Journal of Research of the National Bureau of Standards Vol.

53, No, 1, July 1954 Research Paper 25 16

Self-Ignition Temperatures of Combustible Liquids

Nicholas P. Setchkin *
, l~he m ~ t,hod s prev iously used fo r dete rminat,ion of the ignition temperatures of liqllid s~
a l e, blleft y l evl ewed, and the la rge dlscrepanc lCs 111 repo rted values no ted, Var iou s factors
~vh~ch affect the determmed values of ign it ion te mperat ure are d iscu ssed. A p ract ical
IgmtlOn appa ratll s cons l ~t ll1 g , In ]Jart of an ,in sulated spherical flask, des ig ned to prov ide
cOlldltlOns favorab le to low Ignition tempe rat ure values, IS desc ribed, and data obtai ned
With thiS apparatus on a co nsiderable number of combustible liquids a re prese nted. The
usefulne ss of , t un e-temperature cu r ves of a t.hermoco uple junction p laced in mix t ures of
?om bu" tIble liqu id a nd a ll', as a means of studying the p reign it ion react ions in s Ll ch mixt ures
IS Ill ustrated .

1. Introduction r esul ts of satisfactory reproduci bili ty. The present

The fire h azards associ~ted :vit~ th e use, storage,
and shIpment of combustIble lIqUIds ar e so familiar
as to need no discussion, and the t remendou s and
varied consumption of such liquids carries th e
problem of protection against these h azards into
every el em~nt .of modem economy. For the develop-
ment of effectIve pro tectIve measures, as well as for
efficient use of Lhese liq u id s, ex tensive and accurate
~mo wl eclg e of their ignition characteristics is highly
Impor tant.
Although standard definitions and methods of
determination h ave b e~n esLablish ed for m any of
the phYSIcal and ch emlCal properties of materials,
such as density, viscosity, solubility, etc., th ere h as
been no gen eral agr eement on the definiLion or
determin ation of ignition temp erat ure. Con-
seq,uently, d et~['min ations of Lhis quantity by
dIfferent lllvestigators h ave varied widely bo th in
numerical valu e and significan ce, with much result-
ant confusion and di,[ficul ty in the inLerpretation
and pr actical application of Lhe information.
. P reparatory to th e experimen tal work r epor Led
III thiS paper a st dy was made of the vario s
methods previo sly employed for the determinat ion
of ignitio~ temperature .. ~t appear ed Lhat, although
the Ii?;mtIOn charactenstics of a material were
doub q ess a funct ion of some actual property of the
matenal, th~ meas,;,rement of th at property by any
mcans readIly avaIlable would be greatly affected
by the ambien t conditions. H ence, any practical
definition of ignition temperature which might b e
adopted must continue to be based on a careful
definition and standardization of the test apparatus
and procedure. It was further concluded that a
criterion that indicated the lowest tcmperature
producing self-ignition of the material under condi-
tions as favorable as migh t normally occur, would
b~ t,he most useful in the practical analysis and
ellmmatlOn of hazards, and would also provide a
sui table basis for data of research interest.
Accordingly, the apparatus and test procedure
described in this paper were designed to determine
values in th e lower temperature range in which
igniLion m ay be possible. The method developed
app ears well suited to th e purpose, and in tests of a
large number and variety of materials it has glvcn
• Preseut address, Library of Congress, Washington 25, D. C.
paper covers the work carri ed out over a period of
about 15 years on a considerable number of com-
monly used combustible liqu ids.
2. Gener al Considerations
2. 1. Previous Determina tions of I gnition
Te mper a ture
Most of the methods that h ave been used in the
determinn;tion of igni tion temperature may be
grouped m to two general types , th e " rising-tem-
p eratur e" m ethod, and the" constant-tcmperature"
m eLh od . In the form er, a co mbustible m ixture is
in troduced jl~to the ignition appar atus, and its
temperature lS then continuously increased until
positive ev idence of ignit ion is obsenTed. Thc
self-ignition temperature is usually taken as the
po int at which the time-temperatu re curve for the
m aterial shows a defi.nite incrcase in slope or as
the point of i.ntersection betwecrr the time-tempera-
tUre CUl'Ve for the material and th at for the h catinO"
mcd ium [1).1 In th e constant-temperature method
of determination, the igni tion appar atus is preheated
to a selected initial constant temperature before the
specimen is introduced, and no adjustment of h eat
IllpUt to the apparatus is made after introduction of
the .specimen. . The test is rcpeated with fresh
speCImens at different initial temperatures until the
lowest temp erature at which ignit ion is produced
has b een establish ed. It b as been determined as
th e temperature of the h eating bath surrounding the
reactIOn chamber, as th e temperature of the com-
busti.on chamber wall, or as the temperature of the
ail' within the chamber.
Within these two general approaches to the
problem, numero us and diverse methods of determi-
n ation h ave b een developed (C. R. Brown [2] gives
r eferences to 16 different m e thods of the rising
temperature type alone). Followirrg are brief
outlmes of a number of procedures that have b een
used, and the data in tables 1 and 2 illustrate the
~vide ,variation in values obtained by differ ent
lllvestigators.
Oil-drop m eth.od. E arly determinations of ignition
temperature WIth the so-called "oil-drop m etho d"
were m ade by Holm [3] in 1913 with a heated
1 Figures in brackets indicate the literature references at the end of this paper.

