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Bulletin 627
BUREAU OF MINES
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FLAMMABILITY CHARACTERISTICS
OF COMBUSTIBLE GASES AND VAPORS
By Michael G. Zabetakis
/ ',··· ~ - - :
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l.
Bulletin 627
BuREAu oF MINEs
FLAMMABILITY CHARACTERISTICS
OF COMBUSTIBLE GASES AND VAPORS
By Michael G. Zabetakis
This publication has been cataloqed as follows:
Zabetakis, Michael George, W24-
Fiammahi 1 i ty l'hnrtH'.It•rist i1'H of ('{'Jllhust gas('..'l nnd
vttpors. r.Wnshinl,l'fon
1
U.S. Dept of t.ltb Bm't'>nu of
l\f m es
1
1965
1
1:!1 p. lllus., tables. (U.S. Bureau of Bull.l!tln 627)
Includes b!bllography.
1. gases. 2. Oases. 3. Vapol'!!. I. Tltll'. II. Tltll!:
Comb11stlble gases. (Series)
TN23.U4 no. 627 622.06173
U.S. Dept. of the Int. Library.
For 1ale by the SuJMtrintendenl of Documente, U.S. Government Printing Office
Walhinqton, D.C., 20402 • Price 75 cent•
..
CONTENTS
A he tract __________________ . _______________ _
Introduction. ______________ .. ______ . _______ _
Definitions and theory _______________ . _____ ._
Limits of flammabilitY---------------------
Ignition. __ • ____________________________ _
Formation of flammable mixturf'S __________ _
Presentation of data. ___________ . ___ . _____ .. _
Deflagration and detonation processell .... _____ _
Deflag-ration. ___ .. _______ . ____ •... ______ _
Detonation _________ • ____________ • ______ _
Blast pressi.'re. ___ . _______ . ______________ _
PrevePtive measures. ___ .. __ . ______________ _
Inerting ________________________________ _
Flame arrestors and relief diaphragms ______ _
Flammability characteristics._.____ • _______ _
h_ydr?carbons •• ___ •. ________ . ___ .. _
L1m1ts 1n a1r _______________ .. __________ _
Limits in other atmospheres _____________ _
Autoignition. __________ . ______________ _
Durning rate_. _________ . _________ . ____ _
.. __ • _______ . __ • _
Lnmts 111 air __________________________ _
atmospheres _____________ _
A utorgrutwn _________________________ . _
Burning rate .. _. __ • ___________ ._. _____ _
Stability ____ • ___ . _______ . ___ ._ ... _ ... _._
hy_drocarbons. _ _ _ _ . ________ . __ _
Lrmrts tn a1r _______________ . _________ . _
_othl'r atmosplwres. ___ . _ ... _. __ . _
A lltorgn1t10n ___ .. _. ___________________ _
llurn.iug ratf'. ____________ . ____________ .
Stability _____________________ .. _. _ . ____ _
_hyd_rocarhons_ .. _____ . ____ . _____ _
I.rmrts m arr _ .. _. _ .. _. __ . _ _ ____ .. _ .. _ ..
Pare
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Flammability
Aromatic hydrocarbons-Continued
Li.nits in other atmospheres. __ ..••• ______ _
A utoignition ___ . __ . __ .. _______ • _____ . _. _
Burning rate.--------------.-----------
_. ________________ _
L1m1ts m a1r __________________________ _
Limits in other atmospheres ______ - ______ _
Alcohols.----·----------.-----------------
Limits in air __ -------------------------
_other atmoi!phercs ••• __________ _
AutOJgnJt,on. ___ . _________ .. __________ - _
Durning rate ________________ -----------
Ethers. _____________ - ------ _- _.-- __ -- __ . -
Limits in air ____ .. ______ .. ___________ .. __ _
Limits i';l, _other atmospheres. ______ ...... __ _
Autorgnllron ___ .. _____________________ _

Aldehydes and ketones __ . ________________ _
Sulfur compounds ______ ·------------------
Fuels and fuel blenciR ____________ . _____ . _
Ammonia and related compounds. ___ ._-_
Boron hydr idetJ __ . ______ • _ .. ______ • _____ _
Gasolines, diesel and jet fuels._._ .. ___ . __ _
Hydrogen _____ • __ . _ . ___ .• _ - __ .. _. - . - __ --
Hydraulic fluids and engin·: oils. ________ . __
Miscellaneous. ___ . _____ .. __ ..•• ______ ._._.
Acknow ledgmt>nts. __ ... ___________ . __ •. __ . __ _
Bibliography ___ ._ _ __ . _. _ .. __ ---- _--.- _-- _--
App<•ndix A. Summary limits of flammability_
\pp<'IHiix B. -Stoichiomf·tric composition ____ _
Appt>llrlix C. -ll•·nt contf'nts of gascR ..... ___ _
Aprwnrlix D. --Definitions of principal symbols_
Subject index ... _--------------------------
IUUSTRA TIONS

I. Jguitihility cun·f' and of tlammabilit:l'· for nwthnnP-nir mixtur<'R at atmospheric preRsure and 26° C _
:.!. Eff•·et of tl'lll!Wrature ou of flnmmahility of a • vapor in air at a constant initial pres-
surf' _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ .. _ _ _ _ _ _ _ _ _ _ __ . __ .. ___________________ .. _______________ _
a. Tin11• d .. Juy IH•forl' ignitiou of :-il'.:\' in air at 1,000 in th•• t!'mpl'rahlrP range from 150° to 210° C._.
.1 Logurid11n of t irnl' rlPlay !wfore ignition of :-i in air nt I ,000 psig i11itiul pr!'ssur••. _ .. _ .... _ .. - ...
:;_ Simplifil'd mixl'r. _ .. _ _ _ _ ____ . __ . . _ ... __ .. .. . . . .. - .. -... --. . --- . - . ---------. - - -
0. of gas in chamiH•r :.!, /i (instantaiwous rnixing) __ ........ __ . __ . ___ . _ ...... ___ .. .
i. of gas in rharnlH'r :.!, fil/;llrt' /i (d .. Iayl'd mixing) .. _ .............. _. ___ -------- ... -- .. -
\'arint ion in Jow•·r limits of flanllnHhility of various ('Olllhustih)l's in air ll!! a function of droplPt dianwtf•r
H. Flnrnrnahility diagram for th•· .. m • at • pr••l!l!Url' ami 26° C ..
I fl. l·')llmntuhility diagram for tlw syst•·m at atwoRplu·ric pr••ssurP and :.!6° (' .
II. Etf•·•·t of init-ial t•·mpl'rutun· on limits of flammability of 11 romhustihk vapor-irwrt-air systl'rnat atmos-
ph•·ric • ___ .. _ _ _ _ . ___ . _ _ . ______ . _ .. ___ . __ . _. _., _. __ ..
I:.!. EffPct of initial pn•ssurc• on of flanunahility of JP-4 in air at 26° C ..... _ ....
Ill
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CONTENTS
Effect of tomptlraturo and pr!lssurtl on limits of flammability of a oomhustlhlo vapor in R sp!loltlcd
oxidont. ____________ .. _____ .. ___ .. ___ . ________ . __________________ .. _ . ______________ . ______ . _
I•'lammahlllty diagram for tho system gasolhw vapor-watm· vapor-air at 70" F and nt 212° F and atlnol!-
phorio prPssur«'. __________________ .. _ .. _____ .. _ .. ___ ... ____ . ___ .-- _____ .. ___ - .... __ .. _. ___ .. ____ ....
Pr!lsl!lure produced hy lp;nition of ll 0.6 volum«'-pt•rm•nt. mPthnrw-Rir mixturl' In ll ll-lltPr oylimlPr .. _. __ _
Detonation v••locity, ·; at.ic prnsAUrf', 1'.; and refll'ct.Pd I'" dPvt'io}wcl hy a dt'tonation
_
Pressure variation following of 11 flammllhle mixtur«' in unprot .. ct.Pd nne! protPelo•d Pllclosureij .. _
PrPssuro producPd by ignition of 11 tlarnmalle mixtur" in 11 VPnt ... d ovt•n ..... __ -. _ ..... __ . _____ . __ _
Effect of molnculnr WPight on lowPr limits of llnmmahilit.y of parntfln hydrocnrhonH &t C _____ . __
Effect of tt,mperature on low!'r limit. of tlnmmahility of tnt•t.hnnt• in l'.ir nt nlllH18p!u;rin prPHHilre. _ .. __ _
Effuct of tPmperature on lowPr limits of tlammnhilit.y of !0 pnrnffin bydrotlllrhons Ill 11ir nt ntmosplu•ric
on lowl'r ·ii,;,it.s of IIHmmahility of 1 u purut-ti,; ;,;,- ;, (.

L-,i ut.
Effect of tempemture on l! tiC' r.ttio of pnmflin hydro<"nrhons iu nir at pt'l'HHure in thu
absenc<' of cool flam<'"---------------------------------·----- ... ____ - ----- ___ ..... -
Effect of pressure on limii-H of llammitbilit.y of pentmw, lll'xane, and lwplnht' in air at 26° c __ .. _ .... __ ..
Effect of pressure on limits of llnmmability of natural in air nt :.!So C ______________ . ___ .. ___ - __ _
Effect of on lower temperature limib of fh1mmahility of pontnnl', hcxam•, heptane. nnd odane
in uir ___ .. _____ .. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _____ . _____ . __ ... ___ . _ .. __ ... _______ .. ______ .. ___ .. ___ .. __
Limits of flammability of vnriouH methane-inert mixturps tit 25° C anrl utmospheril' pressure __ _
Limits of flammability of Ptlmne-cnrbon dioxi!IP-air and mixtures 11t 25° C and
atmosphnric pressure .. _________ .. ________ .. ___ .. ______ .. _ .. _______ .. ___________ .. __ .. ___ ....... __ - _ .. -
Limits of flammability of propanu-rnrbon dioxide-air and propanc-nitrogen-nir mixtures nt 25° C nne!
atmoBpheric pressur(l ........ __ . _ .. _______________ .. __ ... ___________________________________ - __ _
Limits of flammability of butane-cr.rbon dioxide-air and buta, mixtures at 25° C nnd
2-5°- C-
I.irnita of flammability of various n-hcx:me-inert p;as-nir mixtur ·H nt 25° C and atmospheric pressure_-
Limits of flammability of n-hcptune-watcr \'apor-air mixtures at 100° and 200° C and atmospheric
pressurr ___________________________ , __________________________________ .. _________________ _
• limits of flammability of hiv,hPr pamffin hydroenrbons • in carbon dioxide-
lllr and nitrogen-air mixtures at 25° C nnd atmospheric press•1rc. ________ .... _ .. __ .. ____________ - .. __
Effect of pressure upon limits of flammability of naturnl mixtures at 26° C_- ___ -- .. _-
Effect of pressure on limits of flammability of ethanP-carbon dioxide-air mixtures at 26° c_---------
Effect of pressure on limits of flurnmnbility of ethnnu-nitrogen-uir rnixturus :tt 26° C ___ .... _______ - __ -
Effect of pressure on limits of flammability of propunP-earbon dioxide-air mixtures. _____ .. _______ - .. _-
Effect of presHure on limits of flammnbilit.y of prop:uw-nitrogen-air mixtures._ .. __ .. __ .. _______ .. _ .. - __ _
Effect of pressure on minimum requirements for flume propap;ation natural gas-nitrogen-
air, ethanc-nitrop;c•n-air, und mixtures nt 26° C ________________ .. _______ - . __
Low-temperature limit of flammability of dccmw-uir, rlodeeane-uir, and decune-dorleeane-nir mixtures.
Minin.mm uutoignition temperatures of paraffin hydrocarbons in air us a function or uvernge carbon
chum length ______ .. _______ .. ____ .. _______________ .. __ .. ___________ .. _ .. --- _--- ___ -- - --- - -- ---- ..
Burning velocities of methnne-, ethane-, propane-, nnd vupor-uir mixtures ut atmospheric
pressure and room .... __ . _________ .. ____ .. __________ .. _____ - _ .. _-- _ .. __ - .. - ... - .. ------
Burning velocities of methane-, ethane-, nnrl propnne-oxygcn mixtures at ntmospht'Tic pressure and room
temperature ________ . __ .. ______________ .. ______ . __ .. ____ .. _____ .... ______ .. __ .... _____ - __ .. __ ------
Varint1on in burninp; vplocity of stoichiometric and propane-air mixtures with pressu1•: ut
26 °c- -----.. --. --.. --------. ---------. --------.. ----------- . -.. --------.. ------- ------------
Variation in burning velodty of stoichiometric mcthnne- und ethykne-oxvgen mixtures with prcssurt:
at 26 °C _______________________ . __________ .. ______ .. __ .. ___________ · ___ .. _____ .. _______ .... ___ .. __
Effect of temp<"ruture on burning veloPitiPs of four paraffin hydrocarbons in nir n.t atmospheric prl'ssure.
Detonntion veloeitieH of nwtlmnc-air mixturPs 11t atmospheric prcMsurn_ .. ________ .. _ _ _ _________ - __ -
velocities of methane-, ethane-, propane-, butnne-. and hexane-oxygen mixtures at u.tmos-
phenc pressure.__ _ __ . __ .. _ .. ____ .. ___ .. _____ .. ___ ...... ___________ .. _. _______ .. - - ____ ----- __ .. -----
Detonation velocitit•!i of n-heptane vapor in WFN A (white fuming nitric ncirl)-nitrogen gas mixtures ut
atmospheric pressure and 400° K .. ___________________ .. __ .... _____ .. ___ .. _______ .. _____ .. _______ .. __
Relation but ween liquid-burning mtc. .. pool diameter) nnd ratio of net heat of combustion to
sensible heat of vnporizn tion. ____ . __ . ___ . ____ . ______ . __ .. ______ .. _ _ _ _- -- _--- .. --- - -- - .... -- - - - -
Elfeet of tem)ll'rature on lowPr limit of flamnlllbility of ethylene in air at atmospheric pressure .... _-_--
Limits of flammnhility of ethylene-carbon dioxide-air anti ethylene-nitrogen-air mixtures ut atmosph(lrif'
pressure and 26° C ______ .. _____ .. _ _ _ _ .. _ .... _________ .. _ .. ____ .. ____________ .. __________ .. _____ _
Limits _of flammability o! bropylene-carhon dioxide-air anrl propylene-nitrogen-air mixtures nt atmos-
of' •

c- • .-
of flammability of butcrw-1-('arbon dioxidu-air anrl butune-1-nitrogen-air at lltmosplwrie
preHtiUre lllld 26° C .... ________ . ___ ... __ .. ___ .. ____ .. _. __ . _ .. ___ ... ______ ... _____ . _ .. ______ .. ____ _
Limits of flammability of :i methyl buterw-1-carbon dioxide-.Lir and 3 methyl-butcne-1-nitrogcn-air
mixtures at lltmoepheric preliSUrc u.nd C ... ____________ .. ________________ • ______ ...... ____ -----
. ......
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CONTENTS
LirnitR of flummubility of dioxide-nir :md butadiene-nitrop;cn-air mixtures at ntmoe-

-0,-
through neetylenn gtlH ......... _ .. _________ .. ______ .. _ .. ___ -- _-- ___ .. - .. - .. -.-- .... ----- ..... - _--- _- .... ___ _
of flammnble mixtures for methylacotylene-propadione-propylene systmn at 120" C and at 50
and 100 psig_ --··-------------·--·------------···---- .. ------··· ------- ................... ..
limitli of flamrmli.Jilit.v of nc:etylene-enrhon rf;,)xiJe-ILir ILnd mlxturetl
11t atmospheric pn•HKllrt' and 2!1° C obt11inecl in n 2-inch tube __ .... _ .... ___ .................. ___ .. __ .......... _ .... ..
nut.oi!(niti"l' LcrnperaturcR of ncPtylenc•-air nnd ncetylene-oxyp;en mixtures at atmospheric
cmd devnterl pressureR .... _ .... __ .. _____ . _ ...... _. ___ ...... __ .... __ .............. _ .. _ .... __ ................ - .... ----- .. -- .... ..
Burning vl'loeit.y of tu:etylene-11ir mixtures at ntmospheric• pressure anrl room temperatuw ...... ___ .. __ .. ..
.:\faximurn /,/ D rutio rc•quirerl for tmnHition of 11 deftagrntion to c. detonation in acetylene vapor at 60"
F and from 10 to 70 psia ______________ -· -------------------------------------------------
Final-to-initial pressure ratios developed by neetylene with det.onati,m initiation at ·;arious points
ntonf( n tube __ ...... _ . __ . ___ .... _ .. _ . _ ....... __ . _ ..... _ ........... __ .... _ ...... - ...... - ......... --- .. --- .. - .
of flumrru;bility of benzPni'-IIIPthyl hromiclt•-:lir mixtures at 21>" C and benzene-carbon dtoxidt ... air
ancl IH'IIZI'IH!·nitro!(cn .. uir mixturPH at :.!!i
0
und 150° C and atmospheric prC88Ure ........ __ .......... _. _ ....... .
Limilt! of flammubility of

ut. 154° C und 1 ntmosphere pressure _____ ----- ___ _
Limit,; of flammability of 90-weight--pcrl'l'nt

Clh)
1
-IICOOH at 154° C and 1 atmosphere
\lf!'HSliTI' ..... -- _ .. _ .. _. __ .. _ .... _ ... __ ..... _ .. _ ....... _ .......... _ .............. __ .................... _ ......................................... ..
Minimum uutoignition tPmpcrutures of ttromntic hydrocnrbons in air ns a function of correlation
par:under D., ____ ...... __ .... _ .. ____ . __ ... _. ______ .. ____ . __ .. __ .. __________ .. _________ .. ___ .. ___ ... _
of of cyclopropane-nitrogen-air, and cyclopropane-
behum-utr nuxturPs at 2o C and utmosphcrw pressure .. __ .. ____ .. ________ .. ___ ._ .. ___ ........ __ .. _ ...... __
Limit!:! of flmnmability of unci cyclopropane-nitrous oxide-oxygen mixtures
at 25° C and atmospheric preRsurc. _. _ . ___ .. _ .. ______ ... ___ .. __ ....... ___________ ... ______ .. __ ...... __ .. _ ..
Limits of flammability of cycloprop:mc·-lu•lium-nitrous oxide mixtures ut 25° C and nt.mosphl'rir pressure.
Limits of flammability of methyl alcohol-carbon dioxide-air and methyl alcohol-nitrogen-air mixtures at
25° C and a tmosplwric pressure_ .. ____ . __ . __ .. ____ .. _ .... ___ .. ____ .. _ .. ________ . _ .................................. ..
Limits of Flammability of methyl alcohol-water vapor-air mixtures at 100°, 200°, and 400° C and
tl' ·nospheric pressure __ .. ___ .. __ . _ ... ___________ .. __ .. _ ..... _ .. ____ .... _ .. _ .. __ .. ________ .. ____ ........ _ .. __ ....
Limns of flammability of ethyl nlcohol-carbon dioxide-air and ethyl alcohol-nitrogen...air mixt,ures at
25° C and atmospheric pressure _________ .. _______ .. ______ ------------------------------------
Limits of ftnmmnbility of ethyl alcohol-wut:·,· vapor-air mixturee at 100° C and atmospheric pressure ....
Limits of flammability of tert-bu tyl alcohol-wtttc·r vapor..nir mixtures at 150° C and atmospheric pressure ..
Limits of flammability of tert-butylalcohol-curbon dio'l:idc-oxygen mixtures at 150° C and atmospheric
prcssurP ___ .. __ . _ ... _. _ .. _ ... ___ .. __ .... _____ .. _______ .... ___________ .. _ _ _ _ .. ________ .. ___ .. ___ .. _ .. ___ _
Limits of flammability or 2-Pthylhut.anol-nitrogc>n-oxyg••n mixtures at 150° C and atmospheric pre88ure ..
Limits .?f flummuhility of dimc>thyl etlll'r-curbou dioxide-air and dimethyl ether-nitrogen-air mixtures at
2.'}
0
C. and at.mosplll'ric _________ ............... ------------------------------------------
Limit!l of flammability of c icthyl Ptlll'r-carbon dioxidc-air and diethyl ether-nitrogen-air mixtures at 25°
C and pr<'ssnre _ .. _ ... _ . _ _ _ .. _ . _______ ... ___ .. ____ . _ .. _ .. ______ .. ___________ .. _ ... __ ....... _
Limits of flammability of di!'lhyl PtlH'r-hdium-oxygen and diethyl ether-nitrous oxide-oxygen mixtures
at :.!5° C :md atmosplwric pr<·ossllr<'. _.... _ .. _ .. _ .. __ ... ___________ .... _ .. _ .......... _ .. - ....... - ......... ---------
Limits of flnmrnnhility of dif'!hyl PthPr-uitrouH oxiclc•-helium mixtur<'S at 25° C and atmospheric pressure_
Limitt! of flammability of nwthyl formntP-cnrhon dioxiclc•-air and nv>thyl formate-nitrogen-nir mixtures_
Limit 11 of fl!unrnabilit y of isohtl t yl formatP-cnrbon dioxi•lc•-air and isobutyl formate-nitrogen-air mixt.ures_
Limits of flammability of mt'thyl ac·l'tat•·-t•arhon rlioxiclc·-air tmd methyl aeetttte-nitrog"n-air mixtures __
Etf .. ct. of tt•mpPraturP 011 lowt•r limits of flnmmubility of MEK-tolucne mixtures in air a.t atmospheric
oi of-Tii
pr .. rP ... _ . .. . _ .... _ .. __ .. _ . .. . .. . _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ .. ___ .. __ . ___ .. _____ .. ______ _
Effptt of liquid t'omposition on lcwPr of flammability of MEK-toluene mixtures in air at 30° attd
20\.1° c ___ . _. _ ..... _ .. _ .. __ .. _ ... _ _ .. .. . ___ .. ____________ ...... ___ .. _____ .... _ .. ___ .. _____ ... ____ .. ___ _
EfTet·t of liquid cmnposition on lowt•r limits of flammability of TIIF-tohwne mixtures in air at 30° and
200 . c .. -.......... - - - . --.. ---.. -.... ---.... -- -.. -.. --. - . ----.. --------..... --..... ----.. -... -.. - ... -- ... -
Limit !'I of flnmmabili:y of aePtoru•-rnrhon dioxidc'-air and tlCI'tOtH'-nitrogt•n-nir mixturc•s_. ___ ... __ .. _.-
LimitR of flammnhilitv of nwthyl Pthyl kl'lonP (CBM)-air, MEK-carbon
clioxiciP-air ancl mixtHr<'S nt. 25° C and atmosplwric pressure ____ . ___ ... ____ .. __ _
Limits of flamnmhility of enrhon disttlfidP-eurbon dioxidc·-air, carbon dioxidt•-nitrop;Pn-nir mixtnrPsnt 25°
C nnclat mosph<'rie unci e.nhon disnlficl<'-watPr vapor-nir nt 100° C and ntmoRpht•ric prt•sRnre.
of flammnhility of MulfidP-enrhon dioxide-nir mixtures nt 25° C and ntmospheric
r<' . _ _ _ _ __ . _ .. _ _ __ .. _ _ _ _ ... _ .. .. ___ ... ____ .. ___ ...... _ .. __ . _ _ _ .. _ ... __ .. _ _ .. _ _
Limits .of tlummnhility of l'thyl mt•rc•nptan-F-12-air and Pthyl mcre:Lptan-F-22-nir mixtures nt ·
(lhl'fll' pri'HHIIrP 111111 27° C ..... _.. . .. ... . _ ... _ .. _ ...... _ ...... _____ .. ____ . _. _ ...... _ _ _.... _ .. _
Limit>< of flnmmnhility of nmmoniu, l;D:'Illl, :'11:\111, and hydrnziul' nt atmosplwric prt'SI!ure in saturnted
IIJHinPnr-!mturntP!I vnpor-nir rnixturPs____ _ .. .. ......... ____ .. ..... ..... ..... ......... .. ... -
FlnmmnhiP mixtnrP c•ompositiouH of hyllrn7.iru·-lwpttuu'-tlir nt 125° C tmd approximntPly ntmoHplwric
pri'S"II rl' ...... _ _ _ _ _ . _ _ _ .. _ .... _ .. _ .. . __ .. __ .... _ ..... _ . _ ..... ___ . _ .. _ .. __ .... ___ ......... _ ........... _ .. _
:'lllllimmn spont:wPons i;cnition IPIIIJWrttturt•s of liquid hyclrnzirw, 1\11\111, and Ul>l\111 at an initial
tc•mp••raturP of 2!i
0
(' in C'Onttu•t with ]I;O,•-ttir mixtun•s nt 740 J: 1tlmm Hg as a funetion of l'\0
1

c•onc•l'lltration. ........... ...... ................. . .......................................... ___ ..
:'lliuimum HpontttrH'OUs ignition t•·mpPrnturPH of liquid hydrazirw at various initial t.Pmpt•raturc'l< in
l'\'0
1
•-air mixtures at 740 !10 mm H11: as a function of NU
1
• concentration_._ .... _ .... _ .. _ .. _. _- ...
v
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104.
lOIS.
106.
107.
lOS.
109.
110.
ill.
112.
113.
114.
11/S.
116.
117.
118.
119.
120.
121.
122.
123.
124.
125.
126.
127.
128.
129.
130.
131.

\llnlmum 11pontaneoue Ignition of llguld MMH at various Initial In N0
1
•-
air mixturtlll at 'l40 ± 10 mm Hg n11 a function of N0
2
• oonc(mtration. __ . _ ... _________ . ____ . _____ ..
Minimum spontanooua ignition temperatur011 of liquid UllMH at various Initial temperatures in
N0
1
•-air mixturce at 740 ± 10 mm Hg as a function of N0
1
• conccntl'ation .. ________ .. ________ .. _
Minimum spontaneous ignition ternperaturlll! of 0.05 oo of liquid UDMH in llc-OrN0
1
• atmoephl!ll'llll
at 1 atmosphere for various lle/0
1
rati011 .• ____ . ____ ..... _. ___ . __ -. _.-- _- __ .. __________________ . _
.. c_c_
Minimum spontaneous Ignition tempN'aturoo of vaporb;ed UDMH-air in contact with 100
pet N0
1
• at 25° C and 740± 10 mm Jig u a runctlon of UD MH concentration In air. ___________ _
Limite of flammability of dlborane-ethane-air mixtures at laboratory temperatur• and 300 mm Hr
i ooii ao; -8; ·;ai0iii1e: · iiacie-i faii 4&;
C aviation jet fuel, grade Jr-1; D, aviation jet fuel, grade JP--3; and, E, aviation jet fuel, gnde
JP-4------------------------------------------------------------------------------------
Limlts of flammability of aviation gasoline, grftdes 115/14/S vapor-carbon dioxide--air •nd 116/14/S
vapor-nltroRen-alr, at 27° C and atmospheric prll6Surc _____ . _______ . ________________________ . __
Limite of flammability of JP--4 vapor-oarbon dioxide-air and JP-4 vapor-nitrogen-air mixtures at 27° C
• ·isci -d
and atm011pheric prtlllllurc •• _. _ • _. __ .•. _- _--- __ - -- - - --- ---- - . - --- .. - -- --- . - . - -- -- . - - -
Limite of flammabiht.v of Hr NO-N
1
0 at approximately 2R° C and 1 atmoeph.,,·c. _________________ _
Limite of fiammabi!it.y of HrN
1
0-air at 2R° C 1 atmosphere. _________________ . _
Limite of flammability of H,-NO-air at approximately 2R° C and I atmosphere._. __ .. _ . ____________ _
Rate of vaporiaat.ion of liquid hydrogen from p11raffin in a 2.H-inch Dewar ftuk: Initial liquid depth-
6. 7 Inches _____________________________________ . _ . ___ . __ . _______________________________ _
Theoretical liquid regr088ion rates following !!pillage of liquid hydrogen onto, A, an average soil; B, moillt
sandy eoil; and C, dry sandy soiL ___ .. __ .. __ .. ___ .. __ . __ .. ___ ... ____________ .. _________________ _
Theoretical decreue in liquid hydrogen ll'vel following l'pillago onto, A, dry sandy soil; B, moist sandy
soil; and C, an average soiL ___ - __ ._._-- __ .... -- ... - ... - . -. ---.----- . ------- .. ---- .. ------------
Extent of flammable mixturlll! and height of vlsiblc cloud formed after rapid !!pillage of 3 litera of liquid
hydrogen on a dry macadam 11urface in a quieact"nt air at 1 :S" C _______________ .. ____ _
Motion picture sequence of villible clouds and flames resultinR fron. rapid spillage of 7.8 litera of liquid
hydrogen on a gravel surface at 18° C. __________ .. __ . ________ . ________ ... _________________ • __ _
Maximum flame height and width produced by ignition of vapor-air mixtures formed by sudden apil-
lap;e of 2.8 to 891it!'rs of liquid hydrogen ________ ·--------------··----------------------------
Burning rates of liquid hydrogen and of liquid methane at thf' boiling points in 6-inch-Pyrex Dewar
fluke ____________________ .. _________________________ .. ____ . _ .... ___________ .. _______________ _
Variation in minimum ftutoignition temperature with prei!Bure of commercial phosphate ester and
mineral oil lubricftntd in in n 450-cc-atainletll! steel bomb. _______ ... __ . _________ . ____________ _
Logarithm of initial pr!'8sure-ATT rat;.o of seven fluids in air for various reciprocal templ'raturcs. ____ _
Variation in Tr/ T; of air with V,f Vr and with P
1
/ P; in an adiahatic compression procesM .. ___________ _
Variation in air temperature with P,/P; in lln adiabatic compr088iou process for five initial air tcm-
pl'raturE'S. __ . _____ . ______________________________ . ____________________________ . _________ _
Limit!! of flammability of carbon monoxide-carbon and carbon
mixtures at atmospheric pressure and 26° C _ . __ . _____________ .. _____________________________ _
I.ower limite of flammability of N PN vapor-air mixturlll! over tlw pressure range from 0 to 1,000 psig

-r-ariic. rion-; o-io p;ig- 5o"-and
125° c ________________________________________________ . ---------------------------------
Variation of explosion pressure following spontanoouM ignition with N PN conct>nt.ration. _______ .. __
Minimum spontaneous ignition and dccompOI!ition tcmp<'raturcs of n-propyl nitratl• in air as a func-
tion of P.ressure ______________________ . _ . __ .. ______ . ___ . _ _ _ _ .. ___ .. ____ . _ .. __ .. __ .. ___ .. _.- .. - _ ..
Flammability of trichloroethy mixtures. ___ .. ______ .. ______ . _______________ .. ___ . _________ . _
TABLES
84

