-inches-
ID) resulted in a narrowing of the flammable
TABLE 6.-Limits of flammability of ethane in range; the uipper limit decreased from 7.5 to
ch.,o ine 5.7 volume-percent. n-hexane vapor in air while
the lower linmit remained constant. The
(volume-percent) amount of methyl bromide required for extinc-
tion decreased from 7.05 volume-percent in the
Prsur, Liis Temperature, C13a'-inch tube to ti.0 volume-percent in the 4-
Pssure Liis____
inch tube. However, again this is not in line
25 100 200 with the results obtained by Hill with meth vI
______ ____bromide-air mixtures (84). Accordingly, winkl
the data obtained in approximately 2-inch tubes
9------------ {9wer-- 6. 1 2. 5 2.5 ' eeue ocnsc iue3,the Hill data,
Lppe ---- 58 58 - - - -
100 --------- JLowr-- 3.5 1 .0 1 . 0 obtained in *t larger apparatus, tire also used to
Ulpper_ __ 63 75 82 form the approximate, broken, flammability
200 --------- Lower.------------- ------- ----------- curves for the hiexane-inethyl bromide-air
~Upper~. -- (6 73 76 system.
______________________________ -- The limits of flammability diagrams for the
systemi n-hieptane-w.ater vapor-air tit 100' and
position. This 'oas been done for methane 2000 C (fig. 34) show the effects of temperature
through hexane (figs. 28-33). C onmpositionis on it systemi that, pro~iuces both nornial anid
aire determined directly fromi the abscissas (inert Cool flu~nes at atm~osphieric pressure (192). In-
conicent ration) amnd orintes (comnbust ible eonl- terestinigly enough, the mininima o xygen re-
centration-); the air in tany mixture is thle differ- quirernent for flaine propagation (Mii 002 t
emice between~ 100 percent and the sum of inert 200- C is thc samie for the (coo1 and normnal
and coinbuitible. Data of 13urgoyne amid flame regions in this instance. Further, the
XWiIliainr-. Leir for inethane-miethmyl bromide decrease in zninimnuni oxygen requirements
(.MeBr)-air an~d niethane-carbori tetrachlloride- 11 Trade names are Used for leniificatiol (only; this does not imply
atir mixtures aire included in figure 28 (29). endorseinent by the Bfureau of Wines.
FLAMMABILITY CHAP ACTERISTICS 29
16
-1- --
1
%air =100%--% methane.-% inert
14
12
MeBr
U~10
CCI4
E C02
Lj Flammable
H0H
0 10 20 30 40 50
ADDED INERT, volume-percent
FioUnt 28. -Limits of Flammability of Various Methane-Irer, '*ts.Air Mixii rs at 250 C and Atmospheric
Pressure.
(fromn 1:3.50.3 vourne-percent tt 1000 C to extinction (peak values) at 250 C and atmos-
12.80.3 volutre-pereent kit, 200' C) is wit' in pheric pressure tire about 28 and 42 volurne-
the range predicted by the miodified Burgess- percent, respectively. Ti. 7utio of these values
Wheeler law (equation 35 and fig. 231), HIow- is appro:, ,dtely inversel y proportional to the
ever, the a~'iiable data ve14)' to mear-r ait ratio of tfieii nieat capacities at the temnperature
present to permit at realistic evaluation of the ait which co .bustion occurs. Accordingly,
vaitidity of this latw, genieralized flammability diagramns of the type
N'Spection of the liinit-of-flaniuability curves given in figure 35 can be constructed for the
in figures 28 to 33 reveals that c cept for higher Itydr -arbons, ignoring Lhe presence of
miethatn( and ethane, Clio miinium amounts Of cool flamies. 31uch diagralms do not appear to
carbon dioxide and nitrogen required for flame be applicable to the Maogenated hydrocabons
14
%air =100%-% ethane-% inert
12
10-
-
E Flammable
La N2
z 6
4-
2-
0 10 20 30 40 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 Similar dtai atre given for ethane-carbon
in flames of limnit-mixture composition and, ats dioxide-atir (fig. :37) and ethie-nitrogen-atir
noted, may themselves propagate flamne. Cole- (fig. 318) (121), andl for propane-carbon dlioxideC-
man (37) hats found that time ratios of the peak air (fig. :19) and propaine-nitrogen-air (fig. 40)
values of a hialogenated hydrocarbon tire not (122). Miiii oxygen reqluiremuents for
constant but are proportional to the heats of flame propagation (inin 02) through natural
combustion of the combustibles to which the gas-nitrogen-air, ethane-nitrogen-alir, and pro-
halogenated ht'ydrocarbon is added. Jpane-nitrogen-itir att atmospheric and elevated
Few data aire available for the effects of pressures and 260 C are summarized in figure 4 1.
pressure on the limits of flammability of coin- [he inininmum 02 values in v'oluie-Vpi-rcent
b ustible-inert-air mixtures. One such set of are related to pressure ats follows:
data is sumnmairized in figur 36, which gives
the limits of flammability of natural gas for natural gas:
(85 pct nethane+15 pet ethane) nitrogen-air
at 260 C and 0, 500, 1,000 and 2,000 psig (106). Miil. 02= 13.98-1.68 log P;, (4:3)
10
% air = 100%-% propane-% inert
8
4,-
a)
) 6- Flammable
E N2 = mixtures
CL
0
0
2-
II I I
0 10 20 30 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: mixture containing 80 volume-percent methane,
15 volume-percent ethane and 5 volume-percent
Min. (=12,60-.36 log P; and (44) propane has a lower limit in air at 250 C and
for propane: atmospheric pressure of:
Min. O=13.29-1.52 log P; (45) 100 v
where I' is the initial pressure in paia.
80 5 5
The lower limit of flammability of any 5.0+3.0
-
2.1
mixture of the paraffin hydrocarbons can be
calculated by Le Chatelier's law (40, 12.9, 235): Liquid mixtures can be treated in the same way
if tie relative escaping tendencies of the various
300 ", components are known. Since the paraffin
L . _- X-, 100 (46) hydrocarbons obey Raoult's law (143), the
I I
partial pressure of each component can be
-,
calculated as follows:
where C, and L, are the percentage composition p=paNj (48)
and lower limit, respectively, of the -tb com-
bustible in the mixture. For example, a where p, is the vapor pressure of the i
'
com-
10 - 1
% air = 100%-% butane-% inert
8
6- ,N2 4-.
E
Flammable
> mixtures
z 4-
/Cst C02
2-
SI I
0 10 20 30 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 Ashman and Biichler (6), and Kuchta, Lam-
of the pure com ponent and N, is its mole biris, and Zabetakis (127). These are not
fraction in the solution. This procedure has normally used for safety purposes, unless there
been used to calculate the lower temperature is some assurance that the contact time of
limits of decane-dodecane blends in air (fig. 42). combustible and air is less than the ignition
The vapor pressures of decane and dodecane delay at the temperature of the hot zone. The
and the calculated low temperature limits are minimum autoignition temperature (AIT) is
given by solid lines and four experimental usually the quantity of interest in safety work,
values by circles, especially when combustible and air can remain
in contact for an indefinite period.
Autoignition Some AIT values for paraffin hydrocarbons in
air obtained by Setchkin in a 1-liter spherical
Two types (,f autoignition data are obtained Pyrex flask (194) and by Zabetakis, Furno, and
depending upon whether the objective is to Jones in a 200 cc Pyrex Erlenmeyer flask
cause or to prevent the ignition of a combustible (237) are given in table 4. Interestingly
in air. The first type are usually obtained at enough, experiments conducted in these and
high temperatures, where the ignition delay is other flasks generally indicate that flask shape
relatively short. Typical of these are the data and size are important in determining the AIT.
of Mullins (153), Brokaw and Jackson (15, 90), The AIT data obtained in the 200 ce flask may
8
% air =100%-% n-pentane-%00 inert
7
6-
4-
0
3--N
z
L&J
0 10 20 30 40 50
FIGURE 32.-Limits of Flammability of Various n-Pentanc-Inert Gas-Air Mixtures at 250 C and Atmospheric
Pressure.
8-11
% air =100%-% n-hexane-% inert
7
6
4-'
E
MeBr
zj
F-12
3- C02
2N
117
0 10 20 30 40 50
FIOURE 33.-Limits of Flammability of Various n-I Iexane-Iiiert (ias-Air Mixtures at 25 C and Atmospheric
Pressure.
35
30
%air =100%-% n- heptane-% water
25--
~20
E~c \200' C
Cool flame
z
5-
Normal flame
1000 CCs
0 10 20 30 40 50
WATER VAPOR, volume-percent
FtouiE 34.-Limits of Flammability of n-llcptane-Water Vnpor-Air Mixtumres at 1000 and 2000 C and Atmospheric
Pressu re.
4
F
I 1 1
% air = 100%-% combustible-% inert
-,
E
.2_3
0
46
C
0
N2
Flammable
IJmixtures
Cst
0
C-,
L
0 10 20 30 40 50
FIGuRE 35.-Approximate Limits of Flammability of Higher Paraffin Hydrocarbons (C.H
2
.+3, n>5) in Carbon
Dioxide-Air and Nitrogen-Air Mixtures at 230 C and Atmospheric Pressure.
FLAMMABILITY CH{ARACTERISTICS 37
%air =100%-% nitrogen-% natural gas
56
1 4
w 4 2,000 psig
E
32 -100pi
U 500 psig
24 24
:D Flammable
!ZC mixtures
Z 16-
Atm ospheric
8-
0 8 16 24 32 40 48 56 64
ADDED NITROGEN, volume-percent
Fi' tiE 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
R 500 psig
Ld 24- 250 psig
z
16-
8-
0 s 16 24 32 40 48 56
CARBON DIOXIDE, volume-percent
IIG(LkL Ig.-L(1ect of IPrcsiiri oil Ljimit- of Ihirnriinality of Ethancj-('nrbon Jioxio-Air Nhytire'. at 26' C
FLAMMABILITY CH{ARACTERISTICS 39
561
%0 air =100%7-10% ethane-%07 N
2
48
40
a) 900 psig
0
>24
z
w
16-
Atmospheric
8
0 8 16 24 32 40 48 56
Fmumn. 3s".- iI-rof I'russire on Limits of FIaimability of Ethaict-Nitrogen-Air Mixtures at
26
' C.
40
1 I
I
% air = 100%-% propane-% C02
32
C
0)
9-24-
4)
E
> 200 psig
Ld
z
g 16- 100 psig
0
..,,,,,,.,. At mos phe ric
8
0 8 lb 24 32 40 48
CARBON DIOXIDE, volume-percent
FIGuRE 39.-Effect of Pressu.-c on Limits of Flammability of Propane-Carbon Dioxide-Air Mixtures.
4U [ I I I I
% air = i00%-% propane-% N2
32-
24- L
d24
E
0
,/200 psig
L
S16 100 psig
0
,, I I I I I
0 8 16 24 32 40 48 56
FIOURE 40.-Effect of Pressure on Limits of Flammability of Propane-Nitrogen-Air Mixtures.
be correlated with molecular structure by length as abscissa (fig. 43). The data fall into
p lotting them against the average carbon chain two regions-a high-temperature region in
length defined as which the AIT is greater than 4000 Cand a
low temperature region in which the AIT is less
2 gjiN, than 3000 C. These regions coincide with those
La~ (49) of Mtilcahy who found that oxidation proceeds
Lay.- 4('-(4)) by one of two different mechanisms (162), and
by Frank, Blackham, and Swarts (60). The
where g, is the number of possible chains each AIT values of combustibles in the first, region
containing N, carbon atoms and 31 is the tIum- are normally much more sensitive to the oxy-
her of methyl (--('113) groups. For example, gen concentration of the oxidizing atmosphere
n-nonane and 2,2,3,3-tetraniethyl pent e each and to the spray injection pressure than are the
have 9 carbon atoms, but the former has 2 combustibles in the second region. Unfortu-
methyl groups and the latter ha 6. The former nately, the available consistent AIT data about
has only one chain of 9 carbon atoms with a the effec's of oxygen concentration and in-
methyl group on each eml, and the latter has jection pressure are too meager to permit a
LI maximnuni of 4 chains with : carblon at oms, 8 detailed comparison.
chains witi 4 carbon atoms, and 3 chains with 5 The physical processes (206) and reactions
carbon at oms. Thus, n-nomanc has an average that lead "to autoignition are of interest in any
chain length of and 2,2,3,3-tei ramnethvl detailed st uidy of this ignition process. Salooja
pentame has am average of 3.9. 'The more highly (18.J), Terao (207), Affens, Johnson and Carhart
branched e combustible is, the higher its (1, 2), and others have studied the autoignition
ignition temperature will be. .ininium auto- of various hydrocarbons in an effort to deter-
ignition temperatures of 20 paraflins were mine the mechanisms that lead to the ignition
plotted as ordinate against the average chain reaction.
4,000
2,000
1,000
800--
600
La 400-
1A
L
U' 200 -
U)
LiJ
in
0-
100 -
Natural gas
80 Propane
80-
60-
40
Ethane
20-
10
I
6 8 10 12 14
OXYGEN, volume-percent
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 where T is the AIT at in initial pressure P, and
the AlT of a .n )If ustible in a given oxidant. A and B are constants. Accordingly, the & IT
For example, the AIT of a nat undl ga-; il air v'almes obtained at atmospheric pressure should
decreased front 530 (C at I atmosphere to 240' not he used to assess ignition hazards at high
(' at 610 atmospheres (9,000 psig) (7S). The pressures.
AIT's of several hydrocarbons were found to
obey Semnenoiv's eq uation over a limited pressure
range (248): The burning velocities, S., of various hydro-
carbons have been measured by numerous in-
P A" '
log / A +B (50) vestigators in air and other oxidants (68, 131).
At one atmosphere and 26' C, the burning
-P
FLAMMABILITY CHARACXERISTIC13 43
TEMPERATURE, 0F
32 68 104 140 176 212 248
I f I
t'O 101.32 CL
7_Flammable
1.05 6
E
E
E Calculated,.. .79 _
W.,
.39 0
0- Decane
.26
0
C
.5-
0 20 40 60 80 100 120
TEMPERATURE, 0C
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 0.2 to 2 atmospheres (fig. 47). The effect
from a few centimeters a second near the limits of temperature is more consistent. For a given
to about 45 cm/sec near the stoichiomietric pressure and mixture composition, an increase
mixture composition; much higher values are in temperature raises S.. In general:
obtained with paraffin hydrocarbon-oxygen miix-
tures. Figure 44 gives results obtained by (51)BT,
Gtibbs and Calcote for four paraffin hydrocar-
bon-air mixtures at atmospheric pressure and where A and B are constants, T is the tempera-
roomi iemperature (68). The datta are ex- ture and n is; a constant for a particular mixture
pressed in t.?ris of the stoichio)letric composi- composition. Dugger, Heimel, and Weast
lion. C,,; burning velocities aire given for the (50, 51, 81) obtained a value of 2.0 for n for
composition range front 0.7 to 1.4 (',,. These some of the paraffin hydrocarbons (fig. 48).
nut hors hanve presented1 similar dtai for comn- The burning velocity of the stoichionietric
biistibles ait 25' and 100' C. Figure 45 gives inethane-air and mietthane-oxygen miixtures given
results ob~tained by Singer, Giuner, and Cook in figures 44 and 45 (10 not, agree with the values
for three paraffin hydroearbon-oxygen mnixt ures given in figures- 46 to 48 but, in each catse, the
ait at mospheric p1 essure and roolin temperatuire burning velocity data are internally consistent.
'in thle range from 0.3i to 1 .4 (",, (198) . Buirning The actualil flamle speed relative to at fixed
x'elecities range front !t low of 125 ('il/sec to at observer maty be much greater than S. since
high of 425 i/s& e; th~ese vluies aire coI nsider- the burned gases, if not vented, will expand and
ably greater thait those obtainmed in akir. A impart it inot ion to~ thle flamne zone. If detona-
chllge in eithber temperatuare or pre11suret will t ion occurs, thle reacetioni speed increases nmark-
ailter S,, for at particulari t Pie For. exam ple, edly. For example, figure 40 gives t hi Kogarko
A~gnew aind ( iaifi (3) found t hat an inicrease in data oil velocities; wit li which at dot onattiomi wave
Jpressure caus~es S,, of si oichiioietri n nlt hane-air piropagat es t hroumgh various miet hane-air inix-
andl propatne-atir mixtuares to~ decrease in thle t ares ait atmnosphieric pressure iii a 310.5 CII-
pr.isim range from 0.5 to 20 atimospheres (fig. diamieter pipe (12;5). Similar results hatve been
46l)) S, of stoichioniet vie nmetillne-uxygeii mix- obtained b y (en:t cim, (C
t
arlson, and Hill t low
tunes, however, increasedi in the pressure range pressuires with natural gas-air mixtures (67).
550 -CH
4 I
i I I I
1 I
C
2
H
6
500-
C3 H
8
, o ---C-C-C
.- .
9 C-C-C-C-C
6 96
m 400- C-C-C-C.C
- C-C-C-C tC C
I-. /~~-
z 6
n-C
4
H
1 0
1
z 350-
C
300-
z n-C
5
H
12
C
n-C 2 /n-C10H22
250n n-C
6
H
1 4
- 7.C
8
H
18
n-CI
2
H
2 6
n-C16H34
n-CH -
nC14H30
2001' 1 1 1
1 3 5 7 9 11 13 15 17
AVERAGE CARBON CHAIN I ENGTH, Lovg
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 is s,. reait t'mt pre., rq ,vaves are net sent ott
to obtain a detonation in relat,velv large ip'-. ahea of the :lctnati,,n frwit Thus, pressure
Theenergyrequiremanausforignitioii srere uce, detect j- that are 'sef 1 -1 e.\plosion preven-
if oxygen is used as the oxidant in place of air. tion witi loflagrati i i'ovi ire useless with
Further, the detonation velocity incre ,s as de 'fnatioj
the oxygan content of the atmosphere in- With liqi i fuels,, t bthriiing rote depends
creased. Detonation velocities ,,tained k , r),rt ,i tI et o 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.o- v=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
r-r-
" .Ethane
40 -
,-/ / n-Heptane-
. \
"Propane
E 30- /*'Methane
o/
20
10
0 _ I I I
0.6 0.8 1.0 1.2 1.4 1.6
COMBUSTIBLE, fraction of stoichiometric
FIGuRE 44.--Burning Velocities of Miethane-, Ethane-, Propane-, and n-fleptane Vapor-Air Mixtures at Atimos-
pheric Pressure and Room Temperature.
46 FLAMMABIUTY CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS
5 0 0 - - - T I ' I I I 1 I
450-
400
N" 350
E
0 300-
rpn
CD
z
250
200
150
100 1I
I I I I I
0 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 vhric 1Prvssurr
anOd Room "l'ipI eraturtv.
mp
_ 50 - -T - I I '
4o -
E
30
Propane
020
zMethane-
106
10
0.2 0.4 0.6 1 2 4 6 10 20 40
PRESSURE, atmospheres
FIGURE 46.-Variation in Burning Velocity of Stoichiometric Methane-Air and Propane-Air Mixtures With
Pressure at 26" C.
expressed v_ as: lower limits of flammabilit of the olefins
((Iv,) excluding ethylene fall in the range
0 0076 ( net heat of combustion, AIh" from 46 to 48 ng combustible vapor per liter
- sensible heat of vaporization, Aif! of air (0.046 to 0.048 oz combustible vapor per
cubic foot of air).
em/mai. (53) The effect of temperature on the lower limit
Figure 52 gives a summary of the r,, values for of flammability of ethvlene in air at atmospieric
it number of cojubustibles, including several prsure. assunilng a (onstant limit flame
temperature, is sh own by (he curve labeled
p~araffin hydlroarbos (21). Of special igiifi- "U pwird propagation of flane" in figure 53.
calce here is tlat Al J.All is niearliv cipnsti t 1 ifirtunatlel, ml downward Ilate pro paga-
(about 100) for the paraffin liydrovarbons, s tion dta art, available over an extended tern-
tliat their linar bitrnlinl[ rate,' t lre . l
are tir l i per ininrate perat"ure range (2,22); these are included in
figure 53. As in the case of similar data ob-
tained with i nellane, tliese define a straight
UNSATURATED HYDROCARBONS
line parilhl tip t ll' "(',,istant flame t:emipera-
,,, )ur, . pward pro I pagation of flari)'" line.
Again, the nodifiel Burgess-Wiheler law,
equation (33), give., a variation in lower limit
Limits in Air with temperature that Is ('lose tip t iot given I)y
The iniecilar weight, .pecific gravity, iiid t he ( 'ntnt flauin temiperature" line. so that
1the.- properties of tile 3I"rmlr'aimouin, cosid- either u he il eI lit temllp)erat Uires below tile
ered here ire inluded in' table 7. At roonm AlT (of ethylere (-|ttf)' ('. .I*,:,The
"
, C)as tile
peniperat ure and atmospheric pressure, tit lilnit Hlati' te nperatniras of ohclins are no t toot
TABLE 7.-Properties of unsaturated hydrocarbons
Lower limit In air Upper limit In air
Combustible Formula A4 (Air In air /e L, L u
(vol pct) \till) ( -(Vol Ref. (vol e---- ef.
pet) C pet) ,
Ethylene... . ............ C-----------28.05 0.97 6.53 316.2 2.7 0.41 35 (115) 36 5.5 700 (26)
Propylene--....-- . C sla ............ 42.08 1.45 4.45 460.4 2.4 .54 46 (102) II 2. f 210 (40)
Butene.l -------- -------- Coils .---- .---- 56. 1 1.194 3.37 17.7 1.7 .50 44 () 9.7 2.9 270 (1)
ite-Butene-2-------------Cdl,------------'6.10 I 1.94 3.37 (a6,0 !.8 .i 46 (40) 9.7 2.9 270 (40)
lobutylene .............. lC,- ......... 56.10 1.94 3.37 (04. i 1.8 .53 46 (40) 9.6 2.8 260 (26)
3-M ethyl-butene-I ... .. . l---- .. ...-------- 70.13 2.42 2.72 752.3 1.5 .5,5 1 48 (40) 9.1 3.3 310 (40)
P adiene............-- -40.06 1.3 4.97 443.7 2.6 53 48 (2)---
1,3- Nutadiene............--C if............ 54.09 1.87 3.67 576.3 10 .54 491 (10P) 12e 3.3 320 ())
I Figures compiled at Explosive Res. Center, Federal Bureau of Mines.
ICalculated value.
800
700
41)
E Ethylene
0
-J
E 500 -
w
4 00
0.2 0.4 0.6 1 2 4
PRESSURE, atmospheres
IIOUFtE 47.-Variation in Burning Velocity of Stoi-
chiomntric Methane- and Etltylcne-Oxygen Mixtures
With Presaure at 26C.
FLAM3ABILITY CHARACTERISTICS 49
200 I
KEY
0 Methane
* Propane
150-
o n -eptane
A iso-octane
0 100o
>
0A
z S -, 10 + 0.000342 r
2
z
a=50-0
ca
0
200 300 400 500 600 700 800
TEMPERATURE, a K
FGuRz. 48.-Effect of Temperature on Burning Velocities of Four Paraffin Hydrocarbons in Air at Atmospheric
Pressure.
,000
-
3.000
1,500 0 2.500
01
00
EE
L 1,000 - : 2,000
z
0 o
z
o I
500- -i 9 1,00
z
KEY
0A Hexane
c1 1,000- A Butane -
6 8 10 12 14 03 Propane
METHANE, votume-percent * Ethane
0 Methane
F'ww rip; 49 -- letoratiolt Velocjtis of ),ttiume-kir 500
Mixtres at At liospheric I'ressuire. (Initintor: 50 70 0 10 20 30 40
grams of armitol exlloive. Pipe diiietcr 30.5 er.) COMBUSTIBLE, volume percent
different froin those of p[araflili hNI(II'(W1L1)orIs, ')etoyjti Vejociiies of \letrharl-,
he generalized pralph fir IL,,'L (fig. 23) (an 14- Ethanet*-, l'rolpar e-, Butane-, ald Ilexrie-()xgr'l
used for these un iaturated hydfocalbOmls. Nlixture- at .itmospheric PtI.-.i.ure.