49
 T AB L E l. Igniti on tempemture (in degrees centi gm de) of various combustible liquids determined with oil-dro p method [7 ]

Inve s ti ~a tors

lV[ aterial Masson Edgerton Sot'tman Jcn tz,ch

Holm Moore Tausz and a nd T hompson an d and and
Shulle H a milton Gates Bea tty Von Zerbe
- - ----- ----
v -Heptan e ___ _____ ______ _ 451 430 259 560
n-Hexanc . ___ ._. _. _._. __ . 520 248 5GO
n-Pentanc _____________ ___ 579 4R7 .179 308 515 418 .180
Ben zene. ________ _________ 520 566; 656 740 656 580 700 625 720
Toluen e _________ _________ 516; 633 810 633 553 780 630 730
Car bon disulfi de _________ 343 12.5 120
E th yl ctheL _____________ 410 347 343 487 193 440 500
Eth yl alcohoL ___________ 510 518 558 50S 420 515 575

T A BLE 2. Ig niti on temperature (in de grees centi grade) of liquids determined with different methods [151

T emperature initial oxi dation I Cold fl a mc 1\1i nimum ignition temperat u re

-------~-------~--------~--.--~--------

Material
T(l')~- C-(fur I T. (6i R· I T.(%{ (D) (B ) (E) (F) (G)

Bomb Adiabatic
T n be method E vacuatccl vessel compression
----
n -Pentane ____ ___ ________ _____ ____ ______ ____ _ 295 255 225; 243 254; 263 255; 259 510; 548 225; 237 336
n-Hexa ne_ __ __ _________ _____________________ 265 230 330 220; 230 253 232 285; 570 222; 2:1 2 300; 306
n-Heptane ____________________________ _____ _ 209 300 220 256 219 225 283
n-Octane _______________________________ - ___ _ 197 210 248 203 320 278
n-Nonane_ ____ _____ __________ ____ ______ _____ 205 193
Isooctane _______ ___ _________________________ _ 500
Cyclohexane _____________________ - _-- __ -- - -- 345 235; 260 262 324
Bcmene_ _ ________ ___ ___ __ __________________ 670 650 570 695
Toluene__ ____ _____ __ ___ ________ ____ ______ ___ 550 600 585

l Im-cstigators: ( A ) Callendar; (B ) Lewis; (C) E stradere; (D) Prettre; (E ) Townend and Cohe11; CF) Dnmanoi s a nd others; (G ) 1' izard a n d Pya.

porcelain surface. Moor e [4] used a platinum
crucible submerged in mol ten m etal or embedded in a
steel block. Sor tm an and Beatty [5] made a small
cylindrical cavity of 43-ml cap acity in a stainl ess-
s teel block and provided for the circulation of
preh eated air. J en tzsch and Von Zerb e [6] also
used a steel block with four cylinders (7.1 ml) and
circul ation of oxygen or air. A m odifi ed type of th e
Moore app aratus, heated elec tri cally, h as been
widely used by m any investigators [7] . The ini tial
temp er ature of the b ath , or wall of th e ignition vessel,
leading to ignition is usu ally considered as the self-
ignition temp er ature. The values given in table 1
are reprodu ced from reference [7].
Dynamic tube method. In this m ethod , a Pyrex
tub e is h eated in a conven tion al electric furn ace t o
th e desired temp er ature indica ted by a th ermocouple
in contact with th e ou tside surface of the tube. A
combustible substan ce, being preheated sep ar ately
or togeth er with air or oxygen, is allowed to p ass
through th e tube_ The tests are repeated at differ-
en t temperatures of the tube un til evidence of igni-
tion is ob served . Appar atus of this type was used
bv Dixon and Coward in 1909 and 1934 [8, 9], by
Nl ason and Wheeler [10], and by m any others.
Dixon and Co ward limi ted th eir test t o 15 second s.
Callendar [11] and M oureu [12] m ade a study of slow
combustion and determined the " T emp er ature of
Initial Combustion" (T _ L C. ) in an improved ap-
p ar atus. This temp er ature was defined as the tube
temperature necessary to provide t he first appear-
ance of products of combustion (steam , carbon
50
dioxide, aldehyde, etc.) and was determined by
ch emical an alysis of samples taken periodically
during various phases of the r eaction.
This temper ature h as some r elation to the " T em-
perature of Th ermal R eaction" (T _ T. R. ) intro-
duced by E str adere [1 3], and th e "Critical Inflection
T emp erature" (C. LT .) in troduced by L ewis [1 4].
All t hese temperatures ar e related to the " T emper a-
ture of Ini tial Oxidation" [1 5] or , in other words, to
the temp er ature of incipien t self-heating. P rettre
defi.n ed th e igni tion temp erature by m eans of two
cri teria, th e appearance of "cold fl am e" (T . C. F .)
and the appearance of norm al fl am e at " Minimum
Ignition T emper ature" (M . I. T .) _ A tabulation of
ignition temperatures m easured b y this m ethod is
incl uded in ta ble 2, which is reproduced from
reference [1 5].
E vacuated-vessel m ethod . In this m ethod a com-
bustible mixture is suddenly admi tted in to an
evacuated vessel preh eated to the desired tem per a-
ture. This m ethod was origin ated by M all ard and
L e Ch ateliel' in 1880 and was u sed subsequently
by M ason and Wh eeler [1 0] and T ownend [16].
Igni tion was indicated by rapid. rise in pressure.
Lewis and also P idgeon and E gerton [17] modified
this m ethod by admission of the cold combustible
mixture into an evacuated vessel h eated at a steady
rate (rising-temperat ure m ethod) _
Bomb method. Th e bomb method was used by
Neumann [1 8] and oth er investigat ors for determina-
tion of the igni tion temperatures of combustible
mixt ures at high pressures.