80
87
117
88
HH
lUI
HH
80
.ill
Ill
IJ2
93
U3
94
!14
95
96
96
!18
!l!l
100
101
102
102
10:}
104
104
105
Pare
1. Conditions of failure of peak overpr-urc--lll'n8itiv<' ell'ml'nta _____________ .. ___ . _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 17
2. Propertlee of paraffin hyrlrocarbona __ . _ . _ _ _ _ _ _ . . . _ . _. _ . _ _ _ . _ _ _ _ _ _ _ _ ... ____________ . _ _ 21
3. Uppl'r flammability of m!'thanc-air mixturf'l! llt IIi p11ig _.. __ .. ___ .... _ .. ___________ .. _ _ _ _ _ _ _ _ _ _ _ 24
4. I.owcr t!lmperature and autoiguition t<·mp1.•raturt•s of paraffin hydrocarbons at atmosphl•rle
pr-ure __ .. _ _ _ _ _ _ ________ .. ________ ... _ . _ . ___ . ___ ... _ _ _ ____ . _ .. _ _ _ _____ . ______ . _ _ __ . __ .. 25
5. __________________ --------------·--·-··---·-·- 'J.7
6. Limits or flammability of Pthane in chlorlnl'.-- --- -.-----.- ------. ---.---------------.------- 211
7. Properti('!l of unaaturatNI hydrocarbonH __ . _ . . _____ . ___ . ___ . ______________ . _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 4H
8. Limit" of flammability or unsaturated hydrocarhons at atmosphl'ric pr!'lllurr and room In
combust! hiP vapor ___ . . ___ .. __ . _____ . _. _____ . ___ . _ _ _ _ _ _____ . ___ . _ _ ___ . _ _ _ _ 52
P. Minimum autoignitlon temp!lr!lturee of unsaturated hydrocarbons at atmospheric prc881Jrr .. _____ ..... _. _ 52
10. Heats of formation of unsaturated hydrocarbons at 2/S
0
c ___________ ·----------------------------- li:i
11. Propertlea of selected aromatic hydrocarbona. _______________ ... ______ . _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 60
..
CONTENTS
12. of at>leoted alicyclic hydrooarbono ............ _ ....... _. __ .. ___ ..• _ ..... _ ........................................ .
13. Propertil'll of selectt>d. simple alcohol!! ........ _ .............. _ ............ _ ............. _ .............................. .
14. Propprtif'8 of selected ethers .. _ ........ _ .. _ .......... __ ..................................... --.-- ... - ....... ---.- .. ..
15. J>rop!'rt.if's of &f'l!'ctcd estt•rs ....... _ .. _ .... _ ..... _ ......... _ ................................ - -- .. - .................... .
16. Proper! iPs of sl'lccted aldnhyd!'s and ketones .... _ • __ .• _ .. _ .. _ .• _ .. _ ....... _ .............. _ ..... _ ... _ .............. _ ...
17. J>ropt>rtil's of lll')ectf'd sulfur compounds_ .. _ ......... _ ............ _ .. ____ ............. _ ...... _ ................................... ..
I H. l'ropt•rti!•s of st•lectf'd fuPI.I! and fuel hil•nds ........ _ ... ___ .. _ .. _ ...... _ .. __ ... _ ............ _ .... _ ....................... _ .... ..
19. Limits of flammability of ammonia at room tPmpl!rature and near atmospheric prt'88ure ..... _ .............. .
20. A utoignition tPmpt•rature value11 of various fuP)s in air at I atmosphPrt•.............. . .. .. • .. . .. . . .. .. ........ _ ....... ..
21. Limits of flammability of hyrirog!'n in various oxidant!! at 25° C and atmoaplwric prl'&llure ..... _ ........... ..
A-I. :o;urnmary of limits of flammability, Jowf'r tempPraturc limits, and minimum autoignition temperaturC8
of individual g11.11e11 and vaport:1 in air at atmospheric ptllii8Ure .................. _ ... _ ............ _ ......... ..
VD
• • •
6 ..
67
70
71
73
7"
77
7R
88
8\}
11 ..
FLAMMABILITY CHARACTERISTICS OF COM-
BUSTIBLE GASES AND VAPORS
----------·--------------·------------·---·---··-··-
Abstract
T
HIS is a summary of the nxailablt> limit of flammability, &utoignition,
und buruinK-ratt> dtLtn for more thun 200 and vapurs
in uir nnd other oxiduuts, ns \n'll as of empirical rules and g;-aphs that
Ct\11 be used to predid similnr dnta for thousands of other eombustibles u:1der
n \·uriety of environmental conditions. Specific. data are presented on the
pnrutfinie, unsuturntl'd, arornntic. tLnd tLlieydic hydroearbons, alcohols, ethers,
aldehydes, ketone..'>, nnd sulfur contpoun<ls, nnd an assortment of fuels, fuel
blends, hydraulic fluids, engine oils, and miseellaneous combustible gases and
vapol'8.
I ntroductt:on
Prevention of unwanted fires and explosion disastern require.• a
knowledge of flammability characteristies (limits of flammability,
requirements, and burning rules) of pertinent eombustible and vapors
likely to be encountered under various conditions of use (or misuse). A-•uilable
data lllllJ not always be udequate for use in n partieular application since they
may htn·e been obtuint>d at.!! lower temperuture ».nd pressure than is eno)unt.ered
in practire. J<'or exnmple, the qunntity of air that is re11.uired to d-,wrcal$(1 the
eombustible vnpor ronrcntrntion to u safe le,·el in ,._ purllcular pro(·ess l'arried
out at 200 oc should be based on flummability data obtnined at thts tempemturt>.
When these are not a\·ailable, suitable approximations can be made to permit a
realistic evaluation of the hazards assoriutf'd with the proces..o.; eonsidert>d;
such npproximations can serve as the basis for suitable saff'ty dPvires
for the proteetion of personnel and equipment..
The purpose of this bulletin is to present a general rt•view of the subject
of llnmmnhility, and to supply sE.'lect expt•rimentnl dllta tmd t'mpiri('IAI rules on
the fltunmabillty charu<·teristirs of various fumilies of combustible and
,·apors in nir and other oxidizing utmospheres. It eontains what are belie,·ed
to bA the lutest and most relinhle dntn for more tlum 200 combustibles of
intere:o.t to those concernE.'d with tht• pren'lltion of gas
ln nddit ion, the empirienl rull.'s und grKphs prl'sen tl'd here ean used to
predil'l similnt· da tn for other ('Om bust ihlf's under a of coradit ions.
This bulletin supplcntl'nls Durf'llU bulletins (40F nnd otlwr ptihliclltions (1li8).
Basi<' of comhustion is dc·:-;irnhlt• forti thorough
of t hi' llltltt'riul, which t'llll bt- found in numt'rous Jmblit'at ions (6.CI, 1.9.9, 1!02).
Tht-refore, only thost> nspt•l'ls rt>quired for an un of flammability
are considered here; t'\'1'11 tht>se nrl' considert'd from a fairly
viewpoint. ' •
IJ'hyslcw chemist. pro)eet coordinator. lias Expl<l$lon.'l, l!xpllliiV .. R-..rt"h l't'ntor. PIUaliUI'Ih. , ••
•ltallcl&ed numl>tVI In partonth- R>lor to hNna In tho blbll..,-aphy at tho end ol thlt rt'INII1
Worll: on maouacrlpl oomplele<l Nay 10114.
1
l<'LAMMABJLITY CHARACTERISTICS OF COMBUSTIBLE OASES AND VAPORS
DEFINITIONS AND THEORY
LIMITS OF FI..AMMABILITY
A combustible gl\8-l'.ir mixture can be burned
over a wiie range of concentiations-when
either subjected to elevated temperatures or
exposed to a cat.alytic surface at ordinary
temperatures. However, homogeneouc; com-
bustible gas-air mixtures are flammable, that is,
they can propagate flame within a.
limlted range of For example,
traco 1\mounts of methane in air can be readily
oxidized on a heated surfane, but a flame will
propagate from an ignition source at ambient
temperatures and pressures only iC the sur-
rounding mixture co['Jtain!l at least. 5 but less
than 15 volume-percent methane. The more
dilute mixture is known as the lower limit, or
combustible-leu.v limit, mixture; the more
COflcentrated mixture is known as the upper
limit, or combustible-rich limit, mixture. In
practica, the limits of flammability of par-
ticular system of gases nre affected by the
tempernture, pressure, direction of flame propn-
gation, gravitational field strength, nnd sur-
roundings. The limits are obtained experi-
by determining the limiting mixture
compositions between flnmmable nnd non-
flammable mixtures (244). That is,
and
LT.P= l/2[C,,.+Cttl.
UT.P= 1/2[0,,+
(1)
(2)
where LT,P and UT.P are the lower anti upper
limits of flammability, respectively, at a speci-
fied temperature and pressure, C," and e
11
, are
the greatest and least concentrations of fuel in
oxidant that are nonflammnble, and C
11
and
ell! are t.he least and grentest concentrations of
f11el in oxidant th11t nre flnmmnble. The rute
at which n tlnme propttgates through u flum-
mable mixture depends on tl number of
including Lemperuture, pressure, tllld mixture
<'olllpPsition. lt i!-. a minimum at the limits of
llummabitity nnd n mnxirnum tll netu· stoichio-
metric mixtures (1:30).
The Burel!u of Mines has udopted 11 st undu.rd
npprtrtttus for hmi!-of'-flumnwbility dett•l'lllirut-
tions (40). Origirutlly designed for us<• at
11 tmo;,p/ierie fWCHsun• and room t ('Ill pem tur·p,
it wus lutPI' modilied for u:,.;c tli. redt:eed
,;m·es by tl ignitor
the hns!' of tlw 2-inl'h, g-lass, llnllH'-J)ropag-ution
tube. This nwdifil'ntion introdU<'I'I a diilil'ult
thnt wns not iilillll'di,ttPI)' uppnrent, us tlt.P
spnrk PnPrgy wus not ttlways ad1•qunte for· usp in
1' llllllluhility dPtl'rminations. FigmP I
illustru.o . ti1P pffPI'I of mixturp co:upo,.;ition on
t hP eleetrienl spark ener!!,y re!{Uir·erneub for
r
I
:. .8
VI .6
.4
L_
1
J
X limits-----...

\
X""<.,.x

METHANE, volume-percent
Frouu 1.-lgnitibility Curve anrl Limits of Flam-
mability for Mcthano-Air Mixtures at Atmospheric
Pressure and 26° C.
ignition of methane-air mixtures (75). For
example, n 0.2-millijoule (mj) spark is inade-
quate to ignite even a stoichiometric mixture at
atmospheric pressure and 26° C; a 1-mj spark
can ignite m1xtureB containing between 6 and
11.5 volume-percent methane, etc. Such limit-
mixture compositionB that depend on the igni-
tion source Btrength may be t\S limits of
ignitibility or more simply limits;
they aroe thus indicative ol the igniting abilit.y
of the energy source. Limit mixtures that 11re
independent of the ignition source
strength nnd t.hat give u. measure of the nbility
of n tlnme to propugu.te from the ignition
source nmy he defined tls limitfl of
Considerably gre11.ter stark energies nre required
to estnblish lirni ts o flnmmalLilit.y than nre
required for limits of ignitibility (218); further,
more em•rgy is usually re<I,uired to estnblish the
upper limit thnn is reqmred to estnblish tho
lower limit. ! n gPnernl, when the source
strength is udequnt.e, mixtures just. outside tlH'
mnge of flnmmnble compositions yield flame
when ignited. These flume ctLps propagatP
on .Y tL :,.;hort distancp from tlw ignition souretl
in tt uniform rnixture. The r·etLson for this
nlll,V he seell in figure 2 whirh shows the effect of
tt•rnperntun• on limits of flamrnnhilit.y ut tL
('on,.;tnnt initial pressurl'. As the tmnpemtun•
is iw·reusPd, t lw lowl'r limit dt•cronses and t.ltl'
IIPJWr limit ir:cn•u.ses. Thus, sitH'I· a lol'ali:wd
Pnt'rg-,v sourt't. the temperntur<' of
IIP!ll'hy !'VI'Il ll lhlllflllllllllllhle mixtllft' ('1111
proprtgu t 11 lhmP a short distnm"(\ from t Itt>
DEFINITIONS AND THEORY 3
Upp41r
limit
Flammable
mixture a

I
I
I
8 l
___ Lbw•r
limit
I
I
I
I
AIT
TEMPERATURE--
F1ouu 2.--E.Ifect of Temperature on Limits of
of a Combustible Vapor in Air at a
Constant lmtial
source. That is, a nonflammable mixture (for
example, composition-temperature point A,
fig. 2) may hecqme flammable for a time, if its
temperature is elevated sufficiently (composi-
tion-temperature point B).
Flammable considered in figure 2
fall in one of t,hree regions. The first is left of
the saturated vapor-air mixtures curve, in the
region labf.'lled "Mist". Such mixtures consist.
of droplets suspended in a vapor-air mixture;
they are discussed in greater detsil in the section
on formation of flammable mixtures. The second
lies along the curve for saturated vapor-air
mixtures; the last and most common regton lies
to the right of this curve. Compositions in the
second and third regions make up the saturated
and unsaturated flammable mixtures of a
combustible-oxidant system at a specified
pressure.
In practice, complications may arise when
flame propagation and flammability limit deter-
minatiOns are made in small tubes. Since beat
is transCerred to the tube wa.lis from the flame
front by radiation, conduction, and convection,
11 flame may be quenched by the surroun.iing
walls. Accordingly, limit determinations must
be made in apparatus or such a size that. wall
Qllenehing is minimized. A 2-inch-ID vertical
tube is suit11ble for use with the paraffin
hydrocarbons (methane, ethane, ete.) at at-
mospheric pressure and room tempernture.
However, surh a tube is neither
under these eonditions Cor nuwy
lind other <'ompounds nor Cor parnffin hydro-
cnrbons nt \"ery low 11nd pressures
(1.97, £44}.
Be<·nuse of the many difficulties associated
with ehoosing suitable apparatus, it is not
surprising to find that the very existence of the
limits of flammability bas been questioned.
After a thorough study, I...innett and Simpson
concluded that while fundamental limits may
exist there is no ex{>erimental evidence to
indicate that such llimts have been measured
(1Sf). In a more recent publication, Mullins
reached the same concluston (154). Accord-
ingly, the limits of tlammability obtained in an
apparatus of suitable she and with a sat,is-
factory ignition source should not be tenDed
fundamental or limits until the exist-
ence of such limits bas been established.
However, as long as experimentally determined
limits are obtained under conditions similar to
those found in practice, they may be used to
design installations that are safe and to assess
potential hazards.
lndustnally, heterogeneous single-phase (gas)
and multi-phase (gas, liquid, and solid) flam--
mable mixtures are probably even more
tant than homogeneous gas mixtures. Un-
fortunatel;v, our knowledre of such mixtures
is rather !united. It is important to recogni?.e,
however, that heterogeneous mixtures can
ignite at concentrations that would normally
be nonflammable if the mixture were homoge-
neous. For example, 1 liter of methane can
form a flammable mixture with air near the top
of a 100-liter container, although a nonflam-
mable (1.0 volume-percent) mixture would
result if complete mixing occurred at room
temperature. This is an importai!t concept,
since layering can occur with any combustible
gas or vapor in both stationary and flowing
mixture..'!. Roberts, Pursall and Sellers (176-
180) have presenteaan excellent series of review
articles on the layering and dispersion of
methane in coal mines.
The subject of flammable spra.vs, mists, and
foams is well-documented (5, 18, ff, f7, 76,
£05, 215, f45). Asain, where such hetero-
geneous mixtures exiSt, flame propa.gat.ion can
occur at so-called average concentrations well
below the lower limit of flamml\bility (86);
thus, the term "average" may be meaningless
when used to define mixture composition in
heterogeneous syst-ems.
IGNITION
Lewis and von Elbe (180). Mullins (158, 154):
and Belle..'! nnd Swett (156) have prepa.re<l
excellent reviews of the processes associated
with and spontaneous-ignition
of 1\ flammable mixture. In general, many
flammnhle mixtures can be ignited by sparks
having a relatively small energy content (1 to
100 mj) but a large power density (greater
t.han 1 megawatt/em
8
). However, when the
source energy is diffuse, as in a sheet
even the totnl energy requirements for ignit10n
4 FLAMMABILIT'Y CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS
may be extremely large (79, Bt, 85, 1$3, 181,
2$8). There is still much to be learned in this
field, however, since electrical dischttrges are
not normally as well defined in pra.ct.ice as
they are in the laborator,Y.
When a. flammable miXture is heated to an
elevated temperature, a. reaction is initiated ihat
may proceed with sufficient rapidity to ignite
the miXture. The time that elapses between the
instant the mixture temperature is raised and
that in which a flame appears is loosel,Y called
the time lag or time delay before ignit1on. In
general, tLis time delay decreo.ses as the t.em-
perature increase.'i. According to Semenov
(198), these quantities are related by the
expression
0.22E
log T=-r-+B, (3)
where T is the time delay before ignition in
seconds; E is an apparent activation energy for
the rate controlling reaction in calories per
mole; Tis the absolute temperature, expressed
in degrees, Kelvin; and B is a constant. Two
types of ignition temperature data are found in
the current literature. In the first, the effect of
temperature on time delay is considered for de-
lays of less than 1 second (127, 153). Such data
are applicable to systems in which the contact
time between the heated surface and a flowing
flammable mixture is very short; they are not
satisfactory when the contact time is indefinite.
Further, equation (3) is o! little help, because
it gives only the time delay for a range of tem-
peratures at which a.ut.oignition occurs; if the
temperature is reduced sufficiently, ignition does
not occur. From the standpoint of safety, it
is the lowest temperature at which ignition can
occur that is of interest.. This is called the
minimum spontaneous-ignition, or autoignition,
temperature (AIT) and is dl!termined in a uni-
formly heated apparatus that is sufficiently
large to minimize wall quenching effects (194,
237). Figures 3 and 4 illustrate typical auto-
ignition-temperature data. In figure 3 the
minimum autoignition-temperature or AIT
value for n-propyl nitrate is 170° C at an
initial pressure of I ,000 psig (243). Data in
this figure may be used to construct a log T
versus plot such 11.8 that in figure 4. Such
graphs illustrate the applic:lbility of equation
(3) to autoignition temperature dntn. The
equation of the broken line in figure 4 is
log T=

-25.1.
(4)
In t.his specific case, equation (4) is applicable
only in the temperature range from 170° t.o
195° C; another equation must be used for
at higher tempemtu.,res. The so!id lines
in figure 4 define an 8 C band that mcludes
the experimental points in the temperature
range from 170° to 195° C.
FORMATION OF FLAMMABLE
MIXTURES
In practice, heterogeneous mixtures are
tllwa:vs formed when two gases or vapors are
first dis?Wlsin.g
fonnation of such m1xtures m detail, a snnph-
fied mixer such as that shown in figure 5 will be
considered briefly. This mixer consists of
chambers 1 and 2 containing A a!1d JJ,
respectively; chamber 2, whiCh a
stirrer, is from chamber 1 and pls.ton
3 by a partition With a small holf', H. At tune
tc, a force F applied to piston 3 drives gas A
into chamber 2 at a constant rate. If gas A
is distributed instantaneously throughout cham-
ber 2 as soon a.s it pnsses through H, a compo-
sition diagram such as that given in figure 6
results· the (uniform) piston motion starts at
to and at t,.. However, if a time interval
is required to distribute a samll volume from
chamber 1 throughout chamber 2, then .at any
instant between to and t,. + At, a vanety of
mixture compositions exists in
This situation is m
figure 7. The interval of t1me dunng wluch
heterogeneous gas mixtures would exist. in the
second case is determined in part by the rate
at which gas A is added to chamber 2, b,r the
size of the two chambers, and by the efficiency
of the stirrer.
In practice, flammable mixtures may form
either by accident, or design. When they are
formed by accident, it is usually desirable to
reduce the combustible co!lcentration quickly
by udding enough air or inert gas to produce
nonflammable mixtures. Under certam con-
ditions, it may be possible to increase the com-
bustible concentration so tls to produce a
nonflammnble mixture. Such procedures !ire
discussed in greater detail in the followmg
section.
Flu.mnutble mixtures are encountered in
production of many chemicals and in cert!tin
physical operations. These include
tl tank containing a combustible gas
drying plttstic-wire coating, and recovermg
sofvent from n solvent-air mixture. Whe.n
layering can oecur, as in drying operations, 1t
is not enough to ttdd nir tlt such a rate that the
overall mixture composition is below the
limit of flnmmability (assuming that umform
mixture.'! result). Special!rtwnutions must. be
tuken to as."!ure the rupi formution of non-
fliWlmable mixtures (235). When a batch
..
DEFINITIONS AND THEORY
..
g
u
I
z
2240
....
z

"'20
a:
0
&&..

I

It
0
0
Sample
vol,c:c
... 0.50
• 0.75
• 1.00
)( 1.50
D 1.75
0 2.00
0 2.25
6 2.50
v 2.75
• 3.00
• 3.25
ReQion of
au toiQnitlon
FIGURE a.-Time DP.lay Before of NPN in Air at 1,000 ir. the Temperature Range From
150" to 210° C. (1-33 npparntus; typc-347, stainless steel test chamber.)
process is involved, an added precaution must
be tukcn; u constituent at a pnrtittl pressw-e
nettr its vupor pressure \'ulue nmy eondense
when it is moment.urily compressed by addition
of other gases or vapors. Accordingly, mix-
tures that are initially abova the UJ>per limit of
flammability may become flammable. A simi-
lar effect must be considered when mixtures are
sampled with equipment that is cooler than
the original sample; if vapor condenses in the
6 FLAMMABILITY CHARAcrERISTICS OF COMBUSTIBLE GASES AND VAPORS
TEMPERATURE, OC
210 200 190 180 170
400
en
200
0
u
G)
en
-

....
z
Reoion of

outoiQnition
""
0::
0

""
m

..J
l&J

0

""
c
:E
....


6V
to
0
RECIPROCAL
FroURB 4.-Logarithm of Time Delay Before Ignition of NPN in Air at 1,000 Palg Initial Pressure.
(Data from figure 3.)
sampling line, the test sample will not yield
accurate data. A flammable mixture sampled
in this manner may appear to be nonflammable
and thus create a hazardous situution (286).
A flammable mixture can a!so form at tem-
below the fla.sh point of the liquid
combustible either i( the latter L'l tnto
the air, or if a mist or foam forms. With fine
mists and sprays (particle sizes below 10 mi-
crons) the combustible concentration at the
lower limit is about the same as that in uniform
vapor-air mixtures (17, 18, 22, 24, 76, 245).
However, 8.\; the droplet diameter increa.ses, the
lower limit appears to In studying
this problem, Burgoyne found that coaJ'He drop-·
lets tend to fall towards the flame front in an
..
DEFINITIONS AND THEORY 7
Chamber I Chamber 2
Figure 5.-Simplified mixer.
Fiouu 5.-Simplified Mixer.
.
"':
Ul

,,
ELAPSED TIME
FIGURE of Gas in Chamber 2, Figure
5 (Instantaneous Mixing).
upward propagating flame, and as a result the
concentration at the flame front actually ap-
proaches the value found in lower limit mixtures
ELAPSED TIME
l
I
1
FIGURE 7.-Compoeition of Gas in Chamber 2, Figure
5 (Delayed Mixing).
of fine droplets and vapors (14). With sprays,
the motion of. the droplets also affects the limit
composition, so that the resultant behavior is
rather complex. The effect of !IWt and spray
droplet size on the app_arent lower limit is illus-
trated in figure 8. Kerosine vapor and mist
data were obtained by Zabetakis and Rosen
(145); tetralin mist data, by Burgoyne and
Cohen (14); kerosine spray data, by Anson
(5); and the methylene bistearamide data, by
Browning, Tyler, and Krall (18).
Flammable mist-vapor-air mixtures may
occur as the foam on a flammable liquid col-
lapses. Thus, when ignited, many foams can
propagate flame. Bartkowiak, Lambiris, and
Za.betakis found that the pressure rue llP pro-
lOOr------------------------------------------------.
- - - - -- Stoichiometric
cv
0:
80
mixture (decane-air)
-
:0
.06
.1:
-
tiO


Kerosine spray
'i ;:, ...
-
.0 ·n;
-&,
E
cv
-
.05 :a

0 0
u ...
60
Kerosine vapor t;
tiO
cv
.<::
and mist
;:, ...
E
.0 'ii
.04 E
z
0
u
0
i=
.03
z
< 0
0:: __ Methylene
i
1-
z
bistearamide spray
UJ
(.) .02
....
z
z
UJ
0 (.)
(.)

/ Tetralin mist
z
L_
Tetralin mist

.01
8
_..L_
..L .:r:.-- 0
0 20 40 60 80 100 120 140 160
.. ET DIAMETER, micron::;
FtOI'RE R.-VariatiOil in Lower Limits or Fllllllrnability of Various Combustibles iu Air ft.' a Function of Dro!Jiet
Diameter.

8 FLAMMABILITY CHARACTERISTICS OF COMBUS'riBLE GASES AND VAPORS
duced in an enclosure by the eompletf:' combus-
tion of a layer of foam of thickness h
1
is propor-
tional to h
1
and inversely proportional to h
0
,
the height of the air space above the liquid
before foaming (7). That is
AP«.!!Y_·
h4
(5)
in excess of 30 psi were l?roduced by
the ignition of foams in small contamers.
ThomalS found that an additional hazard
could arise from production of foams by oxygen-
enriched air at reduced pressures (215). Air
cam become oxygen-enriched as the pressure
reduced, becn.use oxy!Xen is more soluble tluLil
nitrogen in most liqmds (83). Thus the pres-
ence of foams on combustible liquids nre a po-
tential explosion hazard.
A flammable foa\m can also form on nonflam-
mable liquid if the foam is genemted l>Y a flam-
mable gas mixture instend of uir. Burgoyne
and Steel, who studied this problem, found that
the flnmmnbility of methnne-uir mixtures in
water-bnse foums was ufTected by both the wet-
ness of the fonm and the bubble size (28).
...
PRESENTATION OF DATA
Limit-of-flammability data that have been
obtained o.t o. specified temperature and pressure
with a particular combustible-oxidant-inert
system may be presented on either a triangular
or a plot. For example, figure 9
showH a tnangular flammability diagram for
the system methane-oxygen-mtrogen. This
method of presentation is frequently used
because all mixture components are included
in the diagram. However, as the sum of all
mixture cornl?ositions at. any point on the tri-
angular plot Is constant (100 pet,\ the diagram
can be simplified by use of a rectangular plot
(244). For examp1e, the flammable area of
figure 9 may be presented as illustrated in
figure 10. As noted, the oxygen concentration
at any point is obtained by subtracting the
methane and nitrogen concentrations at the
point of interest from 100 as follows:
With either type of presentation, addition of
methane, oxygen, or nitrogen to a particular
mixture results in formation of a series of mix-
tures that fall along the line between the com-
position point (for example, Ml in figures 9 and
10) and the vertices of the bounding triangle.
For example, addition of methane ( +CH.) to
mixture M1 yields initially all mixture com-
positions between M1 and C (100 pet CH
4
).
After a homogeneous mixture is produced, a
new mixture composition point, such as M2, is
obtained. Similarly, if oxygen is added ( +0
2
)
to the mixture represented by point Ml, all
compositions between M1 and 0 (100 pet 0
2
)
are obtained initially; if nitrogen 1s added, all
compositions between MI and N (100 pet N
2
)
are obtained initially. If more than one gas is
added to Ml, for example, methane and oxy-
gen, the resultant CQmpusition point may be
Pet 0
2
= 100 pet-pet CH
4
-pct N
2
• (6) obtained by considering that the mixing process

FIGURE 9.--Flammability Diagram for the Ryatem Met.hane-Oxygen-Nitrogen at Atmoepb.erlo P..-ure and 26° C.
9

10 FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS
..
c

e

c;a- 60

E
:I
0
>

20 40 60 100
NITROGEN, volume-percent
Frouu 10.-Flammability Diagram for the System Mcthan&-Oxygen-Nitrogen at Atmospheric Presa•arc and C.
(Data from fig. 9).
occurs in two steps. First, the methane is added
to Ml and the gases are mixed thoroughly to
give M2. Oxygen is then added to M2 with
mixing to give a new (flammable) mixture, M3.
IC the methane and oxygen were added to u
fixed volume at constant pressure, some of All
and then of M2 would escape and mix with the
surrounding atmosphere. In many instanees
this is an importnnt ('OJisideration be!'nuse the
resulting mixtures may be flamrnuhle. .For
example, even if an inert gas is udded to a
eonstant-volume tank tilled with rnetlumf>,
flammuble mixtures <'tUI form outside the tnnk
us the displu<'ed metlmne es!'npe,.; into the
atmosphere. If the metharw is not dissipated
quickly, u dangerous situutiori ctlll nrise.
When u mixture l'ompoueut is removed hv
condensation or ubsorptwn, the corre.'lponding
composition point (for example, Ml in figures 9and
10) shift.'! away from the vertices C, 0, and N
along the extensions to the lines MI-C, A/I
-0 and Ml- N, indicated in figures 9 and 10
by the minus signs. The final composition is
determined by the percentage of each component.
removed from the initial mixture.
Mixtures with constant
ratio (as in air), are obt1Lined in figures 9 and 10
by joining the apex, C, with the appropriate
mixture composition along the basehne, ON.
'J'hu!!, the Air line, CA, (fig. 10) is formed by
joining C with the mixture A (21 percent 02
+79 percent N
2
). Using this lnttor point, A,
one ean readily determine the mixture composi-
tions thnt are fonued mixture Ml i!'l
displaced from an enclosure and mixed with air.
Initially, all mixture compositions between M1
PRESENTATION OF DATA
11
and A would form. Since these wouid pass
through the flammable mixture zone
1
a hazard-
ous condition would be created. Similarly, if
pure combust.ible ca. were dumped into the
atmosphere (air)
1
all mixtures between C and A
would form. Tnese would include the flam-
mable mixtures alonff CA so that a hazardous
condition would &g&lll be created, unless the
c>mbustible were dissip&ted quickly.
Mixtures with constant ondant content are
obtained by constructing straight lines paraillel
to zero oxidant line· such mixtures also have a
constant combustibie-plus-inert content. One
particular constant oxidant line is of special
lDlportance-the minimum constant oxidant
line that is tangent to the flammability diagram
or, in some cases, the one that passes through
the extreme upper-limit-of-flammability value.
This line gives the minimum oxidant (air,
oxygen, chlorine, etc.) concentration needed to
support combustion of a particular combustible
at a specmed tempGrature and pressure. In
9 and 10, the ta!lgent line gives the
mmimlWl OXfgen value (Min 0
1
, 12 volume-
percent) requll'ed for flame propagation through
methane-oxygen-nitrogen mixtures at 26° C
and 1 atmosphere.
Another important construction line is that
which gives the maximum nonflammable com-
bustible-to-inert ratio (critical C/N). Mixtures
along and below this line form nonflammable
mixtures U{>On addition of oxidant. The critical
C/N ratio JS the slope of the tangent line from
the origin (Figs. 9 and 10), 100 percent oxidant,
teO the lean side of the flammable mixtures
curve. The reciprocal of this sloJ?e gives the
minimum ratio of inert-to-combusttble at which
nonflammable mixtures form upon addition of
oxidant. It is of interest in fire extinguishing.
An increase in temperature or pressure
usually widens the flammable range of a
particular combustible-oxidant system. The
effect of temperature is shown in figure 11;
two flammable areas, T
1
and T
1
, are defined for
a combustible-inert-oxidant system at constant
pressure. The effect of f..tlmperature on the
its of flammability of a combustible in a
specified oxidant was previously shown in
figure 2. This type of graph is especially
useful since it gives the vapor pressure of the
the lower and upper temperature
limits of flammability ( T
1
• and Tv), the flam-
mable re¢on for a range of temperatures, and
t.he autotgnition temperature (AlT). Nearly
20 of these graphs were presented by Van
Dolah and coworkers for a group u( eom-
bustibles used in flieht vehicles (t18).
The lower temperature limit, is essentially
the flash point of a combustible
1
in which up·
propagation of flame is useQ; in general, it
1s somewhat lower than the flash point, in which
'r. air • 100 \- \ combuetible vapor-\ inert
Flammable
midurtl
INERT, volume- percent -
Frouu 11.-Etrect of Initial Temperature on Limite
of Flammability of a Combuetible Vapor--Inert-Air
System at Atm01pherio Preeaure.
cr:
0
Q.
"' >
'It
I
Q.

9r---------------------·-------,
" air • 100" - " J P4 vapor
u
0 200 800
INITIAL PRESSURE, mm HQ
Froua11: 12.-Etreot of Initial Preeaure on Limite of
FlammabiUty of JP-4 (Jet Fuel Vapor) in Air at
26° c.
downward propagation of flame is used. Since
is the mtersection of thP lower-limit and
vapor-pressure curves, a relationship can be
developed between or the flub point, and
the constants defining the vapor pressure of a
combustible liquid. An excellent summary: of
such relatioiJShips hM befln presented by Mullins
for simple fuels and fuel blends (164).
At l",onstant temperature, the flammable
range of a combustible in a specified oxidant can
be represented as in figure 12. Here the flam.
mabie range of JP-4 vapor-air m.ixturee is given

12 FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE OASES AND VAPORS
Pvapor/P
Frouaz 13.-Eifect of Temperature and on Limit11 of Flammability of a Combu11tible Vapor in a Specified
Oxidant.
as a function of pressure (£41). A more
generalized flammability diagram of a particular
combustible-oxidant system can be presented
in a three dimensional plot of temperature, pres-
sure, a.nd combustible content-as illustrnted
in figure 13 (£-'4). Here, composition is given
as the ratio ol partial pressure of the cornbw;tible
vapor, PvAP<>R, to the total P. For lillY
vAlue or P, the Jimit.'i of flammability arb given
as a function of the temperature. For example,
at 1 atmosphere (P = 1), the flammable range is
bounded bv the lower limit curve L
1
L,L,L
4
, and
the upper limit curve U1 Ua; all mixtures
the vapor pressure curve

U, are
The flammable range is the same as that de-
picted in figure 2. At constant temperature
(for example, T
1
), the flammable range is
bounded by the lower limit curve L
1
Pu and the
upper lim1t curve U
1
Put; the broken curve
PL
1
Pu
1
represent..'i the low pressure (quenched)
limit. The flammable range is the same as
that depicted in figure 12. A similar range is
defined at temperatures T
1
, and T
4
which
are less tht\n T
1
• However, at T
1
and T
4
the
upper limit curves intersect the vapor pressure
curves, so that. no upper limits are found above
u; and In other words, o.ll COII!Positions
along and are flamUlable. The curve
PRESENTATION OF DATA 13
1
"air= 100- !C aasolimt vapor- !C water vapor
70 100 120 140 150 160 170 180 190 200 210 212
Fwuu: Diagram for the s,·stern Gasoline Yapor-Wnter Yapor-Air at 70° F (21° C) and at
212• F (100
6
C) and At::1.uspheric Prt>esure.
L
4
P£U.U;U
2
defines the range of limit mixtures
which are satur!lted with fuel ntpor. Furtht>r,
since L
4
is the saturated lower limit mixture at
one atmospht>re, T. is the flash point.
Sonae of the points considered in this and the
pre' ious :,fiction are illustrated in figure 14
(282). This is the flammability diagram for
the system gasoline vapor-Whll'r ntpor-air at
70° F (21° C) and 212° F (100 °C) and utmos-
pherir pressure. The uir saturation tempera-
ture, that is, the temperature at whirb satur1tted
air contains the quantity of Wlltl'r giwn on the
water Vllpor axis, is :\lso included. For vn•cise
work, a much gTaph or an enlnrgNnent
of thl' region from 0 to 8 perrcnt gnsoline vapor
and from 0 to :m percent wMer vapor would
be used. However, figure 14 is ndequ1tte here.
If water vnpor is added to a particular mixture
..t, all mixture rornpositions between ..t and
purt> water vapor will form <ts notl'<l (if the
temperature is at least 212° F), and the eorn-
position point will shift towards the 100-
percent-water-vapor point. If water vapor is
by eondensation or absorbtion, the
composition point will move along the extension
to the line drawn from A to the 100-percent-
watt>r-vapor point. The same applies to the
other t•omponents, air and gasoline, as indicated
earlier. if more than one component
is involved, the final composition point can be
found by considering the effect. of each com-
ponent separately.
Figure 14 is of special interest since it can be
ust>d to evaluate the hazards associated with a
operation. .For example, mixture
A represents n saturated gasoline vapor-air-
water vapor mixture at 70° F. A more \·olatile
gasoline than the one used here would give a
saturated mixture with more gasoline vapor
and less air in a closed a less volatile
gasoline would give less gasoline vapor and
more air. In any event, if a continuous supply
of uir saturated with water vapor is added to a
tank containing mi:'l:ture A, all compositions

14 FLAMMABILJT'/ CHARACTERISTICS OF COMBUSTIBJ,E GMIES AND VAPORS
between A and B (air plus water vapor) will be
formed until all the vapor is flushed
!rom the tank, and mixtun B alotHl
If steam is used to flush mixture A from the
tank, all compositions between A tmd 0 will
form until e.ll the gasoline vapor bas been
flushed from the tank and only steam remains
(at 212° For higher). If the t:ank is permitted
to cool, the steam will condense and air will be
drawn into the tank mixtures along
C-B. At 70" F, only arr plus a small amount
of water vapor will remain.
If hot water and water vapor at 17 5° F are
used to flush mixture A from the tank, the
comiJosition can only shift along AO to
E. Muctures between A and E that are flushed
from the tank mix with air t,o give mixtures
between points along AE and B. Again, as
the water vapor in t.best3 mixtures condens11'1
outside the tllnk, the co!uposition of the result-
ant mixtures will shift awtty from the 100-
percent-water-vapor point, 0. 'rbe mixture in
the tank will remain at E unless air is used to
flush the tank, in which ca..'!C mixture composi-
tons between E and B will form. Again, if
the water vapor within the tank condenses, the
mixture c.omposition will shift away from C.
In any event, at t.his temperature (17 5° F), the
addition of air to mixture E will lead to forma-
tion of flammable mixtures. Thus, mixture A
cannot be flushed from a ta11k without •
flammable mixtures, 11nless steam or some other
inert vapor or gas is used.
...
DEFLAGRATION AND DETONATION PROCESSES
Onct> a flammable mixture is ignited, the
resulting flame, if not extinguildaed, will
attach itseiC to the ignition source or propagate
fram it. If it propagates from the !luurctl, tlw
propagation rate will be either subsonic {de-
flagration) or superoonic (detonation) relath-e
to the unburned gu.s. IC it is the pres-
sure will equalize at t.he speed ol sound throuJ,Ch-
uut the enclosure in which combm;tion is takmg
place so that the pressure drop acroHH the flame
(reaction) front will be relatively smn.ll. H the
rate is supersonic, the rate of pressure equaliza-
tion will be less than the propagation raw and
thare will be an appreciable pressure drop aeross
the flame front. Moreover, with most com-
bmtible-air mixtures, at ordinary temperatureM,
the ratio of the peak-to-initin.l pressure within
the enclosure will seldom exceed about 8:1 in
the former, but may be more than 40:1 in the
latter l.'llse. The pressure buildup is especin.lly
great when detonation follows a large pressure
rise due to deftagration. The distance required
for a deftagration to transit to a detonlltion
depends on the flllmmable mixture, tempernture,
p_I'_essure, the enclosure, and the ignition source.
With a sufficiently powerful ignition sourbe,
detonation may occur immediately upon igni-
tion, even in the open. However, the ignition
energy required to initiu.t3 a detonation is
usun.lly many orders of magnitude greater than
that required to initiate a deflagration (82, 24-9).
DEFLAGRATION
Where a deflagration occurs in a
enclosure of volume V with central ignitwn, the
approxirn1tte pressure rise l:lP at IlL v instant t
nfter ignition is given by the expres;-;ion..c;:
l:lP=KP <P
IV - "''
{7)
and
{N)
where [(is n constnnt. Su is the hurning \'e)()(•ii-Y,
1', is the initi1Ll pre;;sure, /',. is th!' rnnxirnuin
T, is the initial temperuture, n
1
is th(•
nUI.nbM of moles of g-us iu the iuitinl mixtun•,
tlh I>! the nu·nber of 111oles of g'tts in the hurrwd
g-ns<';;, M, is the uvemge moleculut· wei1.d1t of the
initi1J mixture, •\1
6
is tlw uveruge molt•culut·
nf t.lae burned gaaes, and TJ is the final
(n.• · hlllk) tmnperature of the pro ucts. With
otlitl' c:IC'loMUrM, or with non<'.entral ignition,
the fltuue front iM diHturbed by the walls before
l'lllllhustion is completed, so that ct\lculated
preMsure etLnnot be to approximate
uctu.U prcmsure. Even with spherical encl011ures,
t.lw flame front is not actually spherical, so that
the wallA tend to disturb the flame before com-
bustion iH complete (118, 130). A graph of the
preHMure developed by the combustiOn of a
stoichiometric methane-air mixture (central
ignition) in 11 19.7 em diameter, 9-liter cylinder
is given in figure 15. The calculated pressure
for a 9-liter sphere is included for comparison;
K in equation (7) was evaluated from the
experimental curve at 70 milliseconds. The
calculated curve follows the experimental curve
closely about 75 milliseconds, when the latter
curve has a break. This suggests that the
flame front was affected by the cylinder walls
in such a way that the rate of pressure rise
decreased, and the experimental curve fell below
the cn.lculated curve. Further, since the com-
bustion gases were being cooled, the maximwn