50 FLAMMABILITY CIIARAC'rERISr01CS OF COMBUSTIBLE GASER AND) VAPORIS
".001- T II I
V 3 -Downward proplagationl
9,400of
flame
E
2 Modified Burge'ss Wheeler Law
*WFNA
0 z~aUpward propagation
ui 2.000 - Constant flame temperature- " of flame
WFNA N2
z(Mole fraction N12 =0.5) i 0_
t~1,500-- 0 ?l'0 400 600 800 1,000 i1200
oTEMPERATURE, C
FIGURE 53.-Effect of Temperature on Lower Limit of
1,000Flammability
of Ethylene in Air at Atmospheric
lOOC I I Pressure.
0 5 10 15 20 40
------
n-HEPTANE, mole-percent
%air =100%-% ethylene-% inert
FIGURE 51.-Detonation Velocities of n-Heptane Vapor-
in WFNA (White Fuming Nitric Acid)-Nitrogen
Gas Mixtures at Atmospheric P'ressure and 400' K. 30
1.42
1.0z
S.8 C41-11 2 0 10 20 30 40 50
\1 C61 11-O ADDED INERT, volume-percent
4 LNG
.6 - C
8
1-
10
-0 -Cg
6
,, FIGURE 54.-Limits of Flamm~bility, ef -Hthylenie-
Carbon 1)ioxide-Air anid Ethylene-Nitrogen-Air
Mixtures at Atmnospheric Pressure and 26' C.
.4 UDMHO -i (100, 1101, 103), (figs. 154-60). The first two
figures are modifications of the limit-of-
.2 CT
flainniability diagramns given in (.40); the third
C C 0
is essentilly the same ITs that viven in the earlier
Cf130H Publication hut include., the experimental
points.
The oither curves were constructed1
0 50' 100 150 200 250 300 Irom originail, unpublished data obtained t
He /N Hthe Explosives Res. Center, Federal Bureau of
Mines.
Firo;i 52-Relation Between Litrnid-Butrning Rate Other liniit-of-flarnm-ability determinations
(LarV r- Pool Diameter) and Rtatio of Net Heat of have been made in oxygen and nitrous oxide.
Comb -ltion to Sensible Heat of Vaporization. These data are included in table 8 (40, 100,1007).
Limiis in Other Atmospheres Autoignition
Th~e limits of flammability (if ethylene, propy- There have been few determinations of AIT's
lene, isobutylene, but ene- I, :3 methyl butene-1I, of the unsat orated liyplrocarbonus in air or other
and butadienie in various inert-air atniosphleres oxidants; the available data (9./j, 116, 191) are
hii've been determined by Jones and coworkers summarized in table 9.
FLAMMABILITY CHARACTERISTIC435
12 -1-
%air =100%-% propylene-% Inert
10
-%
E
Flammable
>6 mixtures
LAS
N
2 z
W
-j
a>, IctCO
2
0.42
2-
0 10 20 30 40 50
FI"ouRE 55-Lrnits of Flammability of Propylene-Carbon IDioxide-Air and Propylene-Nitrogen. Air Mixe Cat
Atmospheric Pressure and 26' C.
itla
fill?-ina rliiz,
110 ' I itk '-f 9i .
lbustib e,; have positive heUL, of formiation,
The burning velocity of ethylene has been AJI, (table 10) iunri Would therefore it~erat-a
(leterinined in air, oxygen), and o)xygen-nitrogen
heat if (iecomiposed to thle elements carbon and
atmiospheres by numerous investi .gators (8, 7, hydrogen. Even miore heat would be liber-
P/, O'S, 131). In generatl, it is higher than the ateol if gases with it negative heat of for-
b rning velocities of the paraffin hydrocurbons nation -~ for example, inetane-form froin thle
under the samne comiditionls (fig. 47). Simmnilar elenments. In practice, at mixture of products
results tire to Ibe expectedl for other unisaturatedl results ulpon decoinposition of such conibusti-
hydrocarbonis, although thie available datat are bles. F~or examlple, at propagating decompo-
rather mneager.
sition reaction can be initiated -ill pure ethylene
Stability
in at 2-inch-iD tube at 230 C an dlpressures as
low as 750 psig, using 2 gramso guncottoll.
Many unmsaturated hydrocarbon vapors can A reaction can lbe initiated at 2 1 'C and pro;;-
propagate flame in the absence of air at, elevatedl sures ats low as 975 psig with I grain of
temperatures and pressures; that is, they have guncotton. 'IFie decomuposition products are
52 FLAMMAB.LI'Y CHARACTEREISTICS OF COMBUSTIBLE GASES AND VAPORS
80
.4- N2 -
02 C02
Ljd
Flammable
Uj
mixtures
4-
0 10 20 ZG 40 50
FIGURE 56.--Imits of Flammability of Iobutylfne-Carbon Dioxide-Air and Irobutylen -Nitrogon-Afr Mixturre at
Amosphcrio Prewure and 26* C.
TABLE 8.---Limit qfflammability of unsaturate'] TAimL 0.-M.finimum autoignition temperatures
hydrocarbons at atmospheric pre sure and room oj unsaturated hydrocarbons at atmospheric
temperature, in 2olume-percent combustible prtssure
vapor
....... L Autoignition temperature
In ai: In oxygen In nitrous - .................
oxide Combustible In W'r In oaygen
CombustibleI
.. .
0 ~ ~ 0 C
0
f 'C F Ref.
SL
1
UIL IU L IU oC
0
F Ref. - O FRf
Ethylere ------- 2. 7 36 2. 9 80 1.9 40 Ethylene --------- 490 914 (116) 485 9 (116)
Fropylene ---- 2. 0 11 2. 1 53 1.4 29 Propylene ------- 458 156 (9) 423 793 (1)
Butene-i_-.----- 1.6 10 1.7 i 58 ----- .. Butene-l -------- 394 723 (I) 310 590 (1)
Butene-2- ----- 1.7 9.7 1.71 55 i '3261Butene5 (1 )
1,2Jutadiene 418 784 (19 33 " 35 ( 91)
I Figures oompiled by Explosives es. Canter, Federal Bureau ox
prinarily carbon, methane, and hydrogen: Mte.
approximately 30 Kcal are reieased per iwole of
ethylene decmposed. Propylene yielded si i- Propadiene and buiadiene also decompose
lar products followig explosive decimposition readily under the action of powerful igijitors.
during compression to 4,860 atmospheres (34). Propadiene vapor has beon decomposed in a
FLAMMAI3ILITY CHARiACTERIBTICS
53
60
% oxygen 100% -% isobutylene -% water vapor
50
2~Min 02
(1)40
16%
E
-5
030
a-
Flammable
m~ixtures
w
0
CC)
024060
80 100
FIGURE 57.-Limits of Flammability of Isobutylene-Water Vapor-Oxygen Mixture at 150* C and Atmosperie
Pressure.
~-,,wh ;1be at 120' C an(' 0 psig using a ACETEN Nihl~hQCARBONS
piatir'umn wire ignitor. Decomposition of buta-
( R
diene in an industrial accidJent resulted in a
itpopcorn" polymer; the reaction was a pparently
Af
initiated by an unstable peroxide (.4).Lnt i i
TAHLE lO.-Heats ol formation (Kcal/miole) of Acetylene forms flammuble mixtures in air
unsaturated hydrocarbons at 25' C. at atmospheric pressure and 250 C, in a range
Combustible: all/ from 2.5 to 100 volume-percent acety'lene.
Acetylene ----------------------------- ~ 54. Quenched and apparatus limited upper limits
Propadvne -_-----------_--
45. 9 have been obtained in 1-, and 2-, and 3-inch-
1-3, laetadjene.- - --------------- 4,3 diameter tubes (40), but pure acetylene can
1-, thyene-----------------
---------- 6. propagate flame at atmospheric pressure in
Propylene -------------------------- --- ~ 4. tubes with diameters of at least 5 inches.
1-Butce -----------------------------.
3 Sargent has summarized availablo data on
I Refs. (114,18P),
initial pressure requirements for deflagration and
54 FLAMMABIITY CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS
10( 1 1 1 detonation through acetylene in horizontal
air 100%-% butene-I-% Iner, tubes of about .02 to 6 inches ID at 600 F. (89,
185). His curves are given in figure 61, which
8 also includes an experimental point from the
data of Jones and coworkers obtained in a
.vertical 2-inch-diameter tube. The existence
N2 of this point, at a pressure below that given by
Sargent's curve for a 2-inch tube, indicates that
E C02 this curve should be used only for horizontal
systems. The point labeled "Industrial explo-
SFlar.am bl
sion" was reported by Miller and Penny (144)
W 4 and presumably refers to a deflagration. The
..j third experimental point is discussed, along
with the detonation curve, in the section on
to 2-
stability.
21 The effect of temperature on the lower limit
of flammability was determined by White in a
2.5-cm tube with downward propagation of
Iflame (2). Although the actual limit values
0 10 20 30 40 50 tire not satisfactory for our purposes, they can
ADDED INERT, volume-percent be used to check the applicability of the fL-/'2
5
ratio data presented in figure 23. The White
Fiouaz. 58.-Limits of Flammability of Butene-l- ratio of lower limits at 3000 and 200 C. is
Carbon Dioxide-Air and Butene-l-.Nitrogen-Air
Mixtures at Atmospheric Pressure and 260 C. 2.19/2.90=0.76; the corresponding ratio from
10 I
% air = l00%-% 3 methyl butene.l-% inert
8
43
0.
E
_6--N
FiGuRE 59.-Limits of Flamma- N2
bility of 3 Methyl Butene-1- " L-
Carbon Dioxide-Air and 3 z
Methyl-Butene-l-Nitrogen-Air
Mixtures at Atmospheric Pre. M Flammable
sure and 260 C. 01 4- mixtures
-2
10 20 30 40 50
ADDED INERT, volume.percent
FLAMMABILiTY CHARACTERISTICS 55
12 1
% air = 100%-% butadiene -% inert
10I
E
FGuRE 60.-Limits of Flamma- .
bility of Butadiene-Carbon > 6-
Dioxide-Air and Butadiene-
Nitrogen-Air Mixtures at At- z Flammble NZ
mospheric Pressure and 260 C. W mixtures
t C 0 2
24
SI I I
0 10 20 30 40 50
ADDED INERT, volurtie-percent
"Constant flame temperature" curve in figure The quantities of propylene required to
23 is 0.78. Accordingly,, this figure should be prevent flame propagation through methyl-
satisfactory for use wit i acetylene at tempera- acetylene-propadiene-propylene mixtures at
tures in the range from 20' to 3006 C. 120' C and 50 and 100 psig have been deter-
The lower limit of flammability of methyl- mined in 1-, 2-, 4-, and 12-inch tubes (fig. 62),
acetylene (propyne) in air at' atmospheric and at 120' C and 100 psig in a 24-inch sphere.
pressure is 1.7 volume-percent, equal to 0.34 C,, As noted, the propylene requirements are
which compares favorably with the value for strongly affected by temperature, pressure, and
acetylene (0.32 0,,). Upper limit investiga- container size. As the tube diameter increases,
tions have been conducted bv Fitzgerald (59) the quantity of propylene required to prevent
in a 2-inch tube at 20' and 1200 C to determine flame propagation increases; this effec, is less
the low-pressure limits or lowest pressures at pronounced in the larger vessels (diameter
which a flame will propagate through methyl- greater than 4 inches) than in the smaller
acetylene vapor at these temperatures. He vessels (diameter less than 4 inches). The
fouwd these to be 50 and 30 psig at 20' and results obtained in the 24-inch sphere were
120' C, respectively. In a 4-inch tube, Hall similar to those in the 12-inch tube.
and Straker (77) obtained a low-pressure limit
of 43 psig at. 20' C. This indicates that the Limits in Other Atmospheres
upper limit of flammability of methylacetylene
in air is probably less than 100 percent at 200 C Gliwitzky (71), and Jones and coworkers
and 1 atmosphere.
determined the effects of carbon dio.-ide and
56 FLAMMABILTY CHARACTERISTICS OF COMBUSTIBLE GASEE AND VAPORS
400 ---- , I 1 i I 11I
200 -Deflagration
100-
80
C,,
60
CLJ
= 40
Sargent
20 0 Miller and Penny (Extrapolated)
0 Industrial explosion
A Jones and others
10- NN
0.02 0.04 0.06 0.1 0.2 0.4 0.6 1 2 4 6 10
DIAMETER, inches
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 gel, or charcoal lowered the pipe temperature
atmospheric pressure and room temperature. required for ignition to a 280

to 300' C range.
Unfortunately, all measurements were made in The presence of 1 gram of potassium hydroxide
tubes that were too narrow to give actual upper lowered tile pipe temperature still further to
limit data. Nevertheless, the resulting 170' C. The impact of a 0.25-inch steel ball
quenched-limit data are summarized in figure falling from a height of 15 inches against a
63, because they show the relative effects of fragment of copper acetylide produced a hot
adding two inert diluents to- acetylene-air spot that ignited the surrounding gaseous acety-
mixtures in a 2-inch-ID tube. lene at room temperature and 3 atmospheres.
Autoignition
Burning Rate
A summary of available autoignition tem- The burning velocity data for acetylene in
perature data for acetylene, acetylene-air, and air obtained by Manton and Milliken at 1
acetylene-oxygen mixtures in clean systems is atmosphere and room temperature are given in
given in figure 64. They are based on measure- figure 65 (158). The burning velocity ranges
ments by Jones and Miller (110), by Jones and from a low of a few centimeters per second near
Kennedy in quartz tubes (99), and by Miller the lower limit to a high of about 160 cm/sec
and Penny in a 0.5-inch steel pipe, 15 inches on the rich side of the stoichiometric composi-
long (14). Jones and Miller found minimum tion. Parker and Wolfhard (164) have found
autoignition temperatures of 3050 and 2960 C considerable variation in the burning velocity
for a variety of acetylene-air and acetylene- of acetylene in various oxidants. The burning
oxygen mixtures, respectively, at atmospheric velocities in stoichionetric mixtures with oxy-
pressure. Miller and Penny report little waria- gen, nitrous oxide, nitric oxide, and nitrogen
tion in the autoignition temperature of acety- tetroxide were found to be 900, 160, 87, and 135
lene in a clean pipe at 4 to 26 atmospheres initial cm/sec, respectively; for comparison, the burn-
pressure. However, the presence of I gram of ing velocity in a stoichiometric acetylene-air
powdered rust, scale, kieselguhr, alumina, silica mixture (fig. 65) is 130 cm/sec.
FLAMNMAIILTTY C'I I AltA(Tl.Ei1STICS 57
'000
,Z
\Flammable mixtures -
12-inch-I D bomb,l0O psi
2-inch-I D bomb,IO0psig '\ \-"2-inch~-i D
~~0 I~~-inch-ID bomb,IO0psig \ \obs~i
00 90 80 70 60 50 4 00 1
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 m1ix- required for propagation ait subsonic (deflagra-
lures were found to ibe indlependcit, of pressure tion) and supersonic rotes (detonation) into
b~et ween 0.1 and 1.0 atmnosphlere (138). Sint- the unhurijod gats tire giveni for ai range of pipe
ibrly, A 'new andt( 'raiffl (3) and Parker andi~ (I. -41er.s i!, ''',ure 61 (185). D~eflagration is
WVofhard (164~) found U'h, 1urninq, velocities LIscussed briefly under Liniits of Flan-iniability;
of stoicliioietric, acetylene-oxygen and1( acety- dletonatio : 1s dfiscussed in this section.
lene-nitrous oxide inixt tires wereo independent (of The cuirse labeled ''Detonation'' in figure
p)ressure bet ween approxiimately 0,5 and 2 61 gives thle iniimui pressure required for
atmuospheires and~ 0.03 and I atniospliere, re- propagation (of it (detonalt ion, once initiated, inl
spectively. Th'le b~urning velocities (if st ojchio- tuibes of 0.3 to 1(0 inches (liv ieter. In ipraw-
Inetric 1cctylene-mitiic ox'ide and( acetyliene- live, at (detonat ion inay be initiated directl
11i rogen let rt xide iiixtures incrca:~ed slightly front it defla grittion t hat hias lpropaglited throu l
o vern thiis pressurme range 0.03 tot I at mospier'e at rat, her ill -definied distance, know itsi Its
(1 ((.4). pedletInait) 0n or run-up) distanimce. This (us-
Stabfitytanlce depends ontc itemneritutre, pressure. tuhbe'
Staili~r Ijittiieter, conidition iof tube watls, and onl
As noted, iicetyleiie canil propagatte fltiie inl igilit ion-s( urce streligtbI. Fori exampiJle, using
the absence (if air (39, 165). The pressures it fulsed p~itiiui wir-e ignit(Ir, Miller anid P~enny
100 (144) found the predetonation distance for
% air 100%-% acetylene-% Inert 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.
80 Extrapolation of these data yields the point
in figure 61 for a very large predetonation
distance. This point (44 psia and1-inch diam-
eter) lies fairly close to the detonation curve
established by Sargent (185). The maximum
A,
lenth-to-diameter ratios (LID) given by Sargent
for establishing detonation in acetylene is
9plotted
against intial pressure in figure 66.
Z In tubes, Fa ving ta diameter greater than those
40 - given along the top of the figure and having
L mixtures 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
20 N2bound of LID and the approximate quenching
C02 - diameter; a better value for the quenching
est diameter can be obtained directly from figure
~61.
Although predetonation distances are diffi-
o 20 40 80 cult to measure and experimental data often
ADDED INERT, voiurre-percent exhibit much scatter, they are of interest in
safety work because they can be used to evalu-
FIUnt 63.-Quenched Limits of Flammability of ate the maximum pressures likely to occur in
Acetylene-Carbon Dioxide-Air and Acetylene- a system due to cascading or pressure piling.
Nitrogen-Air Mix~'rcs at Atmospheric Pressure and -'bis phenomenon presents a sp..-:-ial problem
26' C, Obtained in a 2-Inch Tube. because the final pressure achieved in a detona-
700 1 1 I
KEY
Oxidant Pressure Tube
* Air 1 atm 131 cc quartz
0 Air 1 atm 200 cc quartz
600-
.L Air 2 atrm 200 cc quartz
0 Oxygen 1 atm 131 cc quartz
None 4-26 atm !-inch steel pipe
500-
FiGURa 64-Minimumn Autoigni- z
tion Temperatures of Acety- 9
lene-Air and Acetylene-oxygen
mixtures at atmospheric and Z
elevated pressures.
4 00
- Region of autoigntion
300I-
200
0 20 40 60 80 100
ACETYLENE, volume-percent
FLAMMABILITY CHARACTERISiTICS 59
2001g 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 deflrgra-
tion, the maximum initial pre3sure to be ex-
pected upon tranisiticn from deflagration to a
00 150- detonation is approximately 1i times the frac-
N. tion of acetylene that has been burned times
E the initial precombustion pressure. Fifty times
U this pressure is -. ho ap'proximate maximum
pressure that rould be o ;ained when a detona-
- tion occur-. '.Lo illustrate this, Sargent has
3 100 r-plotted the final-to-initial pressure ratio (P,/Pj)
W ~against the predetonation distance-to -tube
>
length for acetylene. A siniliar graph is given
z/ in figure 67. To use this graph, the maximum
z redetonation distance to be expected must
-s be deemndfo figure 66. Tb.-n'z
maximum final-to-initial pressure ratio.
____ ____ ____ ____(C.H
2
. ,)
0 5 10 1s LiMitS inaAir
ACETYLEJE, volume-percent
Fso.-s, 65.-Burning VnIocity of Acetylcnc-Air Nfx The combustibles considered in this section
tures at Atmospl.cric k'ressurc and Room Tempera- are listed in table 11, with pertinent properties.
ture. At atmospheric pressure and room temperature,
the lower limits of flariimabilit ofte aromatic
tion depends on the initial pressure at the onset hdoabn arap oately 502 mg/l
of detonation. F, r example, the maximum (0.050 0.002 oz combtustible vapor per cubic
pressure to be expected from the deflagration foot of air).
of Lcetylene at moderatc pressures is about 11 The lower limit of toluene was determined
times the initial pressure (144); the maximum by Zabetakis and coworkers in air at 300,
QUENCHING DIAMETER, inches
0128 421
0.5
FIOURE 66.-Mlaxiimum LID ratio .S
Rea uired for Transition of a
Deflgration to a Detonation *:. 40-
in Acetylene Vapor at '*01 F C
and from 10 to 70 Psia.
.
10 20 30 40 50 60 70
INITIAL PRESSURE. psia
TABLE 1 1.-Properties o selected aromatic hydrocarbons
Lower limit in air ' Upper limit in air I
C, in net Ali .....
('ombustihlm Formula M Sp gr air (vol /Kcal -
Wr ) pt(volle 110
m 1
j00 (L o I I.. [Ii
PCtI pet)
Blzeee ('1,1 78. 11 2.,69) 2. 72 757. 5 1, 31 0. 48 47 7. 9 2. 9 300
"IhUe(_( (... l711, 92. 13 3. is 2.27 101. 5 1.2 . 53 50 7. 1 3. 1 310
IE'thl ihmnzene - (!e C 116. 16 63.17 1.96 104s. 5 1. 1) 51 48 6. 7 3. 4 341)
omI-X'vn. ..... (l10 106.t 16 . 7 1.96 1045., 9 1. 1 56 53 6. 4 3. 3 320
rn-Xvmmmle ----- cjl 106. 1 6 :3. 67 1, 96 1045. 5 1.- 1 .56 53 6. 4 3. 31 321)
p-Xl.n_-- C---- 106. 16 3. 67 1.96 1145. 7 1 1 56 53 6. 6 . 4 340
(IIinmI----------C
1 2
120. 19 4. 15 1. 72 111,.2 .8,8 .1 4S 6 .5 3. 8 3170
p-Cym--en--.....--Co11,
4
134.21 4.63 1. 53 1341.8 . 85 56 51 t.5 3.6 350
I Re. (147).
400 -- ---.--------... T ....... T
300 j
FiorRaE 67.--Final-lo-Initial Pres -
sunr Ratios Decvvopied y Acet- 200
yeime With I),olitiol l 1litim-
tion at Various Points Along a
Tube.
100 ,--
0 0.2 0.4 0.6 0.8 1 0
PREDETONATION DISTANCE/ TUBE LENGTH
1000, and 200' (i (235, 247); the varintion in Their values rmiuge f'rin 8.8 percent (ctiinieiie
lower limit with tonipertlikre is given by eqaui- (80' (' aid a) tii pherie pres,.re) (if 10.8 per-
tions (31) and (33') derived for parafflin h 'dro- (,ett ctiiniiei (I4i' (' kiind 11) psig pressutire).
carbons, aid the vorresponding curves of filgure
23. For example, jImp, rIL.3, ,. vwits folund to he Limits in Other Atmospheres
1.07/1.24 or 0.86; the ratio predicted by the
curve in figtire 23 is 0.87. The !iniit ,,if flhininititilitl ,dtgiiumed hv ir.
Ihe u )p(er litijts of tie irminiics (iin.idered g(li. (;29) mrid lhv r.
1
,i (.t[)) f iur zlmc'l-
here it 1000 ( nire inchded in t able 11 (270. miirl)lml di~xhNle-iir and eli? 'mi.-iitrmigeu-nuli
These were otlaiiied it ntnisl)lierii' fpreslr mixilt tires at tit Iiimmli'n jtreslilre nllml a 25

(' mie
iii it 2-incl-diwnietr Itihe, oiin ait line eid. glixen in igtre WS , ; simiillir dall mire :ivlii fir
Blier nind W~elbb 4lobtiL Ined uppier iliii n miatit i the last two Ililiires t 1it n111, m1hwric pes~olrt
R mtmilinrciil grade m'iieriv (9;.1 prt riiiet-e) 1i11ml I 1 (' The iiertint rpqtltrm'liieit tit 2i
;ii nir tit elevated tenimer ires anm iiimmmtheic t ire liprixhlihitek lile silmie 1 tihfse if It-
milld 'el'vtted pressures Ii it chim1ed b1 1111 (I ). Ilexine (fig. 33). Agnili, it sloi le hi II l!
FLAMMABILiTY CHARACTERXSTJCO 6
10.
. ......