L
 Adiabatic compression method. H eating of a
combustible mixture to the ignition point by adia-
batic compression was used by Tizard and !:'ye. [.19]
and Pignot [20]. It is hardly likely that Iglllt~on
temperatures measured by this m ethod, whlCh
involves the use of rising temperature and pressure,
arc directly comparable to those m easured at
constant pressure. .
ASTM standard method. Commlttee D- 2 on
P etroleum Products and Lubricants of ASTM in
1930 adopted a standard m eth od and apparatus
(D286-30) [21] for the determination of the "Auto-
o-eneous Ignition T emperature." Th e standard ap-
paratus consists of a conical Pyrex flask of 160-ml
capacity, submerged in molten s~lde.r h eated by a
gas burner. A few drops of the hqUld to be tested
are allowed to fall into the flask , previously heated
to different initial temperatures. Th e ignition
temp erature is defined as the lowest temperature of
the solder bath, indicated by a thermoc~uple placed
in a silica protection tube submerg?d ~ the bath
near the flask , necessary to ca use IgmtlOn of the
sp ecimen.
2.2. Selection of Method and Definition of Self-
Ignition Temperature
~With the rising-temperature procedure of. deter-
mination, th e ignition temperat.ures vary. wIth th~
rate of temperature rise and wIth th e cn tel"lon of
ignition. Elaborate control equipment is n ecessar)~
to obtain reproducible resul ts 8lther on t):l e ~a~ls of
a fixed rate of h eating or on that of mam tamlllg a
fixed temperature difference between any part of th e
sp ecimen and its s UrJ·o~ndings . Furt~ermOl:e, tl~e
comparatively slow h eatlllg of ~he ~ specnnen m thIS
m ethod is not generally well sUl ted to the stud y of
liquids, many of which apparen tly produce vapors
that form rela tively stable compounds wl tl~ ox}:gen
at low temperatures. If the sy.s tem has tlm? In a
low-temp erature range to perm It th e formatIOn of
such compounds in appreciable amount, the obser,:"ed
ignition temperature !D-ay b ? well above that whIch
might have been obtallled wIth the constant-temper-
ature method. In this latter m ethod , on th e other
hand, precise control ?f th e initial .temp erat~re
may be accomplished wIth r elatIvely sU~1pl e eSlu~p­
men t and the rapid h eating of th e speCImen lImIts
th e time in which low-temperature reactions may
take place. The constant-temperature method of
determination was selected for the present work,
and th e liquid charge was sprayed into the h e~ted
ch amber as a fine dispersion, so that It ra~ld~y
became vaporized and mixed throughout th e au· Il1
the ch amb er .
The characteristic thermal effects when a combus-
tible liquid is thus in trodu ced int? th e chamber at
different initial temperatures are lllustrate~ ~ y th e
time-temperature curves of figure 1. After ~n]~etlOn
of th e dispersed charge, the t~l~ll?erature wlthlll the
ch amb er first falls below the Illltial t emperature be-
cause h eat is absorbed in vaporizing and heating the
sample. In a shor t time, h eat supp~ied mainly: f~'~r[1
th e walls of th e chamber reestablIshes the Il1ltml
51
['5
6
1\
- SE L F -IG NtT tO N k' EAC TlON
uJ
f--
----- -- - - --- - -- - ----- - \
/
tl Q. / '
lX_I - 1--
\I
Lo f I
- ->----r----- -----
\/ I
T I ME
FI GUR I, l. I dealized time-temperatlu·e CU1·ves for self-ignition
and nonignition reactions of combustible liquids.
temp erature. At relatively low ini tial temp era t ures,
th ere may be no furtl1er therm:;tl effects, and t~e
temperature of the sample-au· mIxture may remalll
constant at the initial value, as at to . At hIgh er
ini tial tempera.tures, exothermic reactions within the
sample-air mixture may be induced and the tel1'!-p~ra­
t ure ~ of the reaction mixture raised above the mItlal
value. The exten t of this temperature rise depends
upon the differ en ce between the rate of heat gen era-
tion within the mixt ure and the rate of h eat loss to
the chamber walls. At ini tia.l temperatures th at
produce relatively mild reaction within the mixture,
the h eat generated is even t ually lost through the
chamb er walls \vithout visible effect on th e mDcture,
and the temperature r eturns to the initial value after
a period ?f time. depen~ ~n t on t~e i.nt.ensItr, of t he
exoth ermIC reactlOn. 'IbIS slt uatlOn IS Illustrated by
initial temperatures t1 , t z, t3 , and t4 in figu~·e.1. How-
ever , at some temp erature, ch ar3;cten stlC of t he
material under study and of th e partIcular test ch am-
ber employed, th e reaction with~n the mixture will
become sufficiently intense to rmse th e temperature
to th e ignition poin t, a.s eviden ced by flame or ex-
plosion. The initial temperatures t5 a~d t6 r epresent
such ignition reactions and fur th er Illustrate the
reduction in ignition lag, which usually results as th e
ini tial temperature is increased .
For the present stud?, the following definition of
self-ignition temperature was adopted:
The self-i gn ition te mperat ure (SIT) of a li q uid !s t he
minimum te mperat ure from whi ch a comb us tIble rl1l xt ure
wi t h air wi ll pass in to a condition of o bse r vab le comb us-
t ion in t he ex perim enta l apparat us employed .
 2 .3 . Factors Affecting the Observed Values of SIT
a. Thermal C h ara cteristics of the Apparatus
Inasmuch as ignition depends upon the tempera-
ture reached by the reacting mixture, the governing
factor in its development is the amount of heat re-
tained within the mixture and available for increas-
ing the temperature. Hence, ignition will result only
when the reaction is intense enough to generate heat
more rapidly than it is lost from the reaction mixture
to its surroundings, and the initial temperature of the
chamber must be high enough to induce such a
reaction. Therefore, the higher the rate of heat loss,
the higher will be the initial temperature required
to accelerate the reaction to ignition, that is, the
higher will be the determined values of the SIT.
Thus, the design and construction of the reaction
chamber affect thc SIT values that will be obtained.
In order for the determinations to approach the low-
est temperaturcs from which there may be danger of
ignition, the chamber walls should be constructed
with as low heat capacity and heat conductivity as
may be practicable. The size and shape of the
chamber, as well as the structural materials, must
also be considered.
b. Pressure and Uniformity of Temperature
The relation between the pressure within the
ignition chamber and the observed value of the SIT
has not been determined. However, for the develop-
ment of a practical test method, it is reasonable to
assume that atmospheric-pressure variations will
havc little effect on the determined values of the
SIT.
It is probable that the ignition reaction between
the combustible substance and the oxidizing agent
initiates with the most highly energized molecules of
the mixture, and supplies the heat necessary to raise
the energy level of adjacent molecules to the ignition
point, thus propagating itself throughout the mixture
[22] . If all of the molecules present are very close
to the required energy level at the same instant, the
spread of ignition through thc mass will be extrcmely
rapid. Hence, the maintenance of uniform tempera-
ture throughout the reaction chamber will fa VOl' rapid
propagation of the ignition reaction.
c. Reaction Mixture Ratio
The ratio of the combustible substance to aIr III
the reaction mixture has an apprcciable effect upon
the SIT. Mixtures that are excessively rich or
excessively lean usually ignite at higher temperatures
than those close to some intermediate composition
characteristic of the material. Carbon and soot,
which may have been deposited from previous
detcrminations with over-rich mixtures, may also
influence the SIT value obtained.
d. Method of Temperature Measurement
Temperature measurements are usually made by
means of one or more thermocouples either embedded
52
i
L ~. ~
in the heating bath or medium outside the chamber
walls or installed directly inside the reaction cham-
ber. Reproducible rcsults may be obtained with
any of these methods, but because heat loss from the
chamber cannot be conveniently eliminated, lower
values of SIT are usually observed with the last
arrangement. Fur thcrmore, a thermocouple placed
inside the chamber may also be used to indicate
temperaturc changes during the reaction.
e. Criteria of Ignition
The intensity of the visual evidence of ignition
varies decidedly with the initial temperature from
which the reaction proceeds. At high initial tem-
peratures, self-ignition usually occurs in more or less
violent form, such as a bright flash of flame and
audible expulsion of gases (explosion). At somewhat
lower initial temperatures the flaming becomes rela-
tively mild, whereas at the lowest temperature from
which ignition is detected, the flame may be very
dull violet or blue, often visible only under dark-
room conditions. The latter may be confused with
cool flame reaction, which is not generally recognized
as evidence of ignition even when, occasionally, it is
accompanied by a rapid rise in the temperature of
the reaction mixture.
The time lag before the development of ignition is
also affected by the initial temperature of the reac-
tion. It is an inverse function of the initial temper-
ature and may be only a fraction of a second at high
initial temperatures and may amount to a number of
minutes at the lowest temperature from which
ignition occurs. For example, methyl cyclohexane
showed an ignition lag of 30 seconds at 275° C, and,
using the same test equipment, the lag was 20 min
10 sec at 248 ° C. By limiting the tests to 10 or 15
seconds, as some investigators have done, the self-
ignition temperature would have been determined as
well above 275° C .
In addition to the visual evidence of ignition, the
time-temperature curves for many liquids provide
supporting indication of its occurrence. The curves
at t5 and t4 in figure 1 illustrate typical differences in
the curves for ignition and nonignition reactions
proceeding from only slightly differing initial tem-
peratures. Although the rate of temperature rise
was at first about the same in the two cases, it soon
became much more rapid and pronounced in the
ignition reaction and was followed by a sharper drop
from the peak temperature. This decid ed difference
in the time-temperatme curves for ignition and non-
ignition reactions is often helpful in the final deter-
mination of the SIT, particularly vvhen the detection
of flame becomes difficult and somewhat uncertain.
f. Extraneous Stimuli of Ignition
The ignition reaction may be induced by a number
of means extraneous to the reaction mixture itself,
and devices used by various investigators have in-
cluded pilot flames , sparks, detonators, overheated
surfaces, and catalytic agents . The introduction of
such stimuli is often accompanied by complex effects
on other ch aracteristics of th e equipment, and in TUDE