----Pm
Calculated /
(9-liter sphere)--{
I
1 Experimental
I (9-liter cylinder)
0
160
TIME, milliseconds
FJOHKE 15.---l'n'tll!urc Produced by Ignition of a !1.6
Volumn-l'crcent Methane-Air Mixture in 11 9-I.itPr
( :ylindt>r ( Expt•rimen tal).
16
16 FLAMMABILITY CHARACTERISTICS OF' COMBUSTIBLE OASES AND VAPORS
pressure fell below the calculated value. The
minimum elapsed time (in milliseconds) re-
quired to reach the maximum pressure appears
to be about 75 W for the paraffin hydrocarbons
and fuel blends such as gasoline; V is the
volume in cubic feet in this case.
DETONATION
Wolfson and Dunn (51!, 1!30) have expressed
the pressure ratio P
2
/P
1
across a detonation
front as
Pa ___ l_ ('Y M 2+ 1) (9)
P,-'Ys+ 1
1 1
'
where 'Ya is the specific he11.t ratio of the burned
gases, 'YI is the_ s_pecific heat ratio of the initial
mixture, and M
1
is the Mach nwnber of the
detonation wave with respect to the initial
mixture. M
1
is given in terms of the tempera-
tures T and molecular weights W of t.he initial
and final mixtures by the expression:
('YIMI
2
+1)
1
('Ya+l)
2
T2WI


- 'YaT,Wa
(10)
P,. (theoretical)
0
P,. (experimental i
E
2,000
Wolfson and Vunn have developed generalized
cba.rts that simplify the operations involved in
obtaining the pressure ratio as well as the den-
sity and temperature/molecular weight ratios
across the detonation wave and the energy
release in the detonation wave.
Many investigators have measured and cal-
culated detonation and reBooted pressures
resulting from detonation waves (54
1
57, 1!04).
Figure 16 from the data of Stoner aM Bleakney
(204) gives the detonation vruocity, the static
or detonation pressure, and the reflected pres-
sure developed by a detonation wave propa-
gating through hydrogen-oxygen mixtures at
atmospheric pressure and 18° C.
BLAST PRESSURE
The pressures produced by a deflagration or
a detonation are often sufficient to demolish an
enclosure (reactor, building, etc.). As noted, a
deflagration can produce pressure rises in excess
of 8:1, and pressure rises of 40:1 (reflected
pressure) can accompany a detonation. As
ordinary structures can be demolished by pres-
sure differentials of 2 or 3 psi, it is not surpnsing
45
40
35
30
P
5
(experimental)
25 E
...
0
20
15
10
5
I ,500 L-----'-----...1.---...L...-----'---·-L----....L-----l 0
20 30 40 50 GO 10 eo 90
H
2
, volume- percent
FIGURII 16.-Detonatlon Velocity, V; Statio Preuure
1
P,; and Reflected Prell8ure, P., Developed by a Detonation
Wave Propagating Through Hydrogen-Oxygen !\U:a:turea in a Cylindrical Tttbe at Atmoephorlo Prtlllure and
18° c.
..
DE.FLAGRATION AND DETONATION PROCESSES 17
that even reinforced concrete structures have
been completely demolished by explosions of
near-limit flnmmable mixtures.
.Jacobs nnd coworkers hnve studied the dam-
nge potential of detonation waves in great detail
(91, 170). They hnve considered the principles
involved in rupturing of pipes and vessels by
detonations and the relevance of engineering
and metalJurgical data to explosions. More
recently, Randnll and Ginsburg (171) have in-
vestigated bursting of tubular specimens at
ordinary and reduced temperatures. They
found that the detonation pressure required to
burst such specimens was, in general, slightly
higher than the corresponding static-bursting
pressure. Ductility of the test specimen ap-
peared to have little effect on the bursting
pressure, but ductility increased the strength
of pipes containing notches or other stress
raisers.
When a detonation causes an enclosure to
fail, u shock wave may propugate outward at a
rute determined bv characteristics of the
medium through wliich it is transmitted, and
the twuilable energv. ll the shock velocity, V,
is known, the overpressure, (P-P,),
is given by the expressiOn (20.1)
(11)
where 'Y is the ratio of specific heuts, und a is the
velocity of sound in the medium through which
the shock wu ve passes. The upproximate
potentiul cun be assessed from the dutu
in table I (217).
In conducting experiments in which blast
pressures mny be generated, special precautions
must be taken to protect the personnel and
e9.uipment from blnst ttnd missiles. Browne,
Hileman, and Weger (16) have reviewed the
design criteria for suitnble barricndes. Other
authors have considered the design of suitable
lnboratories and structures to prevP.nt frag-
ment damage to surrounding (44, 174,
203, 220).
TABLE I.-Conditions of failure of peak over-
pressure-sensitive c!tments (217)
I Approx-
imate
incident
Structural element Failure blast
Glass windows, large
and small.
Corrugat<Jd

Carr· Igak'<i st,eel or
aluminurr: panel-
ing.
Wood siding panel8,
standard house
construction.
Concrete or cinder-
block wall panels,
8 or 12 inches
thick (not. rein-
forced).
Brick wall p1'1ncl, 8
or 12 inches thick
(not reinforced).
over-
pressure
(pei)
Usually shattering, 0. 5-1. 0
occasional frame
failure.
Sh \ttering. 1. (}-2. 0
Connection failure, 1. (}-2. 0
followed by buck-
lil•g.
Usually failure oc- 1. (}-2. 0
cure at main con-
nectJons, allowing
a whole panel to
be i>lown in.
Shattering of the 2. (}-3. 0
wall.
Shearing and flexure I 7. o-s. 0
failures.
MEASURES
INERTING
In principle, a gas explosion hazard can be
eliminated by removing either all flammable
mixtures or all ignition sources ($3, !!40).
Howeveri this is not always practical, as many
industria operations require the or-esence of
ftammable mixtures, and actual or potential
ignition sources. special pre-
cautions must be taken to mirumize the damage
that would result if an accidental ignition were
to occur. One such precaution involves the
use of explosive actuators which attempt to
add inert. material at such a rate that an
explosive reaction is quer.dwd before structural
damage occurs (70, 7$). Figure 17 shows how
the pressure varies with and without such
protection. In the latter case, the pressure
rise is approximately a cubic function of time,
as noted earlier. In the former case, inert is
when the pressure or the rate of pressure
rise exceeds a predetermined value. This
occurs at the time t
1
in figure 17 when the
actuators function to add the inert.
As noted, the pressure increases momentarily
abo,re the value found in the unprotected
ca.se and then falls rapidly as combustion
reaction is quenched by the inert.
FLAME ARRESTORS AND REUEF
DIAPHRAGMS
Inert atmospheres must be used when not
even a small explosive reaction can bv tolerated.
However, when the ignition of tL flammable
mixture would create little hazard if the burning
mixture were vented, flame arrestors and relief
diaphragms could be used effectively. The
destgn of such systems is determined by the
size and strength of the confining vessels, ducts,
etc.
In recent studies of the efficiency of wire
gauze and perforated block arrestors (161, 16!!),
Palmer found the velocity of approach of the
flame to be the major factor m determining
whether fio.rne passed through an arrestor. For
thflse two types of arrestors, he found the
critical npproach velocity to be
and
18
V' =
mo.eQ/r.
(12)
(13)
I
w
a::
;:::)
rn
rn
w
a::
0..
Unprotected
Protected
TIME --•
FrouaE 17.-Pressure Variation Following Ignition o(
a Flammable l\lixtur<' in Unprotl•eted and Protl•cterl
Enclosures.
where k is the thermal conductivity of the
m is the mesh width; T
11
is the men.n bulk tem-
perature of the flame gases through the arrestor;
To is the initial temperature of the arrestor; Q is
the heat lost by unit area of flame; x. is the
thickness of the flame propagating at the burn-
velocity, S; dis the diameter of an aperture;
A is the area of a hole in unit area of the
arrestor face; and t is the arrestor thickness.
Equations (12) and (13) can be used to
determine the mesh width or aperture diam-
eter needed to stop a flame having a particulnr
approach velocity. In practice, application of
these equations assumes a knowledge of the
flame speed in the system of interest. Some
useful data have been made available by
Palmer and Rasbash and Rogowski (172, 178),
as well as by Jost (118) and Lewis and von Elbe
(130).
Tube bundles also may be used in place of
wire scraens. S<.)tt found that these permit.
increased aperture diametern for a given ap-
proach velocity (19!!).
In practice, it may be desirable to install
pressure relief vents· tv damage to duct
systems where flc me may Rasbash
and Rogowski (173) found that with propane-
and pentane-air mixtures, the maximum pres-
sure PM (pounds per square inch) deveioJ?ed in
an open-ended duct, havin(; a t•.ross sectiOn of
1 rt: is:
..
PREVENTIVE MEASURES 19
and 6=::;
(14)
is the ratio of duct length to diameter.
However, the presence of an obstacle (bend,
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
the maximum pressure as well as the flame
speed. For values of K (cross-section area
of duct/area of vent) greater than 1, th1138e
authors found
(15)
L
where 25K532, and 6'5zf'530. To keep the
pressure at a minimum either many sme.ll
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
before the flame has traveled more than 2 feet.
When possible, relief vents should be used
with flame arrestors. The vents tend not only
to reduce the pressure W:thin a system following
ignition but also to reductJ the flame speed,
thus making all arrestors more effective. Un-
fortunntel.v, in certain large applications (for
example, drying ovens), it is d1fficult to use
flame <trrestors effectively. In such cases,
grenter relinnce nnst be placed on the proper
funrtioning of relief vtmts. Simmonds and
Cubbttge (42, 43, 195) huve the
design of ..Jffeetiw• vents for industnul ovens.
They found tw<> pettks in the pressure re,.ords
obtttined during the V"nting of cubical ovens
(fig. 18). The first peak, P
1
; the oven volume,
F; the fnctor, K; and the weight per unit
urea (lb/ft
2
) of relief, w, were relttted ns follows
for '\ 25 penent town gas
3
-air mixture:

(16)
i\lore genemlly,
PI l'
113
=-oS.(0.3Kw+OA), (17)
where S. is the burning velocity of the mixture
nt the m·en temperuture.
The first. pressure pulse WtlS nseribt>d to the
rrlt'nse und motion of Lw relil'f Vl:'nt following
the second pulse, to eontinul:'d .. mrn-
ing ut nn inr·r·ettsed rute. '.!'he secor:d pulse
represents th!'" pressure drop ncross the vent,
I Town 'f\.1\ rontalnr.l npprostmr.tf'ly A:.! J)r\ 17 pet rnrhon
munoxldt•, pet nwthanto; ttw lmlaiiOP "a, .. ottwr hydrtJrurhons, 3 pet;
nllrt>l(cn, v pet; carbon dlo•IU., :1 pel; and
a:td it i.s thus proportional to K.
ve.lues of Kit. was found that
Pa=K.
For small
(18)
As with ducts
1
larger pressures Wicirf> obtained
wheu obstructions were plll.(",ed in t.htl oven.
t
ELAPSED TIME--
FIGURE 18.--Pressure Produced by of a
l<'larnmablc Mixture in a Vented Oven.
In designing explosion reliefs for ovens, Sim-
monds and Cubbage pointed out that (1) the
reliefs should be cc...'lStru('ted :.n such a way that
they do not form dangerous missiles if an explo-
sion occurR; (2) the weight of the relief must be
small so that it opens before the pressure builds
up to a dnngerous level; (3) the areas and posi-
tions of relief openings must be such that the
explosion pressure is not excessive; (4) sufficient
free spnce must be utilized around the oven to
pl:lrmit sntisfactory operation of the relief and
minimize risk of burns to personnel; and (5)
oven doors should be fastened securely so that
they do not open in the event of an explosion.
Burgovne and Wilson have presented the
results ti'f an experimental study of pentane
vapor-air exJ>losions in vessels of 60- and 200-
cubic-foot volume (30). They found t,he rates
of pressure rise grenter than could be predicted
from burning velocity data, so that the
effect of 11. relief area in lowering the peak
pressure was less than expected. All experi-
ments were conducted at an initial pressure of
1 Vent data for use at higher
initiul pressues tlre in nn nrticle
bv Block (10); ll code for designing pressure
relief systems htts been proposed in this article.
Other authors httve considered the effects of
temperature and characteristics of the flam-
mable mixture on vent requirements (14, 35,
38, 45, 46, 134, 145, 168, 221).
FLAMMABILITY CHARAcrERISTICS
The flammability data (limits of flamma-
bility, flash point, ignition temperature and
burning veloctty) of t.he various chemical fll.m-
ilies exhibit many similarities. Accordingly,
the data presented here are grouped under the
various commercially important families, blends,
and miscellaneous combustibles.
PARAFFIN HYDROCARBONS
(C,.H2n+2)
Limits in Air
Lower and upper limits of flammability at
25° C (or at the temperature noted) and 1
atmosphere (£
26
and U
35
) for many members of
the paraffin hydrocarbon series are given in
table 2, together with the molecular weight, M,
vapor specific gravity, sp gr, stoichiometric
composition in n.ir, 0,, (appendix B) and heat
of combustion, ill. (183). At room tempera-
ture and atmospheric or pressure, the
lower limits of flammability of most of this
series fall in the range from 45 to 50 mg com-
bustible vapor per liter of air at standard con-
ditions, that is, 0° C and 760 mm Hg (0.045 to
0.050 oz combustible vapor per cubic foot of
air) (247). This is illustrated in figure 19 in
which some lower limits of flammability are
plotted against molecular weight; except for
methane, ethane, and propane all limit values
fall in a band between concentrations of approx-
imately 45 and 50 mg/lr.
The following may be used to
convert from a lower limit L in volume-percent
of vapor in the vapor-air mixture to one in
milligrams of combustible, per liter of air at
standard conditions:
L (mg)= L (v_o!_pct) _,
1
[100-L (vol pct){sp vol
(19)
specific volume being volume of combustible
vapor per milligram of combustible. At stand-
ard conditions (0° C and 760 mm Hg) this is
about 22.414/l,OOOM, where M is the molecular

cr:

0
...J
0 I
MOLECULAR WEIGHT, orams/mole
Frouam 19.-Ef!'ect of Molecular Weight on Lower Limits of Flammability of P!\raffin Hydrocarboll! at 25° C.
20
FLAMMABILITY CHARACTERISTICS 21
TABLE 2.-Properties of paraffin hydrocarbons
Lower 11mlt In air
Combuatlble M Formula
Ref. (;::1 ...f:!. Ref.
pet) c., 1
-------1-----1-------------------------------
Methane................. CHo............. 16.04
Ethane.................. CoHo............ 30.111
Propane................. CaHa............ .W.llll
n-Butane ................ CoH10........... 66.12
n-Pentane................ Coil.,........... 72. 16
n-Hexane ................. Coli,............ 88.17
n-Heptane. .. ............. c,H,._ .......... 100.20
n-Oetane ................. c,n,. ........... 114.23
n-Nonane. ............... Callao........... !28. 26
n-Deeane.. .............. Coolin........... 142.28
n· Undecane.............. CnH,............ 166.30
n-Do<lecnne.............. CuHn........... 170.33
n-Tridecane .............. Culln ........... 184.36
n-Tetradeeane. •....•.... c,.nao.... ....... 198.38
n-Pentadeeane ........... Cull11........... 212.41
n-Hexadecane.... .... .... Cull,............ 226. o&4

IIE63° c.
•t-86' c.
I
1.62
2. Ol
2.49
2. 98
3.46
3.94
4.43
4. 91
6. 40
6.88
6. 37
6.&
7. 33
7. 82
9.48
6.66
4.02
3.12
2.66
2.16
1.87
1.66
1.47
1.33
1.22
1.12
1.04
.97
.DO
.&
weight of the combustible. Since L (vol pet)
of most members of this series is much less than
100 percent, the lower limit can be expressed
RS
L (vol pet). (20)
At any specified temperature, the ratio of
the lower limit to the amount of combustible
needed for complete combustion, 0,, also is
approximately constant. This was first noted
by Jones (95) and later by Lloyd (133), who
found that for paraffin hydrocarbons at about
25° c,
(21)
For the complete combustion of the paraffin
hydrocarbons, we have:
C,H2n+2 + (1.5n +0.5)0
2
-nC0
2
+ (n+ 1)Ha0,
so that in air
{22)
100
C',= 1 +4. 773(1.5n+0.5) vol pet, (
23
)
where 4.773 is the reciprocal of 0.2095, the
molar concentration of oxygen in dry air. The
values of 0, (appendix B) are included in table
2. By weight tliese become
(',,= mg, (
24
)
22.414X4.77:3(1.5n+0.5) 1
or
C =
9 34
[14.03n+2.02J (
25
)
,, . 1.5n+0.5 1
Thus,
mg/1, (26)
191.8
341.3
488.6
636.4
782.0
928.11
1076.8
1222.8
1369.7
1616.6
1663.6
1810.6
11167.4
2104.3
2261.2
2398.2
6.0
3.0
2.!
1. 8
1. 4
1. 2
1. 06
.06
•.&
I. 76
1
.68
:gg I .liO
.46
.43
0.68
.68
.62
.68
.66
.66
.66
.68
.68
.66
.66
.64
.68
.62
. 61
. 61
38 (.jOi 16. 0 1. 6 128 4/1)
41 (.jO 12. 4 2. 2 190
42 (III 11.6 2.4 210
48 (118 8.4 2.7 240
46 (.jO 7. 8 3. 1 270 •
47 fi-161 7. 4 3. 4 810 .jO
6.7 8.6 .... ..
49 t.m ............. .
48 (l.j6) I 6. 6 4. 2 380 ..... .
48 -------- -------- ................ -----M
46 (1) ............................. .
m ::::::::,:::::::: :::::::: ::::::
'" <'> ................ ········r···--
• Calculated value extrapolated to 26" C at BzplOIIVIIS Ree. Cmter,
Federal Bureau of Mlllee.
Combining this equation with equation (21),
we have

""'48 mg/1, (27)
for paraffin hydrocarbons, except methane,
ethane, and propane. Substitution of this
value into equation (20) gives
(28)
The following expression may be used to
convert a lower limit value in volume-percent
to a fuel-air (weight) ratio:
M [ L (vol pet) J
L(F/A)=28.96 100-L (vol pet) .
(29)
The reciprocal expression gives the air-fuel
(weight) ratio:
28.96 [ 100
L(A/F>=-xr L (vol pet)
(30)
As noted, the lower limits given in figure 19
were determined at room temperature and at-
mospheric or reduced pressure. Lower limits
vary with temperature as shown for methane in
figure 20. The limit values obtained with up-
ward propagation of flame ($1) fall fairly close
to a straight line that passes through the lower
limit value at 25° C and the flame temperature
(1 225° C). This is in accordance with the
White criterien that the flame temperature is
constant at the lower limit (ttt). The data
obtained by White with downward propagation
of flame fall along a line parallel to the line
through the limit values obtained with upward
propagation. Taking the value 1,300° C as
22 FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE OASES AND VAPORS
5
Vapor pressure
curve
% air= 100%-% methane
Flammable mixtures
Downward propagation of flame
Upward propagation of flame

-200 0 200 400 600 800 1,000 1,200 1.400
TEMPERATURE, • C
Frouu 20.-Effect of Temperature on Lower Limit of Flr.mmability of Methane in Air at Atmospheric Pressure.
the approximate flame temperature for the
paraffin hydrocarbon series (55), and using the
lower limit values at room temperature in table
2, the limits of the first 10 paraffin hydrocar-
bons are represented as in figures 21 and 22.
Figure 21 _gives the lower limits in volume-per-
cent and figure 22 in milligrams per liter. By
weight, the lower limits of most members of
this series again fall in a fairly narrow band
("higher hydrocarbons" region). Individual
adiabatic flame temperatures can be determined
lor lower limit mixtures using the data in table
2 and appendix C (55).
The straight lines of figures 21 and 22 are
by:
L L L2&" ( 2 o
,= u• (1,300o·-25o) t- 5 ),
(a I)
or
L,
-L =l-0.000784(t-25°). (32)
u•
They are described in more general terms by a
plot ol L,jL
25
• against the temperature (fig. 23,
solid line) .
These data are also correlated fairly well with
the modified Burgess-Wheeler Law suggested
by Zabetakis, Lambiris, and Scott (242):
L,=L26·- (t-25°), (:J3)
where t is the temperature in °C and flHc is the
net heat of combu:stion in kilocalories per mole.
Then,
L
L, =1-L

(t-25°). (:34)
n•
Substituting the value I ,040 for Las·All. ob-
tained by Spakowski (201), we have
L
L, =l-0.000721(t-25°), (35)
2a•
which iR also given in figure 23 (or a limited
temperature range with the broken line.
..
FLAMMABILITY CHARACTERISTICS 23
% air = 100%-% combustible
5
Flammable mixtures
0 200 400 600 800 1,000 1,200 1.400
TEMPERATURE, • C
FIGURE 21.-Effect of Temperature on Lower Limits of Flammabil!ty of 10 Paraffin Hydrocarbons in Air at
Atmospheric Pressure.
Only the lower limit n.t 25° C and atmospheric
pressure is needed to use figure 23. For exam-
ple, assuming n. constttnt fltlme temperature, the
ratio LJL
26
• ut 600° C is 0.55. The cnlculttted
lower limit of methane nt 600° C therefore is
5.0X0.55, or 2.75 volume-percent. The sume
value cnn be obtnined directly from figure 21.
From the modified Burgess-WhAeler l..nw cur,·e,
L,/L25.=0.585 at 600° C, so that Leoo·=2.92
volume-perrent.
l..imit-of-flammabilitv measurements are com-
plicated by surface and vnpor-phtlse reactions
that occur at temperatures abO\·e the uuto-
ignition temperttture. For example, Burgoyne
and Hirsch (25) have shown thnt metlumE>-air
mixtures contnining Uf to 5 perrt>nl mrthane
burn readily nt 1,000 <'. vn•re
conducted with eontnining us lit ilf' us
0.5 percent metlume; figure 20 prt>dirts thnt u
flame would not propngnte throu11:h surh n
mixture.
Flammability experiments ut elevated tem-
peratures indicl\te that in the absence of cool
flames (87, 88), the upper limit also increases
linet1rly with temperature. The effect of
tempernture appears to be fairly well correlated
by the modified Burgess-Wheeler law:
If we assume that the heat release at the upper
limit is equal to that at the lower limit, then
A plot of U,, Un• temperature (fig. 24)
Wlls used to compare recent experimental values
of and coworkers (18£) (or methane-
uir mixtures ut 15 psigwith those predicted h,Y
the modified Burgess-Wheeler la.w. The experi-
mental and calculated upper limits IU'e given in
tnble 3 together with the difTerem·ei
Uupor· In each CII.S(>, th('O difference is than
24 FLAMMABILITY CHARACTERISTICS OF COMBUSTIBJ"E OASES .AND VAPORS
50 Higher
hydro-
carbons

-200 0 200 400 600 800 1,000 1,200 1,400
TEMPERATURE, • C
FIGURE 22.-Effect of Temperature on Lower Limits of Flammability of lO Paraffin Hydrocarbons in Air at
Atmospheric Pressure by Weight.
4 percent of the experimental value, which is
approximately within the limit of experimental
error. Earlier experiments of White (222) at
temperatures to 400° C, with downward flame
propagation, also are represented quite ade-
quately by equation (37). For example, White
found that the upper limit or pentane in llir
(downward propagation) increased linearly from
4.50 volume-percent at about 17° C to 5.35
volume-percent at 300° C. The rntio of 5.35:
4.50 is 1.17, which compnres quite well with
1.20 obtained from figure 24.
Given the vapor pressure curve and the lower
limit of ftammttbihty, the low .. temperature
limit or approximate tlash point of a combustible
can be calculated from either equation (32) or
(35) (218). A pproxirnu te flash points were
obtained previously, using onlY the \'llpor
pressure curve and the lower limit nt ordinary
or e)e,·ated temperatures (1.54). The vnlues
obtained with this procedure ure somewhat
low because the lower limit at any tempt>rature
the flash point is less than at the flash
point. The lower temperature limits of paraffin
hydrocnrbon at atmospheric pressure are :_>;i,·en
in table 4.
TABLE 3.-Upper flammability limits, U, of
methane-air m·i:cturcs at 15 psig
U.aprrl (VOl u .•.• (vol Uoale-UeapPr
( C) percent) perct>nt) (vol percent)
------
25 •....••. _ 15. 5 15. 5
()
100 ________
16. 3 16. 4 . I
200 .... - ... 17. () 17. 5 .s
300 ...... --. 17. !I 18. 6 .7
I (/811.
:\foderate changes in pressure do not ordi-
narily nffE'Ct the limits of flammability of the
pnruffins in nir, ns shown in figure 25 for pen-
tane, hexane, and heptane in air (241) 111 u
range from 75 to 760 mm Hg. The lower
...
FLAMMABILI1'Y CHARACTERISTICS
TABLE 4.-LoWt'r temperature lim·ils and auloignition tempera.rures of poraflin hydrocarbons at
atmospheric prtsS'Ure ·
ha!le. __ ..... _ ..... ___
Ethane_ - ...• _., .. __ . _. __
Propane .•. ______________
n
-Butane _______ . _____ . __
Isobutnne. _. __ ... _
n-Pentnne ..•.•... ________ r
II
-Hezane _______________
n- Heptnne ___ . ___ .. ____ .. _
-Octane __ - _ .. _____ - -- ..
-Nonane ________________
-Decnne _____ ... __ .. __ . _
- Dodectme ____ . _____ . ___
n
n
n
n
n
- Hexndecane __ •• ________
1
Caculated value.
. 4
.2
0
Autoignition temperature
Lower limit
-
In air
In i>ir In ozygen
·c
-187
-130
-102
-72
-·81
I -48
-26
I
-4
13
31
46
74
126
200
I
"F ·c "F Ref. ·c
----
-305 (i) 537 999 ( 168)
--------
-202 {l) 515 959
(197)1 506
-152 (•) 466 871
(t 58) . -------
-96 (1) 405 761 (l.i7) 283
-114 I (I) 462 864 (158) 319
-54 (1) 258 496 (194) 258
-15 (159) 223 433 (19.$) 225
25 (16.9) 223 433 (B87) 20<1
56 (169) 220 428 (I.-J7) 208
88 (169) 206 40a (B.i7)
--------
115 (169) 208 406 (187) 202
165
I
(159) 204 399 (187)
--------
259 (1) 205 401 (197)
----·---

Burgess-Wheeler Low


.....
"F
--------
943
-------··
542
606
496
437
408
406
......................
396
--------
--------
400 600 800 1,000 1,200
TEMPERATURE, °C
I
Ref.
-··------
(94)
_ ... _ .. _-
(191)
(9-')
(144)
(94)
(,Q4)
(191)
-----·--
(94)
--- ..............
-----·--
1,400
Frouu 23.-Efteet <>f Temperature on L,/L.,.• Ratio of Paraffin Hydrocarbons in Air at Atmoepheric Pressure.
26 FLAMMABILITY CHARACTERISTICS OF' COMBUSTIBLE GASES AND VAPORS



1.4 -----,- --- --,----r---·-.---l
I
1.3 ·-
1.2
l.l
I.CJo ...
TEMPERATURE. • C
F'JOURE 24.-Effcct of Temperature on Ratio
of Paraffin in Air at
Pressure in t.htl AbJSencc of Cool Flames.
eoincide, but the upper limits, by weight,
increase with incrensing moleculnr weight.
Bl volume, nt atmospheric. pressure and 25°
C, Sptlkowski (201) found thnt the upper nnd
low£'r limits were reltd.ed by the exprt'ssion:
(38)
However, the data presented ure correlated
precisely by a somewhat. simpler expres-
siOn:
(39)
Neither expression applicable when cool
flames are obtained. Substitution of equation
(21) for Lu,. into equation (39) gives
U
350
=4.8 .JO:,. (40)
The limits of flammability of natural gas
(85-95 pet methane nnd 1.5-5 pet ethane)
have been detenuined over tm extended pres-
sure rnnge by ,Jones nnd coworkers (78, 106).
They are given in figure 26 for pressures from
1 to 680 1\tmospheres (10,000 psig). An
anu.lysis of these dnta shows the hmits vnry
linea.rly with the log11rithm of the initial
pressure. That is,
L (vol pct)=4.9-0.71 log P (a.tm), (41)
and
u (vol pet)=14.1+20.4 log r (atm), (42)
with a Rtn.ndnrd error of estimate of 0.53 vol
pet for L nnd 1.51 vol pet for U.
Although the limits of flammnbility are not
nffeeted signifieuntly by moderttte changes in
pressure, the ternpemture limits are pressure
dependent. As the tolttl pressure is lowered,
the partin! pressure of the combustible must
also be lowered to maintain n constant com-
bustible eoncentru.tion. The effeet of pressure
on the lower t.empemture limit of the normal
pttrnffius pentane, hexane, heptane, and octane
in air, for pressures from 0.2 to 2 atmospheres,
Heptane
z
0
300
a::
f-
ffi .::
I ::::: '

Pentane
uro
z-

(.)"""
I.LIIll)

f=
en
::1
aJ

0
(.)
100

0 100 200
Flammable mixtures
Cl:XJ
I I I
300 400 500 600 700 800
INITIAL PRESSURE, rnm Hg
Fwuu: 25.-Effcct of Prc811ure on Limite of Flammability of Pentape, Hexane, and Heptane in Air llt 26° C.
..
FLAMMABILITY CHARACTERISTICS

% air = 100%-% natural gas
Flammable mixtures
10
o· 100 200 400 600 700 800
INITIAL PRESSURE, atmospheres
FwunE 26.-EifPI't of Pressure ou Limits of Flammability of Natural Gas in Air at 28° C.
is shown in figure 2i. The temperature limits
WN'e euleuluted from the L
26
, vulues, the \'llpor
prt'ssure t·un•es, und the dutu of figure 23.
Limits in Other Atmospheres
Limits of tlummubility of some pntnffin hy-
droeurbons hn \'fl been determined in oxygen,
l'blorirH', und oxides of nitrogen, w£'11 us in
rnixt urt•s of uir and ntrious irwrts. ThP lower
limits in oxygt•n 1111d in 11 widP \'lll'it'IY of
oxygPII-nitrogt•n mixturPs un' ('Sst•ntirdly the
sallH' 11:- tho,.;p in uir ut th<• S!llll(' lt'lllflt'raltrr(•
and presstrn• (fig. 10). Limit -oi-flurnrrrabilit v
lllt'llSlll'Pillrllls b\' Bartkowiak und
for lllPt.hurw und PthurH' in l'ldorirll' ut I, i.S,
14.{) I'Hil!-!'illg froru :.!!i" to 200°
< , un• ''llllllllurrzPd Ill tuhl<•;o; !i and ti (8).
( 'em nrd und .Jorw,.; (-iiJ) hu \'t' prPst•nll·d
gmphil'ally tlw limits of flrlllllllllbilityof till' fir·st
;-;ix llll'llllll'r-; of t ht> purnl!in ,.;prit•s in uir con-
t uining- vurious irH'rts, bust•d on u l'l'(>l'l':il'lltn-
t ron found ust•ful in sollll' ruining- upplicut ions
und tr'l'!Liiug iul'rt gas or vupor as purt uf the
TABLE 5.-Limits offlam.mahih"ty of methane in
chlcrine
Prt'!!Hnl'C,
psig
Lirn:ts
----···-----
Temperaturt•, °C
--------.,.----
100 200
------- ___ .. __ ------------
ut mosphPre with which the combustible is
mixPtl. Till' ('nmpo:;it ion of u point on such u
diugrnrrr, PXCPpt onP thut rt'prt'sPnts only com-
bustiblt> nnd air, ennnot be rend d1reetly.
on(' must dt•trrrnine Ute compo!<ition
of thP utrrrospherP, ndd tlw <'ombustiblP eon-
tent, nnd then compute the total mixture com-
28 FLAMMABILI'fY OF COMBUS7'IBI.E OASES AND VAPORS

20L
(,)

0.4 0.6 1 2
PRESSURE, atmospheres
F'IGURE 27.-Effect of Pressure on Lower Temperature
Limits of Flammability of Pentane, llcxl\ne, Heptane,
and Octane in Air.
TABLE 6.-Limits of flammability of Fthane w