%air =100%-97o benzene - qV inert
8
150
6,
25
>Ee~
z 4
Zi
r-W
N
0 10 20 30 40 50
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 expressed in mole-percent as in the ori~ia
with those obtained by Hlill (rompare figs. 28 presentation. 'Plur system has no lower mit
an3), Tjhese lattter (lain (80) were used to, mixtures, as a flamie can be initiated in hydrogen
construct. thle approxitnate (broken) flaninma- peroxide vapors (186). As a 90-weight-percent,
hility curves for the benzene-iriethyl bromide- hydrog en peroxide was actually used to obtain
itir system,. these flawinability data, all compositions were
Tlhe decrease in the minimium oxyNgen require- cailculated to) yield values based on a 10-cercent,
mnents for flaine p~ropatgationi (fronti 14.2+0.3 hydrogen per(')xidle co nten t. This co~uld be done
vohiinw-percent ait 250' C to 1:3 1 013 volumve- here because only three cemiponients are consid-
[)ere~ont ait 150t' in it carbon dioxidle-air atnmrs- Pred. Where four components aire considered,
phere; fromt ! 1.4 0.3 voluine-jiercent at 250 the flumnahiiity 6ata can be presented in a
C to 10.1 -f.0.3 v'ohiine-percemit fit I 50, in) at tiiree-itnenginn plot ; if two of the cornpo -
initri pgcm-air tttJ11iO~jpher'e) iS withilin(fhe Irange mient 11 ppear in fixed proportions, at triangular
predic ted lv (flie miodified ilurgess4-Whepeler plot (,an Ce used wit It the two compnets (for
lakw (equialion (05), fig. 23). exaniple, 90-weight. Iercemit hydrogen peroxide)
Tlhe limlits of 1f1ilnifilalitY of ort Iioxvknle C40mnsid ered ats a sinigle c~npinemlt. Such a
(( df1
1
(('i,)
2
)-water-h' dogemi peroxide hu- plIot is presented in figure 70 for 00-weight-
I wres were dri crmin ed tit I 54' C and I titimu14- percent hydroigen 1)eroxidle-4 rthoxyvilenie-forinic
l'ohere rs'weby Matrt iiidill, Lang, atid acid (HMUMO~) at 1540 C and I 'atmnosphere.
4itbem skis (1T).hle (lait tire pretiented iii rhit; was considered to) he at plane in a regular
it triangular plot. in figure t19; emflposiionS are tetrahedIron in the original article and is there-
.-- -.- --- -. ...... ,-......
62 FLAMMABMI1TY CHARACTERISTICS ul, COMBUSTIBLE GASES AND VAPOUIS
100 0
80 20
Composition line formed with
82.6 mole % (go wt %) H
2
0
2
600
200
2
aoe eseo
g p d Flammbble
mixtures l co
Decmpsitonof hepeoxideloers th upe eaadpr-oitos epciey.T'
100 so 60 40 20 0
H202, mole-percent
FimuRi 69.--Limits of Fladsmabity of HiOrCH4 (CH3)rHO at 154i C and I Atmosphere Prature.
fore not a regular triangle. As before, onl~y an -CHa group (24 1). When the benzene ring
upper limit curve is given because 90-weight- contains two side groups, L, is determined
percent hydrogen peroxide is flammable. In first for the side roup that yieds the largest
addition, a calculated curve based on Le Chate- average value and d to this is added l, , or
lier's rule is given, as is the upper liait curve of the average chain length of the second side
obtained with decomposed hydrogen peroxide group; (a, p, and correspond to the ortho-,
Decomposition of the ide lowers the upper meta-, and para-positions, respectively). T-
limit appreciably ane o ields a system wLch data again fal into high- and low-temperature
has a lower limit of flammability (not deter- regions (fig. 43).
mined in this study).
Autoignition
Burning Rate
Burning rates and detonation velocities of
The minimum autoignition temperatures of benzene in air and oxygen appear to be ap-
a series of aromatic hydrocarbons in air at proximately the same as those of the higher
atmospheric pressure are given in figure 71 as paraffin hydrocarbons. For example, the re-
a fntion oF the correlation parameter L ... sults of Golovina and lFyodorov (211) show
This parameter was determined by use of that the maximum burning velocities of benzene
equation (49), treating the benzene ring as a in nitrogen-oxygen mixtures range from about
6Ao
100 0
80 20
.60 4
00
Oxtdant; ecompose
0 VaV100
100 so 60 40 20 0
90 weight-percent H 202. mole-percent
Fioun. 70-Limitaof Flammability of 90-Weight-Paeent IIOrCH# .(CH3)rlICOOH at 1540 C and I Atmnosphere
Pressure.
295 cm/sec in oxygen to 45 cm/sec in air; the table 12. The lower limits of flammability in
maximum burning velocities of haxane in air at atmospheric press ire and room tempera-
various nitrogen-oxygen mixtures range from ture fall in the range from 48 3mg/i (.048
abouit 260 cm/sec in oxygen to 40 cm/sec in .003 oz combustible per cubic foot of air).
air. Similarly, Fraser (0!) found the maximum By volume, this is equivalent to approximately
detonation velocities of benzene and n-octane 0.55 02,,, which is the same as for paraffini
iii oxygen to be 2,510 and 2,540 rn/see, hydrocarbons. The ratio of the upper limit
respectively, to C,, appears to increase with molecular
weight.
ALICYCLIC HYDROCARBONS According to Jones (40), the lower limit of
(CA.,,) cyclohexane in air at atmospheric pressure and
260 C determined in a 2.0-inch tube is 1.26
Limita in Air voluine-percent. Under thea same conditions,
Burgoyne and Neale (26) found the lower limit
A summary of the pertinent properti&; of to be 1.34 volume-percent, using a 2.5-inch
some of the members of the series is given in tube. Matson and Dufour (141) found the
64 FlAML4DIITY CHARACTER18TICS OF COMBUSTiBLE GAGES AND VAPORS
57-
-1
~~CH
52
CHH-H
ICH
a-wH C
3
CCH3
02475 -
F- 0H CH
3
-CH-CH
3
S425
CH3-H
3
-H3-C
2
2H
37 -
CH
375 1 C2H5 1
0 12 3 4 5 6
L avg
Fiaunu 71.-Minimum Autoignition Temperatures of Aromatic Hydrocarbons in Air as a Function of Correlation
Parameter L.,..
TABLE 12.-Properties; of selected alicyclic hydrocarbons
Net A J....... limit In air Upper limit in air
S9 !r, C.0 k.0l
Combustible Formula M (Au) inair mole ) L. LM L U,, U
(Vol pet) (Vol * ~(mg) Ref. (vol Un mg) Rat,
pe) T pot) C.,
C corpn ------- Cas.. 4208 1.48 4.45 465 2,4 1 0.54 46 (107) 10.4 2.3 220 (107)
Cy lb(ae- ----- 11. . -- ----- .10 A'94 3.37 1'600 1,8 .5 46 (1) ---- - ---- -- -
C eoAnse_.----- lo - -- _I... - 70.13 2 42 2.72 740.8 1.'5 .M 48 (I)6 -i
C coeae---- --- - (:11------ 84.16 2.91 2.27 81. 7 1. .6 :7 49 (40) -7.8 3.4 32 0
Eflif1eycobutane-- --- lhg. 84. 10 2. l '2.27 MW) 1.2 .53 41 (40) 7. 7 3.4 310 (40
lower limit to be 1.12 volume-percent, tit 21' C cordingly, the data of Jones and of Burgoyne
in a 12-inch diamieter chamber about 15 inches and Neale are used here.
long: however, there is evidence that they did
not use the same criteria of flammability am did Limits in Other Atmospheres
the other authors; only one observation window
was provided at the to p of a rather squatty The limits of flammability of cyclopropane-
chamber, whereas with the glas's tubes used by carbon dioxide-air, cyclopropaiie-nitrogen-air,
Jones and by Burgoyne and Neole the flame and cyclopropanc-helium-air mixtures at 250 C~
could be observed along the entire tube. Ac- and atmospheric pressure are given in figure
LI
FLAW&ADILITY CHARACTERISTICS 0
% air 100O%-% cyclopropane-% inert
10-
E
FiGUaRE 72.-Liits of Flamma- Flmae
bility of Cy clopropane- Carbon Flmal
IDioxide-Air, Cyclopropane-Ni- U36 mixtures
trugen-Air, and Cyclopropane- z
1Iihum-Air Mixturcs at 250
and Atniospheric Pressurc 0
-
01020 30 40 50
72 (106). The first two curves are similar to ALICOHOLS (0
5
H
2
.+
1
0H)
those obtained with naraffin hydrocarbons (fig.
35).LiisiAr
& ~~~Thp limits of flainmability of cyclopropane-LiisiAr
heliumn-oxygen and cyclopropane-nitrous oxide- The alcohols considered here are listed in
oxygen mixtuires at 25' C and atmospheric pres- table 13 together with L~s. and U
2
6.. The
sare are given in figure 731 (106). The latter ratios Lzso/C., are approximately 0,5. How-
clurvn diffctrs from the former, as both additives ever, the L (mg/i) values decrease with increase
are oxidants (oxygen andl nitrous oxide). in molecular weight. If L* is taken to be the
The limits o! flammability of cyclopro pane- weight of combustible material (exclusive of the
lielirnt-ii~itrons oxide initires at 25' C and oxygen in the molecule) per liter of air, then for
atinospherie. pressure are giren in figure 74 (106). the simple alcohols:
Hlere the minimum oxidant, concentration
*LM- 16 (4
(nitrous oxide) required for flame propagation L*~ M.(4
is approximately twice the corresponding con-
centration of oxygen in the systems cyclo- This eqkuation gives the value,; listed in paren-
propane.-heliumi-air (fig. 7-2) and ('yclopropane- theses in the mg/I coluimn; these are in fair
helium-oxygen (fig. 73). agreement with the values obtained for the
-- p on eo2 corresponding L*. from figure 19 for ethyl
oxygen - 100c-% lopropne-( He, or N20) alcohol (M=-46) is 2.2 volume-percent. Then,
from equation (54), L is 3.4 volume-percent; the
50 - iN
2
0
measured value is 3.3 volume-porcent.
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
40 temperatures are 6.7, 6.5, and 5.9 volume-per-
cent, respectively.
rhe calculated
values
ob- 4tained
from the modified Burgess-Wheeler
law
Flammable He
(fig. 23) at 1000 and 2000 C are 6.4 and 5.8
I3 mxtue
volme-percent, respectively.
Limits in Other Atmospheres
20- C
5
1 (in 02 + N
2
0)
The limits of flammability of methyl alcohol-
carbon dioxide-air and metnyl alcohol-nitrogen-
air mixtures at atmospheric pressure and 25'
o cal (in 02
and 50' C are given in figure 75; flammability
determinations
on mixtures
containing
more
I
than 15 percent methyl alcohol vapor were
I conducted at 50

C. The maximum amounts
S 20 40 60 1 of carbon dioxide and nitrogen required to
20 40 6o s loo prevent flame propagation in these inixtures
NITROGEN OR NITROUS OXIDE, volume-percent
40
FIGuRa 73.-Limits of Flammability of Cyclopropane- % ] = i t
Helium-Oxygen and Cyclopropane-Nitrous Oxide- X air 100%-% methyl alcohol-% inert
Oxygen Mixtures at 250 C and Atmospheric Pressure.
40 I I35
% N
2
0 = 100%-% cyclopropane-% He
30-
30
V
\k
E2 Min N20 6= 25-\
21\ \
uz 20-
o Flammable
> 20\
10 i smixturesS
z Flammable \ XSaturated at
10! mixtures 25' C and 1 atm.
C s.CO
C02
10-
0 20 40 60 80
HELIUM, volume-percent
FiGURE 74.-Limits of Flammability of C clo ropane- 5
flelium-Nitrous Oxide Mixtures at 250 JandAtmos-
pherio Pressure.
saturated hydrocarbons. Approximate L (mg/ i 0 3 4
I) values can be obtained from the higher DE10 20 30 40 50
hydrocarbon values given in figure 22 by ADDED INERT, voiume-percent
multiplying these by the ratio M/(M-16).
Further, figure 19 can be used to obtain L* and FIGURE 75.-Limits of Flammability of Methyl Alcohol-
Carbon Dioxide-Air and Methyl Alcohol-Nitrogen-
values in volume-percent. For example, at Air Mixtures at 25* C and Atmospheric Pressure.
250 C, L" is about 47 mg/1 from figure 22; the (Broken curve at 500 C and atmospheric pressure.)
i
TABLE 13.-Propertes oj 8elected simple akohols
Lower limit In air Upper limit In air
NetalHe
Combustible Formula Al (AirI in ai jj uLu, U
(Vol pct) (vol . ,g Ref. (Vol Ref
pet) C., / pct)
Methyl alcohol----- S....... oH _-- 82.04 1.11 12.25 IN1 8.7 0.65 1103 (40) '31 2.0 , f5
Ethyl alcohol ............. CH OH ........ 46.07 1.59 6.58 306 3.3 .5 70 (40) '11 2. 9 1 )(086)
n-Propylalcohol ........ CHF O- ........ 60.09 2.07 4.48 448 '2.2 .49 1460 (40) 814 3.2 420 j (4
n-Butyi alcohol --------- CiHoOH ........ 74.12 2. M 3.37 e 41.7 .50 87 I (S) 412 -------------- ()
pri-n-Amyl alcohol -... C&IIIsOH ----- 83.15 3.04 2.72 742 '1.4 .51 { VO (6) 10 .................
n.-..exyl alcohol.-- ------ - 102.17 3.53 2.27 888 1.2 .53 ............
t L.. L- .
t-100
e
C.
M*Fgures compied by Explosivu Re. Center, Federal Bureau of
it -60'. Min o. At saturation temperature. I Calculated value.
were compared with the corresponding maxima 60 T
for paraffin hydrocarbons (figs. 28-35); it was a ir -100%-% methyl alcohol-% wa \
found that appreciably more inert is required to
make mixtures containing methyl alcohol non- so
flammable. Conversely, methyl alcohol re- 400 C
quires less oxygen to form flammable mixtures, 2W C
at a given temperature and pressure, than paraf- 40
fin hydrocarboni do. This may be due in part
to the oxygen of the alcohol molecule. For the -
simple alcohols, we have: 30
C.H,,OH+
1.5nO
2
--*nCO
3
+ (n + I )H
2
0. (55)
C
20 - Flamrmable
Thus, the ratio of oxygen required for complete mixtures
combustion of an alcohol to that for complete rz
combustion of the corresponding
paraffin,
10
equation (22), is:
(56) 0 L 20 30 40 5O 60
WATER VAPOR, volume.percent
When n-- 1, this ratio is 0.75. The correspond- FIGURE 76.-Limits of Flammability of Methyl Alcohol-
ing ratios of the experimental minimum oxygen Water Vapor-Air Mixtures at 1000, 2000, and 4000 C
values from figures 75 and 28 are 0.82 with and Atmospheric Pressure.
carbon dioxide and 0.85 with nitrogen as inert.
The limits of flammability of methyl alcohol- ity data for the systems tert-butyl alcohol-
water vapor-air were obtained by Scott (192) carbon dioxide-oxygen and 2-ethylbutanol-
in a 2-inch-ID cylindrical tube at 1000 and nitrogen-oxygen are given in figures 79-81.
200' C and in a '4.9-liter cylindrical bomb at
4000 C and I atmosphere (fig. 76). Similar Autoignition
data were obtained by Dvorak and Reiser in a
2.2-liter apparatus at 1000 C (58). The minimum autoignition temperatures in
The limits of flammability of ethyi alcohol- air and oxygen of a number of alcohols at
carbon dioxide-air and ethyl alcohol.nitrogen- atmospheric pressure are given in appendix A.
air mixtures were obtained at 25' C and Comparison of these values with those of the
atmospheric, or one-half atmosphere, pressure as corresponding paraffins (methyl alcohol and
noted (fig. 77). Additional flammability data, methane; ethyl alcohol and ethane, etc.),
obtained for ethyl alcohol at 100' C 'and I shows that the AlT values of the alcohols are
atmosphere are given in figure 78. Flammabil- generally lower.
68 FLAMMABILITY CHARACTrERISTICS OF COMBUSTIBLE GIASES AND VAPORS
15It air m 100%-% ethyl alcohcl-% Inr air an l00%-% alcohol-% water vapor
vkq"2- '13.8%
10- Flammable8
Flammable 0
C02 mixtures
0 10 20 30L 40 so 0 8 Cs,
ADDED INERT, volume-percent _
Fiounia 77.-Limits of Flammability of Ethyl Alcohol- 0
Carbon Dioxide-Air and Ethyl Alcohol-Nitrogen-Air t 24
Mixtures at 250 C and Atmospheric Pressure. P
(Broken curves at one-half atmosphere.)
251
III
% air -100%-% ethyl alcohol-% water 0 10 20 30 40
*20
Fioumz 79.-Limits of Flammability of ter-Butyl
Alcohol-Water Vapor-Air Mixtures at 1500 C and
E
iO 601
15Mi 2.3 % oxygen 100% -% 1\alcohol-% C02
50-
0 Flammable nmlbe 0
400
WaX Vao-i Mixure at100CadAmop2i
5r sre
and Cacote or a rnge o mixtue comositios Alchol-Cros Dixd-xge itrs t10
ate 5 apC;-the mxmmturni 00 n veloispwereinctoshrcPrsue
fosutre 5. n 14c/e
1
rsetvl
(8.Thes rinvesotiaos o otland th hlt 00 CRO the IDE aximumves were 72.
burning velocities of methyl and n-propyl alco- and 64.8 cm/sec, respectively. These values
Lik
FLAMMtABILU/Y CHARCTERISTICS 89
60 ----- -
40 T "
I Xygsk'plt a lei tenoI-.% n
% air 100%-% ether-% Inert
Cool flames
40- t
20
\
0 2
30
5
400
0 FlammF
oble 8 - t o\ a i o D m h N2Ner
.1mixtures 9.3%9
920-
C-st
10-
FiauaE 82.-imxits of Flammability of Dimethyl Ether-
Carbon Dioxide-Air and Dimethyl Ether-Nitrogen-
*Air Mixtures at 250 C and Atmospheric Pressure.
0 20 40 60 80 100 40 [ I 1 i
NITROGEN, volume-percent
air - 100%-% ether-% inrt
FiOuRs 81.-Limits of Flammability of 2-Ethyl-
butanol-Nitrogen-Oxygen Mixtures at 1500 C and K
4 30 Cool flames
are in fair agreement with the corresponding -
values of the paraffin hydrocarbons.
Q:
The methyl alcohol liquid-burning rate ob- 20-
tained from equation (53) is in fair agreement a
with that obtained experimentalir (fig. 52). FlammbIe N2
The relatively low AHeIL JJ. ratios .or the alco- mixtures
hols indicates that they should be characterized o 0C02
by low-burning rates in large pools. t
ETHO S (CUH,.,.OCAj)
0iit 1n0i 20 30 40 50
Liitsn r
The properties of a few common ethers are FIGURE 83.--Limits of Flammability of Diethyl Ether-
listed in table 14. Unfortunately, the limits Carbon Dioxide-Air and Diethyl Ether-Nitrogen-Air
data show appreciable scatter, so it is difficult Mixtures at 250 C and Atmospheric Pressure.
to establish any general rules with the given
data. However, as a first approximation, the limit of the cool flame region in air is 48.4 vol-
L/C,, is about 0.5 for the simple ethers. ume-percent, according to Burgoyne and Neale
(26). The limits of the systems diethyl ether-
Limits in Other Atmosphereo helium-oxygen and diethyl ether-nitrous oxide-
oxygen are given in figure 84 and the limits of
Because of the importance of ethers as anes- diethyl ether-helium-nitrous oxide are given in
thetics, limits of flammability were determined figure 85 (106). Again, as with the alcohols,
in several atmospheres. The limits of the sys- more inert is needed to assure the formation of
tems dimethyl ether-Freon-12 (CCI
2
F2)-air nonflammable mixtures than is needed for the
dimethyl ether-carbon dioxide-air, and dimethyl corresponding paraffin hydrocarbons. Also,
ether-nitrogen-air obtained by Jones and co- cool flames are encountered at lower tempera-
workers are given in figure 82 (114); the tures and pressures.
limits of the systems diethyl ether-carbon di- Comparison of curves in figures 84 and 85
oxide-air and diethyl ether-nitrogen-air are shows that the minimum oxidant requirement
given in figure 83 (26, 166, 108), Cool flames for the formation of flammable diethyl ether-
exist above the upper limit as noted; the upper helium-oxidant mixtures is approximately twice
TABLE 14.-Properties Of 8elected ethers
- -Lower limit in aW Upper limit ill air
orml,
is Ls L Tin Us
Comba~lbe Fomula M ~ (Vol pct) moe (vol C. ) /,\ elf. (vol K)ig Ref.
pet) pet) 0
Dimetllyl ether ......... C~igOCH .... 4&. 07 1. 50 6. 83 0.16 3.4 0.562 { 7 1 1 4.1 760 (114)
Dletliyl ether----------Cils- 74. 12 2. N6 3.37 608 1.9 . 56 ( 4 (40) g 36 11 1,880 (40)
Eth~yl propyl ether---- CiHsOCa,, - 88. .8&15 3. 28 2. 72 5 760 1.7 .62 68 } (3.) M0 (8)
Dl-t-propyi ether-....C~I1,OCI,?--102.17 3.53 2.27 '900 1.4 .87 1 501 (40) 7.9 3. 291) (40)
Dlvtnyl ether----------...CillOCifla ... 70.00 2.42 4. 02 31,770 1.7 .42 54 11) 2 6. 7 1,160 (97)
IVLM-16
I Calculated value.
V--- 'cool fiames: Ua.'>16 vol pot.
'Cool flsmes: tVag-53 vol pot. I Ref. (165).
100 30 10%- dity ete-%H o 2)3
% 02= 10%-%diehyl lhe-
1
% e o N20 ~ 100%-% diethy! ether-% He
',
20
E 0
K
Flammable Min N20
E
6
wmixtures22
401
5 ~N20
Csf~n 02+ N0) H HELUMvolume-percent
Csj in 2) 2 ,, FioTTasE 85.-Limits of Flammability of Diethyl Ether-
- Nitrous Oxide-Helium Mixtures at 250 C and At-
0 20 40 60 80 100 mospheric Pressure.
HELIUM OR NITROUS OXIDE, volume-percent
Fzouaai 84.-imits of Flammability of Diethyl Ether- Since the ethers tend to formn peroxides under
Helium-Oxygen and Diethyl Ether-Nitrou's Oxide- a -variety of conditions, they inay appear to be
Oxygen Mixtures at 25' C and Atmospheric Pressure, unstable at room temperature (238).
as great with nitrous oxide as with oxygen.ES
RS(n n_0 CH.I
However, if .1 mole of nitrous oxide furnishes The properties of several esters are listed in
one-half mole of oxygen during combustion, table 15. The ratio of the lower limit at 25' C
then the minimum oxygen contents in the two to the stoichiometric concentration is about 0.55
cases are otearly equa. Unfortunately, the for many of these compounds. This is tile
available data are too meager to permit a more same ratio as in equation (21) for paraffin
detailed comparison, hydrocarbons. The lower limit values ex-
pressed in terms of the weight of combustible
Autclinitioper liter of air (see section about alcohols) are
AuFistetdo in parei.these,3 under L(mng/1). These ore
In genere.l, ethers are readily ignited by hot larger than thle corresponding values for the
surfaces. These combustibles usually hlave a hydrocarbons and alcohols. The inert require-
lower ignition temperature in air and in oxygen nients and minimum oxygen requirements for
than do the corresponding paraffin,; and the firs,.t member of the series, methyl formate,
alcohols. The available at'toigraion temipera- tire neI4 rly the same as for mnethyl alcohol and
ture data are included in app-ndix A. diniethyl' ether (figs. 76, 82, 86). This is not
FLAMMABILrITY CHARACTERISTICS 71
TABLE 15.-Properties of selected esters
Lower limit in air Upper limit in air
Sp. gr. C., Net ll,
(omlunstibh" Formula M (Air-1) in air ( Kcal L2 & L U., [ U
(vol pct) \i0 )(vol ( g Re. (vol (ng\ Ref.
pet) I. .T pet) \I
Methyl formate-...... II('OOCJI ... 60.05 2.07 9,48 219 5.0 0.53 142
1
(,,,) 23.0 2.4 800 t111)
Ethyl foruate. ......... |COO(',ii .... 74.08 2. b0 5,65 307 2.8 .50 { M (40) 16.0 2.8 630 (40)
n-Buty1 forniate ......... COOCI,n..... 102.13 3.53 3.12 2650 1.7 .M 1 7 (40) 8.2 2.6 410 (40)
Methyl acetoe-......... CIICOOCIh, .. 74.08 2,50 L.65 358 3.2 .57 (146 40) 16.0 2.8 630 (40)
Ethyl acetate ......... CICOOC11,.. 88.10 3.04 4.02 504 2.2 .55 I M (40) 11.0 510 (176)
n-Propyl acetato ...... CII3COOCsII?.. 102.13 3.53 3.12 1650 1.6 .58 ( 57 (40) 8.0 2.6 400 (40)
n-Butyl acetate ......... ('1COOC4lt,.. 116.16 4.01 2.55 ........... '14 .55 {73 (') '8.0 3.1 450 (6)
n-Amyl acetate ......... CIICOOC,1j . 130,18 4.50 2.16 ---- 1.0 .51 1 40 5 ) ' 7.1 3.3 440 (')
Methyl proplonate ...... CHCOOCIIs.. 88.10 3.04 4.02 ........ 2.4 .60 7 (0) 13.0 '5.2 580 (40)
Ethyl propionate ....... C 11COOC,21. 102.13 3 53 3.12 2650 1.8 .58 { (40) 11.0 3.5 510 (4())
L- LM -32 4 1=100 C.