general it tends to complicate th e problem of accurate

interpretation and evaluation of the r es ults. Until
more extensive research has been carried out on
problems related to th eir use, it would appear
advisable to carefully avoid their introduction,
either intended or incidental.

3. Test Apparatus and Procedure

3.1. Development of Apparatus
ASBES TOS
PAPER
Preliminary experiments were conducted with the
ASTM standard ignition apparatus [21] with solder
bath and gas burner. B ecause of difficulties in ElfCTR IC
CU RRENT
controlling the temperatures and poor reprod cihili ty S UPPL 1

in th e results, this apparatus was modified to incl de

electric beating elements, a 0.2-li ter spherical P~Trex
flask , a stirring arrangement in the bath, and di rect
measuremen t of temper ature in the flask. In order
to reduce th e heat loss from the reacting mixture to
the surroundings and improve uniformity of temper-
ature control in tIle flask , the solder b at,h was la ter
replaced with two sets of h eating clements made of
nichrome wire, in asbestos sleeving, wound around
the upper ann lower halves of th e spherical flask
and protected with a refractory cement. The fi nal
design of the igni t ion apparat s consisted of a l-l iter
sph erical Pyrex flask , as shown in figure 2, placed
concentrically inside a refractory casing so that a
~-in . air space w as provided be t ween the flask and
t he casing for f rther r ed ction of h ea t loss. The
h eating wires WeTe wound around the up per and
lower halves of the casing and the neck , witiJ indc-
pendent temperature controls. T emper atures of
th e three heaters were indicated bv three thermo-
couples made of cluomel-al umcl '(26 B&S gage)
wire placed b ehind each group of h eating coils.
Two additional th ermocouples wer e placed in con-
tact with th e upper and lower surfaces of th e flask.
The sixth thermocouple, insulated by glass sleevin g
T ABLE
ASBFS TOS
PAPER
ALL OVEft
Fre ORE 2. One lil er spherical pYTex fla sk ignition appamtus
fo r li quids with air space and r-efractOl'Y casi ng.
and also of 26 (B&S gage) wire, was placed in the
lower part of the flask for indicating the tempera-
tu re inside Lhe flask. The flas k ncck was closed
with a cement-asb es tos stoppe r having two p assages,
one for the thermocouple wires and the other for
injection of the ch arge.
The eITect of chamber size on th e observed srlf-
ignition temp eratur e was studied by m eans of add i-
Lional tes t units of the following capacit ies : 0.008,
0.035, 0.2, 12, and 15 liters. These units were con-
str cted in substant ially the sam e manner as sh own
in figure 2, with the exception of the 15-1iLer appara-
tus, the chamber walls of which were m ade of opaque
s'li ca about % in. thi ck , with no air space b et ween
the walls anel th e heating coils. From the results
shown in table 3 and figure 5 it is ev iden t th at, over
3. EjJect of fl ask size on i gnition chamcter'istics