(volumo-perC('nt)
Pressure,
psig
Limits
Temperature,
0
('
25 100 200
-----·-----·-------------
(} ____________ {Lower .. ..
Lpper .. ..
100 ...... _ .. _{Lower ... .
Upper .. ..
200
__________ --liil'" '"7:i"
6. 1 2. 5
58 58
3. 5 I. 0
03 75
2. 5
1.0
112
76
position. This been done for met l11tne
through hexane 2S-a:l). (
determined directly fmm the (inert
conrentmtion) and onlinut.es (combustible Coll-
centration); tlw nir iu nny mixture is t hr diffrr-
ence between 100 l'frcrnt. and the sum of inert
und eombu:-3tible. Datu of Burgoyne nnd
Leh· for· met.lume-methyl l>l'omide
(l\1 eBr) -uir ar:d rn<>t lmne-cnrbon tPtm<'hloridt'-
'tir are included in figure 2S (2!J).
Unfortunat.ely, the methane-methyl bromide-
air data were obtained in a 1 %-inch tube.
Although satlsfa.ct.,ry for and other
hydrocarbonP., tube is apparently not
sa.t1sfactory {or many of the lmlogenated hydro-
carbons. n recent induHtrial exj)losion
methyi bromide prompted Hill to
reconsider the fla•mmability of methyl bromide
ht air (84). He found that. bromide was
not. , .nly ilammable in air but that. it ful'med
flammable mixtures •\t I a.tmospberl' a
wider variety o( than Jones had
reportJd (96). This would that there
is no justification Cor ! be as!•Ulltption that
Jones' flammabiW .r data for methyl bromidP.
were influenced by the presence of mcrcur.Y
vapor (196). Hill's limit vulues tLt utmosphertc
pressure nr<'- included in figur{l 28 and arc used
to futm the approximate, broken, fiammabilitr
curves for the methane-methy' bromide-a1r
system.
Data of Moran and Bertschy for pentane-
perfluoropropane-air, pentane-sulfur hexafluo-
ride-air and penta.ne-perfluoromethane-air mix-
tures are included in figure 32 (14-'i'). Data by
Burgoyne and Williams-I..eir for hexR.ne-methyl
bromide-air and hexo.ne-Frflon-12
4
(F -12;
Cli"'
2
Cl
2
)-air mixtures have been included in
figure 33. 'rhese were all obtained in
r%-inch-diameter tubes. An investigation of
flv.mm•1bility of hexane-methyl bromide-air
mixtures in a 4-inch tube indictlted that an in-
crease in tube size (from 1 %-inches to 4-inehes-
ID) resulted in a narrowing of the flammable
range; the upper limit decreased from 7.5 to
5.7 volume-percent n-hexane VtLpor in air while
the lower limit remained constant. The
amount of methyl bromide required for extinc-
tion decreased from 7.05 volume-percent in the
1 }Hnch tube to 6.0 volume-percent m the 4-
inch tube. However, agnin this is not in line
with the result:;; obtained by Hill with methyl
bromide-air mixtures (84). Accordingly, while
the dnta obtained in tlpproximtttely 2-inch tubes
were used to construct figure 33, the Hill
obtttined in •t larger •tre nlso used to
form the broken, flnmmtthility
curves for the hexane-methyl bromide-air
system.
The limits of flammn.bility dia!tfams for the
syst.em n-heptune-\•ater Vttpor-air n t 100° nnd
200° C (fig. 34) show the effects of tempernture
on u system that, prvrluces both normal unrl
eool fhmes ntr.wspheric pres1-mre (W2). In-
teresting!;' enough, the nunimum oxygen re-
quirement for flume propugtttion (:\tin 02) ut
200v C is the snme for the eool llllrl m•rmnl
regions in this instnnce. Further, the
decrense in :'1inimum oxygen requirements
• Trade names are used (or 11nly; this doo• not tmply
endoraement hy the Bureau or N.'.tnes.
..
FLAMMABIL.ITY CH.Al' 29
. I
%air= 100%--;,; methane-% inert
12
4 \ \
\ \
\ \
' \
2 \ \
\ \
\ \
\
"-\
0 10 20 30 40 50
ADDED INERT, volume-percent
FIUUIU: of Flammability of Various Mcthanc.Iner. ·,s-Air Mixtures at 25° C alld Atmospheric
Pressure.
(from l:l.5±0.3 volume-percent, tlt 100° C to
12.8±0.:3 volume-pen·ent at. 200° C) is wit' in
the predi(•t.ed by the modified Hurgess-
\\'lu•eler ltlW (equntion a;, nnd How-
ever, the n vnilnble dn t.n 1: "C too nt
present to permit n ren.listie <n-ahmtion ,,f the
v t\iidi tv of this In w.
I IISJlectionof the limit-of-fltunnutbility eurves
in figUI'es 2S to 33 reveuls thut c ·;cept for
methuuc und Pthane, the minimum amounts of
carbon dioxide and nitrogen required fo!" flame
extinction (peak values) at 25° C and atmos-
pheric pressure nre about, 28 and 42 volume-
prrcent., respectively. T;_ of these values
1s npprm · · ;1\tely inverselr pr0portional to the
mtio of theli
1
1ent capncittes at the temperature
nt which <'t>.''bustiOn occurs. Al".cordingly,
generalized flamm»bility diagrams of the type
given in figure 35 can be constructed for the
higher hyd" "t\rbons, ignoring the presence of
cool flames. 3uch diagrams do not appear to
be applicable to the halogenated hydrocarbons
30 FLAMMABILITY CHARACTERISTICS OF COMBUS'l'IBLE GASES AND VAPORS
%air= 100%-% ethane-% inert
-
c
Q)

!.
8
cV
E Flammable
:::J
mixtures

LLi
z
6
<
:I:
!:;:;
4
0 10 20 30 40 50
ADDED INERT, volume-percent
Fu; :JRE 29.-Limits of Flammability of Ethane-Carbon Dioxide-Air and Mixtures at 2.'i° C
and Atmospheric Prl's!!ure.
since these materials tend to decompose even
in flames of limit-mixture composition nnd, as
noted, may themselves propugute flume. Cole-
man (J7) hns found that the mtios of the peuk
values of u halogenated hydrocnrbon ure not
constant but ttre proportionul to the hents of
combustion of the combustibles to which the
halogenu ted h.vdrocarbon is added.
Few data are ttvniluble for the etfpets of
pressure on the limits of flammability of eom-
bustible-inert-air mixtures. One such set of
data is summarized in figure 36, which gives
the limits of flttmmability of nttturnl gas
(85 pet methane+ 15 pet ethane) nitrogen-air
at 26° C ttnd 0, 500, 1,000 and 2,000 psig (105).
Similnr dttttt nre given for ethnne-cnrbon
dioxide-nir (fig. and Ptluuw-nitrogen-nir
(fig. (121), IUHI fot· propnne-eurbon dioxide-
nir (fig. a9) und propnne-nitrogen-nir (fig. 40)
(122). Minimum oxygen requirements for
flame propngtttion (min 0
2
) through nntuml
gns-ni trogen-uir, ethnne-ni trogen-nir, und prn-
pane-nitrogen-nir at utmospheric nnd elevnted
pressures nnd 26 °Cum sumnutrized in figure 41.
fhe minimum 0
2
vulues in volume-p:,rceut
11re reluted to pressure 11s follows: ·
for nuturnl gus:
Min. 0
2
= 13.98-1.68 log P; (4:$)
...
FLAMMABILITY CHARACTERISTICS
31

% air = 100%-% propane-% inert
-
c::
Q)
u
...
Q)
a.
6
ci.l
Flammable
E
mixtures ::I
0
>
t.J'
z
<C
4
Cl.
0
0::::
0..
2
0 10 20 30 40 50
ADDED INERT, volume-percent
FIGURE 30.-Limits or Flammability or Propane-Carbon Dioxide-Air and Propane-Nitrogen-Air Mixtures at 25° c
and Atmospheric Pl'essure.
for ethane:
Min. 02= 12.60-t.a6 log P; and (44)
for proptme:
Min. 0
2
=13.29-1.52 log P; (45)
where P is the initial pressure in pBia.
The luwAr limit of flammability or any
mixture of the ptmtffin can be
calculated by Le Chatelier's law (40, 12iJ, 235):
100 "
-n--,' ') (
1
t = 100 (46)
'5: (I 1:1
1=1 L.
where r. and L. are the percentagll comP.osition
and lower limit, respectively, of the 1'b com-
bustible in the mixture. For example, a
mixture containing 80 volume-percent methane,
15 volume-percent. ethane and 5 volume-percent
propane Las a lower limit in air at 25° C and
atmospheric preBSure of:
100
L2.10=so-t;s-5=4.a vol pet. (47)
-+-+-
5.0 a.o 2.1
Liquid mixtures can be treated in the same way
if the relative escaping tendencies of the various
components are known. Since the paraffin
hydrocarbons obey Raoult's law (143), the
partial pressure or each component can be
calculated a.s follows:
(48)
where p
1
is the vapor pressure of the illl com-
32 FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS
1 0 ~ - - - - - - - - ~ - - - - - - - - r - - - - - - - ~ - - - - - - - - r - - - - - - - ~
% air = 100%-% butane-% inert
-
c:
" ~
6
"
a.
cb
E
Flammable :l
g
mixtures
LLJ
4 z
~
Cst :;)
CD
2
0 10 20 30 40 50
ADDED INERT, volume-percent
FrouaJD 31.-Limits of Flammability of Butane-Carbon Dioxide-Air and Butane-Nitrogen-Air Mixtures at 25° C
an:i Atm1.1spheric Pressure.
ponent in the blend, Po is the vapor pressure
of the pure component and N, is its mole
fraction in the solution. This procedure has
been used to calculate the lower temperature
limits of decane-dodecane blends in air (fig. 42).
The vapor pressures of decane and dodecane
and the calculated low temperature limits are
given by solid lines and four experimental
vo.lues by circles.
Autoignition
Two types <,f autoignition data are obtained
depending upon whether the objective is to
cause or to prevent the ignition of a combustible
in air. The first type are usually obtained at
high temperatures, where the ignition delay is
relatively short. Typical of these u.re the data
of Mullfus (159), Brokaw and Jackson (15, 90),
Ashman and Buchler (6), and Kuchta, Lam-
biris, and Zabetakis (127). These are not
normally used for safety purposes, unless there
is some assurance that the contact time of
combustible and air is less than the ignition
delay at the temperature of the hot zone. The
minimum autoignition temperature (AlT) is
usually the quantity of interest in safety work,
especially when combustible and air can remain
in contact for an indefinite period.
Some Al'r values for paraflin hydrocarbons in
air obtained by Setchkin in a !-liter spherical
Pyrex flask (194) and by Zabetakis, Furno, and
Jones in a 200 cc Pyrex Erlenmeyer flask
(237) are given in table 4. Interestingly
enough, experiments conducted in these and
other flasks generally indicate that fla..-.k shape
and size are important in determining the AlT.
The AIT data obtained in the 200 ac flask may
..
FLAMMABILITY CHARACTERISTICS 33
8 ~ - - - - ~ - - - - - - - ~ - - - - - , - - - - - - - r - - - - - .
% air= 100%-% n-pentane-% inert
7
6
......
c
C1)
~
5
C1)
a.
cb
E
-= 0
>
0: 4
0
a..
~
LLJ
z
~ 3
z
LLJ
a..
c:::
2
1
0 10 20 30 40 50
ADDED INERT, volume-percent
FIGURE 32.-Limits of Flammability of Various n-Pentane-Inert Gas-Air Mixtures at 25° C and Atmospheric
Pressure.
34 FLA.l'dMABILlTY CHARACTERISTICS OF COMBUSTIBLE G.\BES AND VAPORS
...
c::
Cl)
~
Cl)
c.
cb
E
:::l
0
>
~
0
a..
<
>
UJ
z
~
:I:
c::
8 r - - - - - - - ~ - - - - - - ~ - - - - - - T - - - - - - - - r - - - - - ~
7
6
5
4
3
2
1
0
\
'
'
% air = 100%-% n-hexane-% inert
MeBr
'
10 20 30 40 50
ADDED INERT, volume-percent
FwuRE 33.-Limits of Flnmmnbility of Various n-lll•xnnc-lncrt Gns-Air :\lixtures nt 25° C lllHI Atmospheric
Prc88urc.
..
FLAMMABILITY CHARACTERISTICS
35
FtOURE 34.-LirnitR of Flammability of n-ll<'ptan(•-Wnt!'r Ynpor-Air :\lixturcs at 100° and 200° C and Atmospheric
P r c t ~ ~ ~ u r c .
36 FLAMMABILITY CHARACTJo:RISTICS OF COMBUSTIBLE GASES AND VAPORS

L
0
% air = 100%-% combustible-% inert
Flammable
mixtures
10 20 30 40
ADDED INERT, volume-percent
50
FIGURE 35.-Approximate Limits or Flammability or Higher Paraffin Hydrocarbons (C.Hso+J• n in Carbon
and Nitrogen-Air Mixtures at 25° C and Atmospheric Pre88ure.
FLAMMABILITY CHARACTERISTICS

8
0
%air= 100%-% nitrogen-% natural gas
Flammable
mixtures
8 16 24
1,000 psig
32 40 48
ADDED NITROGEN, volume-percent
56 64
FI<·t:RE 36.-Effect of Pressure on Limits of Flammability of Mixtures at 26° C.
37
38 CHAR.,CTF:HIHTICfl OF COMBUISTIBLE OASES AND VAPORS
%air= 100%-% ethane-% C02
40
-
s::::
Q)
0
....
Q)
0.
32
cV
E
:l
0
>
u..i
24
z
<
:I:
1-
LLJ
16
CARBON DIOXIDE, volume-percent
Fl<..l"kt: :!7.-Eff,.et of 011 Liruit .. ot l'lnrnmnhility uf Ethallt•.('arholl ))joxido·-Air • • ar :.!t\ · I·

..
F'LAMMABII.ITY CHARACTERISTICS 39
...
c:::
Q)
u
....
Q)
32
0.
ci>
E
;:::)
0
>
24
w
z
<(
J:
1-
LLJ
16
0 8 16 24 32 40 48 56
ADDED NITROGEN. volume-percent
FJUI'RJ: :\'<.- LIL·;·t of • • on Limits of Fl:tmmability of Ethtlllt'-:'\itrog••n-Air :\fixtures at 26° C.
40 FLAM_11;!ABILITY CHARACTERISTICS OF COMDUSTIIH .. f; GASES AND VAPORS
4 0 ~ - - - - - - - ~ - - - - - - · ~ - - - - - - ~ - -
-
c:
QJ
~
32
QJ
a. 24 -
cil
E
::l
~
LJ..i
z
Cf 16
0
a::
a..
8
0
% air= 100%-% propane-% C02
~ 2 0 0 psig
Atmospheric
B 1b 24 32
CARBON DIOXIDE, volume-percent
40
FIGURE 3H.-Eifect of Prcssu:c on Limits of Flammability of Propane-Carbon Dioxide-Air l\fixtureR.
48
..
FLAMMABILITY CHARACTERISTICS 41
4U ---r-
% air= 100%-% propane-% N2
32
-
c::
Q)
u
...
Q)
c.
24 cil
E
:::s
0
:>
L..l,j
z
16 ca:
ll..
0
0::
ll..
Atmospheric
8
0 8 16 24 32 40 48 56
ADDED NITROGEN, volume-percent
FIGURE 40.-Effect of Pressure on Limits of Flammability of Propane-Nitrogen-Air Mixtures.
be correlated with molecular structure by
plotting them against the nverage carbon chain
length defined 8.'1
II
2:;:; g,N,
L • .,=M(M_:_I )'
(49)
where g, is the number of possible chnins each
c·ontnining N
1
etlrbon atoms nnd ,\/ is the nm:t-
her of methyl {---( '11
3
) groups. For example,
n-nontme und 2,2,:J,'J-tetramethyl pent tine each
have !l carbon nt01ns, hut the former has 2
methyl groups tmd the lntter hu' li. The former
hns only one dtuin of !l l'nrbou atoms with n
methyl ·group on ench end, und the lntter h11s
ll IOII.Xillllllll of 4 dmins With a l'llrhon Ill oms, S
dtnins with 4 l!loms, und :l dtnins with 5
ut mns. Thus, 11-liOilllllC hns an 11 veruge
rhuin l••ngth of ' und 2,2,:!,:\-tetnunethvl
I
lenlnlll' hn..; 1t11 n vernge oi :Ul. The more highly
muwlwd " c•omhustihh1 is, I higher its
ignition ll'mpemture will bt>. .\linirnmu unto-
ignition temperutures of 20 were
plotted lUI ordinate against the average chnin
length as abscissa (fig. 43). The data fall into
two regions-a high-temperature region in
which the AIT is greater than 400° C and a.
low temperature region in which the AI T is less
t.han 300° C. These regions coincide with those
of Mulcahy who found that oxidation proceeds
by one of two different mechanisms (162}, aud
by Frank, Blackham, and Swarts (60). The
AIT values of combustibles in the first region
are normally much more sensitive to the oxy-
gen of the oxidizing atmosphere
and to the spray injection pressure than are the
c·omhust ible.'> in the second region. Unfortu-
nately, the avuilable consistent AIT data about
the effec's of oxygen concentration and in-
jection pressure are too meager to permit a
compurison.
The physical processes (206) ano reactions
thnt lead 'to aut.uignition are of interest in any
detailed study of this ignitinn process. Salooja.
{18-D, Terao (20'7), Affens, ,Johnson and Carhart
(1, 2), and others have the aut.oignition
of vnriom; hydrocarbons in an effort to deter-
mine the mechanisms that lead to the ignition
reaction.
42 FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS
2,000
1,000
800
600
IV 400
"iii
c.
uJ
0::
::J
en
200
en
LLJ
0:::
c..
100
80
60
40
20

6 8 10 12 14
OXYGEN, volume-percent
FIGtr!IE 41.--Effcct of Pressure on Minimum Oxygen Requir!'ffit'nts for Flume Propagutiou Through Gus-
Nitrogcu-Air, Ethune-:\'itro!(Pll-Air, uud l'rop111H'-:..;itrop;m-Air :\lixtun·s at 26° C.
An increase in pressure !!Pilerally deC'renses
the AIT of a combustible in It givrn oxidunt.
For exumple, the AIT of n llntuml gas in nir
deerrused fmm 5:W
0
(' ttl I nt mospiH•rt> to 240°
(' nt tiiO atmospheres (V,OOO p,.;ig) (78). Tlw
AIT's of seveml hydroetlrbons were found to
oht•y Semenov 's tHpiution over ulimited pre;:sure
range (24H):
(.'iO)
where Tis the AJT nt ttn initinl {>ressure P, ttnd
A nnd lJ ttl"e constunts. Aeeor< ingly, the AIT
vnlm•,.; ohtnined at at mospherie should
not he used to ass<•ss i!!nition ha:mrds ut high
pressures.
Burning Rate
The burning velocities, Su, of various hydro-
carbons hav<• been mensured by numerous in-
vestigator;: in nir und other oxidnnts (68, 131).
At one n.tmosphere and 26° C, the burning
...
FLAMMABILITY
TEMPERATURE, o F
32 68 104 140 176 212 248
-
c::
OJ
u
....
1.32
OJ
0.
1.05
cb
.79
E

w
0
.53
>
0::

::::::1
en .39
0
en

UJ <t
0:: .26 >

UJ
0:::
.....1
0
co

1 .13
i=
oes: en
> =>
co
:E
0
u
0 20 40 60 80 100 120
TEMPERATURE, o C
FiauaE 42.·-Low-Temperature Limit of Flammability of Decane-Air, Dodecane-Air and Decane-Dodecane-Air
Mixtures (Experimental Points 0).
velocities of paraffin hydrocarbons in air range
from a few centimeters a second near the limits
to about 45 near the stoichiometric
mixture compm1ition; much higher values 11.re
obtained with paraffin hydrocarbon-oxygen mix-
tures. Figurt3 44 gives results obtained by
Gabbs and Calcote for four paraffin hydrocar-
bon-air mixtures at atmospheric. pressure and
room iemperature (GB). The are mr-
pressed in Umns of the stoichiometric composi-
Jion. C.,; burning veloeities are given for the
<'omposition rnnge fro111 0.'1 to 1.4 (',
1
• These
nut hors hnve presented similnr dnt n for eom-
bustible.-, Ill 25° and 100° ( '. Figure 45 gives
results by Urumer, tuH.l Cook
for three pamffin mixlme."
nt ntrnosplwrie (He."\sure nnd r·oori1 tempernt ure
in the mnge from to I .4 0, (J.f/8). Burning
vekeities runge from !l low of l2.'i em/see to 11
high of 4:l,i cmjsc•t'; t he,..;e vnlue,.; nrt• <'onsidt•r-
uhl,v tluu, thost• ohtninrd in nir. A
<·hunge in t>ither tempemture or J>I"P,;,;un• will
ultt•r S" for n pnrt icultu· mixture. For l'Xtllll piP,
Ag-new tllld nruiff (8) found t hnt till irH'I'l\11'-l' in
• <'tlll,...es 8. of stoichiPIIletrir mc·tlume-nir
1111d proptuw-uir mixtures to decrense in the
pr,•.;surP mngc from O . .'i to 20 ntmospht'l"l\'i
4(i); S, of ;.toiehiometric metlmrH•-oxygcn mix-
tures, iwwover, increa..'lcd in the pr<ossure
from 0.2 to 2 atmospheres (fig. 47). The effect
of temperature is more consistent. For a given
pressure and mixture composition, an increase
m tempera.ture raises s.. In general:
(51)
where A and Bare constants, Tis the tempera-
ture nnd n is a constant for a particular mixture
composition. Dugger, Heimel, and Weast
(SO, .51, 81) obtained a value of 2.0 for n for
some of the paraffin hydrocarbons (fig. 48).
'l'hc burning velocity of the stoichiometric
methane-nir u.nd methane-oxygen mixtures given
in figures 44 nnd 45 do not agree with the Vt\lues
given in figures 4H to 48 but, in each case, the
burning velocity dntn are internnlly consistent.
The nctunl tlt\me speed relative to a fixed
observer mny be much thnn S. since
the hurrwd gtlses, if not vented, will expand und
impllrt u mot ion to the flnme zone. If detonn-
1 ion occurs, the ion speed inrrctt:.-es mnrk-
edly. For exnmpl(', figur(' 40 gives tlw Kogarko
dnta on veltwitie..; with whirh n detomttion Wtwe
propagntes through vurious mix-
tures nt utmosplwric pr·essure in n :W.5 em-
diumetrr pipe (llli). htlve been
ohtuinetl hv <lt•r·.,tl'in, ( 'ttrlson, nnd Hill 111. low
with lltllllrlll ga:;-air mixtures (67).
44 FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE OASES AND VAPORS
(..)
0
uJ
cc
a::
C-C·C·C·C :::::>
....
. .
c( cc
a::
L&J
c
0..
C·C·C·C·C ::iE
UJ
c c ....
z
0
....
z
350
(.!)
0
....
c
:=»
c(
6
::iE
C·C·C·C·C
:=»
300
::iE
c
z
c
::E
n-CgH2o
250
AVERAGE CARBON CHAII\ t ENGTH, Lovg
FIGURil 43.-Minimum Autolgnltion 1 of Pt ·•.ffin HydrocarL .11 Air as a Function of Average
f:arbon Clll'in .-•nl(th.
In each case, powerful initiators were req11ired
to obtain a detonation in relnt, vrly l11rge pip•·-;
The energ;y requ!.rem.anis for ignitioll nm reduce•'
if oxygen IS used 11.'1 the oxidant in pl!U'I' of air
Further, the detonation velocity InCI't\h ''s a.-;
the oxygaa conte11t of the • , in-
Detonation velocitie.'l uhtuined L
Morrison for methane, ethane, • l··•ta1w,
and hexane in oxygen are given in iJ,.,. " 50
(150); similar data obtained by Waymu' r11l
Potter are in figure 51 f·•r n-hepLtuH'-
nitrogen-whlte fuming nitric acid , •tpors (f!9).
Of Erincipal interest here is the n. gnitude of
the detonation velocity; even in air, t1 is velocity
is S• · rre11t I hut pre;, r!l '"ll VflS are net sent OUt
aheu of the fro•ll Thus, pressure
detect '"'' i hat are liSl'f ·I , ., P.\ plosion preven-
tion wit• I••Aagratt 'l \\·•v• .•rt• useless with
det •na.tio1
With liq I j rueb, I 1 "' htll !I i llg rde depEllldS
;mrt "'' u,, !>liP ol 1 ·r·z.ulion 11:1d on the
po •. l SJZI' Stlh-i Ill ·l!ld Lrurner (20)
, •tl '' show1 that tlw liqu, : ··.;.:rt-;siorl • nte 11
gl<' . by
(52)
whm'fl , . is the value of v 1:n 11ng•• pooh, f( is
n eu: ,ftut, and d is the pool diameter.
FLAMMABILITY CHARACTERISTICS 45
40
,
0
/I
Cll
"'
/ ,
E
f- (J
30
Methane

I
0
I
0
....J
LLJ
>
(.?
20 -
z
z
0::
::::>
CD
10

0.6 0.8 1.0 1.2 1.4 1.6
COMBUSTIBLE, fraction of stoichiometric
Fwl!RE 44.--- Burning of !\I ethan£>-, EthanP-, PropanP-, and ?l-ll£>ptane Vapor-Air Mixtures at Atmos-
pheric PrcBBurc and Room Temperature.
46 l<'LAMMABILITY CHARACTERISTICS OF COMBUSTIBLE OASES AND VAPORS
~
0
g 300
L&J
>
<!J
z
z
a::
::::>
Cll
200
150
1 0 0 L - - - ~ - - - - ~ - - ~ - - - - ~ - - ~ - - - - ~ - - ~ - - ~
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
COMBUSTIBLE CONCENTRATION, fraction of stoichiometric
FH;uR•: 45.-Burning Velocitil's of :\[ptharw-, Etharu·-, nnd Proptllli'·Oxyl(<'ll :\fi'ttur<·s nt Atrno,..plH'ric Pr"""un·
nud Hoom T<·mpPrnturl'.
FLAMJ«ABILITY CHARACTERISTICS 47
'
40
',
u
Q,l
'Z
E
u

0
0
__,
UJ
>
(.!)
20
z
z
a::
::l
.:0
10
'
'
0.4 0.6 1 2 4 6 10 20 40
PRESSURE, atmospheres
FroURE 46.- Variation m Burning Velocit.y of Rtoichiometric Methane-Air and Propane-Air Mixtures With
Pressure at :.!6° C.
expressed 11"' as:
!'., =0.00
76
( ru•_t heat of ill/, )
senstble heat of ,·aportzat!On, tJ./1,
em/min. (5a)
52 1\ of the I'" vnlues for
tl number of iududing severul
puruffin hydrocurbous (21). Of :-;pt•ciul .. ignifi-
<'nm•t• here is thllt j.fJ,Ij.// is 1\etlrl'l •
(nbout 100) for tlw pt;r,lffin hydrtH:III"hons, so
t 11111 t lwir lirwur burning rutt•,-. in I urge Jlool,-.
un• ull uhout '. <'Ill pH 111inutt•.
UNSATURATED HYDROCARBONS
Limits in Air
Tlw molrculur wt•igbt ... pt•cilil' :,!fll,·ity, und
otlu•r propt•rtit•,.; of the hydrcll'urholl,., l'oll,.;id-
Prt•d lwn' 11n' indudt•d in. tuhlt• 7. At room
'.ewperat ure and utuwsplwric prcs,-.ure, t lu
lower limits of flammability of the olefius
(C.l/
2
,.) exduding etnylene fall in the range
from 4G to 4S mg combustible vapor per liter
of air (0.046 to 0.04S oz combustible vapor per
cubic foot of air).
The effect of tempt>raturt> on the lower limit
uf tlummubility of rthylt>nt> inuir at atmosplwrie
prt•ssurt>. 1l t•onst unt limit flume
ll'IIIJWrutUrt', j,-. shown hy the <'Urve lnbded
"\ "pw11l'tl ioll of fhllllt'" in fig\11'(' 5a.
r-ufort uuutt·ly, ollly dowuwurd llanw propagn-
t ion d11 t n urt• 11 n1ilable over 1111 t>xtentlt>d tt•m-
pt'rut u:-t• ruuge (2.22): tlwst' tll'l' indudPtl in
A" iu till' <'ust• of ,-.imilur dntu ob-
I uirll'd with lilt' I !111 rH'. t lu'st' t!Pfirw u st ruig-ht
lirlt' pundit• I to the "( 'onst ant tinrnr IPlllfH'rH-
tun•," "i. 'pwurd propngution of flanw'' lim·.
At:uin, tIll' modifit.•d Burgt'ss- \\'"··t•lt•r· lu w,
t'<Jilnt ion (:!:!), gin•,., u vuriutiou in lowPr limit
With IPillpt•ruturl' tlwt i..; clo,.;P to tl111t :,!i\'t'll hy
tht• "( 'onsttu1t !lamP II'IIIJll'I'IIIUn'" linP, so tlutt
Pit • t'oultl !w ll""'t'd at t t'lll pl'rnlun•,; hdow I hf'
.\1'1' of Pthy)t'lll' 1·1!10" ( '). \!,,;·t'o\"t'l', >IS tfll'
hmit fill lilt'. lt'llllJt'l'lll tlrt'"' of oll'lin,; llrt' nnt !ott
48
Combustible
FLAMMABILITY CHARACTERISTICS
1
OF COMBUSTIBLE GASES AND VAPORS
TABLE 7.-Propertus of u·nsaturated hydrocarbons
Formula
I Low0r limit In air
Sp gr c., Net t;.lf,I---:----;---,---1--...---,----.-
(Air= I) In air ( Kcal) Lu lu L flu L'u U
(volpct) inote --(:-;:- C·'n Rei. -C-,,- Uel.
Upper limit In air
-------1------------------------ -------·------
Etl.ylene ___ ........ - ... -. Coil•---------- 28.0.'i 0.97 31A.2 2. 7 0.41 35 (/IS) 36 6.6 700 (!6)
Propylene ____ ..... . .. . f'sllt... .... ... .. 08 l. 45
1
4. 45 4 2. 4 . 64 46 (/Oil II 2. 6 210 (40)
Butene-1. .. _ .. __ ....... ColiJ .... ___ ... 56.1ll 1.94 3.37 t\07.7 1.7 .50 44 (,) 9.7 2.9 270 (t)
<11-Butene-2... .. . c,n, __ ...... ___ 56. to I 1.94 3.37 606.0 1.8 .. '13 411 (40) 9.7 2.9 210 tM
Isobutylene ............. c,n, ___ -----. 56.10 I 1.94 3.37 fll4.1 1.8 .53 46 (40)1 11.6 2.8 200 (ttl)
li-Methyl-butene-1.... .. Csllto _____ ..... 70. 13 2. 42 2. 72 752.3 I. 61 . 5.'\ I 48 (40) 9. I 3. 3 310 (40)
ProKadlene ........... -c,u,_ .. ______ -::-:
1,3- ..
1
c,u,_....... .. 64.00 1.87 3.67 676.3 :1.0 .64 49 (JOt) 12 3.3 320, (ttiJ
t at Esp1ollive Res. Center, Federal Bureau of Mines.
• Calculated value.
u
Q)
"'
"
E
u

C3
0
......J
I.IJ
>
(.!)
z
z
0:
::l
ell
500
400

0.2 0.4 0.6 1 2
PRESSURE, atmospheres
hm:RE 47.- Variation in Burning of f'toi-
chiomrotric M1•thanP- and Etltyhme-Oxyg"ll :\fixtures
With l'rCSIIure at 26°C.
4
FLAMMABILl'TY CHARACTERISTICS 49
200

(..) 100
g
UJ
>
(!1
z
z
a::
::::>
a:l
50
KEY
o Methane
• Propane
0 n+teptane
Li iso-octane
----r---·
ot::.
Su = 10 + 0.000342 r2
______ _. ______
200 300 400 500 600 700 800
TEMPERATURE, o K
FIGURE 48.-Effect of Temperature on Burning Velocities of Four Paraffin Hydrocarbons in Air at Atmospheric
Pressure.
0 .__ __ ____, ___
6 8 10 12 14
METHANE, volume·Pt!rCe'lt
Fwt·nt; 4\1 - -lll'tor.ation \"do<'itir-,. of
at AtrJHHph<'rie • (Initiator: ,·,o ·;o
Jl:r:lflb of amatol Pipe dianll't<·r: :ltl.5 lllll.)
diffPrl'rtt fmm t ho,.;l' of pnndlin hydwcurhons,
t lit' g'l'llt'rulizt•d gmph for f.,!L
1
,.,c' (fig-. :!:l) l'llll bt•
:J,;t>J for these hydwcurbons.
3.000,
u
z
E
2,000
u
g
...,
>
z
@ 1,500
..:
z.
0 ,_
...,
Cl
1,000
--.--------.-----,
KEY
A Hexane

Butane
0 Propane

Ethane
0 Methane

0 10 20 30 40
COMBUSTIBLE. volume percent
Frti!'Rt: ."ofl.-- Dt•tonation • of
Eti:ant·-, l'ropanl'-, Butane-, and
ut _\trnosphcrit• l'r=,ure.
50 FLAMMABILITY CHARAC'TEIUS'riCS 01'' COMBUSTIBLE GASES AND VAPORS
J,OOO j" ·
l
m

'"'-
E
?"";.,
-4
f.
u
0
-'
UJ
>
X::::.,
z
0

j
z:
(Mole fraction N2 = 0.5)
0
l:;j 1,500 -
0
1,000
0 5 10 15 20
n-HEPTANE, mole-percent
FIGURE 51.-Detonation Velocities of n-Heptane Vapor
in WFN A (White Fuming Nitric Acid)-Nitrogen
Gas Mixtures at Atmospheric Pressure and 400° K.
52.--Relation Between Liquid-Burning Hate
(Lar!f J-l'nol Diameter) and Ratio of Net lleat of
Comb 1 ·lion to SenMiblc Heat of \'nporizatiou.
Limits in Other Atmospheres
Th11 limits of flnmrnu.bility of ethylene, propy-
Jen£>, isobutylene, but£>rw-1, methyl l.mtene-1.
und hutndiene in vuriow; irH'rt -uir utmosphNeh
lll'"e been determined by Jones and coworkers
ModtftCld Burgt•ss·Whf!eler Law
propagatton
Constant flame temperature·· of
0
TEMPERATURE, • C
FwuRE 5:l.-Effect of Tcmpcratore on Lower Limit. of
Flammability of Ethylene in Air at Atmospheric

40
-e
30
a.
ci>
E
:>
20
... r
z
w
-'
>-
:I: 10
l:;j
0
Cst
10 20 30 50
ADDED INERT, volume-percent
FIGURE 1>4.-Limits of FlammAbility. c!
Carbon Dioxide-Air and Ethylmw-N!trogen-Air
Mixtures nt Atmospheric Pressure and 26° C.
(100, 101, 10:3), (fif,'s. M-60). The first two
figures are modifiCations of the lirnit-of-
flttrnmability diagrtuns given in the third
essenti,tlly the sunw 11s t.h11t 1•iven in tlw ettrlim·
publieution but the experirnentul
points. The other· curves were constructed
{rom originn.l, unpublished data obtained ut
the Explosives Hes. Center, :Federal Bureau of
Mines.
Other limit-of-flammability det.enninations
huve been rnnde in oxygen nnd nitrous oxide.
These du.taure included in table 8 (40, 100, 100).
Autoignition
There have been few determinations of Al'f's
of the tmsntumtcd hydroenrbons in uir or ot.her
oxidun ts; the u vniluble dultt (il1, 116, l!J 1) arc
summarized in table 9.
'FLAMMABILITY CHARACTERISTIC8 51

T
%air= 100%-% propylene-% inert
-8
c:
Ql

Ql
Q.
cb
E
Flammable
::I

6
mixtures
a.J
N2
z
UJ
_,

0
a::
4 0..
0 10 20 30 40 50
ADDED INERT, volume-percent
FIGtrRE 55.-Limits of Flammability of Propyl!'ne-Cnrbon Dioxidl'-Air and PropylC'nc-Nitrogen-'.!r Midutes at
Atmospheric Pressure and :.!6° C.
The burning velocity of ethylPne Juts been
determined in nir, oKy!!:ell, tmd
n t mospheres by n umerom; igntors (3, .'f 7,
)ii, (18, 131). In geneml, it is highPr thun tlw
huming velocities of the pnraffin hydrocarbons
tmdor the same conditions (fig. 47). Sin:ilttr
IU"e to he expected for other
hydrtiC'urbons, ulthough the availuble dat1t ure
m t.hor menger-.
Stability
:\luny unstlt,umt.l'd hydrocnrbon vapors ean
propugate tltUne iu tbe absence of uir at. elevut(•d
temperatures and pressures; that is, they have
!J(• lirrtit "f 'l.::l:"'l Tl-.
0
<0" ('"'"''··
hustibie, lllwe positive uf formati1m,
t1ll
1
(tnble 10) nnd would therefore liberate
heat if deeornposmi to the elements carbon un(i
hydrog-Pn. EvPn more heat would be lihe.r-
nted if gases with a negative heat of for-
mation - for exnr>lple, methane-form from the
elements. Tn prnctice, tl mixture of products
rl'sults upon decomposition of such combusti-
bles. For exumple, u propagnting demmpo-
r!'1tdion CUll be iuititLted in pure ethylene
Ill tl 2-mch-ID tube at 2:3° ( and pressures aR
low as 750 psig. 2 grams of guncottou.
A reuction Cllll he initlnted at 21" C and
sures us low tls 975 psig with 1 gram of
guncotton. The demmposition products tl.l'e
52 FI.AMMABn,rry CHARACTERISTICS OF COMBUSTifli.E GASES AND VAPORS
lO ---·----·-r--··-----r----·---·-·--r-·-·----,------····-·--1
%air= 100%-% isobutylene --% inert
8
Flammable
mixtures
J

0 10 20 zo 40 50
ADDED INERT, volume-percent
FIGURE 56.-Limits of FlammRbility of IRobutylene-CarbC'n Dioxide-Air and Mixturea at
Pr831!ure and :i:6° C.
TABLE 8.---Limitq vj fto.mmability of unsaturttted
hydrocarbons at atmosphero:,C room
temperature, in combustible
vapor
(L-Iuwer ilmtt; u-nppe·.- !!mil.)
I
Jn IIi::-- oxyg1.•n / In ni_trou:
OXlde
Combustible / ·- ____

Ethylel•A. ______ 2. 7 36 1 2. !l 80 I. 9 40
Propylene._____ 2. 0 11 ,2. 1 1 l. 4 29
Butene--}-------,1.6 10 I. 7. 1 -----
But{•ne-2 __ ., ___ 1.7 9.7 t7 I ao ----------
1 I -
primarily carbon, methane, and hydrogen:
approximately 30 Kcal are relc•tsed per wole ot
ethylene deeumposed. J>ropylene ytelded simi-
laT products following explosive deeomposition
durw.g compreesion to 4,860 (34).
'i'AoL'I!' U.-. .J!finirr,um autoignition temperatures
unsat?J.rr..ted hydroca.rbons a.t a.tmospkcri.c

----·---.,.----
Autoignition ten'ptJraturc
-·-------- -·,--------.. -- ---·
Combustible In R'r
I
In o::ygen
T----·--·-r---
C / °F · Ref. °C °F Uef.
---.--1----,-- ----· ----1-
Ethylenc ......... 490
1
914 (116) 485 go,') 1(116)
Propylene .. ___ ..
1
.356 ( 94) 423 1 7931 (
1
)
Butene-! ________ 31!4 723 (1) 310 i 1\90 (I)
Butene-2 .......... ,324 615 (1) ---··j·-----
l,:}.Rutadiene ...• '.118 '684 (191) 33.'i 63.'.. 1(191)
---·- I I
• l"lgures compiled by E1ploelvM kes. C.Mtor, Fedl!l'al o.
M<ne3.
Prope.diene and also decomJJose
readily under the a<'tion of powerful iguiLors.
Propadiene vapor has ber-n in a
F1 ... AJI1MABlt.lTY CHAHACTE RIB TICS 53
60
"
50
% 100%-% iso\ne-% water
\ \ .....
c:
CLl
0
40
IV
E
::I

rr.
0 30 -
a.