M L-- a Figures eompled by Explosives Res. Center, Federal Bureau of Mines.
Calculated value. 6 P-0.5 atm.
t=90' C.
true of the othei' members for which data The autoignition temperatures of many esters
compiled at the Explosives Research Center are in air and oxygen at atmospheric pressure are
avaialable--.isobutyl formate and methyl acetate given in appendix A. In general, the AIT
(figs. 87, 88). Accordingly, it is rather difficult values of the esters are lower than are those of
to make additional generalizations for this series, the corresponding paraffins.
25 -n1--- I
5% air = 100%-% methyl formate-% inert
20
FIGURE 86.-Limits of Flamma- 0 F
bility of Methyl Formate-Carbon
F
Dioxide-Air and Methyl Formate- W mixtures
Nitrogen-Air Mixtures.
5-
0 10 20 30 40 50
FLAMMABWLITY niiRACTXHISTIC3 or COMBUSTIBLE GAOVI AND VAPORA
10T
air m 100%-% isobutyl formate
aH
81
C02
Fioun. 87.--LUmite of Flimrabfl- tj Flammable
N2
ity of Isobutyl Formato'-Carbon C mixtures
Dioldde-Air and lonbutyl For- a
ia 4eNltrogn-.AIr Mixtures. 0
4&
0 10 20 30 40 50
20T ""I
air 100%,-% methyl acetate-% inert
U 10- Flammable
Fsolua 88.-ALmlit o! Flamnmabil- t M2
Ity of Methyl Aoetate-Carbon t mixtures
Dioxide-Air and Methyl Aoetate- !
Nitrogen-Air Mixture. -j C C0
0 10 20 30 40 50
IP
FLAMMABILITY CHIARACTERISTICS 73
20~ ~ -n- I~- -- i - ------- r r~
____ Flammable mixtures
E
70.5 mole MEK + 29.5 mole %u toene
0
C')
AtmospericiPessure
Fgive i tablEe 1.Thto of Teprte Lower Limits on, Famity sown M -tat he sytues MnEK- a
atDHY E 250 KEO E (C. airO timi the s1ici0n-ri Ccpsto aosen ahd THFo en oe vlue Chitler
is approximately 0.5. law, equation (46). Calculated and experi-
Zabe takis, Cooper, and Furno found that the mental values for the preceding systems in air
lower limits of wethyl ethyl ketone (MEK) and are iven in figures 91 and 92.
MEK-toluene mixtures vary linearly with Te limitsoth systems acetone-carboD
temperature between room temperature and dioxide-air, acetone-nitrogen-air, MEK-chlorc-
20
0
C (36. A summary of these data is bromomethane (CBM) -air, MEK-carbon di-
given in figure 89; broken curves in this figure oxide-air, and MEK-nitrogen-air are given in
were obtained from the modified Burgess- figures 93 and 94. The data in these ftgurcs
Wheeler law, equation (33), taking the lower were obtained by Jones and coworkers (2588).
TABLE I 6.-Pro pertim of 8e.ected aldehydes and kcet ones
NLA. Lower limit lo air Upper limit In air
Combustible Formula Ai (Ag - 1) inA ai 14 LIDU U
mole)
(
4
IL )
. U
(Vol pet) (Vol !E/g\ Ref. (voi C,, /f-g\ Rof.
pet) 'kJ pet) k.
Aretaldehyde.......... .I1aCIIO. . 44.051 L.62 7.73 264 4 40 0.52 82 (M9) ' 36 4.7 1,100 (961)
Pmopionuidehyde. .- CS1tCHO. . &S. 08 2.01 497 409 2.9 .69 7 (9) *14 2.8 420 (96)
1'mraidehy~de ..... (CIIiCHO)s,_.132.16 4.%8 2.72 .. 1.3 .49 78 (40)_ j _i
Acetone (lC I, 8.08 2.01 4.97 403 2.6 .52 70 (98) Ii 2.6
Niethyl ethyl ketone. C 113CC . ,c- 72.10 2,49 3 67 648 1.9 .52 62 (U3) 10 2.7 360 (19#3
hiethyl prcpyl ketone M.sC C~I 813 2.97 2.90 692 1.6 .55 63 (40) 8.2 2.8 340 (40,
a(011CCVI PA. 13 2.'J 2 90 592 I'6 .65 63 (1) - . .
Nfethyl butyl ketone CII,3COC,1it 100.16 3 4A 2,40 840 '1. 4 .58 64 (40) '8.0 3.3 390 (40)
I Cool flameL: U-f0 Vol pet.
' Cool Barnes: Via-17 vol pot.
I CalculatA~ t'Clue.
*f-60 C.
I -100 C.
74
A 1
A ~
~ cR
CVT~
1 I S M S
CO
USSTI
L r, G X~ S VI
ND
VA ?O
BS
2.0
Flammable Mixt'Ures
THE
GD
1.8
6
70.5 mote-%
HE+ 29.5 mo~e%
toluen~e
'14
35.6
mol%
~l-lV * 6
.4m e% toluenle
00
204
1.2U 20
40
60IA
. TEMP~ailt
of T Fo
ue n MlitureB
in Air at
T h eec i
ati T e r r P e r t e s o f v a i u Sfi
L S A N D
n m E L
E O
de
und
'kili u no onrd i
teme rtre s of endIO . Fuis used for
not co eed
aatigpOiS
lowe an inad
d here(tble1
aldehy ~ ~ ~
a5ueaeg~e n ln those t e nIaae O P
at os hei
vr alues
are
low
r
at
e e t~ f5
r
of r-1 h '- para us.
A m o iy
n ,( I ) ~ .' a
of
sulfu
copud
adusnlren
pCflb0 4
,I7
This
theytyl
havei
T h eM
n d
I
S
e
rzin
e ( N2')
' m o n
arerie
give
infu tapo
zse
N,9
di mNle
A)ti
en I
aegni-
theoyi
formCS)S
flammable
ixtuire
s
es ppae 7 1 , g l i , ,l o carb o n an o h r M
.
i i a v r I o f co flcen tr ia
a n
tab~t
A8 anedr
water
ti o
f,
Vht e
and
an
lv l r n e
ase xi at s in . a n i ncae (
n
wide tel am
uerp
en i
-. fr carboan
an m o ra
.
doa be 19
N ~
widn
disk
d~ ~% t m r a d a r'
aon O v n
ton
a noted
in t a n,
us ,(1)
re o
Fl ar n s 4 with
car
bo 4dair ( f 9 5) ;
that
Fue
- .. hy r crbo
s
r,1 a
ie ns
vicarbo
nl diodfor
in t an d
roge
7)fi
e-
(lor m g*an ethe rfa m b e ~ t fa l tem F rt er r iniia
d] meeapanwit chorl ,, (17 (fg. 7) thet trie
1
ne raige.
axrre
in
with chlo
inar
,Eich lO%
j oet
an e in th t it shows
not
press
t a h In e us n wth
er ifoun
qguof
car11bon
disulfd
e essentially
c
th 'a2. flarnt
l rang
fcr.ie
topetthe
guatj:e
of inert
requr
teperature.
t~~ o p r e v e n t
T A 1L t
1 7
. - P r O P e ' " 6 oJ .e te c te d s n tjflr v n ~ n d
p e o t i
-
P
-3
0213
231
FLAMMABILM' Y' CIHARACTERISTICS 75
2.0-r------- --- -
0 Experimental points
1.8
- Calculated
300C
0
9.
0 Flammable mixtures
E
~1.6-
0
CL
LU
0
0 20 4 08 0
MEK, mole-percent
FioUREI 91.-Effect of Liquid Composition on Lower Limits of Flammability of MIEK-Toluene Mixture-s in Air
at 300 and 2000 C.
2.0 I
0 Experimental points
- Calculated
Flammable mixtures
E0
~1.6-
0
U0
~1.4-
C,,
1.0
0 20 40 60 8 0
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.
FLAMMABILY CLARACTERISTICS 77
14 1 f
a air - 100%-% acetone-% inert
12
10
a-
E
.- Flammable Fiovas 9&.-Limita of Flammabil-
mixtures N2 ity of Aoetone-Carbon Dioxide-
ti Air and Aeetone-Nitrogen-Air
z Mixtures.
Cs,, C02
4- -
2 I
0 10 20 30 40 50
TABLE 18.-Properties of selected fue. and fuel blend.
Not Aem limit In air Upper limit In air
I ., / .8a
Combustible Formula AV (22i) iNCS AH -MOWG -- -a (Lu-U
(oPa)(Vol C I (o ~ ( j\ Ia
Pet) IS pot)19'"
Ammonia ------------.-.-- --..- 7.. 17.08 0.0 21.58 .......... 1 0.0 134 (16, 2 1.8 800 (181)
Hydrasine ............... N-.-'".- - 2 06 I 17.32- ......... 4.7 .27 70 -88 10- .3 (... .
?eonomtyl b draem NuCi.:: 46.07 1.:80 7.73------4 .82 so (18)_!----5'.
Unspunmetrl NH*(CHs)s. 60.10 2%OR 4.07..... .2 .40 .6 5 10.1....
Monmtylyn ln.. N E a....4 0 .0i ?? ..... mn ........
Ddioa... .......... D ...... .27.09 ... 88 478 .8 .12 10 (11 8. 1..I ........ 16)
Tetra .......... ..... . 1 4 & 67 4 1........ .---- 10----
Pentaborane ............ B ........... 17 2,18 8 308 0 . .12 12 ............
Deosorae........Da.u . 12.: 4.2 ..--------- 2 .11 It I S ............. U ..... ..... . 7 2 ........ ..... . . ........ ........
Aviation Be lP- ... ............................. (141)....38
Aviation let fuel .1P-I ........................
............ ........... 1.4............."1
71 - Aviation etfuelJ P-4.... .1.2 ......... . ? 8 .
Aviation jet tuel J P-4.........................-.---..-............,...... ... .. .
Aydron ............. Ht ............ 2.0 0 298 87.3 4.-- ---- 8. 7 (40) 7 .84 270.
Calculated value. I-u100. 0.
't-30 0.
12 1 I I I
, air = 100%-% methyl ethyl ketone-% inert
10
E
N2
Fiovaa 94.-Limits of Flammabil- L CBM
it of Methyl Ethyl Ketone z
(E K) - Chlorobromemethane 6
(CBM)-Air, MEK-Carbon Diox-
ide Dioxide-Air and MEK-Nitro- " Flammable
oen- Mr Mixtures at 250 C and -. mixtures
-j 4- C02
/
XI ,Cst
IT
2q
0 10 20 30 40 50
TABLE 19.-Limits of flammability of ammonia following quantities of hydrocarbon vapor were
at room temperature and near atmospheric needed to inhibit flame propagation in a
pressure lY-inch glass tube ' at 1250 C and atmospheric
pressure: 39.8 pct benzene; 35.0 pct toluene;
Oxidant C.o L U Ref. 27.3 pct m-xylene; 23.8 pct cumene; 21.0 pct
_ n-heptane. On this same basis, 95.3 pct air is
needed to prevent flame propa ation (188); this
Air O-e------------. 21.8 15 28 (167, 18) corresponds to a lower limit of flammability of Oxygen ---------------- 57. 1 15 79 ( $25)
Nitrous oxide -------- 40. 0 2. 2 72 (109) 4.7 pct hydrazine vapor. The flammable range
in air at atmospheric pressure is presented
raphically in figure 98, which also gives the
Hydrazine vapor burns in the absence of an fammable ranges of monomethylhydrazine,
oxidizer, so that it has no upper limit and can unsymmetrical dimethylhydrazine, and ammon-
therefore be used as a monopropellant. The ia for comparison (218). The flammability
deomposition flame yields hydrogen, nitrogen, diagram for the system hydrazine-n-heptane-
and ammonia (64, 78). However, hydrazine air at 125

C and atmospheric pressure is given
vapor can be rendered nonflammable by addi- in figure 99. These data were also obtained
tion of stable diluents or inhibitors. The in a 0l4-inch glass tube.
amount of diluent required at any temperature A summary of the autoignition temperature
and pressure appears to be governed in part by data obtained by Perlee, lmhof, and Zabetakis
thA ignition source strength. With a 0.25-inch (166) for hydrazine, MMH, and UDMH in air
spark gap and a 15,000-volt, 60-ma-luminous- and nitrogen dioxide (actually, the equilibrium
tube transformer as the energy source, Furno,
Martindill, and Zabetakis (68) found that the I Comparble results were partialy obtained ina 2-nch tube.
i-
Fp
79
507
20- 1
air - 100%-% carbon disulfide-% Inert air = 100%-% ethyl mcrcaptan-% inert
40 - 1
SF-22
(CH CI 172)
6 ..
CHcCl 172)
3 0
\o
I- Flammable mixtures
= Flammable
\
M 0
mixtures
min 02
C
10-
C02
0 0 5 10 15 20
Fioumm 97.-Limits of Flammability of Ethyl Mereap-
0 20 40 60 80 tan-F-12-Air and Ethyl Mercaptan-F-22-Air Mixtures
ADDED INERT, volume.percent at Atmospheric Pressure and 270 C.
FiouRE 95.-Limits of Flammability of Carbon Disul- mixture NO
2
*-NO
2
NO
4
) is given in figure
fide-Carbon Dioxide-Air, Carbon Dioxide-Nitrogen- 100; short horizontal lines indicate th un-
Air Mixtures at 250 C and Atmospheric Pressure, and
Carbon Disulfide-Water Vapor-Air at 1000 C and certainty in N0
2
* concentrations. These ma-
terials may ignite spontaneously at room
temperature with relatively small NO
2
* con-
50
1 centrations in the air; at 250 C, liquid UDMH
% air 1009-% hydrogen sulfid. -% C02 ignites in N02*-air atmospheres that contain
more than about 8 volume-percent NOa*; MMH
I
and hydrazine ignite in atmospheres that
contain more than about 11 and 14 volume-
40-
- percent NO
2
*, respectively.
In general, even
smaller concentrations of N0
2
* produce spon-
taneous ignition of these combustibles at
higher initial combustible liquid temperatures.
30-- Mi 02 The effect of the hydrazine liquid temperature
11.6%
on the spontaneous ignition temperature in
* , NO
2
*-air atmospheres is illustrated in figure 101.
0_
Similar data are given in figures 102 and 103
J Flammable
Flmmatue
for MMH and UDMH; there is an apparent
u' 20 mixtures
Zanomal*
in the data obtained with ivi1il at
0 36' 55
,
and 67' C.
0=
0
The use of various helium-oxygen
atmos-
pheres in place of air results in the spontaneous
S10-
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
S I I NO
2
*-He-O. atmospheres is the same as that
0 10 20 30 40 obtained in N
2
-air atmospheres.
Ignition temperature data obtained with
CARBON DIOXIDE, volumepercent
tTDMH in NO
2
*-air mixtures at 15 and 45 psia
FIwRE 96.--Limits of Flammability of Hydrogen Sul- are summarized in figure 105. These indicate
fide-Carbon I)ioxide-Air Mixtures at 25' C and that although the spontaneous ignition tem-
perature of UDMII in air is not affected ap-
760 1 1 1 100
600 -Ammonia Upper -78.9
- ~limit
400- -DH52.6 .
E
E 200 -Flammable- 26.3 E
-d Cs, mixtures 0
Flovitz 9S.-ljznits of FlamIna- CO 100:
1.
t
7
of Ammonia UD MH, CO0.
MMIH, and Hydrazine at At- W8 so
niOSPheric Presaure in Saturated cr
and Near-Saturated vapor.Akr 0. 60
Cst -7.9 >
Mixtures.
C
51 - w
40- Lower -5. Jt
-limit - I~
20- Hydrazine -2.6 2
0
MMH
10L
1. 3
150O -100 -50 0 50 100 150 200
TEMPERATURE, OC
81
100
10 90
20 0
0
0
30 0 00 70
%30
4000 60o
0KEY
mFlammable
&
50 mixtures 50
016
8 0 4!
60
4
X
70 30
0 KEY
80 ~0 Flammable 2
HEPTANE-VAPOR, volume-percent
F URN 99.-oFlammable Mixture Compositions of 20ydrazine-Heptane-Air at 125* C and
Approximately Atmospheric Pressure.
82 FLAMMABILITY CHARACTP.RISTICS OF COMBUSTIBLE GASES AN) VAPORS
300 I Boron Hydrides
This series includes diborane (B2H,), tetra-
a UOMH borane (B
4
Ho), pentaborane (B '), and deca-
b MMH borane (B
1
oH
4
). However, reliable tipper and
c Hydrazine lower limit data are available only on the first
250 member of this series at the present time.
These were obtained by Parker and Wclfhard
(168) who determined the limits of flammability
of diborane in air in a 5-cm-diameter tube at an
initial pressure of 300 mm Hg; this combustible
200 forms flammable mixtures in air in the range
Region of spontaneous ignition from 0.8 to 87.5 volume-percent. A pale blue
egogflame propagated throughout the tube at, the
upper limit; luminous iltmes were not visible
above 79 volume-perccnt. Limit of flamma-
bility curves for the system diborrnie-ethane-air
S150 are presented in rectangular coordinates in figure
107. Except for the slight dip to the ethine-
axis (zero diborane) in the area in which ethane
forms flammable mixtures in air, these curves
E are rather similar to those obtained with other
100. 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
50 -data obtained by these and other authors; they
a h C 25* C found the lower limit of pentaborane in air to
be 0.42 volume-percent.
The autoignition temperature of diborane in
Dew point line of NO* air is apparently quite low. Price obtained a
0 - value of 135' C at 16.1 mm Hg (169); that of
pentaborane is 30' C at about 8 mm Hg (9).
0 5 10 is 20 25 30 Gasolines, Diesel and Jet Fuels
NOI CONCENTRATION, volume-percent
Fuels considered in this section are blends
FicVRu 100.-Minimum Spontaneous Ignition Tern- that contain a wide variety of hydrocarbons
peratures of Liquid Hydrazine, MMH, and UDMH and additives. Accordingly, their flammability
at an Initirl Temperature of 25* C in Contact With characteristics arc governed by the method used
NO,*-Air Mixtures at 740 10 mm Hg as a Function
of NO,* Concentration. to extract a vapor sample as well as by the
history of the liquid. For example, since the
preciably by this pressure change, it is affected lower limit of flammability, expressed in
in a range of NO,*-air mixtures. volume-percent, is inversely proportional to
The data presented in figures 100 to 105 were the molecular weight of the combustible vap(,r,
obtained with liquid fuel in contact with apor- equation (28), the first vapors to come from a
ized NO* ;n air. Similar data obtained with blend, such as gasoline, give a higher lower
vaporized UDMH-air in contact with NO* limit value than the completely vaporit.sd
are given in figure 106. This figure indicates sample. Conversely, the heavy fractions or
that LTDMH-air mixtures that contain more residue give a smaller lower linit value. For
than 9 volume-percent UDMH will ignite spon- this reason, there is some disagreement aboutI
taneously on contact with NO*; UDMH-air the limits of flammability of blends such as
mixtures that contain more than approximately gasoline and the diesel and jet fuels. These
2 volume-percent UDMH can be ignited by an fuels are, in general, characterized by a wide
ignition source under the same conditions (166). distillation range; the ASTM distillation curves
FLAMMABILITY CHARACTERISTICS~ 83
300 I
200
Lj
M Region of spontaneous ignition
000
100-
36*
770
670
I
x
0 0 15 20
NO CONCENTRATION, volume-percent
FiGuRE 101.-Miniiui Spontaneous Ignition Temperatures of Liquid Il:3drazine at Vafious Initial Temperatures
in NO,*-Air Mixtures at 740 10 mmn lg as a Fuikction of N0
2
* Concentration.
200 .................
x
,.*
/ 67"
C100 -
"36 Region of spontaneous ignition
0o
/
-1
05 10 15 20 25
NO* CONCENTRATION, volume-percent
FhG'RE 102.- Miiniml 111 Spontneous lgniitioii Tiperaturv of Liqih' \IN1\ :t a trius Initil] " tih-ir trci
iil N( ) -Air M[ixtizrtus at 740 10 min lig as a Iwt otion of N02* 'onceittratioth.
200
S
SRegion
of spontaneous ignition
w
D
x
36* and 55* - "
x
0 5 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.
400 -
I
Curve He/0
2
a 0.0/100
b 100/25
C 100/6.50
d 100/1.70
300 U 100/0.30
f
100/0.00
P
V Region of spontaneous ignition
-200 -
we V
cc
FIGURE 104.-Minimum
Spon-
%
taneous Ignition Temperatures
Ratios.
100 - 'i
of 0.05 cc of Liquid UD MNH in
Atmosphere for Various He/O
2
-a ob line of N*
2
~ .
- - - -
-- _ __
- -
0 5 10 15 20 25
22
FLAMMABILrTY CHARACTERISTI( 5 87
300 . . . - . . 250 ---T-T T -T-----T-- i F
a 15 psia
b 45 psia
_ 200
200-
Region of spontaneous ignition
Region of spontaneous ;gnition
i
0 150
I J
100 1
100
Lower limit of flammability
of UDMH in air
I ] ] 50I
0 5 10 15 20
Dew point line
FiouRx 105.-Minimum Spontaneous Ignition Tern- ""
peraturep of 0.05 cc of Linuid UDNIH in NO,*-Air
Mixtures at 15 and 45 Psia as a Function of NO,* I I I I
Concentration. 0 4 8 12 16 20
of two gasolines and three jet fuels considered
UDMH CONCENTRATION, volume-percent
here are given in figure 108. Unfortunately, FIGURE 106.-Minimum Spontaneous Ignition Tem-
such curves give only an approximate measure peratures of Vaporized UDMH-Air Mixtures in Con-
of the volatile constituents in the liquid blend. tact With 100 pct NO; at 250 C and 740 10 mm
Even relatively nonvolatile high-flashpoint, oils Hg as a Iunction of UDMH Concentration in Air.
may liberate flammable vapors at such a slow
rate that the closed vapor space above the grade JP-4 (fig. 110). Combustible vapor-air-
liquid may be made flammable at reduced carbon dioxide and vapor-air-nitrogen mixtures
temperatures. Gasolines can produce flam- at about 25' C and atmospheric pressure are
mable saturated vapor-air mixture at tempera- considered for each. Similar data are given in
tures below -65' C (241), although the flash figure 14 for the gasoline vapor-air-water vapor
points of such fuels are considered to be about system at 21' and 100' C; the effect of pressure
-45' C (158). An apparent discrepancy thus on limits of flammability of volatile constituents
exists if flashpoint data are used to predict of JP-4 vapor in air are discussed in connection
the lowest temperature at which flammable with figure 12.
mixtures can be formed in a closed vapor space Minimum autoignition temperatures of gaso-
above a blend in long-term storage. lines and jet fuels considered here are given in
As noted earlier, the limits of flammability of compilations by Zabetakis, Kuchta, and co-
hydrocarbon fuels are not strongly dependent workers (126, 237). These data are included
on molecular weight when the limits are ex- in table 20.
pressed by weight. However, since results Setchkin (194) determined the AIT values of
measured by a volume are perhaps more widely four diesel fuels with cetane numbers of 41, 55,
used than those measured by weight, typical 60 and 68. These data are included in table 20.
flammability curves are presented by volume Johnson, Crellin, and Carhart (92, 93) obtained
for the light fractions from aviation' gasoline, values that. were larger than those obtained by
grade 115/145 (fig. 109), and aviation jet fuel, Setchkin, using a smaller apparatus.