Flask size
----------~------------,-----------------------,---------.--~-------------

Material 0.008 li tfor 0.035lilcr 0.2 liter 1 liter 12 liters 15 li te rs

- - - - - - - - - - - - - - - - --------,- - - - - - 1 - - - - - - - - - - - ------,------

I_______________ I__
SI_T__ , I_~~ ~ _ ':ag SIT L~ ~.: ___J~ag SIT 1_____
_____
L ag SIT
1____
-----
La g

'C I min:sec °C min:sec °0 min:sec °C min:sec 'C min:sec 'C min:sec

Carbon disulfide ____ __ _____ __ _ 151 ______ 127 ___ ___ 120 0:08 110 0:14 90 0:20 96 0:20
Ethyl ettcL _________________ _ 212 197 180 0:20 170 0:25 1(j() 1:10 102 1:08
Gasoline (65 octan el __________ _
Gasoline (73 octanc) __________ _ I 283 248 2:30 248
258
4:30
5:00
224 10:50 240
252
8: 15
3:35
VarsoL ______________________ _ 237 1:52 235 3:00 215 0:48
Kerosi ne _____________________ _ 283 248 1:00 233 1:30 227 2:55 210 7:25 215 5:55
Cleanor's solvr nt __ ___________ _ 243 2:44 224 9:42 235 4:25
Furnace oil No. 2 ____________ _ 242 0:55 233 2 :40 22(; 2:55 230 2:30
Motor oiL ___ ________________ _ 357 0:05 35 1 0:04 313 0:35 320 0:48
Benzenc _____ _________________ _ 668 619 579 1:05 559 0:48
'rolucnc ___ _______ ____________ _ 6-19 58-[ 538 0:15 519 0:55 482 3:40
Acctone ______________________ _ 676 570 519 0:26 491 0:40 467 1:25
Acetic acid ___________________ _ 611 544 505 0:08 488 0:13 464 1 :30
1'thyl alco hol. _______________ _ 495 0:05 415 '102 O:~8 391 0 :40 363 2:40
M ottlyl a lcohoL __ ___________ _ 498 473 0:23 441 1:10 428 1:30 38G 3 :00
o lyccrlnc ____________________ _ 3S9 0:3 1 371 0:35
E Lhylcnc glycol. _____________ _ 505 447 0:20 398 0: 23
n-P entane ___ ____ _____________ _ 295 273 0:25 258 1 :00
n-llcplanc ___ ________ ______ _ 255 248 0:20 223 0:45

53
 l
I

the size range studied, the observed self-ignition well at high temperatures and would be subj ect to
temperature becomes lower with increasing chamber variable deterioration with repeated use. As it is
size in units of similar construction. This effect important that the thermal ch aracteristics of the ap-
should not be unexpected as the rate of h eat paratus remain as constant as possible, the simple
loss per unit volume from th e reacting mixture will refractory casing was selected for the major portion
be smaller with the larger chambers b ecause of the of the work .
smaller ratio of surface to volume. The higher
values of SIT obtained with th e I5-liter unit than T AB LE 4. Effect of chamber wall construction on self-ignition
with t he I2-liter unit indicate a greater heat loss to temperature with the i-li ler flask
the thicker opaque silica walls. Although slightly
lower SIT values were obtained with the I2-liter T ype of casing
P yrex unit, it was unwieldy and fragile. Conse- Liquids
I Mirror
quently, the standard, easily r eplaceable I-liter Metal R efractory surface
flask was used as the more practical test apparatus,
in making most of the determinations. Acetic acid ____ ______ _________ _____ _
°C °C °C
SOl 488 474
An investigation was also made of the comparative Acetone __________ _________________ _ 50,\ 491
Ethyl alcohoL ____________________ _ :;91
SIT values obtained with different types of casing Gasoline (m otor) ____ ______________ _
405
249 243
385
238
around the I-liter flask. In addition to the refrac- Isooctane __________________________ _ 431 420 409
Toluene ___________________________ _ 529 519
tory casing separated from the flask by a }6-in. air Varso!.. ___________________________ _ 237 235 234
Ethyl etheL ________ ________ ______ _
space shown in figure 2, two other units were con- 172 170