L&J
z:
L&J
_,
j?:

a:l
0
en
0
Flammable

20 40 60 80 100
WATER volume-percent
FmuRE 57.-Limits of Flammability of Isobutylcne-Watcr Vapor-O:::ygen Mixturl'@ at 150° C and AtmOI!perio
Prossurc .
• ..-.11<'11 ;
1
'be at 120° C am' ;;;) psig using a
piatinum wire ignitor. Decomposition of buta-
diene in an industrial accident resulted in a
"popcorn" polymer; the reaet.ion was apparently
initiated by an unstable peroxide (4).
TABLE 1 0.--HeatN of formation (Kcal/mole) of
hydrocarbons at 25° ('. ·
( 'ombustible:
Acet.y 1!-ne ________ .. __________________ .. _
Propndi1•np _. _ _ _ __________________ .. ___ _
MPthyllh1!'ty1Pnl' _______________________ _
1-3, Butndiorw ________________________ _
Ethy!Pne _______ _____________ _
-_- = = = = = = = = = = = = = = = = = = : = = = = = =:
I Rot'a. (/14, Ill$),
illlt'
54. 2
41i. !!
44, 3
26. 8
12. fi
4. 9
.3
ACET' .. '"!..El'.iC DitOCABBONS
(CnHzN-2)
Limits in Air
Acetylene forms flammable mixt-ures in air
nt atmospheric pressure nnd 25° C, in a range
from 2.5 to 100 volume-percent acetylene.
Quenched nnd limited upper limits
have been obtnined in 1-, nnd 2-, nnd :i-inch-
diameter tubes (40), but pure acetylene can
propagate flame at atmosphPric pressure in
tubes with dinmetcrs of lenst 5 inch(ls.
has summarized availu.ble duta on
init1al requirements for deflagration and
FLAMMABILITY CHARACI'ERISTICS OF COMBUSTIBLE GASES AND VAPORS
8
0
10 50
detonation through acetylene in horizontal
tubes of about .02 to 6 inches ID at 60° F. (89,
185). His curves s.re g:ven in figure 61, which
also includes an experimental point from the
data of Jones and coworkers obtained in a
vertical 2-inch-diameter tube. The existence
of this point, at o. pressure below that given by
Sargent's curve for a 2-inch tube, indicates that
this curve should be used only far horizontsl
systems. The point labeled "Industrial explo-
siOn" was reported by Miller and Penny (144)
o.nd presumably refers to a deflagration. The
third experimental point is d i s ~ u s s e d , along
with the detonation curve, in the section on
stability.
ADDED INERT, volume-percent
The effect of tempero.ture on the lower limit
of flammability was determined by White in a
2.5-cm tube with downward propagation of
flame (£22). Although the actual limit values
n.re not sa.tisfo.ctory for our purposes, thtlJ' can
be used to check the applicability of the L,fL
25
°
ratio data presented in figure 23. The White
ro.tio of lower limits nt 300° and 20° C. is
2.19/2.90 =0. 76; the corresponding ro.tio from
FIGURE 58.-Limits of Flammability of Butene-1-
Carbon Dioxide-Air and Butene-1-·Nitrogen-Air
Mixtures at Atmospheric Pressure and 26° C.
10 .-------.----,-----,----r---l
% air = 100%-% 3 methyl butene-1-% inert
FIGURE 59.-Limits of Flamma-
bility of 3 Methyl Butenc-1-
Carbon Dioxide-Air and 3
Methyl-Butcnc-1-Nitrogcn-Air
Mixtures at Atmospheric Pre!!-
sure and 26° C.
-
c:
cu
f::!
cu
Q.
cb
E
;:,
g
;:;:i-
z
w
.....
,;:)
m
....J
?.:
...
l:i:i
::!:
('I')
8
6

Flammable
mixtures
Cst
ADDED INERT, volume-percent
50
FLAMMABILI'I'l" CHARACTERISTICS 55
% air= 100%-% butadiene-% inert
FIGURE 60.-Limits of Flamma-
bility or Butadiene-Carbon
Dioxide-Air and Butadiene-
Nitrogen-Air Mixtures at At-
mospheric Pressure and 26° C.

mixtures
0
"Constant flame temperature" curve in figure
23 is O.iS. Accordingly, this figure should be
sati>'factory for u"e with acetylene. at tempera-
tures in the mnge from 20° to 300° C.
The Jm,·er limit of of methyl-
ncetylene (propyne) in air nt ntmospheric
pressure is I. i volume-percent, equnl to 0.34 C,,
which compnres fnvornbly with the vniue for
acetylene (0.:32 C,,). Upper limit im·estign-
tions hnve been conducted bv Fitzgernld (liD)
in n 2-inch tube nt 20° nnd 120° C' to determine
the low-pressurl.l limits or lowest pressures nt
which tt tlnrne will propngnte through methyl-
ncetylene vapor at these temperatures. He
found these to be !iO nnd 30 psig nt 20° nnd
120° C, respectively. In a 4-inch tube, Hnll
und Strnker (77) obttlined a !ow-pressure limit
of 43 psig nt 20° C. This indicntes thnt the
upper limit of flammability of methylacetylene
in air is probnb!y less than 100 percent at 20° C
and 1 atmosphere.
50
ADDED INERT, volurr;e-percent
The quantities of propylene required to
prevent flame propagation through methyl-
acetylene-propadiene-propy!ene mixtures at
120° C and 50 and 100 psig have been deter-
mined in l-, 2-, 4-, nnd 12-inch tubes (fig. 62),
and ut 120° C nnd 100 psig in a 24-inch sphere.
As noted, the propylene requirements are
strongly affected by tempernture, pressure, and
container size. As the tube diameter increases,
the quantity of propylene required to prevent
flume propng-nt.ion increnses; this efTect is less
pronounced in the !urger vessels {dinmetcr
grenter than 4 inches) than in the smaller
ve>:se!s (diameter less thnn 4 inches). The
results obtained in the 24-inch sphere were
similar to those in the 12-inch tube.
Limits in Other Atmospheres
G!iwitzky (71), and Jones and CO\\'Orkers
determined the efTects of carbon dio;;de and
56
FLAMMABILITY C!HARACTERISTICS OF COMBUS·riBLE GASE!:' AND VAPORS
I I I I I I
KEY
Sargent
20 -

0
Miller anrl Penny (Extrapolated)
Industrial explosion
6 Jones and others
10
s ~ ~ ~ ~ ~ ~ ~ - - - - ~ - - ~ ~ ~ ~ ~ ~ - - - - - L - ~ - - ~ ~ ~ ~
0.02 0.04 0.06 0.1 0.2 0.4 0.6 1 2 4 6 10
DIAMETER, inches
FJGUR'!!i 61.-Effect of Tnbe Diameter on Initial Pressure Requirements for Propagation of Detlagration and
Detonation Through Acetyltne Gas.
nitrogen. on the limits of acetylene in air at
atmospheric pressure and room temperature.
Unfortunately, all measurements were made in
tubes that were too narrow to give actual upper
limit data. Nevertheless, the resulting
quenched-limit data are summarized in figure
63, because they show the relative effects of
adding two inert diluents to· acetylene-air
mixtures in a 2-incb-ID tube.
Autoignition
A summ'l.l'Y of available a.utoi<>'nition tem-
perature data for acetylene, acety1ene-air, and
acetylene-oxygen mixtures in clean systems is
given in figure 64. They are based on measure-
ments by Jones and Miller (110), by Jones and
Kennedy in quartz tubes (99), and by Miller
and Penny in a 0.5-inch steel pipe, 15 inches
long (144). Jones and Miller found minimum
autoignition temperatures of 305° and 296" C
for a variety of acetylene-air and acetylene-
O:\:ygen mixtures, respeetively, nt utmospheric
pressure. Miller and Penny report little varin-
tion in the nutoigni.tion temperature of acety-
lene in a clean pipe at 4 to 26 ntmosphere!' initial
pressure. Howe\·er, the presence of 1 gram of
powdered rust, scale, kieselguhr, aluminn, silica
gel, or charcoal lowered the pipe temperature
required for ignition to a 280° to 300° C range.
The pt·esence of 1 gram of potassium hydroxide
lowered the pipe temperature still further to
170° C. The impact of a 0.25-inch steel ball
fulling ft·om a height of 15 inches against a
fragment of copper acetylide produced a bot
spot that ignited the surrounding gaseous acety-
lene at room temperature and 3 atm11spberes.
Burning Rate
The burning velocity data for acetylenC' in
nir obtained by Manton and Milliken at 1
atmosphere and room temperature are given in
fi<;urc 65 (188). The burning velocity ranges
from n low of a few centimeters per second near
the lower limit to a high of about 160 em/sec
on the rich side of the stoichiometric composi-
tion. Parker and Wolfhard (164-) have found
considerable vnriation in the burning velocity
of acct,Ylene in various oxidants. The burning
velocities in stoichiometric mixtures with oxy-
gen, nitrous oxide, nitric oxide, and nitrogen
tetroxide were found to be 900, 160, 87, and 135
ern/sec, respectively; for comparison, the burn-
ing velocity in a stoichiometric acetylene-air
mixture (fig. 65) is 130 em/sec.
FLAM:.'IABlLITY CJ IAHACTEH!STICR 57
12-inch-ID
4- inch-I D
2-inch-1 D bomb,IOOpsig
1-inch-1 D bomb,IOO psig
\
90 80 70
PROPYLENE, volume- percent
FIGURE 62.-Rangc of Flammable Mixtures for MPthylncPt.ylenc-Propudienc-Propylcuc System at 120° C und at
50 and IOU Psig.
The velocities of tu•etylene-nir rnix-
tur·es were found to be independent of pressure
between 0.1 and 1.0 nt.mospherc (138). Sim-
ilt!rly, nnd ,J-raiff (3) nnd Parker and
Wnlfhard (164) found th· l1urni:1;., \·eloeities
of stoichiometric acetylene-oxygen und a<"ety-
lenc-nit.rous oxide mixtures were independent of
;>resstH'e bet ween upproximtttely ()..'j und 2
utrnospiH•res and und 1 atmosphere, re-
sped i \·ely. The huming velo<"itics of st oi<' hio-
mct,rie u<"ctylene-nit rir. oxide und al·ct.yl!me-
tetroxide ruixturcs inerett:•ed slightly
o vrr this pressur·e range O.O:l to 1 a tmosplwr'c
(W4).
Stability
:wted, nectyll'ne <'UII propttg-ate llnme in
the ubscnee of uir (3/J, 165). The pressures
required for propugntion ut subsonic
tion) and !-lupersonie rutes (detonution) mto
the unhum<1d pls ure 1-'.'i,·en for n mnge of pipe
f
1
: ·"1tlrs
1
;crure fil (185). Veflagrution is
J:s.:usscd bdefly under Limits of Flnmrnubility;
detonation is dis<'ussed in this section.
The eun e lnheled "Dcton11.tion" in figurr
n I gi vcs the minim urn pressure required for
propngution of n det.orllltion, once imtiut.ed, in
tllhes of o.:l to 10 inches diPmeter. In pmc-
t il'e, u dt'tonut ion may be initinted directly
from n dPflu!!l'ution thut lms proJmgnted through
n r!t t ht>r ill-tlt>filll'd disttliH'C, known tlS t lie
predctonution or run-up distance. This dis-
tunee depends on t.emperttture, pressurP, t uhP
dinmeter, condition of t uhe wnlls, nnd on
ignition-soureP streng-th. For PXIllllplr, using
n fu!'led platinum win• ig"nitor, tllld Penny
58 FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS
% air = 100%-% acetylene-% Inert
0 20 40 60 80
ADDED INERT, volurr.e-percent
FIGURl. 63.-Quenchcd Limits or F!nmmnbility or
Acetyl'!nc-Cnrbon Dioxide-Air and Acetylene-
Nitrogen-Air Mix',;•rcs at Atmospheric Pressure nnd
26° C, O!:>taincd in a 2-lhch Tube.
FIGURE 64-l\.linimum Autoigni-
tion Temperatures or Accty-
len!'-Air and Acctylcne-oxyKcn
mixtures at atmospheric and
elevated pressures.

0
r:.
0
I
(144) found the predetonatien dist.ance for
acetylene in a l-inch tube to b£1 :;a feet at 51.4
psia, 22 feet nt 55.9 psia, 12 llt 73.5 psia,
and 2.8 to feet nt 294 psia initu.l pressure.
Extrnpoh1tion of these dnt11 yields the point
in figure 61 for n. very lnrge predetonution
distnnce. This point (44 psiJ. nnd l-inch diam-
eter) lies fuiriy close to the detonution curve
established hy '3nrgcnt (185). The maximum
lent.h-to-dinmeter mtios (L/D) by Snrgent
for estnblishing detontttion m ncetylene is
plotted arrninst intinl pressure in figure 66.
In tubes, hnving 11 diameter great!'r thnn those
given nlong the top of the figure nnd hawing
powerful ignitors, the LiD mtio will be less than
thn.t given by the eurve. Nevertheless, this
figure should b!l of usc in giving the outer
bound of LfD nnd the npproximntc quenching
dittmcter; u better vnluc for the quenching
dinmeter cnn be obtnined directly from figure
61.
Although pr!'detonation distunces are diffi-
cult to measure nnd cxperimentnl dnta often
exhibit much scntter, they nrc of interest in
snfety work because they can be used to evalu-
n.te the mtlximum pressures likely t.o occur in
a aystem due to cascading or pressure piling.
-This phenomenon presents a sp··dal problem
because the finul pressure achieved in a detonn.-
KEY
Oxidant Pressure Tube
Air 1 atm 131 cc quartz
Air 1 atm 200 cc quartz
Air 2 atm 200 cc quartz
Oxygen 1 atm 131 cc quartz
None 4·26 atm steel pipe
of autoignition
I
'1
:
20 40 60 80 100
ACETYLENE, volume-percent
FLAMMABILITY CHARACTERIATICS 59

?3
u
0
...J
I.IJ
>

z
z
c::
::l
CD
0
/\
; \
I \
I
10 15
volume-percent
Fm:::l'.E 65.-Burning V"locity of Mix·
tm!'S at Atmospl.cric l'r!'Ssurc and Room Tempera-
tUrC'.
tion depends on the initial pressure at the onset
of detonation. F..;r example, the maximum
pressure to be expP.cted from the deflagration
of !l.cetylene at moderate pressures is about 11
times the init,ial pressure (144); the maximum
FIGURE 66.-Maxhnum LID ratio
ltC'quirC'd for Transition of a
Deflagration to n Detonation
in Acctylcn(' Vnror nt ,.,y F
and from 10 to 70 Psia. ._,'
to be expected from a dotoDI\tion is about
50 times the initial prese'..lre. As the preRSure
eq•Jalizes e.t, ti-e spGed uf sound ill a defl.&.gra-
tion, the maximum initit\l pr63Sure to be ex-
pected upon tra11si.tic,n from defl.agration to a
aetonation is approximately 1 i times the frac-
tion of acetylene tha.t bas been burned times
the initial precombustion Fifty times
this pressure is t!lo aJ'proximate maximum
pressure that wouM be obtained when a detona-
tion occurc;. •;o illustrate thi.8, Sargen" bas
plotted the pressure ratio (P
1
/P1)
against the predetonat10n distance-to-tube
length for acetylene. A similar graph is given
in figure 67. 'To use this gr11ph, the maximum
predetonation distance to be expe-cted must
first be determined f.rom 66.
tance divided by th6 tube length gives the
maximum final-to-initial pressure ratio.
AROMATIC HYDROCARBONS
(CftHh-e)
Limits in Air
The combustibles considered in this section
are listed in tf!-ble 11, with pertinent properties.
At atmosphenc pressure and room temperature,
the limits of flr..mmability or the aromatic
hydrocarbons are approximately 50± 2 mg/1
(0.050± 0.002 oz combustible vapor per cubic
foot of nir).
The lower limit of toluene was determined
by Zabetakis and coworkers in air o.t 30°,
QUENCHING DIAMETER, inches
2 1
INITIAL PRESSURE, psia
60 FLAMMABILITY CHARACTERISTICS OF • GASES AND VAPORS
TAm.E 11.-Properties selected aromatic hydroca.rbons
I
I
I -""'"':""-------
Lowpr limit in air I Up(l('r limit in nir I
j C,, in net tlll,
I M
1<\mnula
---------·---l----1----------------
lll'tlZI'IH' _ ..
1
Celie I 7S. II :.!. tHl 2. 72 '757. 5,1. 0. 4R 1 47 7. !l 2. fl :wo
Toh•,.m·_____ _ C711, !l2.t:i !i.ISI 2.27 not.5 !.:.! .5:31 50 7.1 :1.1 :110
o-X\·lt•rw.. _ C,ll
10
IOH.Jti 1.\lti !04!i.!l 1.1 .ali 5:1 li.4 :1.:1 :l:.!O
EthvllwnzPIH" 1 (',1! 10 lfl(J. lH :l.lj7 I. !Hi 1 10-tS. S ' I. 0 . !it 4S fi. 7 :!. 41 :i40
m-Xvlt·ru· . ____ -I C,H10 lOti. )(i li7 I. \Hi 110-tll. 5 I. I . !i61 !i:l ti. 1 I :l. :l :320
p-X;·!I'llt•___ C8H10 106. lti :l.li7 l. !Hi 1045. 7 I. I !iii !i:l li. li :!. 41 :!40
<'umPnt•____ C.H
11
t:.W.I\1 4.15 1.7'2
1
11\l.j.:.! .S·" .ill 4S fi.!l
1
:l.S :!70
p-C:_vml'nl'. _ ::: _ · c!OB,. 134. 21 1 4. ti3 1. sa 1341. s . s5 . li6
1
51 u. 5 a. o aso
I Ref. (f47),
-- -r----·--- ......T __
T
FIOt'RE ti7.--Finnl-to-Jnitinl l'rl'f<-
I!Urt· Hat ios Vt•\'PiopNI h,v At•l't-
vh•m• With ll"lounti:m Inilill-
i.ion at \' Points A lung u
Tuol'.
300
200

100 -
........_ ___ __._ ____ _,__ ____ ...._ _______ ._L ___ _j
0 0.2 0.4 0.6 08 1 0
100°, and 200° (: (28/i, 247); thr in
lower limit with tempemture is givrn hy t•quu-
tions (:H) and deri\·ctl for pnmfJin hydro-
carbons, und I he curves of iig11re
2a. For exurnple, r/ /.J,,. <' wus found to hr
1.07/1.24 or· O.Hii; the mtiu predid1•d by
1
ht•
curve in figure is O.S7.
The UJIJWI' limits of tht• nro:unti•·s l'onsidPrt>d
hert> ut ltl0° (' nrP irwllldt•d in tuhlt• II L.?;/1
Thrsr Wt'ff' obtuiiH•d tllruosplu•ric prps.;un•
in 11. 2-irwh-dianH•IPr tuh!', opt'il nt ont• Pnd.
ButlPr urul Wehh ohlttirwd upprr lirrul dutuon
n •·uwmPrl'ittl grudt• t'llllll'lll' pl'l t'llllll'r'el
iii llif Ill dP\'Ilted ft'IIIJH'I'IIIllfi'S nlld llllllO!-l(liH•J'JI'
1llld nt! in 11 closed bout h (.1 1).
PREDETONATION DISTANCE/ TUBE LfNGTH
Tht>ir valut•s fllllg'f' S.S pl'l'l'f'll I C'lillH'Ilf'
(H0° (' und utlll••sphl'ric Jll't•ssurt•) '" IO.S JH'f··
Cf'lll I'Uilll'llt' (J-tti'' {' 1111d ]()f) psig; jli'PASUI'!').
Limits in Other Atmospheres
Tlw of tlamlltuhilit,· nl:iaint•d bv Bnr-
(i.'l) nnd h,v .. f,Hif''. (.)0) for J,,;IIZ''IIP-
.. Ilrhnu tlioxidf'-nir 1111d hi'IIZP!ll'-llit rogl'll··aiJ·
111ixt Ill llfiiiiiS(lhPI'II' lllld :!!">
0
(' 111'1•
g"i\1'11 i11 fig-urf' tiS; sitnilur dnlt: !11'1' j.!'l\'1'11 for
tilt• ln;;t two mixturPs ut • fli'i•s,;urP
und ltl0° ( '. Th1• i1u•rtiugo I'PI(IIIl't'IIH'IIIs 111 :,!;,"
\' ttl'!' appr·nxirnutPiy t liP ,;an11• 11-1 tltn:'l' nf 11-
lrt•xtllll' ;):!). Agulll, it 1-iholllcl rH' llotl'd
FLAM:MABILl'l'Y CHARACTERISTICS 61

% air= 100%-% benzene-% inert
.....
t::
Q)
(,J
8.
cb
8
E 6
:::1


0
0..
<(
>
LIJ
z
LIJ
N
z
UJ
Ill
'
'
'
'
0 10 20 30 40 50
ADDED INERT, volume-percent
1-'IOt'l\t: of Flnrnmnbilitv of Benzene-Methyl Bromide-Air Mixtnrea at 25° C and Benzene-Carbon
Dioxid<•-Air and Benzt•ne-Nitrogen .. Air Mixtures at 25° and 150° C and Atmospheric PreaeurP.
tb!lt the methyl bromide dnta Kre unt CDnsistent
with thos(;, obtnirwd by Hili {C'ornptlre figt-J. 28
and :1:l). Thest• l11.tter dntu (84) wer·e used to
eonstru<'l the nppmxirnnte (broken) tlllntll11l-
bility c·un·es for tht' hl'llZI.'ne-mt'thyl bromide-
uir !'1\'st.em.
Tfw de<·reasf.' in the minimum require-
rn£>nts fnr fllllllt' propuglltion (from
voiUIIH'-pPrC'ent ut 25° ('to};{ l±O:J ''olumt'-
IH'I'l'Nlt ut 150') iu 11 c11rhon dio.xide-nir ntrnos-
phere; from ! 1.4 :tO.:i ,·olume-
1
Jei"<'<'nt ut 25°
(' to J(J.l :± 0 :) volumP-Jli'J'<'<•nt 11t 150° in u
ttt.moHphNt') ill witltin t ht• l'llllfrt>
f
>rt><lil' hy t h <' mml ifif•tl W ht>t•lt>r
uw (equn1ion (:lr>), fiJ!. :,?;{).
Tht• linutR of flumlllllhilit \' of urt hoxvJ(,Ilt'
((

• (< pt•roxide · Joix-
turl'!:l wt•rt• cktHIIIIBNI 111 l.'i4" (' und 1 tilllln!l-
ph••rt> hv :\fIll' I illdill, und
U-V>). 'thf• dtilll nrr in
n triungulur plot in figure 119; <·om positions are
expressed in mole-percent as in the original
Thif· system has no low.er limit,
mixtures, as a fhune can he initiated in hydrogen
peroxide vapors (186). As a 90-weight-percent
hydrogen peroxide was actually used to obtain
theRe flammability d11ta, all eompos1tions were
rtlleulated to yield ,·ulues on a 100-percent
pen•xide content. This could be done
bocauf!e only three cemponents are consid-
(lred. Wht're four c·ornponents are r.onsidered,
the flummnhility t.iatn cnn be presented in a
thr('le-dimen!lionul plot; if two of the eompo-
flt•niR in fixed proportions, t\ triungular
plot <'ltn be URtld with the two components (for
t'.XIIIl.lple, 90-wt•iKht·perc·ent hydrogen peroxide)
eonRuiered as a ('.omponent. "
plot is pr('IKt>J\ted in figurt• iO lor 90-weigbt-
flPI'C'l'lll hvdrogt111 peroxide-ort.hoxylene-formie
ndd (H('(){H{} 1\t 1.'14° (' 111Hl I "atmosphert>.
This was l'onsidered to he " plane in a regular
tetrahedron in the originlil art.icle and is there-
62 FLAMI.\fABILlTY CHARACTERISTICS U!• CvMDUSTIBLE GASES AND V .u'OnS
Composition line formed with
82.6 mole % (90 wt %)

FrouRm 69.--Limita of Flammability of H
1
0rC,H,. (CH
3
),-H
1
0 at 154° C and 1 Atmosphere Pr61111ure.
fore not 11. regular triangle. As before, onl,r an
upper limit curve is given because 90-welght-
percent hydrogen peroxide is flammable. In
addition, a calculated curve based on Le Chate-
lier's rule is given, as is the upper limit curve
obtained wit.h decomposed peroxide.
Decomposition of the peroxide lowers the
limit appreciably and yields a system winch
has a lower limit of flammability (not deter-
mined in this study).
Autoiqnition
The minimum autoignition temperatures of
a series of aromatic hydrocarbons in air at
atmosplJeric yressure are given in figure 71 as
a function o the correlation parameter L.,.
This parameter was determined by use of
equation (49), treating the benzene ring as a
-CHa group ($,41). When the benzene ring
contains two side groups, L.,. is determined
first for the side group that yie!ds the largest
average value and to this is added or Y.
of the average chain length of the second side
group; and X correspond to the ortho-,
meta-, and para-positions, respectively). Th,.
data again fait into high- and low-temperature
regions (fig. 43).
Burning Rate
Burning rates and detonation velocities of
benzem1 in air and oxygen appear to be ap-
proximately the same as those of the higher
paraffin hydrocarbons. For example, the re-
sults of Golovina and ($11) show
that the maximum burning velocities of benzene
in nitrogen-oxygen mixtures range from about
FLAMMABILITY CHARACTERISTICS
...
6
I
I
..
100 80 60 40 20 0
90 wel1ht-percent H
2
0
2
, mole-percent
F1o uu 70.-Limits of Flammability of 90- Weight-Percent H
1
0rC
1
Ht . ( CH
1
) rH COOH at 154,° C and 1 A tmoephere
Pr8118ure.
295 em/sec in oxygen to 45 em/sec in air; the
maximum burning velocities of hexane in
v&rious nitrogen-oxygen mixtures range from
about 260 em/sec in oxygen to 40 em/sec in
air. Similarly, Fraser (6l) found the maximum
detonation velocities of benzene and n··octane
i11 oxygen to be 2,510 and 2,540 m/see,
respectively.
ALICYCUC HYDROCARBONS
(C"Hh)
Limits in Air
A tmmmary of the pertinent properties of
:some of the membel'H of the serieti is given in
table 12. The lower limits of flammability in
air at atmospheric pressure and room tempera-
ture fall in the range from 48±3mg/l (.048
± .003 oz combustible per cubic foot of air).
By volume, this is equivalent to u.pproximately
0.55 C,., which is the same as for paraffin
hydrocarbons. The ratio of the upper limit
t.o G,, appears to increase with molecular
weight.
According to Jones (40), the lower limit of
cyclohexane in air at atmospheric pressure and
26° C determined in a 2.0-inch tube is 1.26
volume-percent. Under the same conditions,
and Neale (SB) found the lower limit
to be 1.34 volume-percent, using a 2.5-inch
tube. Matson and Dufour (141) found the
64 FLA.M:M..Um .. tTY CHARACTZR.l8TIC8 OF COidBUBTlBL& GAt:iES AND VAP(Il'S
(.)

L£I
a:
::;)

0::
L&J
r.L.
2:
UJ

z
0
E
z


::;)
<

::;)
:E
z
:i
575
525
475
425
375
0 1
-- ..
I
-l
FroUBII 71.-Minimum Autolgnitlon Tsmperaturee of Aromatic Hydrocarbol1.8 in Air 8ll a Function of Correhlt.lon
Parameter L. ••·
TABLE J.2.-Properlus of selected alicyclic hydrocarbons
Combllltlble Formula
CyelogropanP .• ___ .... ___
CaH•--
Cydo VIIID<' •.•..... --- c,u,_.: ::. :::
........... CoH1, ••••...•
Cyclo •anc ... _ . . . . . Coli 11- ••........
• c,u,. .......
... I •
E!hylcyclo ntanP. . Crlllf .......
Cal! II--- .....
• Calculated value.
s P•0.6 atm.
•1-130" c.
I
M
42. 0!1 '
116.10
70.13
114.16
114.10
98.18
1111.11!
g(j,IM
112 21

c •.
In air
(vol pet)
------
1.4& 4. 45
1. U4 3. 37
2. 42 2. 72
2. 91 2. 27
2. 91 2. 27
3. 39 1.116
3. 39 1.116
3.39 1.116
I. 71 I. 71
lower limit to be 1.12 volume-percent ut 21° C
in a 12-inch diameter chamber about 15 inches
long: however, there iH evidence that they did
not use the BIUne criteria of flammability as did
the other only one ob:lervu.tion window
was provided at the top of a rather squatty
chamber, whereas with the tubes used by
Jones and by Burgoyne and Neale the flame
could bP observed along the entire tube. Ac-
l.ower limit In air Upper Umlt In air
Nett.H,
(!:!) Lu Lu L u .. u
(vol
c ••

Ref. (vol Uu

Ref.
pet) pet) c ••
-----------------
4M 2. 4 I O.M 46 (107) 10.4 2.3 220 (107)
1600 1.1! .&6 46 (I)
-------· -------- -------- ------
740.1! .M 48 (I)
---
... "3."4 --- ----
I!KI. 7 . 67 49 (40) 7. s 320
I KilO 1.2 .63 46 I (,0) 7. 7 3.4 310 (,0
I Hrl4 1.1 .&6
491
(I) 6. 7 3.t 310 (I)
1026.0 1.1
. &61
49 (40) 6. 7 3.4 3111 (I)
1032.6 1.1 .116 49 {40) 16.7 3. f 310 (40)
1173. 7
'·us .611 tll UO) •e.e 3.9 360 (40)
cordingly, the data of Jones and of Burgoyne
and eale are used here.
Limits in Other Atmospheres
The limits of flammability of cyclopropane-
carbon dioxide-air, cyclopropane-nitrogen-air,
and cyclopropa.nc-helium-a.ir mixtures at 25° C
and atmospheric pressure are given in figure
FLAMl!4ABILl'I'Y CHARACTERIBTIOS

%air= 100%-% cyclopropane-% inert
FIGURE 72.--Limits or Flammr.-
bility of Cyclopropane-Carbon
Dioxide-Air, Cyclopropar.r.-Ni-
troi('n-Air, and Cyclopropli\ne-
Hdimn-Air Mi::<turcs at. 25°
C and Atmospheric Pressure.
flammable
mixtures
0
72 U06). 'rhe first two curves are similar to
th(lse obtained with !lRraffin hydrocaroons (fig.
35).
Thfl limits of flammability of cyclopropane-
helium-oxygen and cyclopropane-nitrous oxide-
oxygen mixtures at 25° C and atmospheric proo-
s.tre are given in n (106). The latter
curv11 tiiffcrs from the former, as b11!h Rdditivoo
are oxidants (Qxygen and nitrous oxide).
The limits of flaroma'bility of cydopropane-
heliunH;itrous oxide mixt.ures o.t 25° ( ttnd
atmospheric pressure are gh·en in figure 74 (JOfJ).
Here the minimum oxidant. concentration
(nitrous oxide) required for flame propagation
is approximately twice the corresponding con-
centration o£ oxygen in the system!! cyclo-
propane--helium-air (fig. 7Q) and cyclopropane-
holium-oxygtm (fig. 73).
ADDED INERT, volume-percent
ALCOHOLS {C .. H:. .. +tOH)
Limits in Air
50
The alcohols considered here are listed in
table 13 together with and Uno. The
ratios L
31
o/C,, are approximately 0.5. How-
ever, the L (mgfl) values decrease with increase
in molecular weight. If L* is taken to be the
weight of combustible material (exclusive of the
oxygen in the moleculfl) per liter of air, then for
the simple alcohols:
M-16
L*=L-M-· <54>
This eq_uation gives the valueR listed in
theses 1n the mgfl column; these are m fall'
agreement with the values obtained for the
66 FLAMMABILITY CHARACTERISTICS OF COMBUSTiBLE OASES AND VAPORS
50

% oKygen • 100%-% cyclopropane-(% He, or N20l
Flammable

NITROGEN OR NITROUS OXIDE, volume-percent
FIOURII 73.-Limits of Flammability of Cyclopropane-
Bellum-Oxygen and Cyclopropane-Nitrous Oxide-
Oxygen Mixtures at 26° C and Atmoepheric Pressure.