88 FLAMMAI3ILIT CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS
100
S air 100 -% diban@-X ethane S air 100X- X psolIne- S inert
lmF lammable
wimm~ mixtures 0
Luminous
20- flame
(cltio\\a 0 to 20 3 40 0
,I i I
ADDED INERT. volume-percent
0 20 40 60 so 1W. Fzoaui 109.-Limit. of Flammability of Aviation
ETHANE. volume-percent Gasoline Grades 115/145 Vapor-Carbon Dioxide-Air
and 115/145 Vapor-Nitrogen-Air, at 27" C and At-
Fnouzz 107.-Limits of Flammability of Diborane- mospherlc Pressure.
Ethane-Air Mixtures at Laboratory Temperatures
and 300 mm Hg Initial Pressure. 10 1
460- % i r00%-% JP4- inert
- 6-
420 -/ !" I8
380- -
// N2
340 /4- Flammable
3407 It mixture
CL C02"
02
- -
S260-
, " 0 10 20 30 40 50
l'- ADDED INERT,. volume-percent
220- Fiouaz 110.-Limits of Flammability of JP-4 Vapor-
Carbon Dioxide-Air and JP-4 Vapor-Nitrogen-Air
/ -Mixtures at 270 C and Atmospheric Pressure.
180-/ , " TABLE 20.-Autoignition temperature ialues of
various fuels in air at 1 atmosphere
Fuel:
140 Aviation gasoline: AlT, -c
100/130 -------------------------- 440
115/145 -------------------------- 471
Aviation jet fuel:
I00 I I JP-1 ---------------------------- 228
0 20 40 60 80 100 JP-3 -------------------------- 238
DISTILLED, percent JP-4 ---------------------------- 242
JS-6 n----------------------.------ 232
FJouaz 108.-ASTM Distillation Curves for, A, Avis- )iesel fuel:
tion Gasoline, Grade 100/130; B, Aviation Gasoline, 41 eetane ----------- ------------ 233
Grade 115/145; C, Aviation Jet Fuel, Grade JP-I; 55 cetane ------------------------ 230
D, Aviation Jet Fuel, Grade JP-3; and F, Aviation 00 cetane------------------ 225
Jet Fuel, Grade JP-4. 68 cetane -------- _---------------- 226
Burning velocities of the fuels considered 80
here are in the same range as those of the ir= 1bo%-% hydrogen-% inert
hydrocarbons considered earlier. Values for
various fuels have been tabulated by Barnett Mn 02
and Hibbard (156). o -%
Hydroqen I 22
Numerous flammability characteristics
studies have been conducted with hydrogen in 0
recent years. Drell and Belles have prepared ,
an excellent survey of these characteristics (48). Cs5
This survey includes all but the most recent .
work of interest.
The low pressure limits of flame propagation 20 Famab_-
for stnichiometric hydrogen-air mixtures are mixtres C02
somewhat lower than those for stoichiometric
ethylene-air mixtures (197) in cylindrical tubes.
In the range from 6 to 130 mm Hg, the limit I
for stoichiometric hydrogen-air mixtureS is 0 20 40 60 80
given by the expression:
ADDED INERT, volume-p.rnent
log P=3.19-1.19 log D, (57) Fiuaz III.-Limits of Flammability of Hydrogen.
Carbon Dioxide-Air and Hydrogen-Nitrogen-Air
where P is the low-pressure limit in millimeters Mixtures at 250 C and Atmospheric Pressure.
of Hg, and D is the tube diameter in milli-
meters.
Hydrogen forms flammable mixtures at curves were found to deviate from the results
ambient temperatures and pressures with oxy- obtained from the Le Chatelier law, broken
gen, air, chlorine, and the oxides of nitrogen, curves; additional data are given in the original
Limits of flammability in these oxidants at article.
approximately 250 C and I atmosphere are The burning velocity of hydrogen in air at
listed in table 21. 25' C and one atmosphere range from a low
of a few centimeters per second to 325 cm/sec
TABLE 21 -Limits of mmability of hydrogen (68). When liquefied, it, vaporizes and burns
T i variouoiatfs a 5la a o an d oen in air at a rate that is determined by the rate
in various o)xidants at 25'C and atmosp~ric at which heat enters the liquid. Heat is
pressure
abstracted from the surroundings and, where a
flame exists, from the flame itself. Figure 115
Oxidant L3 (t Ref. gives the results obtained from vaporizing
.liquid hydrogen from paraffin cast in a Dewar
4.flask; epe ental points were obtained from
Oxygen --------
exper5imental
Air -----------------. . 0 75 (40) gas evolto measurements. The solid curve
Chlorine -------------- 4. 1 89 (em, ike) (theoretical) was obtained by Zabetakis and
S---------------------3. 0 84 (189) Burgess by assuming the heat influx rate to be
NO ------------------- 6.8 66 (189) conduction limited (234); the initial flash
vaporization rates are probably film- and
nucleate boiling-limited. The theoretical liquid
Flammability diagrams of the syatems hydro- regression rates following spillage of liquid
gen-air-carbon dioxide and hydrogen-air-niitro- hydrogen onto three soils are presented in
gen obtained by Jones and Perrott (112) are figure 116, the corresponding decrease in liquid
given in figure 111. Lines that establish level is given in figure 117. Because of its
minimum oxygen values for each system are low temperature, the vaporized hydrogen
also included. Note that although the mini- forms a vapor trail as it. leaves the liquid.
mum value occurs near the "nose" of the However, the position of this trail or visible
hydrogen-air-nitrogen curve, the corresponding cloud does not necessarily coincide with that
value occurs atr the upper limit of the hydrogen- of the flammable zones formed above the liqui,
air-carbon dioxide curve. pool. This is illustrated in figure 118, in which
Flammability diagrams obtained by Scott, the positions of the flammable zones and visible
Van Dolah, and Zabetakis for the systems clouds are defined in a height-elapsed time
hydrogen-nitric oxide-nitrous oxide, hydrogen- graph. Two flammable zones are defined here.
nitrous oxide-air, and hydrogen-nitric oxide-air These are also seen in the motion picture
aregivenin figures 112-114 (189). Upperlimit sequence (fig. 119) of the visible clou 6 and
g0 FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE OASES AND VAPORS
100 0
KEY
* Flammable mixture
0 Nonflammable mixture so 20
40 NO, mleecen
Fiouiaz 112.-Limits of Flammability of HrNt).';2 at Approximately 280 C ane I Atmosphere,
A..AMMABILITY CHARACTERISTICS
91
100 0
KEY
* Flammable
mixture
o Nonflammable mixture 80
20
A Coward and Jones,
Bureau of Mines
o3 Smith and Linnett,
JCS (London),
1953, pp. 37-43
20
80
0
100
100 80 60 40 20 0
N
2
0, mole-percent
FIGURE 113.-Limits of Flammaubility of Ilr-N20-Air at Approximately 280 C and 1 Atmosphere.
92 FLAMIMABILIT CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPOR$
100 0
KEY
* Flammable mixture
* Nonflammable mixture 80 20
A Coward and Jones,
Bureau of Mines
Bull. 503
60 40
1
00
0 -100
10 80 60 40 20 0
AIR, mole-percent
FIOL'Rz 114.-Limits of Flammability Of HrNO..Air at Approximately 280 C and I Atmosphere.
FLAM"MABILITY CHARACTERISTICS 93
Start of liquid transfer to Dewar
10 1----T - -T - T - '
a-
. .- (Film and nucleate boiling limited)
E
I: Theoretical
(conduction limited)
IAI
2 -
Region i
_of vilent
boiling F--1- Quiet vaporization
0 1I I I I 1 1 1 1 1 1 1
-20 0 20 40 60 80 100 120 140 160
ELAPSED TIME, seconds
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 I I I I
.3
2
040 60 80 100 120 140 1'60
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-
0 20 ~ 40 60 8 0 2 4 6
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.
14-
KEY
0 Loer-limit mixture
12 Nonflammable
10 Nonflammable
FIGURE I I.-Extent of Flamma- 8-
ble Mixtures and Height of
Visible Cloud Formed After -Height of visible cloud
Rapid Spillage of 3 Liters of
Liquid Hydrogen on a Dry Mac-~
adam Surface in a Quiescent X 6 -
Air Atznoephere at 150 C.
.
""N
4LPE T-E sNod
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 vaporiza-
tion of about 3 to 90 liters o? liquid hydrogen
are given in figure 120. The data are repre-
sented 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, V
1
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
.375 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 stor-
age sites f certain assumptions are made (83,
2o0- 160, ,34). Additional work is required to
establish such distances for very large quantities
15- of liquid.
The detonation velocity and the static and
10- W reflected pressures developed by a detonation
3 . wave propagating through hydrogen-oxygen
V) mixtures are given in figure i6. The predeto-
0-1 nation 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
at essentially zero runup distance. Numerous
investigators have examined this and related
problems in recent years (11--8, 65, 155-137,
k '161).
.3 HYDRAULIC FLUIDS AND ENGINE
OILS
Both mineral oil derivad and synthetic hy-
draulic 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 qta-
bility, viscosity, load-bearing characteristics,
etc. Such additives affect flammability char-
acteristics 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 I I ,1F- i1-
60- Flame height - -
I- Flame width 0
ME0
2 20
FiounE 120.-Maimurn riane
height and widtk. pitcd-c'd by
Ignitioni U vapor-air mixtures0
formed by sudden spillage of 10
1
II I I L I I I IL
2.8 to 89 liters of liquid hy- 2 4 6 8 10 20 40 60 80 100
drogen (VI). VI, liters
5-
U
.4-
00
Hydrogen
0
z Methane
0 2
FG URE 121.-Burning rates of w
liquid hydrogun %nd of liquid 0
methane at the boiling points in W
6-inch-Pyrex
Dear flasks.
1i
10 20 30 40 50 60
ELAPSED TIME, minutes
FLAMMABILiTY CHARACrERISTIL"S
97
fluid generally plays a predominant role iii de- ambient temperatures can lead to the auto-
ternining limits of flammability and ignition ignition oi ,t mineral oil lubricant (curve 5) if
tAmperaturo of a particular fluid. For exam- sufficient vapo' or mist is in the system. In the
pie, many of the oil-based fluids have lover same pressure range, only elevated initial
limits of flammability that fall in the ranges temperatures could lead to the autoignition of a
given in figure 22 for paraffin hydrocarbons. phosphate ester (curve 4). If the initial pressure
Further, those that have minimumn autoignition is increased to 10 atmospheres, autoignition
temperatures in the lower temperature ranges cin oo-ur at, lower air-intake temperatures in
considered in fiugres 43 and 71 are not affected every case (248).
appreciably by oxygen concentration of the
atmotsphere and by ambient and fluid-injec'ion M C] M OUS
pressures; those that, have minimum autoigni-
tion temperatures in the higher temperature The flammability characteristics of a number
ranges do not follow these generblizat ions (287). of miscellaneous combustibles not considered
Since these fluids are designed for use at ele- elsewhere, are discussed in this section. These
vated temperatures and pressures, they are nor- include carbon monoxide, n-propyl nitrate, and
mally made up of high -molecular weight mate- the halogenated hydrocarbons. The properties
tials. Accordingly, they are flammable at of these and a geat variety of other materials
ordinary temperatures and ressures as mists are included in Appendix A.
and foams. Burgoyne and his coworkers (27) The limits of flammability of the systems car-
found that, lubricating-oi mists were flrmma- bon monoxide-carbon dioxide-air and carbon
ble in air but not in carbon dioxide-air mix- monoxide-nitrogen-air are presented in figure
ture,: that contained about 28 ,volume-percent 126. These curves were constructed from the
carbon dioxide (fig. 1i5). At elevated temper- flammability data obtained by Jones in a 2-inch
Otnre4, the ,A!, vapors cracked Rnd produced vertical glass tube with upward flame propaga-
acetylene and hydrogen, which affected the tion (11); other representations may be found
flarmmability of the resultant mixture; the va- in the original reference and in the compilation
pors are often unstable at elevated tempera- prepared by Coward and Jones (40).
tures. Chiantella, Affens. and Johnson have Materials that are oxidized or decomposed
determined the effect of elevated temperatures readily may yield erratic flammability data
on the stability and ignition properties of three under certain conditions. This effect i illus-
commercial triaryl phosphate fluids (36). trated in figure 127 which summarizes the
Zabetakis, Scott, and Kennedy have deter- lower-limits data obtained by Zabetakis, Mason
mined the effect of pressure on the autoignition and Van Dolah with n-propyl nitrate (NPN) in
temperatures of commercial lubricants (248). air at various temperatures and pressures (248).
Figure 122 gives the minimunm autoignition An increase in temperature from 750 to 1250 C
temperatures for four commercial phosphate is accompanied by a decrease in the lower-limit
ester-base fluids (curves 1-4) and three values; a further increase in temperature to
mineral oils (curves 5-7). In each case, the 1500 C results in a further lowering of the lower
minimum autoignition temperature was found limit at pressures below 100 psig, but not at the
to decrease with increase in pressure over most higher pressures. An increase in the tempera-
of the pressure range considered. A plot of the ture to 1700 C results in an apparent increase in
logarithm of the initial pressure to temperature the lower-limit value because of the slow oxida-
ratio versus the reciprocal of the temperature tion of NPN. A complete flammability dia-
is given for curves 1 to 7 in figure 123. The gram has been constructed for the NPN vapor
resultant curves are linear over P limited tern- system in figure 128; a single lower limit curve
perature range.
and two upper limit curves are given here tc
The ratio of the final temperature attained by show the effect of pressure on the flammable
air in an adiabatic compression process to the range of a vapor-air system.
initial temperature is given in figure 124 as a The spontaneous ignition of NPN in air was
function of both the final-to-initial pressure considered earlier at 1,000 psig (figs. 3, 4). The
ratio and initial-to-final volume ratio. If a explosion pressures obtained at this initial pres-
lubricating oil is exposed to high temperatures sure in air and in a 10 volume-percent oxygen
during a compression process, autoignition may +90-volume-percent nitrogen atmosphere at
occur if the residence or contact time is ade- various NPN concentrations are presented in
quate. Such high temperatures do occur in figure 129. A summary of the minimum spon-
practice and have been kLown to cause disas- taneous ignition and decomposition tempera-
trous explosions (68, 146, 149, 27, 2 1). The tures obtained with NPN in air and nitrogen
curves ii ligure 125 show that in the compression respectively are given in figure 130. The data
pressure range 1 to 10 atmospheres (initial given in this figure exhibit a behavior that is
praesure=l atmosphere), a wide range of typical of that found with other combustibles
98 FLAMMABILITY CHARACTIEISTICS OF COMBUSTIBLE. GASES AND) tAPORS
6.50 .T- .. ............ -T-- r - - -T-T T -TT -1
00
C0
autignti1
IV~
0:500
0. 80 20 416810 0 0
INT2450SSR,
t
FIUR 12.Vrai4i0i0umAtintoiTmeaur ihPesr t(omnrh hsht s
a2 Miea viiurcnsi i na40-cSaiesSellonj
FLAMMABILrrY
CHARACTERISTICS
9
TEMPERATURE,
-C
650 550 450 400 350 300 250 200 175
.6 - M n e ra l
Phosphate
3 ol
.4
esters0
A -X
Regioo of
outoignition
.10
.08
0D6
0
be .04-
FIGUIC~ 123.-togarithm
of Ini- I-,
tial Prpe~ura-AIT Ratio of E
Seven Fluids in Air for Various
Reciproca~lTemperatureb.
Data.
-
from Figure 122. .02-
.0i-
.008-
.006-
.004
.002
V11 VI
I. .40I
1.8
2.4
2.2-
V,
2.0- v-
1.8-
Pf
FiouUm 124.-Variation in T,/T, i -
of Air With V
4
/Vt and With
PIPi in an Adiabatic Corn- 1.6-
preaion Procen.
1.4
1.2
1 2 3 4 5 6 7 8 9 10
vi Pf
vf P,
LAs
FLAMM4ABILITY CHARACTERISTICS 101
500 O tm Re(!ion of
500- autoignition
Fiouaa 125.-Variation In Air 11A;
rIemperature With P,/P, in an
Adiabatic Compnression Proces3
Tepea 30 -/I-t
for Five Initial Air Tepr <~~0P t
tures (00, 250, 5O*, 750, and MAIT
1000 C). Regions of autoignl-
tion for lubricants TV and Vat CL 0.
P,/P, Between 1 and 10 Atmos- 2
phere and P, of Between 1 and W
10 Atmospheres.
20 -P-1
t
P,,i100
80 at elevated pressures; the minimum spontaneous
ignition temperature first decreases with ini-
air - 1009- carbon monoxide- Inert tial increase in pressure and then increases as
the pressure is increased still further (120,
60 248).
Burning velocities were found to range from
I20 cm/sec to 110 cm/sec in NPN-air mixtures
containing 3.0 to 7.2 volume-percent NPN.
id Flammable Detonations were obtained in saturated NPN
0 40- mixtures vapor-air mixtures from 300 to 650 C and 1
atmosphere
pressure;
the detonation
velocit
o0 _,, 'st C02
/
was from 1,500 to 2,000 meters per second
S N2Stable detonations were obtained with liquid
z
NPN at 900 C; the detonation velocity was
cc - from 4,700 to 5,100 meters per second.
5Although many of the halogenated hydro-
carbons are known to be flammable (40) still
others such as methyl bromide, methylene
F
chloride, and trichloroethylene (TCE) have
0 20 40 60 80 been considered to be nonflammable or essential-
ADDED INERT, volume-percent ly nonflammable in air. As noted in connection
witb the methyl bromide data given in figure
Frounn 126.-Limits of Flammability of Carbon Mo- 28 Hill found methyl bromide to be flammable
novide-Carbon Dioxide-Air and Carbon Monoxide- . H
Nitrogen-Air Mixtures at Atmospheric Pressure and in air at 1 atmosphere pressure (84); the re-
2W' C. ported limits of flammability were from 10 to
5
Flammable mixtures
0
0 2 --
1700C (3 hr heating time) -
> /75C /170C (2 hr heating time)
0 - - - - - - - - - -
z
1.500C
.1250C
Z I I
0 100 200 300 400 500 600 700 800 900 1,000
PRESSURE, psig
FIGUaz 127.-Lower Linitq of Flammability of NPN Vapor-Air Mixtures river the l'r,ssijrv Range I.-roi 0 t
1,000 Psig at 75', 125', 150
o
, and 170" C.
FLAMMABILrrY CHARACTERISTICS 103
100 15 volume-percent methyl bromide. At an
initial pressure of 100 psig, the flammable range
was found to extend from 6 to 25 volume-per-
90 -- cent. Similarly, methylene chloride and tri-
chloroethane were found to be flammable in air
at ambient temperatures although the flam-
mable ranges were not determined. In general,
so -
much higher source energies are required with
Impossible vapor-air these combustibles than are required to ignite
mixtures at T &I25 "C methane-air mixtures.
70 An approximate flammability diagram was
prepared by Scott for trich oroethylene-air
60
mixtures (190); a modification is reproduced in
60 .figure 131. The lower limit data were obtained
in a vertical 7-inch-diameter flammabil~ty tube
and the upper limit data in an 8-inch-diameter
0 50- glass sphere with upward propagation of flame.
lammable mixtures of TCE and air were also
0 obtained between 10.5 and 41 volume-percent
a40 TCE at, I atmosphere and 1000 C in an 8-inch-
> diameter glass sphere. Under the same con-
Z ditions, flammable mixtures of TCE and
z oxygen were obtained between 7.5 and 90
30 volume-percent TCE. However, additional
work must be conducted with this and the
other halogenated hydrocarbons to determine
20 Saturated vapor-oir the effect of vessel size, ignition source strength,
mixtures T 1250C temperature and pressure on their flammability
characteristics.
1 o Other useful flammability data may be found
T-50o6C for various miscellaneous combustibles in many
.. Flammable of the publications listed in the bibliography
" , ,(40, 154, 200, 208-214, 118). These include
0 200 400 600 800 1,000 data on the gases produced when metals react
PRESSURE, psig with water (56) and sulfur reacts with various
hydrocarbons (62). Still other references con-
1"1OURE 128.-Flammable NPN Vapor-Air Mixtures sider the hazards associated with the production
Formed Over the l'ressure Range From 0 to 1,000 of unstable peroxides (142, 157, 187, 238) ,and
Psig at 50

and 1250 C. other reactive materials (66, 74, 80, 139).
,.S
5,000--
In
ct 4,000-
o3,000-
a-
z 2,000-
0
Q. 1,000-0
Ai
X ~0-10% 02 + 90% N
2
0 0.3 0.6 0.9 1.2 1.5 1.8 2.1
NPN VAPOR, volume-percent
FIOURZ 129.-Variation of Explosion Pressure Following Spontaneous Ignition With NPN Concentration, Initial
Pressure 1,000 Psig.
2 4 0C
11T
_ T
Regions of spontaneous ignition and
220- spontaneous decomposition
~ Dcoposition in N
2 0
0 400 800 1,200 1,600 2,000 2,400 2,800 3,200 3,600 4,000
INITIAL PRESSURE, psig
FIGURE 130.-Minimum Spontaneous Ignition and Decomposition Temporatures of n-Propyl Nitrate in Air as a
Function ofPressure, Type 347) Stainless Steel Test Chamber,
TEMPERATURE. "C
0 10 20 30 40 50 60 70 80 90 100
1,o000 , r , , I T -F.. .
800 -- 1O
-90
600 L80
- 60/
400 5
30 Upper limit
4 E
300 - -440 "
Impossible mixtures
0 >
200 Flammable mixtures E
E
i, i0 __-e,/,r ower limit 420
60-
40-10
30- Nonflammable mixtures
u
10 I 0 I,
0 50 100 150 200 250
TEMPERATURE, "F
FIouRE 131.-Flammability of Trichloroethylene-Air Mixtures.
ACKNOWLEDGMENTS
Many of the unpublished data reported here Burgess 6 and Robert W. Van Dolah for many
were obtained by the predecessor of the author, fruitful discussions of the material contained in
the late G. W. Jones, former chief of the gas the sections on Definitions and Theory, De-
explosions branch. Other data were obtained flagration and Detonation Processes, and Pre-
by the author and his coworkers, particularly ventive Measures.
Messrs. George S. Scott, Joseph M. Kuchta,
Aldo L. Furno and Henry E. Perlee. In I Presently with Reaction Motors Division, Thiokol Chemical corpo-
addition, the author is indebted to Drs. David ration, Denville, New Jersey.
106
BIBLIOGRAPHY
1. Affens, W. A, J. F. Johnson, and H1. WV. Carhart. 18. Browning, J.A., T. L. Tyler, and W. G. Krall.
Effect of hernical Structure on Spontanleous Effect of Particle Size on Combustion of Uni-
Ignition of Hydrocarbons. J.ChRn., Eng. form Suspensions. 'Id. and Eng. Cher'., v. 49,
Data, v. 6, 1961, pp. 613-619. 1957, pp. 142-148.
2. - - . Ignition Studies, Part V, Study of 19. Buckley, William L., and Howard WV. liusa.
the Processes Occurring D)uring the Spontaneous Combustion Properties of Ammonia. Chern.
Ignition of the Hexane Isomers. N111 Rept, Eng. Prog., v. 58, 1962, pp. 81-84.
5437, January 1960, 15 pp. 20. Burgess 1)., A. Strasser, and J. Grunter. lDiffu-
3. Agnew, J. TI., and L. 13. Graiff. 'file Pressure sive turniing* of l.!Xiuid Fuels in Open Trays.
D~ependence of Laminair Burrning Velocity bly Fire Res. Abs. and Rev., v. 3, 1961, pp. 177-102,
the Spherical lotrib Method. Comnbustion an d 21. Burgess, D~avid, and Michael (s. Zabetgkis. Fire
Flame, v. 5, 1961, pp, 2M~J-219. and Explosion Hazards Associated WAith Liqu,!!-
4. Alexander 1) 8 Explosions in Butadiene Syf.- fled Natural Gas. BuMines Rept. of Inv. 0099,
tents. nd. and Eng. Chemn., v. 51, 1959, pp. 190,2, 34p.