structed . In one of th ese a %-in.-thick copper casing

was fitted as closely as possible around the flask , and
in the other , a refractory casing with mirrored inner Th e possibility that the thermocouple wires might
surface was separated from the flask by a %-in. air exert som e catalytic effect on the reaction was
space. The res ults obtain ed with several different seriously considered. A test apparatus was carefull y
liq uids tested in these three units are shown in table 4. prepared so that h eat losses by conduction were
In each case the high est valu e of SIT was obtained practically eliminated_ Comparative tests were
when using the m etal-encased flask, whereas the conducted, with the th ermocouple remaining in its
lowest v alu e was obtained with the mirrored refrac- usual position in the chamber throughout the
tory casing. However , it appeared that the mirror reaction, and with the th ermocouple removed from
coating on the refractory casing would no t hold up the chamber just before inj ection of the liquid
charge. The self-ignition temperature was a little
higher with th e th ermo couple present th an without
145··, - - - - - - - - - , it, and increased slightly as the length of the wire
in the chamber was increased , but no evidence of
II
II
catalytic action was detected.
140 t-+f--- - - - I Callendar [23] cond ucted experiments on th e
possible catalytic influence of a variety of m etals
placed in a test tub e and, of those studied , only
13~ H-t-- - - - - I
platinum black showed catalytic action. Thompson
[24], and ~![atson and Dufour [25], used differen t
m etals for construction of the entire wall of th e
130 H-+-- - --I
r eaction chamber. D efinite variation of th e se1£-
ignition temperature with th e m etal used was found ,
:! 1z'5 H---!-- - - - I but the effects were evidently related to the h eat
losses to and through th e con tainer walls.
3.2. Test Procedure
The procedure followed in es tablishing the self-
ignition temperature of a combustible material con-
sisted of a series of experimen ts at differen t tempera-
tures and with different proportions of combustible
material and air. In conducting an experimen t, th e
power suppli ed to th e individual heating elements
of the igni tion apparatus was adjusted un til the
temperature inside the flask was uniform to 2 deg C
and constan t at some value estimated to be near
the SIT. A charge of 0.2 ml of the combustible
liquid per liter of flask volume was inj ected into the
flask by means of a hypodermic syringe fi tted with
a fine needle. This provided the dispersion necessary
FIGURE 3. Time-t empemture curves for cm'bon disulfide. for rapid evaporation and nearly simultaneous
I-liter flask, charge eq uals 0.5 ml initiation of th e reaction throughout the flask. The
54
reaction was permit ted to proceed without any
alterations of the power s upplied to the apparatus.
In order to follow the nature of the reaction,
observa t ions of the electromotive force of th e
t hermocouple inside the flask , at intervals of 15 to
20 seconds, were plotted against time as th e reaction
proceeded. Th e temperatures of the heating coils
and flask surface were ch ecked at intervals of 3 to
5 minutes.
The experimen t was repeated at differen t initial
temperatures un til th e lowest temp erature from
which ign ition occurred was determined for the
charge of 0.2 ml of combustible material per litcr of
air. Additional experiments wcre then made with
different charges to establish the lowest temperature
from which the optimum ratio of combustible mate-
rial to air would proceed to ignition.
Generally, ignition was clearly indicated by audible
or visible evidences (explosion, puff, flame), and it
was also shown by characteristic changes in th e time-
temp erature curves, which served as dependable
criteria when the visible evidence became unce rtain
or obscured . As an a id to visual detection in the
final determina tions, the interior of the l"eac Lion
flask was viewed under dark room conditions bv
means of a miITor placed above the flask: opening .
Under these conditions, eve n very weak flames were
distinctly visible, and flam es obsc ured by the produc-
t ion of dense smoke and fumes co uld be detected
from th e illumination of the fum es .
j\i[aterials such as g ums, waxes, and tars, which
were too v iscous at room tem.pera t ure to be h andled
b~' s~Tringe inj ection , were tested by placing th em in
minimum values obtained under th e mo L fa vorable
conditions for ignition of th e particular matcrial.
R epresentative characteristics and time-tem.pcratLlre
curves for the materials under sL udy arc shown in
fig ures 3 to 22, but the.v do no t in all cases include
th e determination that gave Lhe 10wcsL SIT value.
Some minor discrepancies will t berefore be observed
between the SIT values in the tables and tho sc shown
by the curves.
For convenience, the combu stible materials st udicd
in this investigation have been grouped as follows :
1. Liquids of low ignit ion temperat ure.
2. Common petroleum products.
3. P etroleum compounds.
4. R eference fuels.
5. Miscellaneous compounds.
6. :Miscellaneous commercial materials.
4 .1 . Liquids of Low Ignition Temperature
The ignit ion characteri stics of two liquids, carbon
disulfide and ethyl ether , ignitible at com paratively
low temperatLlres arc given in table 3.
a. Car bon Disulfide
The self-ignition of carbon disulfide was llsually
indicated by a violen t explos ion accompan ied by
flame and a very rapid ri se in temperature (sec fig. 3).
The preignition r eaction, however, was of a ver.\'
mild form, indicated by a gradual rise in tempera-
200

a small crucible sus pend ed in the lower part of the

flask by a th in wire. This crucibl e arrangement was
also used for at least Lhe preliminary tests on cer tain 190 -
oils, lacquers, a nd paints, wh ich prodLl ced especially
sooty r esidues, beca use it helped to prevent an I
180
excessive accumulation of soot on the walls of th e I
flask. It was n ecessar y, however , Lo make a COITec- I

t ion for the cooling effect of the crucible, on any rl

SIT valu es ob tain ed in this way. 170

After each test, the produ cts of decomposition u

were blown out of the flask b y a jet of air in order to
r educe the amount of carbon or soot deposited on
o
u,
f'I 160 I
/
::J
t he walls. The interior flask surface was cleaned at t(
I\'
regular intervals during th e preliminary tests for U,
Do.
~I G N IT tON OUR IN ~
2 150 • SCAV~NG I NG -
approximate determinations of the SIT, and before

//
11
IGNITION ZON!;-
each test in th e final determinations. I-
2
g 140
4 . Test Results '2
9
N O N - Ig N ITION
ZONE'-
Th e following ignition characteristics were deter-
mined under the specified test conditions for a
number of combustible liquids:
1. Self-ignition temperature.
2. Character and in tensity of the evidence of
120

y-/
:/
ignition. .~
I/O
3. Favorable fuel-air mixture ratio for minimum o .05 . 10 . 15 .20 .25 . .30
ignition temperatme. CHARGE-, m i
4. Time-temperature curves and ignition lags for FIGU RE 4. Effect of charge on ignition tempemlure of carbon
different initial temperatures. disulfide.
Val ues for the SIT gi ven in tables 3 to 9 are the I-liter flask