HELIUM. volume-percent
FIOURII 74.-Llmite of Flammability of Qyclopropane-
llellum-Nitroue Oxide Mixtures at 26° C Rnd Atmos-
pheric PreBBure.
saturated hydroc&.rbons. Approximate L (mg/
I) values can be obtained from the higher
hydrocarbon values given in figure 22 by
multiplying these by the ratio M/(M-16).
Further, figure 19 can be used to obtain L• and
L values in volume-percent. For example, at
26° C, L• is about 47 mg/1 from figure 22; the
corresponding from figure 19 for ethyl
alcohol (M=46) is 2.2 volume-percent. Then,
from equation (54), Lis 3.4 volume-percent; the
measured value is 3.3 volume-porcent.
The lower limits of methylakohol have been
determined by Scott and at 25 °, 100°,
and 200° 0 (192;. The values at these three
temperatures are 6.7 6.5, a.nd 5.9 volume-per-
cent, The calculated values ob-
tained from the modified Burgess-Wheeler law
(fig. 23) at 100° and 200° 0 are 6.4 and 5.8
volume-percent, respectively.
Limits in Other Atmospheres
The limit-s of flammability of methyl alcohol-
carbon dioxide-air and metnyl alcohol-nitrogen-
air mixtures at atmospheric pressure and 25°
and 50° C are given in figure 75; flammability
determinations on mixtures containing more
than 15 /crc6nt methyl alcohol vapor were
conducte at r,oo C. The maximum amounts
of carbon dioxide and nitrogen required to
prevent flame propagation in these mixtures
l
---,--- -r---

"
% air:: 100%-% methyl alcohol-% inert
,,
,,
,',
\ \
25
\ '
\ \

\ ',
\ \
\ '
\ ',
Flammable \ ' Saturated at
mixtures 25" C and 1 atm _
10
l
0
ADDED INERT, volume-percent
FIGURE 75.-Limits or Flammability of Methyl Alcohol-
Carbon Dioxide-Air and Methyl Alcohol-Nitrogl'n-
Air Mixtures at 25° C and Atmospheric Pressure.
(Broken curve at 50° C and atmospheric pretl8ur('.)
FLAMMABIJ,ITY CHARACTERISTIC8 67
TABLE 13.-Properties of selected 8imple alcohold
Combustible
Methyl alcohol.. .........
Ethyl alcohoL ...........
n·Propyl alcohol.. .......
n·Buty: alcohol ..........
prl·n·Amyl alcohol.. .....
n·Hezyl alcohol.. ..... _. _
•L••LM-16,
M
•t-60°,
Formula
CH10H .........
Col110H ........
CIH!OH ........
CoHtOH .........
C1HuOH .......
ColluOH .......
'At saturation teruparature.
M
82.04
48.07
60.09
74.12
88.16
102.17

c,,
In air
(VOl pet)
------
1.11 12. :m
I. 69 6.68
2.07 4. 46
2. 66 3.87
3.04 2.72
3. 68 2.21
were compared with the corresponding maxima
for paraffin hydrocarbons (figs. 28-35); it was
found that appreciably more inert is required to
make mixtures contaming methyl alcohol non-
flammable. Conversely, methyl alcohol re-
quires less oxygen to form flammable mi"tures,
at a given temperature and pressure, than paraf-
fin hydrocarbom do. This may be due in part
to the oxygen of the alcoho.l molecule. For the
simple alcohols, we have:

(n+ J)H
2
0. (55)
Thus, the ratio of oxygen required for complete
combustion of an alcohol to that for complete
combustion of the corresponding paraffin,
equation (22), 1s:

a, 3n+I
(56)
When n=l, this ratio is 0.75. The correspond-
ing ratios of the experimental minimum oxygen
values from figures 75 and 28 are 0.82 with
carbon dioxide and 0.85 with nitrogen as inert.
The limits of flammability of methyl alcohol-
water vapor-air were obtained by Scott (191!)
in a 2-inch-ID cylindrical tube at 100° and
200" C and in a '4.9-liter cylindrical bomb at
400° C and 1 a.tmosphere (fig. 76). Similar
data were obtained by Dvorak and Reiser in a
2.2-liter apparatus at 100° C (53).
The limits of flammability of ethyi alcohol-
carbon dioxide-air and ethyl alcohol-nitrogen-
air mixtures were obtained at 25° C and
atmospheric, or one-half atmosphere, pressure as
noted (fig. 77), Additional flammabilitv data,
obtained for ethyl alcohol at 100u C ·and I
atmosphere are given in figure 78. Flammabil-
Lower limit In lllr Upper llmltln air
Net.).TI,
--·
(!:;) Lu
Lso
L u ..
u.
u
(VOl
(y)
Ref. (Vol
'!!!!)
Ref.
pet) pet) c.,
(I.
-------------·----
IIIII 6. 7
o. &6 i
108
} (40) 13tJ
"!
}(116
I 62 14()6
306 3.3 .1!0
70
} (40)

2.9
480
'46 1310
12.2
.4V i
60
} (40) 114 8. 2
400
(4/}
'"
1310
696 11.7 .110
67
} (') •12 .. -- .
(I)
'46
------·-
742 11.4 .61 {
116
} (I)
......
'46
........ 1 ....
•888 1.2 .63 {
66
} (1)
'48
•U•••••• •••••
•t-too• c.
• Figures compUed by E.QJioelvee RA. Center, Federal Bureau ot
Mines.
• Calculated value.
0 20 50
WATER VAPOR, volume.,.rcent
FIGURE 76.-Limits of Flammability of Methyl Alcohol-
Water Vapor-Air Mixtures at 100°, 200°, and 400° C
and Atmospheric Pressure.
ity data for the syst,ems tert-butyl alcohol-
carbon dioxide-(lxygen and 2-ethylbutanol-
nitrogen-oxygen are given in figures 79-81.
Autoiqnition
The minimum autoignition temperatures in
air and oxygen of a number of alcohols at
atmospheric pressure are given in appendix A.
Comparison of these values with those of the
corresponding paraffins (methyl alcohol and
methane; ethyl alcohol 11.nd ethane, ate.),
shows that the AIT values of the alcohols are
ger.erally lower.
68 FLAMMABILITY CH.ARAC'rERISTICS OF COMBUSTIBLE OASES AND VAPORS
20
%air • 100911-% ethyl alcohol-% Inert
"'
,,
,,0
'"
b. "'., 0
lt...q_ ........
Flommable ....,_ '
mh<lures .._ ......_ , No
C$1 COz / "'< ....._

ADDED INERT, volume-percent
F10un 77.-Limite of Flamrnabllltv of Ethyl Alcohol-
Carbon Dioxide-Air and Ethyl Alcohol-Nitrogen-Air
Mixturee at 25° C and Atmospheric Pressure.
(Broken curves at one-half atmosphere.)

$fi air= 1009£-9£ ethyl alcohol-% water
0 10 20 40
WATER VAPOR, volume percent
Fiouu 78.-Limitll of Flammability of Ethyl Alcohol-
Water Vapor-Air Mixtures at 100°C and Atmospheric

Burning Rate
The burning velocities of methyl and iso-
propyl alcohol in air were determined by Gibbs
and Calcote for u. range of mixture compositions
at 25° C; the maximum burning velocities were
found to be 50.4 and 41.4 em/sec, respectively
(68). These investigators also obtamed the
burning velocities of methyl and n-propyl alco-
%air • 100%-% alcohol-% water vapor
0
10 20 30 40
WATER VAPOR, volume-percent
FJGURII 79.-Limite of Flammability of tert-Butyl
Alcohol-Water Vapor-Air Mixtures at 150° C and
Atmoepheric Preseure.
60.-----,------.
%oxygen= 100% -% alcohol-% C02
0 20 40 60
CARBON DIOXIDE, 110tume-percent
FloURIII 80.-Limite of Flammability of lert-Butyl
Alcohol-Carbon Dioxide-Oxygen Mixtur!'l! at lli0° C
and Atmospheric Pressure.
hoi at 100° C; the maximum values were 72.2
and 64.8 em/sec., respectively. These values
FLA.MMABl'Lri'Y CHAR/ r.TESIS'l'ICB 69
60
• nltroll'n
Fl•mm"ble MIC'l
mllrt\<rtl 9.3"' \
\
\
0 20 40 60
NITROC.EN, 110lume-percent
\
FlGURil 81.-Limits of Flammabnlty of 2-Ethyl-
butanol-Nitrogen-Oxygen Mixtilree at 150° C· and
Atmospheric Pressure.
are in fair agreement with the corresponding
values uf the paraffin hydrocarbons.
The methyl alcohol hquid-burning rate ob-
tained from equation (53) is in fair agreement
with the.t obtained experiment.alll (fig. 52).
The relatively low tJI,jAH. ratios .or the alco-
hols indica.tes that they should be characterized
by low-burning rates in largo pools.
ETHERS (C,H21&+10C,.H2wo+l)
Limits in Air
The properties of a few common ethers s.re
listed in table 14. Unfortunately, the limits
data show appreciable scatter, so it i3 difficult
to establish any general rules with the given
data. However, as a first approximat.ion, the
Ltft/G., is about 0.5 for the simple ethers.
Limits in Other Atmosphereo
of the importance of ethers as anes-
thetics, lunits of flammability were determined
in several atmospheres. The limits of the sys-
tems dimethyl ethil!lr-Freon-12 (CCI
2
F
2
)-air
dimethyl ether-carbon dioxide-air, and dimethyl
ether-rutrogen-air obtained by Jones and co-
workers are given in figure 82 (114); the
limits of the diethyl di-
oxide-air and diethyl ether-nitrogen-air are
given in figure 83 (£6, 1W, 108), Cool flames
exist above the upper limit as noted; the upper
40 ·---r----T--....----..-
!C air"' 100%-% ether-% Inert
0 50
ADDED INERT, volurn•percent
Frouu 82.-I.Imits of Flammability of Dimethyl Ether-
Cart>on Dioxide-Air and Dimethyl Ether-Nitrogen-
Air Mixtures at 25° C and Atmoapht.'ric PreBBure.
40
0
% air= 100%-% ether-% in--t
Flammable
mixtllres
Cool flames
10 20 30 40
ADDED INERT, •
FIOURE 83.--Limits Qf Flammability of Dfethyl Ether-
Carbon Dioxide-Air and Diethyl Et.her-Nitrogen-Air
Mixtures at 25° C and Atmospheric PreBBure.
!imit of the cool flame region in air is 48.4 vol-
ume-percent, according to Burgoyne and Neale
(£6). 'rhe limits of the systems diethyl ether-
helium-oxygen and diethyl ether-nitrous oxide-
oxygen are given in 84 and the limits of
diethyl ether-heliv.m-mtrous oxide are given in
figure 85 (106). Again, as with the alcohols
more inert is needed to assure the formation ol
nonflammable mixtures than is needed Cor the
corresponding paraffin hydror.nrbons. Also,
cool flames are encountered at lower tempera-
tures and pressures.
Comparison of curves in figures 84 and 85
shows that the minimum oxidant requirement
for tlw formation of flammable diethyl ether-
helium-oxidtlllt mixtures is approximately twice
70 FLAMMABILITY CHARACTERISTICS OF' COMBUSTIBLE GASES AND VAPORS
TABLE 14.-.Properties of selected ethers
CombusUblft
lmethyl ether .•.••..••.
letllyl ether •• __ ... __ ...
D
D
E
D
D
thy! propyl ether .......
l-1-propyt ether .........
I vinyl ether .............
M-16
'L"•L -xr- ·
Formula
CH10CH1 ......
c1H1oc,H1-----
C1H10CaHr •....
c1n,oc1Hr .....
c1H1oc1R1.-- ..
• Cool ftamea: Ua••63 vol pot.
100
M (lf.!t)
---
46.07 1.60
74. 12 2. 66
88.16 3. 28
102.17 3. 15.1
70.00
%02 = 100%-% diethyl ether-(% He or N20l
'E
II

!.
..
E

a:'
....
:c
t;;
..J
>-
:c
t;;
i5
0 20
HELIUM OR NITROUS OXIDE, volume-percent
I
c ..
In air
(val pet)
---·
6.83
3.37
2. 72
2. 71
4. 02
100
FIGURE 84.-I.imits of Flammal•iiity of Diethyl Ether-
Helium-Oxygen and Diethyl Ether-Nitrous Oxide-
Oxygen Mixtures at 25° C and Atmospheric Pressure.
as great with nitrous oxide as with oxygen.
However, if 1 mole of nitrouR oxide furnishes
one-half mole of oxygen during combustion,
then the minimum oxygen contents in the two
cases are nearly equal. Unfortunately, the
available data are too meager to permit a more
detailed comparison.
Autoignition
In generv 1, ethers are readily ignited by hot
surfaces. These combustibles usuall;Y have a
lower ignition temperature in air and m oxygen
than do the und
alcohols. The available al'tmgmtion tempt'ra-
ture data are included in ap!J"·ndix A.
Lower limit In IUr
Net t;.ll,
------
(Kcal)
mole
Ln Lu L
(vol
c •.
(o/)
Ref.
pet)
------ ---------
lil6 3.4 0. 62 {
72
} IU
I 47
1m 1.9 '66 {
64
}
II\()
1760 1.7
liS
} (18)
136
•ooo 1.4 '67
60
} (40)
I 61 M l
I I, 770 1.7 '42 (117)
I
1 Calculated value.
• Cool names: U11>l6 vol pet.
I Ref. (/66),
limit In air
----
r!u
u ..
u
(val
c .•

pet)
--------
71
4. I 760
'36
II 1,880
.
3. 3 800
7 .. Q
3. 6 290
71
6. 7 I, \60
------,----------r--· -----,-----
c
% NzO = 100%-% diethy! ether-% He
...
l:'!
<1>
0.
<i>
E
:::>
0
>
o::'
w
J:
1-
w
...J
>
J:
1-
w
c
0 20 40
HELIUM, volume-percent
Ref.
(1/4)
(40)
(IB)
(40)
(91)
80
FIGURE 85.-I.imits of Flammahility of Diethyl Ether-
Nitrous Oxide-Helium Mixtures at 25° C and At-
mospheric Pressure.
Since the ethers tend to form peroxides under
11 variety of conditions, they appear to be
unstable at room temperature (233).
The properties of several esters are listed in
table 15. The ratio of the lower limit at 25° C
to the stoichiometric concentration is about 0.55
for many of these compounds. This is the
same ratio as in equatiOn (21) for paraffin
hvdrocarbons. The lower limit values ex-
pressed in terms of the weight of combustible
per liter ef a.ir (see section about alcohols) are
li!'tt'd in parer theseG under L(mg/1). These are
larger than the corresponding values for the
hydrocnrbons and alcohols. The inert require-
rnt'nts and minimum (,xygen requirements for
the fir:.;t memht'r of the series, methyl formate,
nrP rwt>.rly t lw snme as for methyl alcohol and
dinl('thyl ether (figs. 76, H2, 86). This is not
FLAMMABILITY CHAHACTElUSTICS 71
TABU of selected esters
Comhusllblo Formula
-------·--- -------
Methyl lornmtt• .. ___ .. IICOOCII, .••..
Ethyl lormutt• ... .,l!COO<'all! .... ---
n-llutyl lormuto ... .. II C'OOC,IIo .....
---·
Mcthylllct•tn,e ..... ___ .
Ethyl Be<>tate_ .• _ .
n-l'ropyl ........
n-llutyl acetate ...... _ ...
II·Amyl acetate .... _ ... _ ..
Methyl propionate.
-----
Ethyl propionate .. ____ . __
I


M
• Calculated value.
I 1=00° C.
C'lhC'OOC'Ih ...
CJ!,COOC'al" ..
C'lhCOOCall? •.
C'lhf'OOC',IIt ..
Ci!,CQOC,llu.
CelloCOOC'Ih ..
c,u,cooc,n,.
Ap. gr. c ..
M (Air-1) In ulr
(vol pet)
---·---- -----
60.06 2. 07 u. 48
74.08 2. btl 6.
a. !13 3.12
7oi.OK 2.110 66
88.10 3. 04 4. 02
102.13 3. !13 3.12
116.1tl 4.01 2.M
130.18 4. btl 2.16
88.10 3.04 4. 02
102.13 3!13 3.12
true of the othe;.· ml'rnbers for which data
at the Explosives Rese1\rch Center are
available--isobutyl forrnat.e und methvl ncetate
(figs. 87, 88). Accordingly, it is rather difficult
to make additional generalizations for this series.
limit In air Upper limit In air
Net AU,
----.-------

J.,.

L Uu
u ..
[!
(vol
<"'n
Rei. (vol

Hel.
pet)
c,,
pet)
r.,,
---
----·---- --- ------- --
219 6.0 0.!13
I 142
}<til) :13.0 2. 4 HOO (1//
\ 100
367 2. M .110

U6
l (40) 16.0 2.8 630 (40
1M
'660 1.7 .64
7U
l (40) H. 2 2.6 410 qo
1110
31>!! 3. 2 . {
106
(40)
16.0 2. H 630 <40
160
2 71
1104 2. 2 .

88
<m
11.0 610 (176
1110
1611(1 l.h .I>!!
M3
} qo> • 8.0 2.6 400 qo
I 67
• s.o I '1.4
.M {
73
l (I) 3.1 4110 (') ---------- 163
'1.0
:]1
66
} (I) 17.1 3.3 440 (I)
---------- I 49
2 .•
97 )
13.0
'3. 21
1180 (40
···-······ 162 (40)
'6110 1. 8
(40)1
11.0 '3. 6 (4n
• t-100° c.
• by Explosives Hes. Center, Federal Bureau of Mines.
•P•0.6atm.
The auto ignition temperatures of many esters
in air nnd oxygen at atmospheric pressure are
givPn in appendix A. In general, the AIT
valuE's of the esters are lower than are those of
the corresponding paraffins.
% air= 100%-% methyl formate-% inert
FIGURE 86.-Limits of Flamma-
bility of !\I ethyl Format-e--Carbon
Dioxirle-Air and Methyl Formate-
Nitrogen-Air Mixtures.
Flammable
mixtures
5
0 50
ADDED INERT, volume·percent
/2 JI'L.\MMAB!l.lTY Cl!JiRAM'E!U8TICf\ OF' COMBUS'l'IBLE OA8tt'l ANI> Vllf'ORI!I
Frou .. 87.--Limtt.e of Jt1.u:cmab!l-
lty of llobutvl
Dlo'ldde-Alr and Ieabut.yl For-
Millturee.
Frouu 88.-Llmlt" o! Flammabll·
lty of Methyl Aoetate-Carbon
Dloldd&-Air and Mllthyl
Nlt.ropn-Air Mlnuree.
10
8
l
0
Flammabll!
mixtures
10 20 30
ADDED INERT, volume-percent
L _I
40 50
--r-----,------.
% air= 100%-% methyl acetate-% inert

0 10 20 30 40 50
ADDED .INERT, volume-percent
FLAMMABILITY CHAitACTERISTICB 73
<' 0 · ·- r· ·- ·· 1 ·- - r·- - · 1 ···---,--- · -.-·· ·· --,---,-- --.-- --·- ·r··--·--r-·--·r---r-···- T ------,------T---,--
flammable m1dures
E
1.8
<1>


E
"
·c;
70.5 mole % MEK + 29.5 mole % toluene
,.
ci
0

<
>
.....
14
....
---
Ill

35.6 mole % MEK + 64.4 mole % toluene
(/)
:::1
al

0
:::-Expenmental
u
12
--- Calculated
Toluene
--
1.0
20 40 60 80 100 120 140 160 180 200
TEMPERATURE. "C
Fmuu 89.-Effect of Temperature on Lowar Limits of Flammebility of MEK-Toluene Mixturee ln Alr at
Atmospheric Preesure.
Pro\)E>rties of some aldehydes and ketones are
given m table 16. The ntio of the lower limit
at 25° C hair to the stoichiometric composition
if, 11pproximately 0.5.
Zabt>takis, Cooper, and Furno found that the
lower limits of met byl ethyl ketone (MEK) and
mixtures vary linearly with
temperature between room temperature lind
2tl0 C (£15;. A summary of these data is
given in figure 89; broken curves in this figure
were obtamed from the modified Burgess-
Wheeler r'luation (33), taking the lower
limit at 100° C a.s the reference value. Similar
<.lata were obtained for tetrahydrofura.n (THF)
aud THF'-toluene mixtures (fig. 90). In addi-
tion, it shown that the systems MEK-
toluene a.nd TH_."'.toluene obey Le Chatelier's
law, equation (46). Calculated and experi-
mental values for the preceding systems in air
a.re given i11 figures 91 and 92.
The limits of the systems acetone-carbon
dioxide-air, MEK-chlorc-
bromomethane (CBM)-a.1r, MEK-ca.rbon di-
oxide-air, and MEK-nitrogen-air are given in
figures 93 and 94. The datu. in these
were obt&ined by Jones and coworkers (198).
TABLE 16.-Properties of selected aldehydes and kefo'Ms
C<>mbustlbl• Formula M
A""ta.ldt• h.r..de. .. • . .. CllaCHO ..
Proplonal hyde. . c,n,cno .... - MI. OR
l'o.ralrlehyde ........
<<"Hac no/' ·-··
132.16
At't'lonr CllaCOCI , &ii.G8
M•thylrthyl krtone. I CllaCoc,-.;, __ · n.1o
Mrthyl krtonr ClloCOCalh . R6. 13
lllrthyl rlon.o c,n,coc,n,_ .. R6. 18
Methyl butyl ketonr 1 cn,roc,H, _ I 100.1e 1
I Cool ftamo•b: u_..-oo vol pet.
I Cool ftllll1n: tr,.•17 vol pllt.
I Ct.lcU)at'ld VII)Ue.
'I•I!OOC,
• 1•100° c.

c ..
In air
(vol pet)

I 62 7. 73
2.01 4.117
4. '!II 2. 72
2. 01
41171
2. 4U 3 61
2. V7 2.110
2. 'J7 I
290
346 2. 40
Lower l!mlt lu air Upper limit In lllr
AH,
<¥>1:
( Kl'Al)
mole L11 Lto u. u. u
(vol

(voi
c;;
(n;')
Ret.
pet) pet)

0. 62 82 (II$) •36 •. 7 1,100'

fOQ 2. .611 '17 (18) 114 2.8 420 M)
.. 1.3 .48 78 (40)
·"is
-····-
. -
403 2.6
.I
70 (98) 2.6 avo (9.'1)
1148 1.11 . 62 62 (1M) 10 2. 7 3.1!0
<'"'l W-1 1.6 .M 63 (40) 8. 2
.. ::: ,.
340 (40
liD2
161
.M 63
\
1
lo>!-•s.·o <4ni 1140 '1.4 .118 64 31l0
74 FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS
flammable mixtures
THf
I l.8
i r-- 70.!)mole-%THF+29.5mole-%toluene - =- -...::::.;..__--:::=
ai ---- .........
1.6


;::
<n f- 35.6 mole·% THF + 64.4 mole·% toluene
1.4 ________ J
8 --- ExperimeMal
---Calculated
-

20 40 60 80 100 120 140 160 180 200
TEMP£RATURE, •c
FtotrR• 90.-Ettoot of Temperature on Lower Limita of Flammability of THF-Toluene Mixtures in Air at
Atmoapherie Preeaure.
The temperatures of various
aldehydes and ketones in and air at
atmospheric pressure are given m appendi.'t A.
In general, the AIT values are lower than those
of the corresponding paraffine.
SUI.Ft.JH COMPOUNDS
The pertinent properties of sulfur compounds
a.re given in table 17. In general, they ha. ve
wide filWlmable ranges and relatively low igni-
t.\on temperatures (appendix A).
Flammability diagrams are $iven for carbon
disulfide mixed witli carbon d1oxide-air, water
vapor-air (SS9) and nitrol{en-air (fig. 95) i hy-
drOgen sulfide-carbon dionde-air (fig. 96); and
eth_y_l mercaptan with chlorodifluoromethane and
dicblorodifluorometbane in air {117) (fig. 97).
Figure 95 is interesting in that it shows not only
the w • ..!e flammable range of carbon disulfide in
air but also the large 9uantities of inert required
to prevent the formatson of 11ammable mixtures.
FUELS AND FUEL BLENDS
Fuels used for propulsion, not covered in
other sections, c-onsidered here (table 18).
Ammonia and Related Compounds
This series includes ammonia (NH,), hy:dra-
zine (NaiL), monomethylhydrazine (N,Ha·CII,)
and unsymmetrical diroethylhydrazine (N3H:·
(CH,),).
Ammonia forms flammable mixtures with s.ir
and other oxidants in a variety ot concentra-
tions, as noted in table 19. White (fS5) and
more re(',ently, Buckley and Husa, (19) reported
that, as with hydrocarbons, an increase in
either temperature or pressure tends to widen
the flammable range. Further, White found
that the }nwer limit. flame temperature remains
essentially constant with increase in initial
temperature.
TABLE 11.-Properlus of 11eltcted 81djur compO'Unds
Lclw• llm1t In 8lr Upper lhD!t In air
Net 4H,
Combustible l'onn\lla N (l&!l)
c.,
<!:)

u ln&lr La

L
u.
(VOl pet) (vol
(1')
Ret.
c.;
(":')
Ret.
pel)
c.,

- ----
--------
-
----------
......... R, ............. u.r. 1.18 If& 4.0 o.aa &a

« lUI l, IVO (IJ

c ·············
TG.IJ :tea 11.68 262 1.3 .XI
"
( ) 60 7.7 8,400 (U)
......... 68.10 1.111 &aa m 3.9 .eo 87
<6
22 8.4 1!00
16
'"b" me ......... ......... 02.13 2.16 t.4A 492 2.8 .ea 80 (I 4) 18
•••
litO (/4)
DIIJMthyl dt ......... CH CU, ....... ti.la :ua
'·"
2.:1 .ao tl:l (I)
I
10 t.6
.,
(I)
.. -
·-
-
c:
Q,)
~
Q,)
c.
I
cv
E
~
g
a::
0
Q..
~
I.&J
_,
al
;:::::
en
::;:)
al
~
0
(.)
1.2
J<'LAMMABILI'I 'i CIU.RACTERISTICS
o Experimental points
--- Calculated
Flammable mixtures
M EK, mole-percent
75
FiGURE 91.-Eifect of Liquid Composition on Lower Limits of Flammability of MEK-'roluene Mixturt-s in Air
at 30° and 200° c.
713 Jt'L·AMMABILITY CHARACTERISTICS OF COMBUSTIBLE GAAES AND VAPORS
o Experimental points
Calculated
Flammable mixtures
THF, mole-percent
FJouam 92.-Efl'ect of Liquid Compoeition on Lower Limite of Flammability of THF-Toluer.Je Mixtures in Air
at 30° and 200° c.
FL.U04ABILI'l'Y CHARACTERISTICS 77
!C air • 100%-!C acetone-,; inert
Flammable
mixtures
Frou .. 93.-Lfmlta of Flammabil-
ity of Aoetone-Carbon Dioside-
Air and Aoetone-Nitrogen-Air

0
Combuattble
10 20 30 40 50
ADDED INERT, volume-percent
TABLE 18.-Propertus of selected frul8 and jtul blends
Formula
SpiJ' C,,
(A1r•1) In ur
('fOI pelt)
N
UpJIII' llmlt In m

<!:)
Lo- Umlt In Ur
u. u. u
Ref.
c.. (1')
-----------1---------1-----------------------------
Ammonia •••.•.••••.•••.. w.ll;:.:::::::::: 0.1141 15 o.ee • 1.1 aoo !',
N.a.cu ........ .e.01 7.n :·
7
88 ::::::::
NeHI(CHI)s •••.. G0.10 2.08 4-W 3 .40 116 I 10.1 .••••••. (Ill)
dlwtbylhydrulne.
DlboraDe ................. BtRt. ••••••••••. :rt.fl8 .N 11.61 t78 .8 .12 to (Iff!) 81 11.6 ........ \IU)
Tetrabonlle •••.••••••.••. ........... ai.M I.IH 1.87 .t .11 10 (') ............................ ..
Pentaborane ............. BoHo ............ 111.17 2.18 !1.17 1010 .u .12 12 .................................... .
l!l&Ji ••••JJ :••:: .. :.: -••t!-· •-::::; :::i.: i ::•,;:• •
I Oaloulated 'fUUtl.
•t•IIIO" 0.
•t•100" 0.
78 FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS
FJOURII 94.-Lhnlte of Flarnmabll·
lty_ of Methyl Ethyl Ketone
(ME K) • Chlorobromemethane
(CBM)-Alr, MEK-Carbon Diox-
ide Dioxide-Air and MEK-Nitro-
gen-Air Mixtures at 26° C and
Atmospheric Pre18ure.
0
TABLE 19.-Limits of flammability of ammonia
at room temperature and near atmospheric
pressure
Oxidant c,,
I L
u Ref.
1-
Air __________________
21. 8 15 28 (167, 182)
Oxygen ___ .. ____ .. _____
57. 1 15 79 (U6)
oxide _________
40. 0 2. 2 72 (109)
Hydrazine vapor burns in the absence of an
oxidtzer, so that it has no upper limit and can
therefore be used as a monopropellant. The
dewmposition flame yields hy<lrogen, nitrogen,
and ammonia (64, 78). However, hydrazine
vapor can be rendered nonflammable by addi-
tion of stable diluents or inhibitors. The
of diluent required at any temperature
and pressure appears to be governed in part by
thA ignition source strength. With a 0.25-inch
spark gap and a 15,000-volt, 60-ma-luminous-
tube transformer as the energy source, Furno,
M"rtindill, and Zabetakis (68) found that the
% air= 100%-% methyl ethyl ketone-% Inert
Flammable
mixtures
10 20 30
ADDED INERT, volume-percent
40 50
following quantities of hydrocarbon vapor were
needed to inhibit flame propagation in a
glass tube
6
at 125° C and atmospheric
pressure: 39.8 pet benzene; 35.0 pet toluene;
27.3 pet m-xylene; 23.8 pet cumene; 21.0 pet
n-heptane. On this same basis, 95.3 pet air is
needed to prevent flame propagation (188); thiR
corresponds to a lower hmit of flammability of
4. 7 pet hydrazine ''apor. The flammable range
in air at atmospheric pressure is presented
graphically in figure 98, which also gives the
flammable ranges of monomethylhydrazine,
unsymmetrical dimethylhydrazine, and ammon-
ia for comparison ($18). The flammability
diagram for the system hydrazine-n-heptane-
air at 125° C and atmospheric pressure is given
in figure 99. These data were also obtained
in a. glass tube.
A summary of the autoignition temperature
data. obtained by Perlee, Imhof, and Za.betakis
(166) for hydrazine, MMH, and UDMH in air
and nitrogen dioxide (actually, the equilibrium
• CCliDparable l'lltlltl wtre partlaliJ obtallled ID a tube.
FLAMMABILITY CHARACTERISTICS 79
0
\ %air • 100%-% carbon disulfide-% inert
"

,,
"



fl11mmable \ \'
mixtures \ \'
,,
20 40
ADDED INERT, volume-percent
80
FIG\.iRE 95.-Limits of Flammability of Carbon Disul-
fide-Carbon Dioxide-Air, Carbon Dioxide-Nitrogt>n-
Air Mixtures at 25° C and Atmospheric Pressure, and
Carbon Disulfide-Water Vapor-Air at 100° C and
Atmospheric Pressure.

% air= 100%-% hydrogen sulfide:-% C02
0 40
CARBON DIOXIDE, 'Jolume-percent
FIOURE ll6.--Limit11 of Flnmmahility of Hyrlrogf'IJ Sul-
fiti<'-Carbon l>ioxidt•-Air at 25° C and
AtmOtiphcl·ic Pressure.
% air= 100%-% ethyl mercaptan-% inert
1:
..