733- 7318. 22. Burgoye,JT.H. Mist and Spray Explosions.
5. Anson, 1). Influence of the Quality of Atoiniza- Chem11i. Eng. Frog., v. 53, 1957, pp. 121-M-
tion onl the Stability of Comnbustion of Liquid 124- M.
Fuel Sprays. Fuel, v. .32, 1953,_p p. 39-51. 23. - . Principles of Explosion Prevention.
6. Ashmnan, L. E., and A. l3tichler. The Ignition of Chem. anid Process Eng., April 1961, p p. 1-4.
Gases by Electrically Hfeated Wires. Combus- 24. Blurgoyne, J. If., and L. Cohen. The Effect of
tion and Flame, v. 5, 1961, pp. 113-121. Drop Size on Flame Propagation in Liquid
7. Bartkowiak, Alphonse, Sotirios Lambiris, and Aerosols. Roy. Soc. (London), Proc. v. 225,
Michael G. Zahetakis. Flame Propagation 1954, pp. 37a-392.
Through Kerosine Foamns. Combustion and 25. Burgoyne, J. If., andl 11. Hirsch. Trhe Combustion
Flamei, v, 3, 1959, pp. 347-353. of Methane at High Temperatures. Roy. Soc.
8. Bartkowiak, Alphonse, and Michael G. Zabe-takis. (London), Proc. v. 227, 1954, pp. 73-93.
Flammability Limits of Methane anid Ethrane in) 26. Burgoyne, J. H., anid R. F, Neale. Some New
Chlorine at Ambient and Elevated Tempera- Measurements of Inflammabilit) Ranges in Air.
tures and Pressure.. Bu~lines Rept. of Inv. Fuel, v. 32, 1953, pp. 5-16.
5610, 1960, 6 PP. 27. Burgoyne, J. H., and J. F. Richardsonr. The
9. Bert, W. G., and W. lienich. The Combustion Inflammability of Oil Mists. Fuel, v. 28, 1949,
of Boron Hydrides. CNI-942, Johns Hopkins pp. 2 -6.
Unliv., Silver Spring, Md., 1958, 53 pp. 28. Burgoyne, J. H., and A. J. Steel. Flammability
10. Block, Benjamin. Emergency Venting for Tanks of Mlethane-Air Mixtures in Water-Base Foams.
and Reactors. Chein. Eiug., January 1962, Fire lRes. Abs. and Rev., v. 4, Nos. I and 2,
pp. 111- 118. 1962, pp. 67-75.
11. Ilollinger, Lorenr E., and Rudolph Edse. Therrmo- 29. Burgoyne, J. if., aind G. Williams-Leir. The In-
dynramric Calcuilatioris of Hydmrogew-Oxygen fluence of Incombustible Vapours onl tire Limits
I )(tuuation Parimtvrs for 'Various Initial of Inflammnab~ility of Gases and Vapours in Air.
Pressirris. ARS J., v. :31, 1961, pp. 251-256. Roy. Soc. (London) Proc., \-. 193, 1948, pp.
12. Bollinger, Lorrr, E., Mficliael G. Fong, and 525-539.
If idr'llul lise. 'xpvririrntaI Measurrvrnents 30. B~urgoynie, J. 11I and M. J. (3. Wilson. The Relief
and lhr114orrtiei Analysis of D~etonartion Inuihctioni of Penitane %apour-A ir Explosions in Vessels.
lDistatices. ARS J., 1961, lpp. 5S.-594. l'roc. Syrup , orr ('hreur. P rocess llazards, lInt.
13.Bolingr, ,oellE.,JaiivsA.Laulin, ad :1.ButIler, JIudson (U., arnd Willian '. W Ib t ppI r
loitrioland Idliction irrtlei I t rog - )Ixposvr( Limrits of ( urriie. (Pier
Iricti,., irrl IirlictoriI )it~rrce inIlvrrr~rrDautai, v. 2, 19.57, lpp. 42-461.
Nitroris Oxidi Mixtres. AitS J., v.:32, I 962, 32, (ussutt, Lrorn If. Lxp,rirriral Irivesligatirri of
PPI. 1%A 1,2
Detonation ill Irieoriiried ( ascous llvrrrgri-
14. Blritish Ctnrricrl Enigirneering. Vse of l1'rt.inr (hygiri-Nitrogeri Mixtures. Alt' J., 1961, pp.
I ises ait Iliglri Terhiiroires. D ee,'inberr 1957, 11 22-Il128.
Ii. 677
313. ( asnitt, L. If., F. E. M addocks, ririrl W. A.
I.5. Blrokaw, Vioiiard S., ranl .Iosih 1- ... aick~rr. Siruv-er. A '-rudlv of ltheIHazirdus in tir, Storagv
1:ffiret of I ,rr rt., Iressiur, arid Courmpostj- andi 'Ilarrilirig (if liquid llYulrogeru. Adelvc
donir oni Ignitrionr Dc)lnivs for l'irltiri 110 inws. iii (r .N.geic Eng., vd, hY K. I). Tilirrvirus.
501~' ip u lilt'l tCrillhi:tiourll, tiiiioldl l'lerrijrrr Press, Inc., New York, v. 5, 196t0,p.
Pubil. C orp. Now Nirk, 195~5, lpp .563 569, 5.5 61.
16i. Brorwrre, IlowarrI C., lI:rr,,ld Jliknianr, anil Lo\ell 341. ('lirnilicrl aii 1Eriginvriirg Nr,%\s. Explosie IDc-
C. Weger. Ki:rriend,, for I ligi I'ressilrri He- corripositiori of l'ropylzi-. V, 30i, 1952, p.1 239.
seaciri.h I arnd Erg. Chclirrr, v, 53, N61il, 35. Cheimrical Frigirruriug. Plle Relievers~ crir t
pp.) 52A-58A.
plosivye I opoel.. -Jan. 22,11962, 1)1) 7r 72.
17. Browning, J. A., aind W. G. Errill. Fffcet of Fuivl 36. (riaritria, A. J., NNV. A. Al~ens, anl T... uruoi
lDrolvts onl Flaril Staluilit.N, Flaiir, VelurcitY, 'Il Effi-ct of High Tlripratures onl th Sli t-
and IruflarurnabilitY L~itmits . 5thr Symrp. (Iner- hirlity sridl Ignition l'ropertics of I onircial
nat.) onl Combustion, Rteinhloldl Putr. Corp., Triaryl Ph'losphrate FlIuids. .N IL It ipt. 58319,
New York, 1955, lip. 159-163. 1962, 15 pp.
107
108 FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE GASES AND 'VAPORS
37, Coleman, F. H1. Effects 4) Fluorinated Hlydro- Nuclear Sci. and Eng., v. 10, July 1961, pp.
carbons oii the Inflammability Limits of Corn- 247--253.
hustible Vapours. Fuel, v. 31, 1953, pp. 445- 57. Evons, Marjorie W and C. MI. Ablow. Theories
447. of D~etonation. i. (Chem. Rev., v. 129, 1961,
38. Conison, Joseph. How to D~esign a Pressure pp. 129-178.
Relief System. Chem. Eng., 1960), pp. 109--i14. 59. Faeth, G. M., and 1). F. White. Ignition of
39. Copeland, N. A., and M. A. Y'ouker. German Hydraulic I luids by Rapid Compr~ession, Ami.
Techniques for Handling Acetylenq- in Chemical Soc. Naval Eng. J., v. 73, 1961, p~p. 467-475.
Operations FT kT Finial Rept. No. 720, Janu- 59. Fitzgerald,' F. D)ecomposition of Methylacetylene.
ary 1946 130 pp. Nature 1960) p. 387.
40. Coward, It. F., nnd G. W. Jones. Limits of 60. Frank, dharles E., and Angus U. Blackhiam.
Flammahility of Cases and Vapors. BuMines Investigation of Hydrocarbon Ignition. Nat.
Bull. 503, 1952 155 pp Advisory Committee for Aeronautics TN 2549,
41. Coward, H. F, 6. V. nes, C. G. Dunkle, and 1952, 33 p p
B. E. Hess. Tfhe Explosibility of Mebhane and 61. Fra 'ser, R.P. Detonation Velocities in Liquid
Natural Gas. Carnegie Inst. of Technol., Min. I uel Vapours With Air or Oxygen at 100" C and
and Met. Inv., Coop. Bull. 30, 1926, 40 pp. Atmnosphieric Pressure. 7th Symp. rinterrnat.)
42. Cubbage, P. A., and W. A. Simmonds. An in- or) Combustion, Butterworths Sci. Pub.
vestigation of Explosion Reliefs for Industrial (London), 1958, pp. 783-788.
Drying Ovens. Gas Council, Rtes. Comniuni- 62. Furno, Aldo L., George H1. Martindill, and Michael
cation GC23 (London), 1955, 46 pp. G. Zahetakis. Gas Explosion Hazards Associ-
43. ~ nIvsiainof Explosion Re- ated With the Bulk Storage of Molten Sulfur.
licfs for Industrial Drying Ovens. Gas Council, Bu Mines Rt.it of Inv. 6185, 1903, 11 p p.
Res. Communication GC43 (London), 1957, 41 63. .Lmits of Flammability of Hydra-
PP.
zine-Hydrocarhon Vapor Mixtures. J. Chem.
44. Davenport, Donald B George B. Huber, and Eng. D~ata, July 1962 pp. 375-376.
Norman R. Zabel. evataininent, of Fragments 64. CGaydon, A. G., andH.0 Wolfhard. Flames,
From Runaway Nulear Reactors. Progress in Their Structure, Radiation and Temperature.
Nuclear Energy, v, 4, Pergarnon Press, New Chapman & Hall, Ltd. (London), 2d ed.. 1960,
York, 1961, pp. 484-503.
383 Topp. Sui . hrhll eoa
45. DavisD S. Emerg3ncy Vent Size for Tanks 65. GealeroyLadtutW.Crcil Den-
Cnainn&s Flarmable Liquids. British Chem. tion Characteristics of Hydrogen-Oxygen Mix-
Eng. Nomogram No. 62, v. 6, 1961, p. 644. tures at High Initial Pressures. AICh1E, v. 6,
46. Dias, E., H. Karam, and C. Jones. Practical Way September 1960, pp. 501-505.
to Size Safety Disks. Chem. Eng., 1961, pp. 66. Gerstein, M. A S-tudy of Alkylsilane Flamnes.
187-190. 7th Symp. (Internat.) on Combustion. Butter-
47. Dixon-Lewis G. and G. L. Thles. Limits of worths Sci. Pub. (London), 1959, pp. 903-905.
Flammabijity." 7th Symip. (Internat.) on Corn- 67. Gerstein, Melvin, Edward R. Carlson, and Francis
bustion, Butterworths Scientific Pub. (London), U. Hill. Natural Gas-Air Explosions st Re-
1959 pp. 475-483. duced Pressure. Ind, and Eng. Chem., v. 46,
48. Drell, Isadore L., and Frank E. Belles. Survey 1954, p p. 2558-2562.
of Hydrogen Combustion Properties. Nat. 68. Glibbs, G. J., and H. F.Calcote. Efffk~t of Molecu-
Advisory Conmmittee for Aeronau'*Ics Rept. lar Structure on Burning Velocity. ,J. Chem.
1383, 1958, 34 p?. Eng. Data, v. 5, 1959, pp. 226-237.
49. Dugger, Gordon ., and Dorothy D. Graab. 69. Glasstone, Samuel. Thermodynamics f'or Chem-
alme Velocities of Propane- and Ethylene- ists. 1). Van Nostrand Co., Inc., New York,
Oxygen-Nitrogen Mixtures. Nat. Advisory 1946, 522 p!).
Committee for Aeronautics RM E52J24, Janu- 70. (ileiidinning, W4. G., and A. M. MacLennan.
ary 153, 2 pp.Suppression of Fuel-Air Explosiond. Nat. Fire
50. DugrGrnL. and Sheldon Heimel. Flame Protect. Assoc. Quart.. v. 45, July 1951, p. 61.
t c~sofMehane-Air, Propane-Air, and 71. Gliwit~ky, W. Prevention of Acetylene-Air Ex-
E~tylne-irMitures at Low Initial Ternm era- plosions by Addition of Carbon Dioxide arid
tures. Nat. Advisory Committee for Ae'ro Nitrogen. Autogene Metalbearheit, v. 33,
nauties TN 2624, February 1952, 25 pp. 1940, pp. 2-5.
51. Dugger, Gordon L., Robert C. Wcast, and Sheldon 72. Grabowski G -J Industrial Explosion Protection.
HeimeI. Effect of Preflame Reaction on Flame J. Am. 6i1 ChePm. Soc., v. 36, 1959, p p. 57-59.
Velocity of Propane-Air Mixtures. 5th Sym p. 73. Gray, P., anid J. C. Lee. Recent Studies of the
(Internat.) on Combustion, Reinhold Pu. Oxidation and Decomposition Flames of Hydra-
Corp., New York, 1955, p. 589-595. zine. 7th Symp. (Internat.) on Combustion,
52. 1)'iz.n, Robert G., and lierna- T. Wolfson. Butterworths Sci. Pub. (London), 1959, p. 61.
Single C ',neralized Chart of D~etonation Pa- 74. 0 reenlee, Konneth. Butadiene-Crotonaldehyde
rameters; for Gaseous Mixtures. J. Chetn. and Explosion. C'hem. and Eng. News, v. 26, 19,
Eng. Data, v. 4, 1959, pp. 124-127. p. 1985.
53. Dvrk Karel, and Arnost Reiser. Influence of 75. Guest, P'. G., V. W. Sikora, and Bernard Lewis.
Water Vapor on the Flame Extinction of Static Electricity in Ilospital Operating Suites;
Methanol in Air. Chem. Listy, v. 49, 1955, D)irect and Related Hazards and Pertinent
pp. 467-472. Remedif-s. BuMines Rept. of Inv. 4833, 1952,
54. Edwards, D0. H, G T Williams, and J. 1). Breeze. 64 pp.
Pressure and {~elocity Measurements on D~etona- 76. Ilaher, F., andl i1. Wolff. Mist Explosions.
tion Waves in flydrogen-Oxygen Mixtures. J. Zeit, angew. Chem., v, 36, 1923, p. 373.
Fluid Mech., November 1959, pp. 497-517., 77, Hall, A. It., and It. A. M. Straker. The Methyl-
55. Egerton, Sir Alfred C. Limits of Inflammability, apetylene (Propyne) D~ecompositionl Flame at
4th Symp. (Internat.) on Combustion, Williams l'ressures of I 0, 20 and 41) Atmospheres.
& Wilkins kCo., Baltimore, Md., 1953, pp. 4 13. Rocket Pr~opulsion Establishment (Weatcott),
50. Epstein, Leo F'. Correlation and Prediction of TN 192, 1960, p. 11.
Explosive Metal-Water Reaction Temperatures. 78. Haara, N. E., M, G. Zabetakis, Rt. W, Van Dolah,
BIBLIOGRAPHY 109
and G. H. Damon. Potential Ignition Hazards Operations. Chem. Rev., v. 22, February 1938,
Associated With Compressed-Air Blasting Using pp. 1-26.
a Compressor Underground. BuMines Rept. 96. . The Inflammability of Refrigerants.
of Inv. 5223, 1956, 33 pp. Ind. Eng. Chem., v. 20, 1928, pp. 367-370.
79. Harris, D. N., Glenn Karel, and A. L. Ludwig. 97. Jones, G. W., and B. B. Beattie. Explosive Prop-
Electrostatic Discharges in Aircraft Fuel Sys- ertice of Divinyl Ether. Ind. and Eng. Chem.,
tems. 41st Ann. API Meeting Preprint, 1961, v. 26, 1934, pp. 557-560.
10 p. 98. Jones, G. W., E. S. Harris, and W. E. Miller.
80. Heck, W. B., Jr., and R. L. Johnson. Aluminum Explosive I roperties of Acetone-Air Mixtures.
Alkyls. Ind. and Eng. Chem., v. 54, December BuMines Tech. Paper 544, 1933, 26 pp.
1962, pp. 35-38. 99. Jones, G. W., and R. E. Kennedy. Effect of
81. Heimel, Sheldon, and Robert C. Weast. Effect Pressure on Ignition Temperature of Acetylene
of Initial Mixture Temperature on the Burning and Acetylene-Air Mixtures. BuMines Rept.
Velocity of Benzene-Air, n-Heptane-Air, and of Inv. 3809, 1945, 7 pp.
Isooctane-Air Mixtures. 6th Symp. (Internat.) 100. - - . Extinction of Ethylene Flames by
on Combustion, Reinhold Publishing Corp., Carbon Dioxide and Nitrogen. Anesthesia and
New York 1957, pp. 296-302. Analgesia, v. 9, 1930, pp. 6-10.
82. Herzog, R. K., E. & Ballard, and H. A. Hartung. 101. . Extinction of Propylene Flames by
Evaluating Electrostatic Hazard During the Diluting With Nitrogen and Carbon Dioxide
Loading of Tank Trucks. 41st Ann. API and Some Observations on the Explosive Prop-
Meeting Preprint, 1961, 7 pp. erties of Propylene. BuMines Rept. of Inv.
83. Hildebrand, Joel H., and Robert L Scott. The 3395, 1938, 14 pp.
Solubility of Nonelectrolytes. Reinhold Pub. 102. . Limits of Inflammability of Buta-
Corp., New York, 3d ed 1950 p. 243. diene in Air. BuMines Rept. of Inv. 3565,
84. Hill Howard W. Methyl Bromie-Air Explosion. 1941, 4 pp.
Chem. Eng. Prog., v. 58, August 1962, pp. 103. . Prevention of Butadiene-Air Explo-
46-49. sions by Addition of Nitrogen and Carbon
85. Holdsworth, M. P., J. L. vander Minne, and S. J. Dioxide. BuMines Rept. of Inv. 3691, 1943,
Vellenga. Electrostatic Charging During the 11 pp
White Oil Loading of Tankers. 41st Ann. API 104. Jones, 6. W., R. E. Kennedy, and W. E. Miller.
Meeting Preprint, 1961, 30 pp. Limits of Inflammability and Ignition Temper-
86. Holtz, John C., L. B. Berger, M. A. Elliott, and ature of Ethyl Mercaptan in Air. BuMines
H. H. Schrenk. Diesel Engines Underground. Rept. of Inv' 3648 1942, 6 pp.
BuMines Rept. of Inv. 3508, 1940, 48 pp. 105. Jones, G. W., R. h. Kennedy, and I. Spolan.
87. Hsieh, M. S., and D. T. A. Townsend. An Exam- Effect of High Pressures on the Flammability of
ination of the Mechanism by Which "Cool" Natural Gas-Air-Nitrogen Mixtures. BuMines
Flames May Give Rise to "Normal" Flames. Rept. of Inv. 4557, 1949, 16 pp.
Part I. The Inflamrpable Ranges of Ether-Air 106. Jones, G. W. it E Kennedy, and G. J. Thomas.
Mixtures in Closed I Vessels. J. Chem. Soc. Explosion Hazards of Combustible Anesthetics.
(London), 1939, pp. 337-340. BuMines Tech Paper 653, 1943, 47 pp.
88. Whc . An Examiriation of the Mechanism by 107. . Explosive Properties of Cyclopro-
Which "Cool" Flames May Give Rise to "Nor- pane. BuMinesRept. of Inv. 3511, 1940, 17 pp.
mal" Flames Part II. The Inflammable 108. - . Inflammability of Ether-Oxygen-
Ranges of Higher Paraffin Hydrocarbons in Helium Mixtures. BuMines Rept. of Inv.
Air: The Establishment of "Cool" Flame 3589 1941, 15
Ranges at Ordinary Temperatures and High 109. Jones, E., and J. C. Kerr. Inflammability Limits
Pressures. J. Chem. Soc. (London), 1939, pp. of Ammonia, Nitrous Oxide, and Air. J. Soc.
341-345. Chem. Ind., .v. 68, 1949, pp. 31-34.
89. International Acetylene Association. Acetylene. 110. 'ones, G. W., and W. IE. MiUer. Ignition Temper-
Transmission for Chemical Synthesis. Internat. atures of Acetylene-Air and Acetylene-Oxygen
Acetylena Assoc., New York (no date), 40 pp. Mixtures. BuMines Itept. of Inv. 3567, 1951,
90. Jackson, J. L., and R. S. Brokaw. Variation of 5 pp.
Spontaneous Ignition Delays With Temperature I 1. Jon-s, G. W., W. E. Miller, and H. Seaman.
and Composition for Propane-Oxygen-Nitrogen Explosive Pro erties of Methyl-Formate-Air
Mixturee at Atmospheric Pressure. Nat. Ad- Mixtures. Ind. and Eng. Chem., v. 25, 1933,
visory Committee for Aeronautics Res. Memo. pp. 694-696.
E541319, 1954 29pp. 112. Jones, G. W., and G. St. J. Perrott. Oxygen
9. Jacobs, R. B., W. L. Bulkley, J. C. Rhodes, and Required for the Propagation of Hydrogen,
T. L. Speer. Destruct'on of a Large Refining Carbon Monoxide, and Methane Flames. Ind.
Unit by Gaseous Detonation. Chem. Eng. and Eng. Chem., v. 19 1927, pp. 985-989.
Prog., v. 53, December 1957, pp. 565-573. 113. Jnes, G. W., and F. k. Scott. Extinction of
92. Johnson J. Enoch, John W. Crellin, and Homer Propane and Butane Flames by Dichlorodi-
W. arhart. A Study of the Autoignition fluoromethane. BuMines Rept. of Inv. 3908,
Properties of Certain Diesel Fuels. Naval Res. 1946, 8 pp.
Laboratory Rept. 3859, 1951, 29 pp. 114. Inflammability of Dirnethyl Ether-
93. - . Ignition Studies. Part I1--The Dichlorodifluoromethane-Air Mixtures.
Spontaneous Ignition Properties of Some Diesel Bu.Mines Rept. of Inrv. 412.5, 1947, 4 pp.
Fuels and Pure Hydrocarbons. NRL Rept. 115. Jones, G. W., W. P. Yant, W. E. Miller, and R. E.
4202, 1953, 14 pp. Kennedy. Limits of Inflammability of )iethyl
94. Jones, G. W. Fire and Explosion Hazards of Ether and Ethylene in Air and Oxygen.
Combustible Gases and Vapors. Ind. Hygiene BuAlines Rlept. of Inv. 3278, 1935, 5 pp.
and Toxicology, ed. by !'rank A. Patty. Inter- 116. . The Ignition Temperatures of
sci. Pub., Inc., New York, v. 1, ch. 13, 2d rev. Dielhyl Ether and Ethylene in Air and Oxygen.
ed., 1958, pp. 511-548. BuMines Itept. of Inv. 3284, 1935, 6 pp.
9A. -- - . Inflammation Limits and Their 117. Jones, (,. W., M. G. Zahttakis, and G. S. Scott.
1'ractical Application in 11azardous Industrial Elimination of Ethyl Mercaptan Vapor-Air
110 FLANLMABILITY CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS
Explosions in Stench Warning Systems. Detonation Wavcs. J. Chem. Eng. Data, v. 4,
Bu.Mines Rept. of Inv. 5090 1954 8 p. 1959d,p p. 133-135.
118. Jost, Wilhelm. Explosion and Comliustio'n Proc- 137. Luker, James A., Paul L. McGill, and Leonard B.
eases in Chases. McGraw-Hill Book Co., New Adler. Knallgas and Knaligas-Steam Mix-
York, 1948, 621 p p. tures at HIPl Initial Temperature and Pressure.
119, Kharasch, M S. Heats of Comhustion of Organic J. Chem. Eng. Data, v. 4, 1951), pp. 136-142.
C'ompounds, NBS J. Res., v. 2, 1929, pp. 138. Mantn J., and B. B. Milliken. Study of Pres-
359.-430. sue ependence of Burning Velocity by the
12. ennedy, It. E., G. S. Scott and M. (7l. Zahetakis. Spherical Vessel Method. Gas DynamicsSymp.
1 . 1"hiirntility' Liints of hydrocarhons at Hi1gh on Aerotlierroochein. Proc., 1955, pp. 151-17.