55
ture, even for temperatures just below the ignition from the neck with a barely audible sound. The
region. :NEnor fluctuations in the time-temperature temperature of the mixture continued to rise and ,
curves sometimes resulted from secondary reactions in about 10 or 15 min, reached its maximum (25
caused by rich mixtures or by gases evolved from deg C above the initial temperature) . However,
deposits on the flask surface if not cleaned before at slightly higher initial temperatures ignition
each test. Both of these factors may have a retard- occurred at a time when the thermocouple indicated
ing effect on the ignition reaction. Normally the a lower temperature of the mixture than the maxi-
lowest self-ignition temperatures for combustible mum observed in the preceding test. This fact
liquids were observed when using charges of 0.2 to seemed to indicate that either the development of
0.25 ml per liter of air. However, self-ignition ignition is not a simple function of gas temperature
temperatures of carbon disulfide showed a rapid (hop or the thermocouple and temperature-indicating
as the fuel charge was reduced from 0.2 to 0.05 system could not accurately follow the rapid tem-
ml/liter of air and remained almost constant for perature changes at the point within the gas where
charges below 0.03 ml, as shown in figure 4. ignition actually took place.
The carbon disulfide-air mixture had one critical
ratio for each initial temperature, above which the 4.2. Common Petroleum Products
mixture remained nonignitible. For example, the
critical charge for the initial temperature of 150 0 C The ignition characteristics of 18 common petro-
was about 0.18 ml. With a charge of 0.25 ml, the leum products were determined, and the final SIT
reaction was not accelerated to ignition during values obtained are given in table 5.
the 27f-m in test period. If a fresh ch arge of air
was admitted at the end of this nonignition reaction, TABLE 5. Ignition characteristics of common petroleum
a violent ignition occurred. This ignition probably products determined in the 1-liter flask
r esulted from reducing the concentration of the
mixture below the critical value of 0.18 ml per Product SIT Lag
liter.
b. Ethyl Ether °C min sec
Gasoline (650ctane) ____________ ______ __________ _ 248 4 30
Gasoline (73 oetanc) ____________________________ _ 25S 5 00
Self-ignition of ethyl ether was characteristically Gasoline (870ctanl') _ _____ ______ ____ ___ _ 41~ 0 06
VarsoL__ _________ ____ _ _________ _____ _
indicated by a violent explosion accompanied by a Kerosine _____________ __ _____ ___________________ _
235
227
3
2
00
55
large flame and rapid rise in temperature. Typical Cleaners' sol '-enL ________________________________ _
Crude oiL __ __ . __________________ _______________ _
243 2 44
262 0 35
time-temperature curves are shown in figure 5 for Diesel fuels:
41 cetanc ____ _____ ______ _. ___ ________ _____ ___
different sizes of ignition chambers. 55 cetane ___ _____ _____ __ __ ___ __ ____ ___________ _
233
230
3
2
00
30
The nonignition reaction of this liquid was 60 cctane .. ________ . _______________ . ____ ._. ____ _
68 ceLa ne. __________________________ . ___________ _
225 2 40
226 1 45
characterized by a slow rise of temperature for a F urnace oil No. 2______________________________ _ 233 2 40
considerable time after injection of the charge. Lubricating oils:
USN Ko. 2075 __ ___ ___________ __ ___ ______ ._. ____ _ 241 2 15
During the first period of the exothermic reaction, US,," No. 8190 ___ ________ __________________ __ __ _ 271 0 15
Chlorinated paraffin oiL _ _____ _ 414 0 03
extending from 5 to 10 seconds, the pressure inside ]\t(otor oiL _____ ____ ______ __ ______ . _____________ __ __ 351 0 04
BcnzcllC" ___ _____ ._. _____________________ . __ _______ .
the flask increased slightly and gases were expelled 48
'ro lucne __ ___________________ . ____ . _______________ _
559
519 °° 55

-+-
2 00
169 0
-- -I a. Motor G asoline
/"---- 167°(,
~,...-
The time-temperatUl'e curves for motor gasolines
---
/'/'
190
./
~ -- were characteristic of a number of refined petroleum
~
~ f 0.2 I,ter 1//
./

I /' ~ /"
Il de,
--- products and differed from those of combustible
liquids of nonpetroleum origin. The exothermic
':J"' reaction appeared to proceed in two stages. It was
~T?J/
(\(

f-
180
't- characterized by a consistently reproducible tem-
<:
porary drop in temperature as the reaction pro-
~~/j//t i
IY
iI.J
"- gressed, probably caused by an interruption of the

V ~ltt-t----
~ exothermic reaction or the occurrence of some endo-
~ 170 ftc
thermic process. The time-temperature curves of
12 /de,
figure 6 show this two-stage reaction , the charac-
.~ - ~-~- r-- -
,u
~59 'C
~V/; :::- fi~ r-- _ _r-- teristics of which were not appreciably altered by
~ ~V
15i.ter - - \6 1°(.
varying the charge or the size of the flask. Ignition

IVI
160 J:l
of gasoline usually occurred during the last stage of
1'/ the reaction, whereas that of kerosin e and cleaner's
11 solvent occurred in the first stage.
150
A comparison of adjacent ignition and nonignition
o 2 3 4 5 G 7 8 9 10 curves suggests tha.t the rate of formation of stable
TIMe , min compounds was highly sensitive to slight variations
FIGURE 5. Effect of chambel' size on SIT of ethyl ether. in temperature. Not only did the tempera.ture in

56
 280

,I
275
- I GN ITION R~A CTION
--- NON - IGNITION Q~AC TIO N
)( !:'-XPLOSION
Jot PUF-F- 270 !'\,

~
• NON -I GNITI O N
L.)
o

~ 2el5 - !- a
I
C HARG~ 0. 10 ml
:J ,0 , 0
" 0.15 ml
~
II<'
~\ ~ . 0 ·20 ...... 1
0 .25 ",I

e-~ :- 1+
,'tzc;.o 0 .30 ",I

~
I-
I

~ -~. i
2
~ "2-5:)
z
!2
<
250
4-
A'
+/

-- -- ;2.45 0 I 2 '3 4.
Z40 ~~~/~/-~'~_~-T=-~~-~---F--+-+-+~P-+-+-4-~2r·0~·rC-+~ 16N1 TIOrJ LAG } min
I; - -
'II
I
FI GU RE 7. l?elation between i gnition lag and ignition tempera-
IUl'e fOT motoT gasoline.
o I Z ~ 4 5 6 7 e 9 10 II 12 " 14- 1:5 16 17 10
T IME- . min J ·Iilcr fl ask.

FIGURE 6. T ime-temperatw'e CUl'ves fOT 65 octane motor

ga soline. 200

I·liler fl as k, charge eq uals 0.2 m I.