!
"'
E
::J

z

II.
<5
a:
UJ
:IE
...J
>- 5
:X:
t;:;
0 20
ADDED INERT, volume-percent
FrouRE 97.-Limits of Flammability of Ethyl Mercap-
tan-F-12-Air and Ethyl Mercaptan-F-22-Air Mixtures
at Atmospheric Pressure and 27° C.
mixture is given in figure
100; short horizontal lines indicate the un-
certainty in N02* concentrations. These ma-
terials 'may spontaneously at room
temperature wtth relatively small N02* con-
centrations in the air; at 25° C, liquid UDMH
ignites in N0
2
*-air atmospheres that contain
more than about 8 volume-percent N02*; MMH
and hydrazine ignite in atmospheres that
contain more than about 11 and 14 volume-
percent N0
2
*, res:pectively. In general, even
smaller concentratiOns of N0
2
* produce spon-
taneous of these combustibles at
higher initial combustible liquid temperatures.
The effect of the hydrazine liquid temperature
on the spontaneous ignition temperature in
N 02 *-air atmospheres is illustrated in figure 101.
Similar data are_giYen in figures 102 c.nd 103
for MMH and UDMH; there is an
anomalv in the data obtained with M.MH at
36°, 55
15
, and 67° C.
The use of various helium-oxygen atmos-
pheres in place of air r11sults in the spontanenus
Ignition temperature curves given in figure 104
for UDMH. Comparison of curve B of this set
with curve A of figure 100 indic!ltf.ls that the
ignition temperature of UDMH in
N 02 *-He-03 atmospheres is the same as that
obtained in at.mospheres.
Ignition tempern.ture dnta obtaint-d with
UDMH in 15 and 45 psia
are summarized in figure 105. These indicate
that although the sl?ontarwous ignition tem-
perature of UD :\f H m air is not affected ap-
80 FLAMMABILITY CHAitACTERIBTICS OF COMBUSTIBLE GASES AND VAPORS
Fxoun11 98.-Limitll ot Flamma-
of Ammonia UD.MH,
MMH, and Hydrazine at At-
Pre&llure in Saturated
and Near-Saturated Vapor·Air
Mixturea.
..
LaJ
0::
;:)
CJ)
(/)
UJ
a:
c.
...J
c:r
....
0:::

20
Upper
limit
Flammable
mixtures
Cst
Lower
limit
100
78.9
-
c
• u

• Q.
I

26.3 E
:::s
0
>
..
13.2
0::
0
c.
c:r
7.9
>
UJ
5.3
...J
m
1-
(/)
::)
m
2
0
u
1.3
200
FLAMMABILITY CHARACTERISTICS
100
KEY
o Flammable
x Nonflammable
HEPTANE-VAPOR, volume-percent
FIGURE 99.-Flammable Mixture Compositions of Hydrazine-Heptane-Air at 125° C and
Approximately Atmospheric Pressure.
81
82 FLAMMABILrrY CHARAC'l'E.iUST!GIS OF COMBUSTIBLE AND VAPORS
200
0
a UOMH
b MMH
Hydrazine
Reaion of spontaneous ianition
Dew point line of
--
--
____ ...
---
10
---
NOt CONCENTRATION,
30
FJCURE 100.-Minimum Spontaneous Ignition Tem-
peratures of Liquid Hydra?Jinc, MMU, and UDMH
at an lnitinl Tempcratul'e of 2i° C in Contact With
N0
1
*-Air Mixtures at 740 ± 10 mm Hg as a Function
of N01• Concentration.
preciably by this pressure change, it is affected
m a range of N02•-air mi.;{tures.
The data presented in figures 100 to 105 were
obtained with liquid fuel in contact with
ized NO: air. Similar data obtained with
vaporized UDMH-o.ir in contact with NO;
are given in 106. This figure indica.tes
that UDMH-atr mixtures that oontn.in more
than 9 volumewpercent UDMH will ignite spon-
tanoously on contact with NO:; UDMH-air
mixtures that contain more than approximately
2 volume-percent UDMH can be Ignited by an
ignition source under the same conditions (166).
Boron Hydrides
This saries includes diborane

tetm-
borane (BcH,o), pentaborane (llaltG), nnd deca-
boraae (B,oHI4). However, relittble upper und
lower limit data are a vuilable only on the first
member of this series ut the present tillle.
These were obtained by P1trker und W<.•lfhnrd
(163) who determined the limits of flnmmability
of diborane in air in a 5-cm-diameter tube ut an
initial r>ressure of 300 mm Hg; this combustible
forms flammable mixtures in air in the rnnge
from 0.8 to 87.5 volume-percent. A pale bh.i.e
flame propagated throughout the tube .ul, the
upper lim1t; luminous were not visible
above 79 vol•1mewperccnt. Limit of flammu-
bility curves for the system dibor11 ne-ethane-air
are presented in rectangular coordinates in figure
107. for the slight dip to the ethhne-
axis (zero dtborane) in the area in which etLane
forms flammable mixtures in air, these curves
are rather similar to those obtained with other
combustiblewOxidant-inert systarns. Burning
velocities in excess of 500 cm/l'lec were measured
in this same study Cor fuel-rkh diborane-air
mixtures.
Berl and Renich have prepared a summnry
report about boron hydrides (9). It includes
data obtained by these and other authors; they
found the lower limit of penta.borane in air to
bo
The autoignitwn temperature of diborane in
air is aypa.rently quite low. Price obtained a
value o 135° C at 16.1 mm Hg (169); that of
pentaborane is 30° Cat about 8 mm Hg (9).
Ga.solines, Diesel and Jet Fuels
Fuels considered in this section are blends
that contain a wide variety of hydrocarbons
and additives. Accordingly, their flammability
characteristics aro governed by the method used
to extract a vapor sample as well as by the
history of the liquid. For example, since the
lower limit of flammability, expressed in
volumewpercent, is inversely proportional to
the molecular weight of the combustible vap<>r,
equation (28), the first vapors to come from a
blend, such as gasoline, give a higher lower
limit value than the completely vapori.t.ed
sample. Conversely, the heavy fractions or
residue give a smaller lower limit value. For
this reason, there is some disagreement about
the limits of flammability of blends such as
gasoline and the diesfll and jet fuels. These
fuels are, in general, characterized by a wide
distillation range; the ASTM distille.tion curves
P'LAMMABXLITY CHARACTERISTICS 83
Region of spontaneous ignition
0
CONCENTRATION, volume-percent
FIGURE 101.-Minimum Spontnnrous Ignition Tempemtnres of Liqnid ut Various lnitial Tl,mpt'ratures
in

Mixtures at 740± 10 mm llg as a Fuurtion of NO,• Concentrution.
84 Fl.A:\1:\IABILITY C'HAHACTEIH8TJC8 OF COMBl'8TtBLE GA8E8 VAPORS
200
P ss• . ..__
uJ
0::
:;)
< 100
0::
w
Q,,
:e
w
1-
__ T ... _ .......
Regi0n of spontaneous ignition
CONCENTRATION, volume-percent
I
l
I
FwntE ](fl ... 1-'pontllll<'OII>' TPmpPmtur<'"' of Li<
1
<ti<
1
\1 :\III at \'ariotJH Initial T•·lltpt·r Jt:u·,.,
ill :\0
2
•-Air :\lixturt•s nt 740: 10 111111 ilg a:; a Fuuct.io11 of :\0
2
* ( 'oul'l'l•tralioto.
FLAMMABILITY CHARACTERISTICS 85
Region of spontaneous ignition
0 5 10
20
CONCENTRATiON, volume-percent
F!Gt:RE 103.-!\finimum Rpontnneous TPmpPratur!'s of Liquid l"D\fH at Various Initial Temperatures
in X0
3
*-Air MixturP!l at i40 10 mm llg as a }'unction of .X0
3
* Concentration.
86 FLAMMABILI'I'Y CHAHACTEHISTICS OF GASES AND VAPOHS
FIGURE 104.-Minimum Spon-
taneous Ignition Temperatures
of 0.05 cc of Liquid UDMH in
• Atmospheres at 1
Atmosphere for Various He/0
2
Ratios.
p
LL.i'
0::
::I
200
a::
w
Q..
:::E
w
.....
0
Curve He/0
2
(J 0.0/100
b 100/25
c 100/6.50
d 100/1.70
tl 100/0.30
f 100/0.00
Region of spontaneous ignition
o,b
5 10 1'5 20
CONCENTRATION, volume-percent
25
FLAMMABILITY CHARACTERISTial
87
300 ---- -- -- 1 - --------r----T-------
200
100
0
11 15 psia
b 45 psia
Regio" spontaneous ignition
5 10 15
CONCENTRATION, volume-percent
20
FIGURE 105.-Minimum Spontaneous Ignition Tem-
peraturet of 0.05 cc of Liquid UDMH in N0
1
*-Air
Mixtures at 15 and 45 Psia as a Function of N0
1
*
Concentration.
of two gasolines and three jet fuels considered
here are given in figure 108. Unfortunately,
such curves give only an approximate measure
of the volatile constituents in the liquid blend.
Even relatively nonvolatile high-flashpoint, oils
may liberate flammable vapor8 at such a slow
rate that the closed vapor space above the
liquid may be made flammable at reduced
temperatures. Gasolines can produce flam-
mable saturated vapor-air mixture at tempera-
! ures below -65° C (241), although the flash
points of such fuels are com•idered to be about
-45° C (158). An apparent discrepancy thus
exists if flashpoint data are used to predict
the lowest temperature at which flammable
mixtures can be formed in a closed vapor space
above a blend in long-term storage.
As noted earlier, the limits of flammability of
hydrocarbon fuels are not strongly dependent
on molecular weight when the limits are ex-
pressed by weight. However, since results
measured by a volume ttre!erhaps more widely
used than those measure by weight, typical
flamme.bility curves are presented by volume
for the fractions from aviation gasoline,
grade 115/145 (fig. 109), and aviation jet fuel,
200
150
w
0::

i


UJ
100
50
0
Re,gion of spontaneous ;gnition
l
Lower limit of flammability I
of UDMH in air
.... -.... --
j
Dew point line
of UDMH
........ --
---
4 8 12 20
UDMH CONCENTRATION, volume-percent
FIGURE 106.-l\linimum Spontaneous Ignition Tem-
peratures of Vaporized UDMH-Air MixturM in Con-
tact With 100 pet NO; at 25° C llnd 740± 10 mm
Hg as a I- unction of UDMH Concentration in Air.
grade JP--4 (fig. 110). Combustible vapor-air-
carbon dioxide and vapor-air-nitrogen mixtures
at about 25° C and atmospheric pressure are
considered for each. Similar data are given in
figure 14 for the gasoline vapor-air-water vapor
system at 21° and 100° C; the effect of pressure
on limits of flammability of volatile constituents
of JP--4 vapor in air are discussed in connection
with 12.
l\Iimmum autoignition temperatures of gaso-
lines and jet fuels considered here are given in
compilutions by Zabetakis, Kuchta, and co-
wo:-kers (126, 237). These data are included
in table 20.
Setchkin (194) determined the AIT values of
four diesel fuels with cetune numhers of 41, 55,
60 and 68. These data are included in table 20.
Johnson, Crellin, and Carhart (92, 93) obtained
values that. were larger than those obtained by
Setchkin, using a smRiler apparatus.
88 FI..AMMAI:ULITT CHARACTERIB'l'ICS OF COMBUS1'1BLI: GASES AND VAPORS
100
!lair .. cilborane-" lth-
20
_L_•I (drlxnM) ______ , __ _
0 20
Frouu 107.-Limitas of Flammability
Ethane-Air Mixtures at Labl)ratory
and 300 mm Hg Initial Presaure.
of Diborane-
Temperatures

20 40 60 80 100
DISTILLED, percent
FruuRE 108.-ASTI\1 Distillation Curves for, A, Avia-
tion Gasoline, Grade 100/130; B, Aviation Gasolint•,
Grade 115/145; C, Aviation Jet Fuel, Grad1! .JP-1;
D, Aviation Jet Fuel, Grade JP-3; and E, Aviation
Jet Fuel, Grade JP-·4.
I
I
;
0
"air • 100•-• psollne-• Inert
Flammable
mbdum
10 20 30
ADDED INERT, volum•p.rcent
50
Frouu 109.-Limitas of Flammability of Aviation
Ouollnel Oradee 115/145 Vapor.Carbon Dioxide-Air
and 1lli 145 Vapor-Nitrogen-Air, at 27° C and At-
mospheric

!I air • 100%- !I JP-4 -% Inert
0 10 20
ADDED INEtll, volume· percent
FroUJu: 110.-Limite of Flammahility of JP-4 Vapor-
Carbon Dioxida-Air and JP-4 Vapor-Nitrogen-Air
Mixtures at 27° C and Atmospheric Pressure.
TABLE 20.-Autoignition temperature IK.£lues of
various fuels in air at 1 atmoHphere
Fuel:
Aviation guo line: A IT, •c
100/130............................ 440
116/146 ••..... _____________________ 471
Aviation jf.'t fuel:
J J>-1 _. ___ • _ •••••• __ ••• _ ••• __ .• _ • • • 22R
J J>-3 .... _. ___ . _ . _ . _ • __ . _ • _ _ 23R
JP-4. __ . _. _. _ ... _. _____ . _. _ 242
Jl'-6 ... -- .. -------.-.- ". -. -- -.---- 232
Dins1•l ful'l:
41 cl'!anl' ________ . _ _ _ .. _ . _ _ . - .. - - 233
51) ('1'1.8111' -- . . - . - .. - - --- 230
6() Cllt.&lll' __ . _ •. _ _ _. 225
68 cctane. _ .. __ .. ___ . _ . - - . __ .. • . . . . 226
FLAMMAHILITY CHARACTERISTICS 89
v-elocities of the fuels consirlered
here are m the same range as those o( the
hydrocarbons considered earlier. Values for
various fuels have been tabulated by Barnett
and Hibbard (166).
Hydroqen
N umerou!l flammability cha.ract.eristics
studies have been conducted with hydrogen in
recent :rears. Drell and Belles have prepared
an excellent survey of these characteristics (48).
This survey includes all but the most recent
work of interest.
The low pressure limits of Baroe propagatinn
for st:lichiometric hydrogen-air mixtures are
somewhat lower than those for stoichiometric
ethylene-air mixtures (1 97) in cylindrical tubes.
In the from 6 to 130 mm Hg, the limit
for stoichwmetric hydrogen-air mixturoA is
given by thE' expression:
log P=3.19-1.19 log D, (57)
where P is the low-pressure limit in millimeters
of Hg, and D is the tube diameter in milli-
meters.
H;ydrogen forms flammable mixtures at
amb1ent and pressures with oxy-
air, chlorine, and the oxides of nitr(lgen.
its of flammability in these oxidants at
approximat\'lly 25° C and 1 atmosphere are
listed in table 21.
TABLE 21 -Limits of jla.mmabi.J:ity of hydrogen
in various oxidants at 25° G and atmosplwric
pressure
Ref. Oxidant I
Oxygen- .. - --- .. - _- ___ -l-..--(40;
!: I <etfJ,
N.o. ____ .. _ _ _ _ _ _ _ _ _ _ _ a. o 84 (189)
NO__________________ 6. 6 I 66 (189)
Flammability of the sy3t.ems hvdro-
gen-air-carbon diox1de and hydrogen-air-nitro-
gen obtained by Jones and Perrott (112) ar£l
briven in figure Ill. Lines that establish
minimum oxygen values for each system are
also included. 1'\ ote that although the lnini-
mum value occurs near the "nos1'" of the
hydrogen-a.ir-nitrogen eurve, the corr1•sponding
value occurs at the upper limit of the hydrogen-
air-carbon dioxide curve.
Flammability dia.grams obtained by Scott,
Van Dolah, and Zabetakis for the systems
hy:drogen-nitric oxide-nitrous oxide, hydrogen-
mtrous oxide-air, and hydrogen-nitric oxide-air
aregivenin figures 112-114 (189). Upper limit
I
i 40
z
I

20
0

• 100%-% hydrogen-% inort

5.2% ..,_,
Flammable
mixtures
20
""'
"'"'
'

5.0%
AO[JEO INERT, volume·perr.ent
Fwvax 111.-Limit! of Flammability of Hydrogen-
Carbon Dioxide-Air and Hydrogen-Nitrogen-Air
Mixtures at 25° C and Atmospheric PreiiiiUre.
curves were found to deviate fr(JID the results
obtained from the Le Chatelier law, broken
curves; additional data are given in the original
article.
The burning velocity of hydrogen in air at
25 °C and one atmosphere range from a low
of a few per second to 325 em/sec
(68). When liquefied, it. vaporizes and burns
in air at rate that is determined by the rate
at which heat enters the liquid. Heat is
from the surroundings and, where a
flame exists, from the flame itseH. Figure 115
gives the results obtained from vaporizing
liquid hydrogen from paraffin cast in a Dewar
tlask; experimental pomts were obtained from
gas evolution measurements. The solid
(theoretical) was obtained by Zabetakis and
Burgess by assuming the heat influx rate to be
conduction limited (234); the initial flash
vaporization rates are probably film- and
nucleate boiling-limittJd. The theoretical liquid
regression rates following spillage of liquid
hydrogen onto three soils are presented in
figure 116, the corresponding decrease in liquid
}eye} is given in figure 117. Be<' a use of its
low temperature, the v11porized hydrogen
forms a vapor trail 1\ii it. leaves the liquid.
However, tlie position of this trail or visiblfl
doud does not necessarilv coincide with that
of the tlarnmable zones formed ubove the
pool. This is illustrated in figure 118, in which
the positions of the flummable zones und visible
clouds are defined in u height-elupsed time
graph. Two flammable zones are defined here.
These are ruso seen in t.he motion picture
sequence (fig. 11 9) of the visible cloud.c and
90 FLAMMABILITY CHARACTERISTICS OF COMBUSTibLE GASES AND VAPORS
KEY
• Flammable mixture
o Nonflammable mixture
FtouRII: 112.-Limit.s of Flammability of HrNo.•,;,o at Approximately 28° C anrl 1 Atmosphere.
KEY
• Flammable mixture
o Nonflammable mixture
• Coward and Jones,
Bureau of Mines
Bull. 503
0 Smith and Linnett,
JCS (London),
1953, pp. 37 ·43
• CHARACTERISTICS
60
.
%
fl

0


ro
FIGURE 113.-Limits of Flammability of 11
1
-::\'
2
0-Air at Approximately 28° C and 1 Atmosphere.
91
92 CHARACTERISTICS OF COMBUSTIBLE OASES AND VAPORS
KEY
• Flammable mixture
o Nonflammable mixture
• Coward and Jones,
Bureau of Mines
Bull.503
FIGURE 114.-Limita of Flammability of HrNO-Air at Approximately 28° C and 1 Atmosphere.
FLAMMABILITY CHARACTERISTICS 93
Start of liquid transfer to Dewar

\
\ I
\ I
\ I
\ I


I
I "
Re1!on f
of violent
bollln1 J--- Quiet vaporization
FIGURE 115.-Rate of Vaporization of Li({uid Hydrogen From in a 2.8-lnch Dewar F'lask: Initial Liquid
Depth-6. 7 Inches.
1
.2
.5
·:.\

60 100 120 140 160
ELAPSED TIME, seconds
FIOIJRI: 116.-ThooreticRI Liquid Heltl"eBSion Hntt>& Following Spillage of Liquid Hydrogen Onto, A, an Anrage
Soil; B, Moist Bandy .Soil (8 Pet. Moisture); and C, Dry Saully Soil.
94 FLAMMAB lLITY CHA
i\At'TERISTlCS OJ<' COMB
-,---1-f USTIBLE OA ' ---r--- SES AND V"
-r--T- -,--
FIGUilll 118
of Flamma-
S Cloud For: eight of
Liquid of 3 t After
adam sJFn on
8
of
Air At aoe in a Q ac-
mOBphere at
16
o
7
FI.AMMABil.JTY CHARACTERISTICS 95
fiiiJiles that resulted following spillage of 7.8
liters of liquid hydrogen and subsequont
ignition of vapors above the spill area. The
heisht and width of firebnlls that resulted from
of vapors produced bv rapid vaporiza-
tlOU of about 3 to 90 litera olliquid hydrogen
are given in figure 120. The data are repre-
sented fairly well by the equation
Hmu.= Wmu=7-v'''fl 17.8-v'M feet, (56)
where Hmu and lVmax are the maximum flame
and width, respect.ively, v. is the volume
of hq,uid in liters, and M is the mass
of th1s volume m pounds.
The rat.e of a 6-inch pool of liquid
hydrogen in air is given as the regressi()n of the
liquid level in figure 121 i burning rate data for
liquid methane are included for comparison.
AD extrapolated ·value of burning rate fol' large
pools of liquid hydrogen is included in 52.
Approximate quantity-distance relationships
can oo established for the storage of liquid hy-
d=ogen near inhabited buildings and other stor-
age sitfls ;f r-ertain assumptions are made (SS,
160, 234). Additional wurk is required to
establish such distances for very large quantities
of liquid.
The detonation velocity and the static and
:reflected pressures devAlupod by a detonation
wave propagating through hydrogen-oxygen
mixtures are given in figure i6. The predeto-
nation distance in horizont&.l pipes is reportedly
proportional to the square root of the pipe
diameter (229) ; this is presumably applicable
to results obtained with a mild igmtion source,
sinc.e a shock front can establish a detonation
at essentially zero run up distance. Numerous
investigators have examined this and related
problems in recent years (11--13, 65, 196-137,
161).
HYDRAULIC FLUIDS AND ENGINE
OILS
Both mineral oil derived and synthetic hy-
draulic fluids and engine oils are presently m
common use (148). These materials are often
used at elevated temperatures and pre;:;sw·es
and contain additives designed to improve 'ita-
bility, viscosity, load-bearing characteristics,
etc. Such additives affect flammability char-
acteristics of the base f!uid. However, the base
FIGtlRE 119.-Motion Picture Sequence (16 Frames per
Second) of Visible Cloud8 and :Flames Reeultmg
From Rapid Spillage of 7.8 Liters of Liquid Hydrogen
on a Gravel Surface at 18° C. Ignition Source: 20
Inchea Above Gravel.
96 FLAl\fMABILJ1'Y ClUHACTERISTICS OF VAPJR,3
F'lounE 120.-!\fn'l:imurn uanw
hPight and widt •. pwd·•c<'d by
lgnit.ioh cf vapor-air mixtures
formlld by sudden spillage of
to 89 Htcl"ll e>f liquid hy-
dl·ogeu (V
1
).
F'IUURE 121.-Burning rates of
liquid hydrogen !l.nd of liquid
methane at tbe boiling points in
fl-inch-Pyrex Dewar tiask.s.
·---.-.---.--
en 60 • Flame height
o Flame w1dth
40
:I
0
:I
i 20
i
5

.&.
u
4 .5
-
..I

...J
0
3
Q
...J

0
z
0
ii'!
U)
lol
0::
C!l
LIJ
0::
v,, liters
'Methane
20 30 40 50
ELAP5ED TIME, rnii"HJtes
60
:\i'LAM.MAl'IILITY C.H.AftACTERIS'.riCS
97
fluid generally plays a predomimmt role iu de-
termining limits of flammability "ind ignition
of a particultU' flutd. For exam-
ple, m.uny of the oil-based fluids have io\\•er
limits of flammability that fall in the rangt>"'
given in figure 22 for par!lfiin hydrocarbons.
I<'urtlwr, those that have mir1imum autoignition
temperatures in tb.e ltlWCr t.emjleruture ranges
cousiclered in 43 and 71 are nut affected
tlppn,ciably by oxygen of the
»tlno1;phere and by ambient and
pressu&-e&; those t!Ja.t. havfl minimum autoigni-
tion tempm·ttt'U'es in the temperature
runges do not follow these (237).
Sirwe these fluids are des1gned for use at ele-
vated temperatures awi :pressures, they ru'e nor-
mally made up of high ·molecular mate-
tinls. Accordmgly, they are flammable at
ordinary tempex·atures and pressU!'es' as mists
and Coams. u11d his coworkers (27)
found that. luhricating-oii. mist,., were flt...mma-
b!P in air but. not in carbon dioxide-air mix-
ture.: that contained about 2g '¥nlume-percent
carbon dioxide (fig. ao). At elevated temper-
the •Jil vapors crRcked Rlld produced
aePtylene llnd hydrogen, which a:tfecteO. the
fl!!.rnn1abilit.y of thl'l resultant mixture; the va-
porH are often unstable at elevated tempera-
tures. Cbiantella, Affens nnd Johnson have
the effect of eievnted temperatt'.l'es
on the stability and ignition prollerties of
commNcial tnaryl phospha ie ftmds (86).
Zabetakis, Scott, and Kennedy have deter-
mbed the effect of on the autoignition
temperatures uf commercial lubricants
Figure 122 gives the mir.imum autoignition
for four commercial phosphate
ester-base fluids (<''li'Ves 1-4) and three
mineral oils (curves 5-7). In each case, the
minimum autoignition temperature was found
to decretl.8e with increase in pressure over most
of the pressure considered. A plot of the
logarithm of the imtial pressure to temperttture
ratio versus the reciprocal of the temperature
is given for curves 1 to 7 in figure 123. The
resultant curves are linear over I' limited tem-
perature rttnge.
The ratio of the final temperature attained by
air in an adiabatic compression process to the
initial temperat.ure is given in 124 as a.
function of both the final-to-imtial pressure
ratio and initial-to-final volume ratio. If a
lubricating oil is exposed to high temperatures
during a compression process, may
occm if the residence or contact tlme is ade-
quate. Such high temporatures do occur in
pra.rtice and have been known to cause disa.s-
explosions (58, 146, 149, 227, 291). The
curves iu tigtu-e 125 show that in the compression
pressure range 1 to 10 atmospheres (initial
pre."sure::= 1 atmosphere), a wide range of
ambient can lead to the auto-
i.gnition oi 11. mineral oil lubricant (curve 5) if
ii'Ufticient or mist is in the system. In the
same pressure range, only elevated initial.
t.emperatt;rcs coul':l lead to the of a
pbosphttttl (curve 4). If the initial pressure
1s i.r.creiiSed to 10 atmospheres, u.utoignition
cnn at, lo?!er air-intake temperatures in
tlVery CMe (248).
MiSCELLANEOUS
The tfammability characteristics of a number
uf miscellaneous combustibles not considered
elsewhere, are discussed in this section. These
include monoxide, n-prop,Yl nitrate, and
t.he halogenated hydrocarbons. The properties
of these and a great variety of other materials
11re included in Appendix A.
The limits of flammability of the systems car-
bon mo::1oxide-carbon dioxide-air and carbon
monoxide-nitrogen-air are presented in figure
126. These curves were constructed (rom the
flammability data obtained by Jones in a 2-inch
vertical glass tube with upward flame propaga-
tion (112); other representat.ions may be found
in the original reference and in the compilation
prepared by Coward and Jones (40).
Materials that are oxidized or decomposed
readily may yield erratic flammability data
under certain conditions. This effect lS illus-
trated in figure 127 which summarizes the
lower-limits data obtained by Zabetakis, Mason
and Van Dolah with n-propyl nitrate (NPN) in
air at various temperatures and pressures (248).
An increase in temperature from 75° to 125° C
is accompanied by a. decrease in the lower-limit
values; a. further increase in temperature to
150° c results in a rurther lowering of the lower
limit a.t pressures below 100 psig, but not at the
higher pressures. An increase in the tempera-
ture to 170° C results in an apparent increase in
the lower·limit value because of the slow oxida-
tion of NPN. A complete flammability dia-
gram hilS been constructed for the NPN vapor
system in figure a single limit curve
and two upper llimt curves are gt.ven here tc
show the effect of pressure on the flammable
ral}ge of a vapor-air system.
The spontaneous ignition of N PN in air was
considered earlier at 1 ,000 psig (figs. 3, 4). The
explosion pressw-es obtained at this initial pres-
sare in air and in a 10 volume-percent oxygen
+90-volume-percent nitrogen atmosphere at
various NPN concentrations are presented in
figure 129. A summary of the minimum spon-
taneous ignition and decomposition tempera-
tures obtained with NPN in air and nitrogen
respectively are given in figure 130. The data
given in this figure exhibit a behavior that is
typical of that found with other combustibles
98
6150

...;

1-

L&J
0.

1-

i=
z350
t!)
0


:I 250
i

:I
FLAMMABILITY CHAHACTElUS'riCS OF COMBU!STTHLF. GASES A;>;D 'l."AP0US
Region of
autoignition

2 4 6 8 10 20 40 60 80 100
INITIAL PRESSURE, otm
·1
FIGURE 122.-Variation in Minimum Autoi;;;nition Temperature With of Cornnwrcia! Phosphate Ester
and Mineral Oil Lubricants in Air in tL 4.'>0-cc-Stu!ult•ss Steel BomiJ.
F1ouaz 123.-L<:>garithm of lni-
tbl f'r.,..eur2-AIT Rat1o of
Seven Fluids in .Air for Various
Reciproclll Temperature&. Data
!rofl'l Figure 122.
FLAMMABILrl'Y CH.ARACTERIS'riCB
:If!

.....
E
'6
.00
R5QIOII of
outoiQnitlon
99
1()() FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS
Ftotru 124.-Variation in Tr/T;
of Air With V,fVt and With
P,/P; in an Adiabatic Com-
PreiiJion Proceee.
V,· P,
v, P,·
FIGURE 125.-Variation In Air
Temperature With PdP; in an
Adiabatic Comrression Procesc
for Five Ivitia Air Tempera-
tu:res (0°, 25°, 50°, 75°, and
100° C). Regions of autoigni-
tion for lubricants IV and V at
Pr/P, Btltween 1 and 10 Atmos-
phere and P1 of Between 1 and
10 Atmospheres.
CHARACTERISTICS
Rer'ion of
autoignition
101
10
102 FLAMMABILITY CHARACTERIEITICS OF COMBUSTIBLE OASES AND VAPORS

0 20 40 60 80
ADDED INERT, volume-percent
Froue 126.-Limits of Flammability of Carbon Mo-
D01ttde-Carbon Dioxide-Air and Carbon Monoxide-
Nitrogen-Air Mixtures at Atmospheric Presoure and
26" c.
,._
4

....

I
at elevated pressures; the minimum spontaneous
temperature first decreases .with ini-
tta.l increase in pressure and then increases as
the pressure is increased still further (110,
B48).
Burning were found to range from
20 em/sec to 110 em/sec in NPN-air mixtures
cont.aining 3.0 to 7.2 volume-percent NPN.
Detonations were obtained in saturated NPN
vapor-air mixtures from 30° to 65° C e.nd 1
atmosphere pressure; the detonation velocity
was from 1,500 to 2,000 meters per second.
Stable detonations were obtained with liquid
NPN at 90° C; the detonation velocity was
from 4,700 to 5,100 meters per second.
Although many of the halogenated hydro-
carbons are known to be flammable (40) still
others such as methyl bromide, methylene
chloride, and trichloroethylene (TCE) have
been considered to be nonflammable or esstmtial-
ly nonflammable in air. As noted in connection
with the methyl bromide data given in figure
28, Hill found methyl bromide to be flammable
in air at 1 atmosphere pressure (84); the re-
ported limits of flammability were from 10 to

3
Flammable mixtures
"5
>_
(L
0
2
r:l.
<[
:>

a.
z
0 100 200 300 400 500 600 700 800 900 1,000
PRESSURE, psig
FIGt'RE 127.-Lower of Fl11mmability of :'\J>:'\ Vupor-Air :\I ixturps Ov"r tlw I· rom 0 to
1,000 at 75", 1:.!5°, 150°, 1111d 170'' ( ',
FLAMMABILITY CHARACTERISTICS 103
a:

z
0..
z
90 --
80 -
70 -
60 -
50 -
40
20 -
10 1
Impossible vopor- air
mixtures ot T 6125 •c
Saturated vapor-air
T = 125°C
\ -T•5o•c
<('
' ... flammable
0 200 400 600 BOO 1,000
PRESSURE, psig
FrouRE 128.-Flammahle Vapor-Air :\fixtures
Form<>rl On•r the l'rPssurc Hauge From 0 to 1,000
Psig at 50° and 125° C.
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-
cent. Similarly, methylene chloride and tri-
chloroethane wel'e found to be flammable in air
at ambient temperatures although the flam-
mable ranges were not determined. In general,
much higher source energies are required with
t.hese combustibles than are required to ignite
methane-air
An approximate flammability diagram was
prepared by Scott for trichloroethylene-air
mixtures (190); a modification is reproduced in
.figure 131. The lower limit data were obtained
in a vertical 7-incb-diameter ftammabil,ity tube
and the upper limit data in an 8-in'ch-diameter
glu.ss sphere with upward propagation of flame.
mixtures of TCE and air were also
obtained between 10.5 and 41 volume-percent
TOE at. 1 atmosphere and 100° C in an 8-inch-
diameter glass sphere. Under the same con-
ditions, flammable mixtures of TCE and
oxygen were obtained between 7.5 and 90
volume-percent TCE. However, additional
work must be conducted with this and the
other halogenated hydrocarbons to determine
the effect ot vessel size, ignition source strength,
temperature and pressure on their flammability
chftJ'acteris tics.
Other useful flammability data may be found
for various miscellaneous combustibles in many
of the publications listed in the bibliography
(40, 154, 200, 208-214, 218). These include
data on the gases produced when metals react
with water (56) and sulfur reacts with various
hydrocarbons (62). Still other references con-
sider the hazards associated with the production
of unstable peroxides (142, 157, 187, 288) .tnd
other reactive materials (66, 74, 80, 189).
104
5,000
.i'
Ill
a.
""
a::
:::>
(f)
(f)
""
a::
Q..
z
0
(f)
0
-I
Q..
)(
""
0
FLAMMABILITY CHARACTERISTICS OF COMBUSTIBLE GASES AND VAPORS
0
0.3 0.6 0.9 1.2
Oxidant
0-- Air
c--10% 02 + 90% Nz
1.5 1.8
NPN VAPOR, volume-percent
2.1
Flouam 129.-Variation of Explosion Pressure Following Spontaneous Ignition With NPN Concentration, Initial
Pressure 1,000 Psig.
Fzouu 130.-Minlmum Spontanoous Ignition and Decomposition Temperatures of n-Propyl !'litrate in Air as a
Function of Pl'eiiii•Jrt!, Type 347 Stainless Steel Test Chamber.
0 10
..------------,
Impossible mixtures
]/
0
I
50
FLAMMABILITY CHARACTERISTICS
TEMPERATURE, •c
Flammable mixtures
/ Lower Iiili it
Nonfllmmable mixtures
I
100
T[MPERATURE, 'F
I
!50
FIGURE 131.--Flammability of Trichloroethylene-Air Mixtures.
I
200 250
105
ACKNOWLEDGMENTS
Many of the unpublished data reported here
were obtained by the predecessor of the author,
the late G. W. Jones, former chief of the gas
explosions branch. Other data were obtained
by the author and his coworkers, particularly
Messrs. George S. Scott, Joseph M. Kuchta,
Aldo L. Furno and Henry E. Perlee. In
addition, the author is indebted to Drs. David
106
Burgess
6
and Robert W. Van Dolah for many
fruitful discussions of the material contained in
the sections on Definitions and Theory, De-
fiagration and Detonation Processes, a.nd Pre-
ventive Measures.
• Presently wltb Reaction Motors Division, 'rhlokol Chemical Corpo-
ration, Denville, New Jersey.
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f·ltiftt r.':tri ... ·l, \·. Jlf). '"''
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( '••
1
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for Gaseous Mixtures. J. Chern. Eng. Data,
v. 1, 1956f pp. 77-82.
Zabetakis, !\ ichael G. Explosion of Dephlegmator
at. Cities S;)rvice Oil Company Hefincry, Ponca
City, Okla., 1959. BuMines Rept. of Inv. 5645,
1960, 16 pp.
232. -----. GRsfreeing of Cargo TankA. Bu-
Mines Inf. Circ. 71194, 1961, 10 pp.
233. ZabctakiR, M. J., M. P. Benoy, and 1'. M. Gussey.
Explosion Hazards of Diethyl Ether. Bu :\lineR
Hept. of Inv. 6051, 1962, 16 pp.
2:1.'),
236.
239.
ZabPtakisi M. G., and D. S. Burgess. Research
on the Iazards Associated \\' ith the Production
and Handling of Liquid Hydrogen. Bu:\1ines
Hept. of Inv. 5707, 1961. 50 pp.
Znbetakis, M. G., J. C. Cooper, anrl A. L. Furno.
Flammability of SolwPt !\fixtures Containing
Methyl Ethyl Ketoue and Tetrahydrofurnn in
Air. BuMiues Hept. of Inv. 604H, 1!!62, 14 pp.
Zabetakis, 1\1. G., und II. II. EngPI. Fltunmnhle
Materials: A Lpctnre Dt'monstratiou. Bu-
Inf. Oirc. SOO.i, 1!Jtll, 17 pp.
Zalwtakis, 1\f. n., A. L. 1•\rruo, aud G. W. Jones.
1\liuirnum Spuntall!oOW! Ignition TcmpPruturPs
of ComhustihiPs In Air. Iud. and Eng. Clwm.,
v. 4tl, 11154, pp. 2173-217R.
ZaiH•talds, 1\f. 0., 1'. 1\f !lusRcy, and G. R. Seott.
Limitd uf Flamrnahilit.y nf Methyl Ethyl }(ptonn
1111!1 Methyl Isobutyl Ketoun in Bromochloru-
methane-Air BuMines H.ept. of Iuv.
5680 19f\O, 12 pp
Zabctakis, M.G., and G. W. Jonlltl. FlammnLility
of Dieullide in Mixtures of Ah' and
240.
241.
242.
243.
244.
BIBLIOGRAPHY 113
Water Vapor. Ind. and Eng. Chem., v. 45,
1953, pp. 2079-2080.
-----. The Prevention of Industrial Gas
Explosion Disasters. Chern. Eng. Prog., v.
51, pp.
Zabetakis, Michael G., George W. Jones, George
S. Scott, and Aldo L. Furno. Research on the
Flammability Characteristics of Aircraft Fuels.
Wright Air Development Center, Tech. Rept.
52-35, supp. 4, 1956, 85 pp.
Zabetakis, M. G., S. Larnbiris .• and G. S. Scott.
Flame Temperatures of Limit Mixtures. 7th
Syrnp. (lnternat.) on Combustion, Butterworths
Sci. Pub. (London), 1959, pp. 484-487.
M. G., C. M. Mason, and H. W. Van
Dolah. The Safety Characteristic!! of Normal
Propyl Nitrate. BuMines Hept. of Inv. 6058,
1962, 26 pp.
Zabctakis, M. G., and J. K. Richmond. The
Determination and Graphic Representation of
the Limits of Flammability of Complex Hydro-
245.
246.
247.
248.
249.
carbon J:<'uels at Low Temperatures and Pressures.
4th Symp. (lnternat.) on Combustion. Williams
& Wilkins Co., Baltimore, Md., 1953, pp. 121-
126.
Zabetakis, M. G., and B. H. Rosen. Considera-
tions Involved in Handling Kerosine. Proc.
Am. Inat., sec. ; v. 37, 1957, p. 296.
Zabetak1s, M. G., G. S. and G. W. Jones.
of. Flammabilitr of Paraffin Hydrocar-
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pp. 212()-2124.
-----. The Flammability Characteristics
of the CRHh-& Aromatic Series. BuMines
Rept. of !nv. 4824, 1951, 9 pp.
Zabetakis, M. G., G. S. Scott, and R. E. Kennedy.
Autoignition of Lubricants at Elevated Pres-
sures. BuMines Rept. of lnv. 6112, 1962, 10 pp.
Zeldovich, Ia. B., S. M. Kogarko, and N. N.
Simonov. An Experimental Investigation of
Spherice.l Detonation of Gases. Zhumal Tekh.
Fizikl (J. Tech. Phys. (USSR)), v.26, 1956, p.l744.
APPENDIX A
TAFLE A-1. Summary of limits of flammability,
lower temperature limits (TL), a.nd mim:mum
autoiynition temperatures (AIT) of indiculual
gases a.nd t•apors in air at atmospheric pressnre
Combustible
Limits of flllm- \
mability (volurne-1
percent) , T,, A!T
I
(o C) (o C)
_________ u,. ---------
AcetaL ......•...•..
Acetaldehyde._ .. _ . _ .
Acetic acid •.. _ .. ___ _
Acetic anhydride ____ _
Acetanilide_ •... _ •. __
Acetone ____________ _
Acetophenone. _____ _
Acetylacetonc .. ____ .
Acetyl __ ... _
Acetylene •••... _____ _
Acrolein __ . _ c .. _ • ___ _
Acrylonitrile .••• ____ _
Acetone Cyanohydrin.
Adipic acid ••.....•. _
AldoL. __ •... _ . _. _ ..
AllylaicohoL ______ _
Allyl amine._ .. _
Allyl bromide _______ _
Allyl chloml"- __ . ___ .
o-AminudiphcnyL __ _
Ammonia ... _. _____ _
n-Amylacetate. _.
n-Amyl alcohol. __ . __
tert-Amyl ah'ohoL .. __
n-Arnyl chloride
tert-Amyl chloride._._
n-Arr.yl_et_hn ... ___ .
1
1
Amyl nttntP ___ ... _. __
n-Amyl propiona!!'. _
Amylrne. _ . _. _. __ .
Aniline .. __ ..
Anthracene ____ .. _. __
n--Amyl nitrate .. __ ...
Benzene •• ____ ..... _ .
Benzyl IH'nzuate ..... :
chloride ..... I
BicyelolwxyL .. _ .. _. _
BiphrnyL _ .......... ..
2-Bipiwnyiumil•:·.. .. _
Brornobenzen!L _. ___ _
Butadiene (l,:l) ____ _
n-Butane .•...... __ _
1 ,3-llutandioL. . ____ _
Butene- I.. _____ . ___ .
Butent'-2. __ ... _. _ ....
n-Butyl acr>tnte.
n-Butyl alcohol ...... _
1er-Hutyl ah•o'Jol. __
tert-Butyl alcohoL._
teri-Butyl ami1w .... __
n-Butyl benzeue .... .
l l I_ . _ _ _ _ :: !fg
: i: 1.8. ---
2. 6 I 13 465
: {: ! = = = = : = = i = : = = =:
I 5. 0 I .. _ _ .. _ • • • 390
2. 5 100 305
2. 8 31 235
3. 0 -----· - -6
2. 2 12
• 1. 6
1
.-- ---- - -. - . _ _ 420
• g i'"i8""' ·j -'22-
250
2. 2 22 - - - . 3'15
• 2. 7 - - - - - -- - 29.')
2. 9 _ __ _ _ _ __ - az 485
. 66 4. 1 450
15 .'2S
I 1. 0 I 7. I 25
:3S I J. 4 I I()
• I. 4
0 I. 6
• I. ,')
•. 7
'I. 0
• ). 0
1.4
7
L 2
•. 65
I. I
1J.:i
•. 7
• I. 2
I , tl.'i
g • 70
•. s
• I. 6
:.l. 0
I.S
• I. 0
1.11
1.7
' I. 4
I. 7
I. i
IJ.!l
I J. 7
I • 8:,!
I 8. 6
1
7 !I
I-
-I
I
'
-I
.I
-I
'!l. I
12
I 'I
1 1 i ()
--- :[
8. 4 I
........ , ..
1 u
1
. _
!1 ... ----
I S. I
I 12
I 9. R :.'1
-I
1-
I H.() I! '
\l 1--
1 5. 8 ...... I
:wo
4100
-135
260
3-15
170
:!lfl
:Jsu
'l75
615
MO
-tll!i

:lSO
-110
8e• toot notes at end or tnbl<'.
114
Combustible
Limits of flurn- --, --
rnu.bility (volumc-
percPnt) T, • A/1'
--------- {0 Q) I (0 C)
sec-But\• I benzene ... _
tert-Butyl benzene_ .. .
n-Butyl bromide. __ ..
Butyl cellosolv!' .... _.
n-Butyl chloride .... .
n-Butyl formate ..... _
n-Butyl stearate .... ..
Butyric acid ________ _
a-Butryoluctone. __ •.
Carbon di9ulfide ..... _
Carbon monoxide .. __
....... _
...... __ .... .
Crotonaldchyde. __ .. _ -1
(' U ffiPII e ... - _ .... - ...
Cy11noe;cn. ____ ... _._-I
Cyclohcptane. __ .... .
Cyclohcxanc ...... __ _
CyclohcxanoL __ .. _.
Cycloh!•xcne ........ _
Cyclohcxyl acetate ..
Cyclopropan!•. __ ...
Cymerw ... ---· __ .. __
_ .. _ .......
Decalin __ . __ . _ . ____ _
n-l>l'CIIlll' .. - ............ .
I>•·utnium _. _. _ ... .
J>i bomne .. __ .... _ ... _
Di!'S1·i ful'l ( liflce'.lll><')
I>icth; I • .. ____ .
f)jl'lhfl ,. H lir·r•
1.1-llwthvl •· ··1.
l.lr.•lhyl !'Yl'lrrlr• 'il 1
')i•·thvl "t!H'r_
;i, !Jfr•l h1·\ )lPII(!>lll
'hv
1
ht t<HIP
L,.
1
0. 77
I. 77
1
2. 5
8 l. l
1.8
1.7
• . 3
j 2. 1
8 2. ()
1.3
12. 5
1.4
8 l. l
2. 1
I. 8S
6. 6
I. 1
1.;{
• 1. 2
1).2
• 1. ()
'l. 4
1
• 8.'i
.2
I • 7-1
12. 7.')
4. !I
.s
l.S
•. s
I • S
. 7!l
1.!1
7
(i
I
u.. I

I f). 8 .... _ .[ 4!)0
- ... - - - -- -- - 265
IO 11 24!)
I JQ ----- --·
l'l. 2
II )(l
1 6. f)
6. 7
7. 8
10.
I fl. 5
I 4. !I
13 5. t:
75

10
21
!)7 i
-l(i I
.. I
I
!
:Hi5
450
HO
li-10
425
:,l;j()
:.!10

I
:w
• c": l·i11oL.
Dtiso 'ltlyl kt·l•··" --1
!
-... "' to ti.
2-4, lJ ..;11P.\"1Jfl8t1'
1
1
__
Diisopr. ,,,,.r , 1 ftpr_
ililllt'lhyl •. II. I
Dirnrth1 ·llrllr.-
:1,:!-l liloll'thy, ·I• :tile
'illlr·lhyJ dt•t1r
j ,',

/;;('ll!l·i '·"'
th
1
11'.
'lirroo·lhyl , ir"l' .•
1,, 'lim• tl1_vl : .. r.rlll-
I
·I
l !
llr . - . .. ., I 1., h
2,:i-l!. ·l,vl)ll'i !Hill'.' L I
:2.2- 1>11 1.)·1 pro'''""' I ., I
IJ,rrl"ti,, ;ulfidt• .... ! :.!.
llirw::,·vl -ulfoxid(• ___ : ...... .
J)jo,.:. '. - ....... --I \1
llipell'llt·
!J·p!\Oii.}'llil'•ill' ___ _I I. 7 !
I li. :.l I
:,
'I)
!I I
I
{' I
II
:!".:
"b. I
I
1:.!0;
·lOll
·1 .-,
•(
I,
.lPl'ENDIX A 115

Limits of flam-
mability (volume-
Combustible percent) TL AIT
(o C) (o C)
Lu U,.
---------1-----1----------
Di):henyl ether ___ .. __
Dipheuyl methane •. _
Dh illy I ether _______ _
n-Dodccane •• ______ _

Ethyl acetltte. ______ _
Ethyl alcot.oL •. ____ _
Ethyl amine ________ _
Ethyl iJenzene_------
r;hloride. _. __ .
Ethyl cyclobLtt&nc. __
Ethyl _ ..
Ethyl cyclopcntane __ _
Ethyl fer mate ______ _
Ethyl lactate ..... __ _
Ethyl rnerCllptan ..... .
Ethyl nitrate. ___ ._._
E.•.hyl nitrite._ .. __ . __
Ethyl propionate .....
Ethyl propyl ether_._
Ethyleu1• . ________ . _
Ethykneimine. _ .....
Ethylene glycoL •....
oxid,._ ••• _
Furfural alcuhul.. _ .•
Gasuliue:
100/130 ... ·····
115/14!i_ __ ----·
filvrt><iuc _. _____ .. __ .
n-ileptane .. _ .. __ _
1<-IIPXII<ICCUll!' ••...•••
n-lii'X!Ulr'- _ ....... .
n-ll<'x\'1 alcohfll.. _
11-llt>x)·l <'!her .. _.
II _ .... _
11,\'dl'Ugf'll. - . - -
II ydrogpn \',\'1111 irh• __ . ·
liYdi'OI--(I'Il ,;ulfidf' ..... 1
_____ I
aleniJnl.. '
'hmhul till<'.
• \'I al<'••hol .•. _'
'"'' •Ill \·i h<•ft Zt'lll'
1
f><o)llll \·I fni'IIIH lt'
b"hilt\·it•lf{'
]:-;op(•ttfar.•· . !
f-..•ljdilH'IIlH' -1
l"'i'""i'_-;Lll·r·t:llr• .1
• a:1•olud
),·,prnpvl hipiii'IIYI
,Jr-t fur·!.
.II
.II' fi
I\ I •)'4\:-->illl'
'ft •t I II
\!,:II vi ... ·,·tal<'
\f, .. :,,-1 tt<'•·! vlo·l .. -
\1,-•1,\·1 :d'·"il<d
\I<-<,,\'! "11\llif' -
\l<-111\'l !.rrHIIiri<-
:1-\lt•l h\'1 bttlt'llt•-1
\It•! !• ,-)·hill yl kr•lflli<'
.\It·! J,·\'1 .-.-iJ.',_,.,J\ ,. _ .
• • • •
lUtt•_
:llo-thyl •·thy! f'lh;·r
l. 05
• . 43
1.2
11,:.!
•. 6
4. 7
4. ()
5. n
4. 0
I I. I
1).4

I J. 7
I .• '-':.!
:.!. ()
1.1-1
I. 4
. "'
' I 7
'.!. .. !
... ti
ti. f'
;(
J. ;
h. I
• 4. 2
)(I
I. 5
I :.!
·; :.!. ;,
.. 1. 7

ftl('fJwtPa nt t
1
nd of table.
75
4ti
4-1
I 7. ()
I !1. i1
:-:. ·l
1
II
111 f)
1-1. !I
\1. ti
....
I;", I I
IIi
I ! ; (i
{;)
\I
I .'-..II
,. :.!1.
i.----- 400
i: =:=:
I 25 i ;lfj(l
-----1 J;i()
---"1 41'·11
-t:w

jfill
1111
:.!Ill
:.!:lO
:.!Ill
-- IS'i [>-Ill
·!
:! .... -,
i
t;;rt
:!,11
·HI
i
I
I
Limits of flam- I
mability (volume- ,.
peJcent.) I 'h AIT
Mothylohloddo ----- __
Combustible
Methyl cyclohexane.- 1. 1
1
6. 7 _- ___ • 250
Methyl cyclopenta-
diene. __ .- ••. _ .. --
1
1. 3
1
7. 6 49 445
Methyl ethyl ketone.. 1. 9 10
Methyl ethyl ketone
peroxide. - ... - . -.- --- - ..... ..
Methyl 5. 0 23
40
Methyl cyclohexanol. ' 1. 0 ..... _____ • __ .
MP.thyl isobutyl car-
390
465
295
binoL _ .. _ •. _ ..... •1.2
40 -----
Methyl isopropenyl
ketone____________ 51.8 0 __________ _
a-Methyl •. 8 . _ ... _. _ . . .. . . . 530
Methyllactate _______
1
I 2. 2 ________ ------ ____ _
2, Methyl penta'le... •I. 2 --------.----- ____ _
Methyl propionatE>_._ 2. 4 13 • _ .•• __ .• _.
Methyl propyl ketone., 1. 6 8 2 ___ •.. ___ ..
Methyl atyrene __ .... I ' 1. 0 ,. _. _. _. _ 49 495
Methyl viny I ether .. ·/ 2. 6 39 _ .. _. ___ _
Methylene chloride ... ------- ... ----- ______ 615
Monoisopropyl bicy- J
clohexy\__________ . 52
18
4. 1 124 230
2-l\lonoisofropyl ,
bipheny ----------
10
.5:3
11
3.2 141 435
Monomcthylhydra-
zin c .. _ ... _ ... _ .. _ .
4 -------- ------ --·--
_____ . _.
............ .
:o_ _________
3. 4 1-- -- .. --.
Nit roet ha m• _ • __ •• __ _
Nitronwthaue. _ •• __ .
1-JIIitropropane. _. __ •
2-:'\itrop1·opane .•..••
.•••. __ •...
n-Octnue .. __ •.. __ .. _
l'araldr.'hyde. _ ••• _. _ ·1
Pentahorane __ .. ____ .,
i. a _ . _____ _
2. 2 ---.---
2. 5 -- .. -.-
21 • R5 -. - - -- . -
0. !15
1. 3
. 42 ------- -
1.4 7. 8
30
33
34
27
31
13
---48 tl·l'entalle. --.--.--. -i
Pentnrn..t!tvlenc 1
. i .- 2- -22 ;,_ --i-ii)-
a-l'iroline •. .' ..... --- • 1. 4 1-
l'iiiUill'. __ ..... _. __ .. n. 74 'a 7.:.! .... i
Propndi<'m'. _.. 2. ltl
205
220
260
335
570
500
l'ropuu.-. _.. :2. I !I. 5
1
102 j ·150
1,:.!-l'roplllldiol ':.!.;:i '-- _
1
__ 1 410
{j-J'ropiolnctoue a 2. \1
l'r••piOIIIIIrh•hyd\'. . 2. \1
1r-l'ropyl ttcdnt••- _. 1.
11-l'rnpvlakohol.
12
:.?. :.!
:.,. fl
17
I ].j
ddorid<•.. ' :.!. ·I
11-l'r"]',\'lllilrat\'_ _
1
' 1. '1: Iiiii
l'n '1•_1 lr·ll<· . :.!. ·I I I
l'ru}:\ !•'"" ;!;,·ldoridt• ':1. I
• ::4 :.?. fi
• u\jdf'. '.!. ·"
1'\'l'i•lll-•· II J_ '-.
l'rup "cvl lth·,,J,.,I_
1
·• -1
4 1. 0

211
I. I
2. 0
p-T·q,!,.·I•Vi . '·!IIi
,, .. •. 5
rrt•t rah \'dn '2 0
T<·tmlii,_ ... '· f--1 "D. o
I
--- -!-
!
:.!I
1-
71
17!)
4GO
5:1.i
:.!011
116 FLAMMABILITY CHARACTERISTICS Oli' COMBUSTIBLE GASES AND VAPORS
TABLE A-1. Surr.mury of limits of flamma-
bility, [,,1ver tern peraturt limit.9 ( T L) and
minimu11, autoignttion temperatures (AIT) of
in4ividua.l ya.•u1s and t'a.pors 'lirt air at atmospltenc
pressur13- Contiaued

Limite of flam-
mability (volume-
percent) TL AIT
1---,---1 (o C) (o C)
CombusMble
-----·----·· L,. 1--u- .. _·l---
0.8 ------ 430
·· i." 2- -I-- i-
Trichloroethane .•.•.. ___ ... _ _I_....... 500
Trichlo:-:>ethylene ....
28
12
26
40 30 I 4:ZO
Triethyl amine...... 1. 2 8. 0 _ ........ .
Triethylene glycoL... s. 9 28 9. 2 •• _____ • _ ..
2,2,3-Trimethyl bu-
tane ... ------------
Trlmeth_yl amine. __ ._
2,2,4-Trtmethyl pen-
tane .••.•.........
Trimethylene glycol ..
Trloxane ............ .
Turpentine .......••...
Unsymmetrical di-
methylhydrazine ...
Vinyl acetate •.......
chloride ...... .
m-Xylene. ____ • __ .. .
o-"_ylene ... _. _. _ .. __
p-Xylene ....... _. ---
1. 0
2. 0
. 95
• 1. 7
• 3. 2
I, 7
2. 0
2. 6
3. 6
I 1. 1
I 1. 1
I 1. 1
1 lmlfl0° C,
'1•47° c.
'1•76° c.
• Calculated.
I • C.
•1-8&
0
c.
7 t-140
11
c.
•1-1150" c.
•1•110• c.
111•17&
0
c.
"t-oo• c.
nt-53° C.
11 t-86u C.
II 1•130° C.
"1•72°C.
II 1•117° C.
"1-125° c.
111•200° c.
"1-78° c.
10 1•122° c.
12
95
420
415
400
33
----
; 3. 4
1
6. 4
I 6. 6
111-43° c.
111-195° c.
tlo 1•160° c.
"1•96° c.
"1•70° c.
•t-2£1• c.
If ··247° c.
111•30° c.
"1•203° c.
sao
465
530
APPENDIX B
STOICHIOMETRIC COMPOSITION
The stoichiometric composition (G,) of a
combustible vapor CnHmOAFt in air may be
obtained from the equation
100
Thus, C,, ( k
2
) volume-per-
1+4.773 n+ m-
4
·-
cent, where 4.773 is the reciprocal of 0.2095,
the molar concentration of oxygen in dry air.
The following table lists the values of C, for
a range of ( n+

values from 0.5 to
30.75:
N
1
o /_o_.2_5_
1
_o_.5o I
o______________ ________ ________ 29.53 1
l______________ 17. 32 14. 35 12.25
2______________ 9. 48 8. 52 7. 73
3 ______________ 6.53 6.05 5.65
4______________ 4. 97 4. 70 4. 45
5______________ 4. o2 a. 84 a. 67
6______________ a 37 a 24 a 12
7---- - - - - - - - - - - 2. 90 2. 81 2. 72
8 ______________ 1 2. 55 2. 48 2. 40
9______________ 2. 27 2. 21 2. 16
10.------------ 2. 05 2. 00 1. 96
0.75
21. 83
10. 69
7. 08
5. 29
4. 22
3. 51
3. 01
2. 63
2. 34
2. 10
l. 91
N• 0 0.25 0.50 0.75
---
}l_ ____________
1. 87 1. 1. 79 l. 75
12 _____________
1. 72 1. 68 1. 65 1. 62
13 _____________
1. 59 1. 56 1. 53 1. 50
14 _____________
1. 4'/ 1. 45 1. 42 1. 40
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
18 _____________
1. 15 1. 13 1. 12 1. 10
19 ______ " _______
1. 09 1. 08 1.06 1. 05
20 _____________
I. 04 1. 02 1. 01 1. 00
21_ ____________
. 99 . 98 . 97 . 95
22 _____________
. 94 . 93 . 92 . 91
23 _____________
. 90 . 89 . 88 . 87
24 _____________
. 87 . 86 . 85 . 84
25.------------
. 83 . 82 . 81 . 81
26 _____________
. 80 . 79 .78 . 78
27 _____________
. 77 . 76 . 76 . 75
28.---. --------
. 74 . 74 . 73 . 72
29 _____ -------- . 72 . 71 . 71 . 70
30_------ ------
. 69 . 69 .68 . 68
-
m-k-2X
t N=n+
4
-; where n, m, X, and k are the
number of carbon, hydrogen, O'<ygen, and halogen atoms,
respectively. iu the combustible.
For example, the stoichiometric mixture com-
position of acetyl chloride (C
2
H
3
0Cl) in air
may be found by noting that
3-1-2
N=n+-
4
--=2+
4
2.0.
The entry for N=2.0 in the preceding table is
9.48 volume-percent, which is the value of C,
for this combustible in air.
117
118
APPENDIX C
HEAT CONTENTS OF GASES
(Keal/mole I)
T,"K co. H,O o, N,
298. 16 0 0 0 0
300 . 017 . 014 . 013 . 013
400 . 941 . 823 . 723 . 709
600 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. 4 ~ 2 4. 29!:1 3. 7849 3. 595
900 6. 700 5.238 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 1a 360 10. 382 8. 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 18. 985 14. 962 12. 353 11. 705
1,900 2v.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. 101 116. 881
16. 012
2. 400 27. 672 22. 371 17. 803 16. 884
2,500
I 29. 140
23. 652 18. 731 17. 758
I Oordoa, 1. li. TbermodynamiCII of Hlcb Temperature Ou Mil·
tUM 11o11d Appllcatloa to Combuatloa Problemll. W ADO Tecbnlcal
Report 67-33, 18DU&ry 11167, 172 pp.
APPENDIX D
DEFINITIONS OF PRINCIPAL
SYMBOLS
Symbol: D•/inillon
A_____ _ _ _ _ Constant.
A'_ _ _ _ _ _ _ _ Al'ea.
a_ _ _ _ _ _ _ _ _ Velocity of sound.
B _________ Constant.
C,, ________ Stoichiometric composition.
Af/, _______ Heat of combustion.
K _________ Hatio of duct area to vent area.
k _ _ _ _ _ _ _ _ _ Thermal conductivity.
L_ _ _ _ _ _ _ _ _ LowPr limit of flammability.
L* __ . _ _ _ _ _ l\loditil'd lower limit value.
LA,.. _ _ _ _ _ A carbon chain lPngth for
paraffin hydrocarbons ami correla-
tion parametPr for aromatic hy-
drocarbons.
L ,_ _ _ _ _ _ _ _ _ Lu\\ Pr limit of fiarnmahility at 1° C.
Lf D _ _ _ _ _ _ _ Length to d ianwtPr ra t.io.
Symbol:
M ________ _
M, _____ ·--
NO; _______ _
n ________ _
p _________ _
P,.. _______ _
::.P ___ .----
P---------
8•--------
T_--------
t_ ________ _
.,. _____ , ____ ,
u ________ _
u, _______ _
v ________ _
V'--------
v _________ _
')'. --------
/1•/iiiUion
Molecular weight.
Mach number.
Equilibrium mixture of NOa and
N
1
0, at a specified temperature
u.nd pressure.
Number of moles.
l'reSE<ure.
Maximum pressure.
Pressure rise.
Partial pressure.
Burning velocity.
Absolute t<:Jmperature.
Temperature.
T:me delay before ignition.
Upper limit of flammability.
Upper limit of flammability at t° C.
Volume.
Critil)tll approach velocity.
Liquid regression rate.
Specific heat ratio.
119
SUBJECT INDEX
A
Ac11ta ltlt>hyclo __ . _ .. _ _ _ _ _ _ __ .. _ .. _ ..... _ ........ --. 7:J
At•t•tylt•uit• hydrot•ur·uoHIL __ .. _______ .. __ .... _.... .. • 53
Air-fuel r11 tio __ .. __ . ____________ ..... __ .. __ .. ___ • 21
Alcohols ...... _ ............ _________ --. - _ ..... _- ...... - t\5
Aldt•hytles ... __ .. - ______ .. ____ .... -- - _____ - _ .... - 73
Arnmouia _________ -----··------------ ·------ 77
n-Amyl alcohoL __ . ___________ .. _ .. _ .. ___ ..... _ .. _ ti7
Aromutic hydrocaroons _______ .. __ . __ . ___ -- .. _- 5\1
Autoignition •• _ •.. ________ .• _____ .. _ _ _ _ _ _ _ _ 4, 32, 41
B
Barr: cades ... ____ ._ ... _________ ... - _____ .---- 17
BlaRt pressure ______ . __ .. ________ .. _ _ _ _ _ _ _ _ _ _ _ 16
Burgess-Wheeler Ia w. ________________ . _____ - 22
Burning velocity---··-··-------- ____ _ __ 42,45
Butadiene .••• _______ • ___ .. __ . _____ • ____ ---- 48, 53
n-Butane. ______ . _______________________ 21, 25, 32
Butene-1. _. ___________________ .. ___ • ____ 48, 50, 52
n-Butyl alcohoL __________________ .________ 67
lert-Butyl alcohoL. __ • _______ . _________ . _ .. _.. 68
c
Carbon chain __ .. ____ .. _________ .. ____________ .. 41
Carbon monoxide .. __ _ _________ .. _ _ _ _ _ _ _ _ _ _ _ 97
Combustion equlltions ______________________ 21,117
Contact time .•.. _______ ------ ______ ··---_____ 4
Cool !tames •• ________ . _ _ _ _ ______________ .. _ 28
Copper acetyl! de.___________________________ 56
Crit•cal CIN-------------------· ----------- 11
Cyclopropane_. _____________ .. _____________ _ 64
D
n-Decane. __ .. __ . ___ -. __ •• _. _-- .. -- _. ___ . ___ -
Decane-dodecan€ blends. ___ . _- _________ . _ •. -
Deco.nposition •.•. ________ .. ______________ .. _
Dlmethy I ether ______________ . _________ . ___ _
n-Dodccane _______________________________ _
E
21,25
32,43
51.
15
16,57
70
21,25
== = = = = = = == = = = = = = = = = =: = === = = = = = Ethane. ______________ • __________ .. _. _ _ _ _ 21, 25, 28
Ethen------------------------------------- 69
Ethyl alcohoL ___________ • __ .. __ .. ________ ._ 67
2-Ethyl butanol. ___ •. __ .. ____ ...... __ .. _ .. ___ .. _ _ _ 67
Ethylene ___________________________________ 48,52
F
Fl11me arreston _________________ .. _____ .. _. _ _ _ 18
Flame caps. ______ ...... __ .. ___________ . _ _ _ _ _ _ _ 2
Flame extinction __ .. ____ • ____ .. _. _____ .. _ .. _ _ _ _ _ 29
Flammability characteristics. ______ .. __ .. ______ 20
Foam ___ .. ___ .. _ .. __ ... ___ .. ____ .. __ .___________ R
F'Jrmic acid_________________________________ 61
Freon-12. _____ • ___________ .. _ ...... __ .. _____ . _ _ _ 69
Fuel-air ratio _______________________ .. _ _ _ _ _ _ _ 21
Fuel blends._ .. ________ .. ____________________ 74
G
Gas frfleing ... _______________ ... ___________ _
Gas mixtures. ________ ... _. _____ • _. ____ .... ___ _
Gasolh•e ... __ • _______ • _ •. _ •• _ .. ______ • _. -- .. _
120
13
3
13,82
H
IJ hydrocarbons. __ .. __ .. __ . -- ... _....... 102
11\'llt of fonnntion _________ ----·-·· .... -------. fll
• __ ---------------------------- 21. 25,35
mixtures .... __ .. __ . _-. _____ .... _- 3
11-Hexntiecane ... -------------- ....... ------··. :ll, 2f>
r1-llexane ............. --- .... ---------- ... __ ----- :.!l, 2[•, :l4
n-llexylall'ohoL ................ -··------·-- .......... li7
l[y(lraulic fluids--------------··----··-----·---- H5
llydro!!en .. __ .. __ .. _____ . __ .. _ .. ____ ... _ ............ ___ 77, H!l
Hydrogen peroxide ..... __ .. _ ...... _ .............. _ .... _ .. __ .. til
I
Ignition_ .. _ .. _ .. _ ................ _ .. _ ..... __ .. ____ .. _____ _
Ignition tt'rnperature ________ ·-·--- ---------
lgnitibility limits. ___ .. _ .. __ .... _ .. _ .... _ ... __ .. ___ .. -
lnl'rtlllg __ .... _ .. _ .. ___ .... _____ ...... ___ .... ____ .. ___ ..
bobutylene .. _ ........ _ .. ___ . _ ........ _ ............ _ .... _ .. _ .. .
J
JP-4 _____________________________________ _
K
Kerosine .. _. __ ............... __ .. ________ .. ___ .. _ . ___ _
Ketones- ...... __ .... __ ........ __ .............. ___ .... __ .... __ ..
L
Layering .... ____ . _________ .. _ .. _____ .. __ . _____ _
Le Chatelier's law ______________________ ......
Limits of flammability ......... ------------------
Liquid mixtures __ . __ .... _ .... _ . _ ... _ .. - .. -.- .. - .......
Lower limit._ .... _ .. _ .. _ .... _ .. _ .. _._. ____ .. ____ .. _-
Low pressure limits_ ... __ .. _ ... _____ .......... __ .. _ ..
M
Methane _____ ...... ___ .. _______ .. _____________ _
Methyl acetylene ..... ------------------- ___ ..
Methyl alcohoL .. __ .... _ .... _ .. __ .. __ .... __ ..... __ .. _ .
Methyl bromide- .. _ .. _ ......... __ . - _ ............ -- ... -
a .. Methyl butene-L ....• --------------------
MeLhyl formate •••.... ---------------------
Methylene bistearamida. __ .... _ .. _ .. _ .. _ .. _ ..... ___ -
\lethylene chloride. ____ - .. ---- __ - .... -- ..... _-
Minimum oxygen value ________ -----··-----··-
1\lis ts ____ .. __ .. ___________________________ .. _
!\fixer ... ··---------------------------------
N
a
-!
2
lS
48
11, !:l8
7
73
:l
:H
2
31
2
12, 811
!l, 21
5:)
117
Ill
48
71
7
102
ll
a. ll
4, 7
Natural gas.------------ -------------··---- '27, :w
n-Nonane ...... ----------------------------- 21,25
0
n-Octane __ • _ .. _ .. _ ..... __ ...... __ . ___ .... _ ....... _ .... _ _ 21, 2:,
p
P11raffin hydrocarbons_ .... _________ .. _ .. __ .......... _ 20, .i!\
n-Pentadecllne .. _ .. _ ... _ ........ ____ .. _ .. _______ .. _ .. _ _ 21
Pentane __ .. _ ...... _. _ ...... ________ .. _ .. __ .. _ .......... _ _ 24
n-Pentane ______________ ·--------------- 21, 25, :l:l
Perft UO:'O metha:-J P _ _ _ ____ .. _ .. ____ .. ________ .... _ 2S
Perfiuoropropane___________________________ 2S
Peroxides .. __ .. _ .. __ ........ _ .... __ .. ___ ...... ______ 53, 70, I O:l
Predetonation distance .. __ .. _ ...... __ .... __ .. _ .. _._.... 57
Pressure piling ..................... ------------ 58
Propadiene ... ---------·--·------------------ 4S
SUB,JEC'r INr>EX 121
Par•
Propane .. __ .......... ______________ ... _. _ 21, 25, 31
lsopropylalcohol ------------------- ..... 115
n-PropylalcohuL ....... _____ . ___ . _............ 67
n-Propyl nitrate .................. _ ......... _. __ .... . . . 97
Propylt•ne ............................. _. ____ 48,51
0
relationships.................... 05
R
Raoult.'s law ........... _ ...................... ..
Rectangular diagrar..... . . . . . . . . . . . .. . . . ..•..
rate .......................................... .
Relief diaphragms ....................... __ ......... .
s
Shock wave .......................... ___________ _
Spark-energy ........................... .
Spontaneous 1gmt10n ................................... ..
Spmy injection ............................. .
Sprays_ ... _ ........ _ •• _ . _ . __ ......................... .
31
9
44
18
17
3
3
97
6
l•n.re
Hulhu ,·ompounds..... ..... .... ..... ........... 74
Sulfur hclmfluorlde...... .. . . .. .. . .. . . . .. .. . . .. .. .. .. .. .. :.!1'!
T
Temperature limit ...... _ ... _ .......... _ .......... _..... 11
n-Tctrndeca!le.- . .. .. . . .. .. . .... .. . . .. .. .. ... .. .... . .. . . .. .. . 21
Tetra lin ..... _ ... - ....... _..... .. .. .. .. .. .. . . .. . . . .. . . .. .. .. 7
-.. = = = = = = = = = :: = = = ·: = =: = = =::: = = 1
Triangular diagram. . .. .. .. . .. .. . . . . .. .. .. .. . .. .. .. .. . . .. . U
Trichloroethylene......................... . . . . . . . . . . 102
n-Tridecane... .. .. . . . . .. . . .. . . . .. .. .. .. .. • . . .. .. . . . .. .. 21
Tube diameter ............. _ ............................. _ 3, 53, 57
u
n- .................... _ ..... _ ...................... _ _ 21
Unsuturated hydrocarbons........ .. . _ •... _ .. _ ... 47
Upper limit ............. __ .......... _ .... _ ••. __ ... _ 2, 23, 26
w
Wall quAnchlng .......................... _____ --------- 3
X
o-Xylene _______ .... _ .. ____ ---- .... - _ ......... .
60
R U.S. GOV£RNMLNT PRINTING Of'F'IC! 1885

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