'l'l'rlturt s and Pressures. Chern. Eog. 139. Mlarsel,J.., and L. D~ramner, Spontaneous Ignition
l'rog., v, 53, l05?74 pp. 125 126. Properties of Metal Alkyls. 7th Sympt. (Inter-
121, K,'nnedy, II. S. ipolan, W. K. Mork, oind C,. S. nat.) on Combustion, lAutterwort hs Sci. Pub.
Seottr. Eiect 'of F] igh Pressures on the~ Ex po0- (London), 1959, p. 906.
sittility of Mixt ures of Ettne, Air, aind Carl toni 1410. Mlartindill, G. If., F. W. Lang, an( 1M. G.
D~ioxide, and Ethane, Air, atid N it rogeni. Zahetakis Flammability Characteristics oft lie
Ito Mint's Retpt of Inv'. 4751l, 11;50, 11 pp. Vapor System lfidrogen Peroxide- Xylene-
122. Kennedy, 1t, IC, . spolan, finti G. S. Scott. Formic Acid-Water.' J. Chemn. Eng. Data, v.
E'xpIlosihiiv, of M ix tnrt's of l1ropa nv, A ir, andt 5, I 960, pp. 355-358,
Carhon I) ioxide anti of Propaine, Air, ando 141. Miatsot,, A. F., and Itl. IE. Dufotir. Limits of
N it rogenr at Elevateld P'ressures. ]it Mint's Flammtabilit y of Methb I v Et hyl Ketone Vapor
lIept. of I if %. -18 12, 1951, 9t pp. in Air ait Initial Twmperatures of 1100', 1500 and
123. Klinkenherg, A., and J . L. vanit'r M mone. Elee- 200'. 1 T'nderwrit ers Laboratory Bull, lRes.
trostatics in ttie lpetroleumn Indoust iv. Elsevier 39, 1947, PP. 5-18,.
Pulising Co,, New York, 1 9)58, 191 p.142. Mci~onald, J. S., and J. IE. Owens. Investigation
12., Kobv, Kenneth A., and Ernest (.1. Long. T hvrnio- of Tetralin ExNplosion. Atomics tinterriat. Ilvt'I.
chemistry for the' Petrochemical Intdustry. NAA-SR-4803, Cianoga Park, Calif., 1960, 58
P'art %11. Acetylenes and I iolefins. Pe-trol. PP.
Refiner, v. 28, 1949, p. 13:3. 14:3. Mfellai, Ibert. Industrial Solvents. 2d ed. Rleini-
125. Kogarko, S. M. D~etonation of M(taeArhold Pub. Corp., New York, 1950, 758 pp.
Mixtures and the D~etonation Limits of Hlydro- 144. Miller, S. A., and EC. PI ' v. Hazards in llant-
carhori-Air Mixtures inl a Larg('-Iiameter Pip~e. duing Ace-tylIene in Chemical Processtes, Particu-
Soviet physics Tech. Phys.. v. 3, 1 95S, pp. larlv Unde:r Pressre Proc. Symp. on Chiem.
1904-1916. (1Transl. 'of J. Tech. Phys., USSRi, Process flazards, Inst. of Chenm.'Eng. (London),
v. 28, pp. 2072-2078.) 1960, p. 87.
126. Kuph ta, Joseph M., Alphonse Bartkowiak, Irving 1415. Mfiissen, It. WV. Pressure D~rop in Vapor-Relief
SPOlanI, and IXI ichael G. Zabetakis. Flammia- S , stems;. Chem. Eng., I1162, pp. 101-102,
bility ('laraicterist ics of High-Temiperature 1.I46. Moore, It. IL. Fire s an(l Explosionisi i Uopre sed
Ilvdrocartor FuIs. Wright Air Devtelopmeit. Air Systemis. Canadian Mfil. and( Met. Boll.
D)iv ision Techt. 11ept . 61- -89, 1961, 29 pp. No. (10)9 . 56S, 1963, pp. 1 8-19.-
127. Kudit I, Joseph XM., Sot irios 1,811) ins, andi 117.,\Morani, Ii. 7.,.Jr., arid A. XW. Ittrtselly. Flamtna-
Aicift'tael GA, '/,atet uk is. Flat muaIfb iiit' afind hilit v I.ito its for lixt tiresof 11 ;, rociromti~ti s,
Aito ign itiott of Hyd(Irocarb on Fuels Unde(1r Air,' and( HIalogeni ( oin ou rids. N IHL Itept.
Stat it asti i.Nrtarnic ('oiidttioris. Itt1iliut's .112 1, 153, 12 pp.
Rept). (if lrt)%. 5992, 11062, 21 pp. I-1S. Mor'to, 1). 11. Iteviitw oif Synthectic L.trbricirnts.
128. Kuio, TI. I,, iand V. 1. Serdlir kov, Imits and lubricat ion Eng~., 19j54, pp. 6.5-73.
leiinwittuirts tof I ;\llo-ionr of Ilydrogiri- I Il. Monrganr, N. 1). Tilt linlioie of tLbricanits ott
Chtloriteo. \IiNtiir(s Ii llvttrog, nI ( Iihtidt-. EC~pdtsioit, in Comripressed Air Sestetis. ('aria-
1.121 1 -130, 150). Mtftrrioti, lhctivrt Bltvtl A Shlock-lTittt Itivesti
to.1 [ , i (P lo luit d Livit of 1 . ti o of Dert ot P., I ihir i %i l. r I'.tu iv ote
It.- tlow, Ni-tv iur Bol Mlich ivan, IltIt. -9,15,. 2 p
12,1 lirir ( it .t r'l k. 1,- 1,91 pp \1":;ti t-, , 1-1t \I l, Mrtoni Po., RitiTr Nt. Mo, rin, Told82
od A a I lv III ,X it,) )Srk Iiil Nh c Iti [061b pp 92-94i.
731 pp 152. N1."F It, lip; inofLw rVral
BIBLIOGRAPHY11
1,58. National Fire Protection Asoociation. Fire-Hazard 180. Roberts, A., B. R. Prill and J1. 13. Sellers.
Properties of Flammable Liquids, Gas". and Methane Layering in Mine Airways. Part, V,
Volatile Solids. NFPA 325, 60 Battery inatrch Studying Layering Phenomena in at Laboratory
St., Boston 10, Mass., 1960, 126 pp. Model. C2i, Guard., v. 205, 1962, pp. 756-763.
1591. Nuckolls, A. H. U nderwriters' Laboratory Method 181. Rogers, D. T., and C. E. Schleckser. Engineer-
for the Classification of the Hlazards of Liquids. ing and Theoretical Studies of Static Electricity
National Board of Fire Underwriters, Chicago, in Fuel%. Proc. 5th World Petrol. Cong., New
Ill1 1921) 20 pp York, sec. 8, paper 10, 1959, pp. 103-121.
160. Ordna*nce dorps, U1j.S. D~epartment of the Army. 182. Rolingson, W. R., John MacPherson, P. D. Mont-
Ordnance Safety Manuial, ORI)M 7-224, 1951; gomery, and B. L. Williams. Effect of Tern-
Sec. 17, May 15, 1958, 68 lPp. perature on the Upper Flammable Limit of
161. Palmer, K. N. The Quenchinjg of Flame by Methane, Ammonia, and Air Mixtures, J.
Perforated Sheeting and Block F lame Arrestors. Chem. Eng. Data, v. 5, 1960, pp. 349--351.
Proc. Srnp. onl Chemical Process Hazards, 183. Rossini, F. D). and others. Selected Values of
Inst. Chem. Eng. (London), 1960, p. 51. Properties of Hydrocarbons. NBS Ciro. C461,
162, ---. The Quenching of Flame by Wire 1947, 483 p p.
Gsauzes. 7th Svinp. (Internat,) on Combustion, 184. Salooja, K. C. Studies of Combustion Processes
Brittcrworths Sci. Pub. (L.ondon), 1959, pp. Leading to Ignition in Hydrocarbons. Corn-
497-503. bustion anid Flame, v. 4, 1960, pp. 117-136.
163. Parker, W. G., and H., G. Wolfhard. Properties 185. Sargent, H. B. How to Design a Hazard-Free
of Diborane Flames. Fuel, v. 35, 1956, pp. System to Handle Acetylene. Chem. Eng.,
323-331. February 1957 pp 250-254.
164. - --- .Some Characteristics of Flames 186. Schumb, W.y C., 6. N. Sit-terfield, and R. L. Went-
Supported by NO and NO
2
. 4th Symp. (In- worth. Hiydrogen Peroxide. Reinhold Pub.
ternat.) on Corn~usion, Williams & Wilkins Co., New York, 1955, 750 pp.
Co., Baltimore, Md l 953, pp. 420-428. 187. Scott, D. A. Hazards With Butadiene and its
165. Penny, E. The Velocity, U Detonation in) Comn- Properties. Am. Chem. Soc., v. 18, 1940, p.
pressed Acetylene. Varaday So'> Ditc., No. 22, 404.
1956, p p. 157-161. 188. Fcott, F. E., J. J1. Burns, and B. Lewis. Explosive
166. Perlee H~enry E., Agnes C: Imhof, find Michael Properties of Hydrazine. BuMines Rept. of
G. iabetakis. Flanimability Chaoract erist ics )f Inv. 4460, 1949, 18 pp.
llvdrazine Fuels i n Nitro'gen Tetroxide At- 181.. Scott, F. E., R. W. Van Dolah, and M. G. Zabe-
inosliheres. J. Ch'em. Eng. Data, 1962, pp. takis. The Flammability Characteristics of the
:377-379. System HrNO-N2O-Air. 6th Symp. (Internat.)
167. Pieters, HI. A. J., J. W. Hlovers, anti B. J. Rietvelr. on Combustion. Rein hold Pub. Co., New
D~eterminat ion of the Explosion Limits of Gases. York 1957, pp. 540-545.
Fuel, v~. 26, 1947, pp. 80-81L 190. Scott, 6. S. Flammability of Trichloroethylene.
164. Porte-r, It. L. Unuisual Pressure Relief D~evices. BuMines Rept. of Inv. 6190, 1963, 5 pp.
Ind. find Eng. Chem., v. 54, January 1962, pp. 191. Scott, G. S., G. WN. Jones, and F. E. Scott. De-
2-1-27. termination of Ignition Temperatures of Corn.
109. Prie, F'raser P. First and Second Liii.s of Ex- bustible Liqu~ids and Gae.Modification of
plosin of I iboranie-Oxygen IMixtures. J. Am. the Drop Met hod. Anal. Chem., v. 20, 1948,
Chou)n. Soc., v. 72, 1956, PP). 5361-5:365. pp. 238-241.
17t0. Rlandall, P. N., J. Bland, W. NM. l)udle. and It. B. 192. :uc;ott, George S., Henry E. Perlee, George H.
J'acobs. Effects of G-aseous D)et onations U~poni Martindill, and Michael G. Zahetakis. Review
Vesisels aiid Piping. J. Client. Eng. Prog., v. 5:3, of Fire aind Explosion Hazards of Flighit Vehicle
1)levernber 1957, pp. 574-580. Conustjhles. Aeronautical Systems Division
71. Rtandall, P'. N., slid 1. Ginsburgh. Bursting of T.-ch. Rvpt. 61-278, supp. 1, 19 62, 43 pp.
Tuhular Specinwins 1)- Gaseous D)etonat ion. 193 ~DSC nnov, N. N. Sonme Problems in Chemical
AS ME, Trans., Paper No. 60-WA-12, 1960, Kinetics and Iteactivitv. Princeton Univ.
9 pP). Press, Princeton, N.J., v. 2, 1959, 331 pp.
1 72. lftsashl, It. J1., and] Z. W. Itogowski. Gaseous '0. tehkin, Nicholas P'. self-Ignition Temnperatures
E :xi dos lors in Ve,..ted Durct s. Cornibt st ion aind of Combustible, Liquids. J. Iles. NBS, v. 53,
I73 Iouni, .4, I ecenter 1960, pp. 301 -312. 1954, Ites. Paper 2516, pp. 49-613.
R7..Ielief of E~xplosionis inl Duct Sys- l , inlmmouds, W. A., and P., A. Cibag. The
teris. Proc. S'yrup, onl Chern . Process P azarils, D esign of Explosion t Reiefs for Industrial Dry-
lost. , ern. Erg. I .on1don ), 11160. l). 58i vns 'o.S iip nCer rcs
1 7-1. Rebei.torf. MIelviri A. I )esigning a It igh Pres- iIg Ovrde nst P. Shevni. Eng on n~ 1he. 60,es
4 sort, Laburator. led, arid Eng. ('lit-rn, v. 15:3, lizrs 69. lvll n.(ono) 90
I!5 WI 1,il)lr). 4t0A - 4 2A.
tu
1
).ios 69. viniI.0 ofad h nlr
15Richiard soni, E . C ., and C. It . Stilton. Explosive 196 Simos R. 1', a~U fN nd If Gur (I'on lfham. Th 'fan
Propt rt it of I acq ji r-Sotlv cut Vsapors.- Iin. I lneo hieth . .51 ,rid 1955 p. ts 1ra211
T"o I 1rig. ('hem., v-. 20, 19289, pp. 197-- 190.
FrdvSvv
1 95 ) 21
7l;. Itobvrts, A-., B3. It. Ptirsall, drid J1. B3. Sellers. 197. Sireo'r, I )orothl M ., Frank I Belle~s, andl Adolph
NIt t io it Lav t ririg ii M in e A irwa vs. (Coil, E. SpI tktwski . Ir vtsigi on iiand Initerlrtt a-
Guiard., v . 205, ( )t'tober ')62, pp.53-4 timu tof i ll(, Fl:mrir iiailit 'v Region ftor Somt Letarn
177 Mlelhant la,ring in Milne Air- II vdrocarun-Air MNtuirts. 4th Srnv. (Intcr-
MovsPr 1 h liryo avi.(ol lint.)A oil (itribisitin, Williamrus & W'ilkins Co.,
t stiai., v.tr 205, 1ii 91jIto ofBa'Iig ('~ ltnimore, Md., 1953, Ill. 1241-1314.
'- 05 92, Pl) 59 53
Id. Methlarne ayvtrin g in MIin e Air- I104. Sinitger, J. M. , J ,ose ph i rutnvr, an rd IE. 11, Cook.
Ulits. Part Ill. Thet Theorv otf Layering Burrnin g ',,eloc itis hv by h Buni~~i-I Inrn r
('ouitintd t. C'oll. ( uard., v. 205, 1 962, jpp Method. 1. 11 vearbori-Oxvygtri Mixtures at
':10-636. I ii, Atinoie~tre. 11.11 v.Ndroca rm- nAi r \f ix-
I 79. .Methasne' layering in Mint Air- ttiri- lit 'uitrinospheric l'ressiires. Proc.
Wavs ., Part IV, Sr iii -itg La~ein ig Pheniomenai Ai-rtt it nocht -in. (;Its I ) -nil- is Nip., 1955,
i a it i~t ory NIotlel. ('oIl. Gu rard. , v-. 205, pp. 1:19-- 150.
1962, pp. 723 -732. 199. Sutill., Marion L., and Karl W.- St inson.- Fuels;
and Combustion. McGraw-Hill Book Co., 220. Weber, J. P., J. Savitt, and K. Krc. Detonation
New York, 1952, 340 pp. Tets lvaluate lligh Pressure Cells. Ind. and
200. Solov'ev, N. V., and A. N. Baratov. Dependence Eng. Chem., v. 53, 1961, pp. 128A-131A.
of the Lower Limit of Flammability on Molecu- 221. Well, N. A. Rupture Characteristics of Safety
lar Structure. Russian J. Phys. Chem. (Zhur. Diaphragms. J. Appl. Phys., 1959, pp. 621-
Fiz. Khim.), v. 34, 1960, pp. 1661-1670. 624.
201. Spakowski, A. E. Pressure Limit of Flame Prop- 222. White, A. G. Limits for the Propagation of
agation of Pure Hydrocarbon-Air Mixtures at Flame in Inflammable Gas-Air Mixtures.
Reduced Pressures. Not. Advisory Committee I1. The Effect of Temperature on the Limits.
for Aeronautics Res. Memo. E52H 15, 1952, J. Chem. Soe., v. 127, 1925, pp. 672-68.
33 pp. 223. . imits for the Propagatiol of Flame
202. Spalding, I). B. Some Fundamentals of Combus- in Vapor-Air Mixtures. Part 1. Mixtures of
tion. Butterworths Sct. Pub. (London), 1955, Air and One Vapour at the Ordinary Tempera-
250 pp.
ture and Pressure. J. Chem. Soc., v. 121, 1922,
203. Stenberg, John F., and Edward G. Coffey. De- pp. 1244-1270.
signing a High-Pressure Laboratory. Chem. 224. . Limits for the Propagation of Flame
Eng., 1962, pp. 115-118. in Inflammable Gas-Air Mixtures. Part 1.
204. Stoner, R. G., and W. Bleakney. The Attenua- Mixtures of Air and One Gas at the Ordinary
tion of Spherical Shock Waves in Air. J. Appl. Temperature and Pressure. J. Chem. Soc., v.
Phys., v. 19, 1948, pp. 670--678. 125, 1924, pp. 2387-2396.
205. Sullivan, M. V., J. K. Wolfe, and W. A. Zisman. 225. . Limitg for the Propagation of Flame
Flammability of the Higher-Boiling Liquids and at Various Temperatures in Mixtures of Am-
Their Mists. Ind. and Eng. Chem., v. 39, 1947, monia With Air and Oxygen. J. Chem. Soc.,
p. 1607.
v. 121, 1922, pp. 1688-1695.
206. Tamura, Z., and Y. Tanasawa. Evaporation and 226. White, A. G., and T. W. Price. The Ignition of
Combustion of Drop Contacting With a Hot Ether-Alcohol-Air and Acetone-Air Mixtures in
Surface. 7th Symp. (Internat.) on Combus- Contact With Heated Surfaces. J. Chem. Soc.,
tion, Butterworths Sci. Pub. (London), 1959, v. 115. 1919, pp. 1462-1505.
pp. 509-522.
227. White, Douglas F. The Unintentional Ignition
207. Terao, Kunio. Selbstzunung von Kohlenwas- of Hydraulic Fluids Inside High Pressure
serstoff-Luftgemischen in Stoss'ellen. J. Phys. Pneumatic Systems. ASNE J., 1960, pp. 405-
Soc. of Japan, v. 15, 1960, pp. 2086-2092. 413.
208. The Combustion Institute. Combustion and 228. Winter, E. F. The Electrostatic Problem in
Flame. Butterworths Sci. Pub. (London), v. Aircraft Fueling. J. Royal Aeronautical Soc.,
1-7, 1957-63.
v. 66, 1962, pp. 429-446.
209. - . 4th Symposium (International) on 229. Wolfson, Bernard T. Harnessing Explosions.
Combustion. The Williams & Wilkins Co., Office of Aerospace Res. Rept. No. 17, 1962,
Baltimore, Md., 1953, 926 pp. pp. 3-4.
210. . 5th Symposium (International) on 230. Wolfson, Bernard T., and Robert G. Dunn.
Combustion. Reinhold Pub. Corp., New York, GCineralized Charts of Detonation Parameters
1955, 802 pp.
for Gaseous Mixtures. J. Chem. Eng. Data,
211. . 6th Symposium (International) on v. 1, 1956 pp. 77-82.
Combustion. Reiphold Pub. Corp., New York, 231. Zabetakis, Nfichael G. Explosion of Dephliegmator
1957, 943 pp.
at Cities Service Oil Company Refinery, Ponca
212. - . 7th Symposium (International) on City, Okla., 1959. BuMines Rept. of Inv. 5645,
Combustion. Butterworths Sci. Pub. (London), 1960, 16 pp.
1959, 959 pp. 232. . Gasfreeing of Cargo Tanks. Bu-
213. . 8th Symposium (International) on Mines Inf. Circ. 7994, 1961, 10 pp.
Combustion. TheWilliam & Wilkins Co., 233. Zabetakis, M. J., M. P. Benoy, and 1. M. Gussey.
Baltimore, Md., 1962, 1164 pp. Explosion Hazards of Diethyl Ether. BuMines
214. The Institution of Chemical Engineers. Pro- Rept. of Inv. 6051, 1962, 16 pp.
ceedings of the Symposium on Chemical 234. Zabetakis M. G., and D. S. Burgess. Research
Process Hazards. Inst. Chem. Eng. (London), on the hazards Associated With the Production
1960, 117 pp.
and Handling of Liquid Hlydrogen. BuMines
215. Thomas, A. Flame Propagation Through Air- Rept. of Inv. 5707, 1961. 50 pp.
Fuel Foams. 6th Symp. (Internat.) on Co m-
bustion, Reinhold Pub. Corp., New York, 1957, 235. Zabetakis, M. G., J. C. Cooper, and A. L. Furno.
pp. 701-707. Flammability of Solvet Mixtures Containing
216. Umland, A. W. Explosive Limits of Hydrogeni- Methyl Ethyl Ketone and Tetrahydrofuran in
Chlorine Mixtures. J. Electrochem. "See,, v, Air. BuMines Rept. of Inv. 6048, 1962, 14 pp.
1lo 1954, pp. 626-631. 236. Zabetakis, M. G., and II. 11. Engel. I'laminable
217. U.S. Atomic Energy Commission. The Effects of Materials: A i ectre De00onstration. Bu-
Nuclear Weapons. Ed. "by Samuel Glasstone, Mines Int. Cir. 8005, 1961, 17 ip.
April 1962, p. 163, 2t7. Zabetakis, N. G., A. L. Farno, and G. I. Jones.
218. Van Dolah, Robert W., Michael G. Zabetakis, Minimum Spontancous I fition Temperatures
David S. Burgess, and George S. Scott. Re- of Combustibles in Air. fnd. and Eng. Chem.,
vie' . of Fire and Explosion 1lazards of Flight v. 46, 1954, pp. 2173-2179.
Vehicle Combustibles. BuMines Inf. Circ. 238. Zabetakis, M. G., P. M, (ossey, and G. S. Scott.
8137, 1962, 8 pp. Limits Of Fla ouinability of Methyl Ethyl Ketone
219. Wayman, D. H1., and R. L, Potter. Detonations nd Methyl Isobutyl Ketone in Broniochloro-
in Gaseous Fuming Nitric Acid-Hydrocarbon methane-Air Mixtures. BuMines Rept. of Inv.
Mixtures. Combustion and Flame, Butter- 5680 1960, 12 pp.
worth. Sol. Pub. (London), 1957, v. 1, pp. 239. Zabetakis, M. G., and G. W. Jones. Flammability
321-329.
of Carbon Disulfide in Mixtures of Air and
BIBLIOGRAPHY 113
Water Vapor. Ind. and Eng. Chem., v. 45, carbon F~uels at Low Temperatures and Pressures.
1953, pp. 2079-2080. 4th Symp. (internat.) on Combustion. Williams
240. - - . The Prevention of Industrial Gas & Wilkins Co., Baltimore, Md., 1953, pp. 121-
Explosion Disasters. Chem. Eng. Prog., v. 126.
51, 1955, pp. 411-414. 245. Zabetakis, M. G., arid B. H1. Rosen. Considera-
241. Zabetakis, Michael G., George W. Jones, George tions Involved in Handling Kerosine. Proc.
S. Soctt, and Aldo L. Furno. Research on the Am. Petrol. Inst., sec. 3 v. 37, 1957, p. 296.
Flammability Characteristics of Aircraft Fuels. 246. Zabetakis, M. G., G. S. 9cott, and G. W. Jones.
Wright Air Development Center, Tech. Rept. Limits of Flammabilityr of Paraffin Hydrocar-
52-35, supp. 4, 1956, 85 pp. bans in Air. Ind. and Eng. Chem., v. 43, 1951,
242. Zabetakis, M. G., S. Lambiris, and G. S. Scott. pp. 2120-2124.
Flame Temperatures of Limit Mixtures. 7th 247. - -. The Flammability Characteristics
Symip. (Internat.) on Combustion, ilutterworths of the C,.H2.-s Aromatic Series. BuMines
Sci. Publ. (London), 1959, pp. 484-487. Rept. of Inv. 4824, 1951, 9 pp.
243. Zebatakia, M. G., C. M. Mason, anid It. W. Van 248. Zabetakis, M. G., G. S. Scott, and R. E. Kennedy.
Dolah. The Safety Characteristics of Normal Autoignition of Lubricants at Elevated Pres-
Propyl Nitrate. BuMies Rept. of Inv. 6058, sures. Bu Mines Rept. of Inv. 6112, 1962, 10 pp.
1962, 26 pp. 249. Zeldovich, Ia. B., S. M. Koarko, and N. N.
244. Zabetakis, M. C., and J. K. Richmond. The Simonov. Ali ExperimntalI Investigation of
Determination and Graphic Representation of Spherical Detonation of Gases. Zhurnal Tekh.
the Limits of Flammability of Complex Hydro- Fiziki (J. Tech. Phys. (USSR)), v. 26,1956, p. 1744.
APPENDIX A
TALILE A-I. Summary o limits offlammability,
lower temperature limits (TL), aml miniMm Limits of flam-
autoignition temperatures (AiT) of inditidual mtibility (vohnme-
gases and vapors in air at atmospheric pressure Combustible percent) Ti. AIT
Limits of flam- Lis Us&
mability (volume-
1
Combustible percent) T
1
, AIT
_. (0 C) (0 C) ,ec-Butyl benzene -- 1 0..77 1 5. 420
ler-Butyl benzene ---- 1 .77 I 5. 8-------- 450
U
1
n-Butyl bromide- - ---- 2. 5 -------- - -- 265
Butyl cellosolve ------ 8 1. 1 10 - --------- 245
n-Butyl chloride ----- 1.8 1 10 .
Acetal --------------- 1.6 10 37 230 n-Butyl formate ----- 1. 7 8. 2
Acetaldehyde --------- -. 0 60 ------. 175 n-Butyl stearate ----- . - ------ 35
,
Acetic acid ---------- 2 5.4 ----- 40 465 Butyric acid --------- 2. 1 - ---- - ......-. 450
Acetic anhydride-----2 2. 7 8 10 47 390 a-Butryolactone -------- 2.0 0----------------_ __
Acetanilide ---------- 1.0 .............. 545 Carbon disulfide ...-... 1.3 50 90
Acetone ------------- 2.6 I 13 . 465 Carbon monoxide .- 12. 5 74 ...
Acetophenone ------- 1. 1 --------------. 570 Chlorolhnzn ---------- 1.4 --------- 211
Acetylacetone ....... 1. 7 ---- ....------ 340 rn-Crosol- _.--.--- - 1. 1 ...... - -.. ..
Acetyl chloride ... . - 5. 0 -------- ------ --- 390 Crotonaldehyde . 2. 1 1 10 .
Acetylene--- -------- 2. 5 100 305 Cumene ------------ 1. 8 ' 6.5 ... 425
Acrolein..-.-...... 2.8 31 ---- 235 Cyanogen ------------ 6.6 -------
Acrylonitrile --------- 3. 0 ------- - -6 Cycloheptane. ------ -- 1. 1 . 6 .7....
Acetone Cyanohydrin. 2. 2 12 ------ ----- Cyclohexane --------- 1.3 7. 8 . 245
Adipic acid ---------- -1. 6 -------- - 420 Cyclohexanol ---------- 1. 2 ----- - 300
Aldol- .-------------- '2.0 -------- 250 Cyclohexene- -------- 1.2
Allyl alcohol --------- 2.5 18 22 --- Cyclohexyl acetate _ 1.0 -. 33"
Allyl amine ---------- 2. 2 22 --- 375 Cyclopropane- -------- 2. 4 10. 5 0 0
Allyl bromHe --------- 2. 7 -----------. 295 Cyniene.... .. . 85 )5 415
Allyl chlorid ---------- 2. 9-......... -32 485 .D,,aborate-------- 2
o-?kminodiphenyl ... 66 4. 1 I--------450 Decalin- - - ........ --- 74 1 1 .1. 57 25i
Ammonia ----------- 15 28 --- -- n---ecane- n----- -1 2 75 3 5. -16 [ 210
n-Amyl acetate- 1. 0 1 7. 1 I 25 36 ).iutrium ---------- 4. 1 75 -............
n-Arnyl alcohol ------ 1 1. 4 1 10 r 38 00) l)iborat -.-----.--.. - - .8 88
tert-Amyl alcohol __._ - 1.4 --------------- *135 Dies fuel (6)ce ahz) . _ .. [ "2,
n-Ainyl chloride..- .. - 1. 6 1 8. 6 260 l)icth I :,ri- -.- . 8 I
ten-Amyl chloride. -.. '1. 570 2 l34l5vl ,, A t 1 - _ 8 .130
0 ' y yll - 1 75 - - 1430
Amyl nitrite_ 1 0 1- . _- xI2 ( -lyl y7 . .. . - '7 24160
n-Amyl propionae- 0. 7)ie hy] (,t(hr-
Anylene----------- 1. 4 7 275 1) l)h.0 p3l i)eot 7 .------- 290
Aniline- .---------- 7 2 .3 615 I), 'hy' 1 ,"_ . ; 450
Anthracene ---------- 4 .65 ..... . 5,10 Di , , ht c) .i,,ol__ t ., o i, I .
n,-Amyl nitrate- ... 1.1 . .. !)5 l)s,, ,utyl ki'-. G .
Benzene ------------ - 1.3 7 . . 5l' 2-4, 1 ,.eyvit, .... 1-'20
Benzyl benzoate_.. . 4 .... ... J * - 4Si l)uisop , x x 1h.r- _
Benzvl chloride-------' 1.2 ,.. l)wthyi ,, I - -11)
Bicyclohe-xyl---------- 65 5. 1 24,5 2 )i't-hc *ln- I 2 _.1 2
Bilihenyl-------- -----. 70 --- . I 110 .4 .;3-0inethy. . ie o j
2fiielini d4. 8 1-- CIO im-I by) hIe- d 2: 15
Promobnzen --------- 1. 6 - ,h. , :,.
Butadiene (1,3) ... . 2, 0 12 42o iWO..
n-Butae-- ----------- 1.8 8.4 I 40 .. iii 1hy ,1-r 3. 35)
1,3-Butandiol- ---------- 1 9 J 1 p , )irn (lhvi or.t-
Butene-I ....... ...- 1. 6 1" 0 " - ---- 1.. s , .135
Butene-2 ----- -- .... I ,7 9. 1 . . . 2,3-1) i !all, v 1. 1 :35
n-Butyl acetate ....... 5 4 8. . 25 2, 2-,D31 Ipro),i l . I 151
n-Butyl alcohol ....... 1. 7 ' 12 I " l), t a a liule - . 0 :05
see-Butyl alcohol -. 1. 7 9.8 21 4)5 )imt I1-ulfoxid . .-- - - -
tert-Butyl alcohol ' 1. 9 9. 0 1I 4SO J)ioxi , - -. . .. . 1 2 . .,)
tert-Butyl amine 1. 7 8. 9 3s0
1
N l)i , . .5 6. 1 - . 7
n-Butyl benze! -----. 82 1 5.8 _-- .110 I)tei.la,,ii. . ' 7
See tootnotem at end of table.
114
APPENDIX A 115
Limits of flam- Limits of flam-
Imability (volume- inability (volume-
Combustible percent) TL AIT Combustible peicent) TL AIT
(00C) (0 C) I__ T
_- (_ (0 C)( ) (0 C)
Los Ulf Lot U.
Dip henyl ether ....... 40.8 ......... 620 Methyl chloride ------- 4 7 - ----- ------
Diphenyl methane . 7---------------- 485 Methyl cyclohexane_ 1. 1 6.7 ------- 250
DiN~ yl ether -------- -1.7 27---------- Methyl cyclopenta-
n-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 car-
Ethyl cyclobatane --- 1. 2 7. 7.--------210 binol------------ -- 1. 2-------- 4 40 -
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. 0 50 ---------- Methyl propyl ketone-, 1.6 8-2 ----------
Ethyl propionate - - 1.8 11 ... 440 Methyl .tyrene ------- 41.0 -------- / 49 495
Ethyl propyl ether - - 1 7 1 9 - ----- Methyl vinyl ether. __ 2. 6 39 ------
Ethylele ......---- 2. 7 36 - 490 Methylene chloride--- -------- --------- ------ 615
Ethyleneimine --------- 3. 6 46 -- .320 Monoisopropyl bicy-
Ethylene 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
Gasoline- Monoinethylhydra-
100/130------------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. 7 100 ----------- 4: 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
lsa-It anl (ti't 1. 1 1 7. 1 25 360 'entaon.tilene I- I
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, 43 - - - 0 .i l.l.allt -- ------------------ 2 3 . 74 23 7. 2
Iulit vi fu-lia, 2. 0 S. 9 - 'ropadicniw, . 1- 2. 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 It .. . . t 1 -Prop~y l' , h l _l 1.2 2. '2 ' 1.1 - ' w o.1
.vI fi l: l'rp It ttiine ,
ii i.: , _ - 210 l'rj, yl ,hlori,ic-_ 2. 4_
6ii _ - -230 t-Kj,'l nitrate- I . 8 100 21 175
K i .,si . . - . 2111 i'r,+ l!1h11 . " . 1 .4 I 460
M' i ,1. ii 1 5 187 54 0 rou; I. 1], hi 3. 1
\h-!110 v,.All 3. 1 f; 44_ .'ri,, nl i. Ityol : 2. 4i
Nio 'li v,',' Ir. l. .. III Ou I i' ..- l', - i ,. . '1 .0 ;7 . . .
N11" 11 tI i hIA t- C 0 NA 1 , 2 17
,h0 ;N-1' U..,~ ,.u 1 12
M cI i i :
t
1111w 4- . 2 1! - I -2 - - .. . .. 2.
.N(l' It- i i - ._ t(------ 2 , t ~ .- E{( 'p1 t]L-IV I -lc-)ht . '. 53. . 5
Q it rtii 1- . ... 1 (I........
3- M ,vI vl I )[ ,I .. on I~ I 1 5 1 St , v I,.- , " 2 I. 1 . .
1. , %1 l' ,ut kelm w), 1. l 2 0 S.1 . . illfi," l '2. 0 - 2.17
, jj c ,'i )1\,, 7 ' 2. 5 "2( ... 3"'11 ,-T ,.orl~ ,\I _ I v. ) I. . ... M ; ,
,.L 'I vIo ).l l ', )" v - it, kt -tr ll.,. . : *.5 . _. 2
i 1 I ' . . . . 1. 7 -.. . 46
I
11 % l'' , \,1h',,filralc . . 2 (0
.,ithi IthYl ,th.r _ 2. 2 . ------. rait........... ... - 5. o 71 315
s,, iii I/tntes ti t end of table.
TABLE A-I. Summary of limits of flamma-
bility, lower temperature limits (TL) and
minimum autoignition temperatures (AIT) of
individual gaves and vapors rn air at atmospheric
pressure- Contiaued
Limits of flam-
mability (volume-
Combusible percent) T, AIT
(0C) (
0
C)
L,.. U,__ ,
,2,3,3-Tetrmnethyl
pentane ----------- 0. 8 --------------- 430
Tetramethylene gly-
col ... --------- ------ 390
Toluene ------------ 1.2 '.7.1 ------- 480
Trichloro~thane ------ ---------I ----------- 500
Trichlo=oethylene -_-- 24 12 26 40 30 420
Triethyl amine ------ 1.2 8. 0 ....--
Triethylene glycol. . 9 2 9.2 ------------
2,2,3-Trimethyl bu-
tane ...------------ 1.0 -------------- 420
Trimeth;yl amine .... 2. 0 12 -----------
2,2,4-Trimethyl pen-
tane -------------- .95 -------------- 415
Trimethylene glycol - 1.7 -------------- 400
Trioxane ------------ 3.2 --------------- -----
Turpentine ------.. '.7 ............
Unsymmetrical di-
methylhydrazine_- 2. 0 95 -----------
Vinyl acetate -------- 2. 6 -------------------
Viniyl chloride ------- & 6 33 ..----......
m-Xylene ----------- 1.1 3.4 ------- 530
o-Xyene------------ 11.1 16.4------ 465
p-Xylene ----------- ' 1.1 '6.6 ------- 530
1 t:100* C, 1:1-0: C. : t-:43* C.
i-47* C. 12g.-530 C. Ug195* C.
8 tm75* C. C. t~ (- 1 m60
o
C.
4 Calclated. . t-130 C. 2 4-96 C.
t-60* C. 1 1-72* C. Ist70O C.
4 t-850 C. Is t-117
o
C. U 9 -29 C.
1- 140. C. 9T - 125o C. C .- 247
o
C.
'1-160O
0
C. "t-200
0
C. "-0 C.
t-110. C. "-78o C. 1 '-203

C.
"t-17*6 C. t-122* C.
APPENDIX B
STOICHIOMETRIC COMPOSITION
N, 0 0.25 0.50 0.75
The stoichiometric composition (C,,) of a .. - -
combustible vapor CnH.O\Fk in air may be ------------ 1. 87 1. 83 1. 79 1. 75
obtained from the equation 12 ------------- 1. 72 1. 68 1. 65 1.62
13 1.59 1,56 1.53 1.50
m k2X14 --------------- 1. 47 1,45 1.42 1.40
CH OxFFk+ .+ - A
2
O--CCO
2
15------ 1. 38 1.36 1.33 1. 31
16 ------------- 1.29 1.27 1.25 1. 24
17 ------------- 1. 22 1.20 1.18 1. 17
rn-k 18 -------------- 1. 15 1. 13 1.12 1. 10
H
2
O+kHF. 19 ....------------ 1. 09 1. 08 1. 06 1. 05
20 ------------- 1.04 1.02 1.01 1.00
21 -------------. 99 .98 .97 . 95
22 -------------. 94 .93 .92 .91
100 23 -------------. 90 .89 .88 .87
Thus, C,,= - - volume-per- 24 -------------. 87 .86 .85 .84
1_ A.73 jn -k-2X') 25 ------------- 83 .82 .81 .81
1+4.773 4 26 --------------. 80 .79 .78 .78
27 ------------- .77 .76 .76 75
cent, where 4,773 is the reciprocal of 0.2095, 28 -----------. 74 .74 .73 72
the molar concentration of oxygen in dry air. 29 -------------. 72 .71 .71 .70
The following table lists the values of C,, for 30 ------------- . 69 .69 .68 68
a range of ( m-k-2X) values from 0.5 to m-k-2 I I I Ihe
30.75: 4 1 N-n+ 4 ; where n, m, X, and k are the
number of carbon, hydrogen, oxygen, and halogen atoms,
N 1 0 0.25 0.50
respectively, in the combustible.
___-- -For example, the stoichiometric mixture com-
------------------ 29.53 121.83 position of acetyl chloride (C
2
H
3
0CI) in air
1--------------17. 32 14. 35 12. 25 10. 69 may be found by noting that
2 -------------- 9.48 8.52 7. 73 7.08
3 -------------- 6.53 6.05 5.65 5.29 n
m
-k-2X 3-1-2
4 -------------- 4.97 4. 70 4.45 4.22 N=n+. 20
5 -------------- 4.02 3.84 3.67 3.51 2=4
6 -------------- 3. 37 3. 24 3.12 3.01
7 -------------- 2. 90 2. 81 2. 72 2. 63 The entry for N=2.0 in the preceding table is
8 -------------- 2.55 2. 48 2.40 2. 34
9--------------2. 27 2. 21 2. 16 2. 10 9.48 volume-percent, which is the value of C,,
10 .------------- 2. 05 2. 00 1.96 1.91 for this combustible in air.
117
APPENDIX C
HEAT CONTENTS OF GASES
(Kcalimole I)
T, - K CO, H,O O, N,
298. 16 0 0 0 0
300 .017 .014 .013 .013
400 .941 .823 .723 .709
500 1.986 1.653 1.4541 1.412
600 3. 085 2. 508 2. 2094 2. 125
700 4. 244 3. 389 2. 9873 2, 852
800 5. 452 4. 298 3. 7849 3. 595
900 6.700 . 238 4.5990 4.354
1,000 7. 983 6. 208 5. 4265 5. 129
1,100 9.293 7.208 6.265 5.917
1,200 10.630 8 238 7. 114 6.717
1,300 11.987 9.297 7.970 7.529
1.400 lM 360 10. 382 & 834 8. 349
1,500 14.749 11.494 9.705 9. 178
1,600 16. 150 12.627 10.582 10.014
1,700 17. 563 13. 785 11.464 10. 857
1,800 1& 985 14. 962 12. 353 11. 705
1,900 20. 416 16. 157 13. 248 12. 559
2,000 21. 855 17. 372 14. 148 13. 417
2,100 23. 301 18. 600 15. 053 14. 278
2,200 24. 753 19. 843 15. 965 15. 144
2,300 26.210 21. 101 16. 881 16.012
2. 400 27. 672 22. 371 17. 803 16. 884
2.500 29. 140 23. 652 18. 731 17. 758
I Gordon, J. S. Thermodynamics of High Temperature Gas Mix-
tuuan-d Application to Combustion Problemn. WADC Technical
Report 57-33, 3anuary 1967, 172 pp.
118
APPENDIX D
DEFINITIONS OF PRINCIPAL Symbol: filcua eigtiUof
SYMBOLS M-----Mach number.
No,--,----Equilibrium mixture of NO
2
and
Symbol: Definition NO at a specified temperature
*A--------Constant. and pressure.
*'--------Avea. n ---------- Number of moles.
a ---------- Velocity of sound. P----lresmire.
B--------- Constant. P --------- Maximum pressure.
C., ------- tStoichiometric composition. n~P-------Pressure rise.
-H------Heat of combustion. p ---------- Partial pressure.
K --------- Ratio of duct area to vent area.S----- Burning velocity.
k -------- T hermal conductivity. T -------- Absolute temperature.
L -------- Lower limit of flammability. t----------T- emperature.
-*-----Modified lower limit value. r- -- -- - -- Tme delay before ignition.
LA-------Average carbon chain length for U -------- Upper limit of flammability.
paraffin hydrocarbons arnd correla- U -------- Upper limit of flammability at P
0
C.
tion parameter for aromatic hy- V -------- Volume.
drocarbons. V'--------Critical approach velocity.
- ----- Lowe(r limit of flammability at io C. v ---------- Liquid regression rate.
/ID ------ Length to diameter ratio. ------- Specific heat ratio.
119
SUBJECT INDEX
A PaeHPg
Acetaldehyde --------------------------- 73 Hlalogenated hydrocarbons -------------- 102
AkaietIIIV hydrocarbons ------------------------ 53 He~at of formation-_ - -- ------------------ 51
Airf1'1!_ ratio--------------------------------- 21 Pi-lleptane ------------------------------ 21.25, 35
Alcohols----------------------- ------------- 6(5 Heterogeneous mixtures---------- ------------- 3
Aldehydes ------------------- ----------------- 73 n-llexadecanm-------------------------------21, 25
Ammonia------------------------------------ 77 Yi-llexano ------------------------------- 21, 25.,34
n-Ainyl alcohol ------------------------------- 6 7 n-ll&'Xy.l floo------------------7
Aromatic hydrocarbons------------------------ 511 Hydraulic fluids --------------------------- 9
Autoignitlon------------------------------ 4,32,41 Hiydrogen ---------------------------------- 77, 89)
B
Hydrogen peroxide.---------------------------1
Barrcades----------------------------------- 17 1
Blast pressure --------- ----------------------- 16 Ignition ----------------------------------
Burgess-Wheeler law ------------------ -------- 22 Ignition. temperature -------------- ------------ 4
Burnling velocity.--------------- - -- - - -4), 45 Ignitihility limits -------------------------------
Butadiwne --------------------------------- 48,53 Inertial is------------------1
n-Butane ------------------------------- 21, 25, 32 Isobutylene----------------------------------- 48
Butene-1-------------------------------48,50,52
n-Butyl alcohol ------------------------------- 671
tert-Butyl alcohol ----------------------------- 68 JP-4 ------------------------------------- 11,88
o K
Carbon chain--------------------------------- 41 Kerosine -------------------------------------- 7
Carbon monoxide ---------------------------- 97 Ketones------------------------------------- 73
Combustion equations-------------------- 21, 117
Contact time_---------------------------------4 L
Cool flames ---------- ------------------------ 28 Layering ------- ------------------------------ 3
Copper acetylide ------------------------------ 56 Le Chatelier's law ----------------------------- 31
Critical CIN----------------------------------11 Limits of flammability ------------------------- 2
Cyclopropane --------------------------------- 64 Liquid mixtures ------------------------------- 31
Lower limit ---------------------------------- 2
D Low pressure limits ------------------------- 12,89
n-Decane---------------------------------- 21,25
Decane-dodecane blends --------------------- 32, 43 M
Deco.nposition-------------------------------- 5A Methane ------------- ---------------------- 9,21
Deflagration --------------------------------- 15 Methyl acetylene --- _--------------------------5)
Detonation -------------------------------- 16, 57 Methyl alcohol --------------------------- - 6i)7
Dimethyl ether ------------------------------- 70 Methyl bromide ------------------------- --- 21N, 61
n-Dodccane ------------------------------- 21,25 3-Methyl butene-1 ---------------------------- 48
E Mehyl formate ------------------------------ 71
JE Methylene bistearamide ------------------------ 7
Enigine oils ----------------------------------- 95 Mlethylene chloride-------------------------- 102
Esters - - ------------------------------------ 70 Minimum oxygen value-------_.- --.- -- ------ 1
Ethane -------------------------------- 21, 25, 28 Mists -------------------------------------- 3, 6
Ethers-------------------------------------- 69 MIixer-------------------------------------- 4,7
Eth' alcohol ---------------------------------
67
2-Ethyl butanol ------------------------------ 67 N
Ethylene----------------------------------- 48, 52 Natural gas------------- ------------------- 27, 30
F n-Nonane --------------------------------- 21, 25
Flame arrestors ------------------------------- 18 0
Flame caps ----------------------------------- 2 n-Octane ---------------------------------- 21, 25
Flame extinction ------------- _----------------29
Flammability characteristics ------------------- 20
Foam --------- ------------------------------- Paraffin hydrocarbons ----------------------- 2(0, 3
Formic acid ------------ ---------------------- 61 n-Pentadecane ---------- ---------------------- 21
Freon-12------------------------------------ 69 ?entane----------------------- -------------- 24
Fuel-air ratio --------------------------------- 21 n-Pentane ------------------------------ 21, 25, 33
Fuel blends ---------------------------------- 74 Perfluo-ometha--- -------------------------- 28
Perfluoropropane ----------------------------- 28
G Peroxides------------------------------- 53, 70, 103
Gas freeing--------------------------------- 13 Predetonation distance---------------------- 57
Gas mixtures --------------------------------- 3 Pressure piling - - - ---------------------------- 58
Gasoline ---------------------------------- 13, 82 Propadiene -------------- -------------------- 48
120
SUBJECT INDEX 121
Page Page
Propane .......................... ------- 21, 25, 31 Sulfw compounds -----. . . . . . 74
Isopropyl alcohol ----------........ .......... 115 Sulfur hexafluoride -------...................... 28
n-irropyl alcohiol ----------------------------- 67
n-Propyl nitrate -------.--------------------- 97 T
Propylene ----------.------------------------ 48,51 Temperature limit --------------------------- 11
n-Tctradecane ----------------------....- ---- 21
Q Tetralin ------------------------------------ 7
Time delay- ........ ..-------- 4
Quantity-distance relationships --------------- 95 Town gas --------------.------------------ 19
Triangular diagram -------------------------- 9
Trlchloroethylene ----------------------------- 102
R n-Tridecane --------------------------------- 21
Raoult's law -----------.-------------------- 31 Tube diameter ------------------------- 3,53,57
Rectangular diagra ------------------------ 9
Rc.gression rate- -..------.-------------------- 44 U
Relief diaphragms -------------------------- 18 n- Undecane ------------------------------ 21
Unsaturated hydrocarbons ...--------------- 47
S
Upper limit ---------------------------
2, 23, 26
Shock wave ------------------------------- 17 W
Spark-energy requirements ------------------- 3 Wall quenching ----------------------------- 3
Spontaneous ignition -------------------------- 3
Spray injection ----------------------------- 97 X
Sprays ..--------------------------- ------ 6 o-Xylene ----------------------------------- 60
* U.S. GOVERNMLNT PRINTING OFICE. 1965 O-761 .-

Flammability Characteristics of Combustible Gases and Vapor-Bulletin 627 Bureau of Mines

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