2-75
the nonignition reaction rise well above the SIT,
but the r eaction mixture had become so stable that
it was not ignitible either by spark or fl ame , or by 270
~
additional hea ting up to 400 0 C, unless dilut ed with
fresh air. {p
L1
The intensity of the evidence of ignition varied ()i 1-65

with the initial temperature. From ini tial tempera- ~

tures close to th e SIT, gasolines of high octane
numb er tended to ignite with a dull blue flame
ex
L1
a. 260
\
2
LL ~ <;"I;\J> IGN ITION Za N .,.
observable under dark-room conditions, and gaso- f-
lines of low octane number generally ignited with a 2
0 255

'\~
mild orange flam e accompanied by audible expulsion i=
of gases ("puff") . Ignition at higher initial tem- '2
\2
perat res was usually indicated by a more violent 250 NON - IGNITION ~
flash of flame or by audible expulsion of gases. ZON.,. ~
It was noted also that ignition from high initial
temp eratures left the s rface of the flask more 245
heavily coated with soot and combllstion products
than did ignition from lower initial temperatures.
240
Ignition lag was found to be closely correlated o 0. 10 QI5 0 .20 0.25 0.30
with the ignition temperature, as shown in figure CI-JARGE'-, m\
7. The lowest self-ignition temperature was usually
FI GU RE 8. Eilect of chal'ge on ignition temperatw'e of mO/OT
determined from tests conducted with different gasoline.
charges, as shown in figure 8. I-liter flas k.

b . Other Gasolines and Varsol

c. Kerosine and Cleaner's Solvent
The ignition characteristics of other gasolines and
Varsol wer e substantially the same as those of motor Kerosine and cleaner's solvent belong to another
and aviation gasolines (supply of 1937) , with a group of petroleum products, the ignition of whi.ch
two-stage reaction and with ignition occurring in seemed to occur during the first stage of reaction in
the second stage of reaction. spite of th e fact that the nonignition r eaction pro-

57
 -
I

:250 2.70

,;
:, 0..
"-----.:.60 0 G

~~
I" ,
I I
I ,
" ~ ~ :: _ 255'"
240

v
, <35
/!\\ 2-55
'/1 fA~ - - - 25 3 'C

I ~ - - - 235 ' (,
!? V~ ~ ~
~
249°(,

'~ ~
lJJ
~
'r:"
::J
2 30'C lJJ
~ ,
&230 3 250 ,

f~/~\/x :<-~:;;~'--~~- ----

):(-

/)/-:~
f-
i(' ','''--- 0: '-
L ,/ ,--;, -.."': ' .... ,_ -...~- --- 2£.4 o C 1>1 ,
U,
u. , 'i'
/
1 / /'
'
' ..... -- ~ - -,- -- 2220G u. - .... - - 2.4Z° c..,
- ~, Z2 3 °c.. .2
r 2.25 2.4 5

,,
, -- 2 3C)°C
. f(//-,-
225 c C - - -----2...21°C - 24-" C.
~{;// /',
UJ
f.-
.. I~/:'/' /",, /"" \ " ""
-- - --~'- - -- , -- ------------!'-f }1-
f
f
/-- -, ,

. :' " -
-/
---
/
.....
__
! , / ;' /
II, / I ,/'"
, /
2 37° C
va 1.40
, ,/
/ ,-

,". --- -- - --, ,

I f -,
-
J .. ,,, " , , , /
,
, ,/
,,
,
--
-f
II .,.-- - - , ,
1 ,//"" '\ ~" f ,
"' __ --"" - - - - - . . . . " .-- ....... ______ _ _ __ _ 2\
-- -- --' 2.34°c...
~ / '
:2.1', 235 ... I, ,------

.. ,{",-[I' I
,--_- - ----Z3;;~
"'J
V __ _

...... \.
---- - -------- -----
I I I I I I I I I I I I , "
210
o ,0 15
TIMf:- , mi n

I I I I I I I I I I I I
F IGU HE 9. Time-temp e1'a ture curves f or kerosine . 21.5
o 5 '0 15
l ·flask , charge equals 0.25 m!. TIM&,m m

F IGURE 10. Ti me-temperatuTe CUTves f OT cleane1" s solvent.

ceeded with a two-stage r eaction, T ypical time-
I -liter flask, ch arge e~uals 0.25 m!.
temp er ature curv es are shown in figures 9 and 10.
" After-burning" of cleaner 's solvent in the region of
high ignition temper atures was more pronounced e . Diesel Fuels
than with other fuels, and ignition at all temp era-
tures was indicated by mild flame and a barely The physical properties of four Diesel fuels, and
audible expulsion of gases . their ignition characteristics determined in th e 1-
liter flask, are given in table 6.
d. Crude Oil The time-temperature curves of figure 11 are
represen tative for these fuels. The two upper
Lagunillas crude oil of gravity 17 API, flashpo in t curves wer e ob t ained for a straight-run fuel (55
15° C, and sulfur content 1.91 percent, was tested cetane); th e two lower curves were obtained with
in connection with a study of th e explosion of an oil th e same fuel, to which 1 percent of eth yl nitra te
tanker . The SIT of this oil was found to be 262 0 C, had been added. A small addition of th e accelera-
with an ignition lag of 35 seconds. The ignition tor reduced the ignition temperat ure from 230 0 to
and nonignition r eactions proceeded in a one-stage 226 0 0 , and th e ignition lag from 2 .\f min to 1% m in ,
pattern , in contrast with th e two -stage r eactions of and the intensity of ignit ion changed from explosion
the gasoline and kerosine groups. to normal flame.

TABLE 6. Physical propeTties and i gn-ition characteristics of Diesel fuels

Property F uel-
- -- --------- ~---- ~~~--~ -------- -- ~~ --~~-------

Ceiane numbeL __ _________ _____ _____ 41 __________ _____ _ 55 ______ __________ 60 _____ ____ ____ __ 68.
P roduction meth od ___ _____ __ _______ _ Cracked d istillate _ Straigh t ru n ____ ___ Straig h t r un ______ _ 55 ce ta ne with
corn bu stion ac-
ce ler:ltor.
S pecific grav ity ____________ ___ _A PL _ 33. i. _____ _______ __ 32.8 ___ __ _________ _ a8.a __ _ 38.2.
Viscosity , Say bolL ______________ see __ 34.7 __ __ 50.4 ___ ___ ________ _ 43.0 ____ ____ _____ _ 36 .2 .
Fla sh point. ________________ ____ o F __ 185-. __ 2 l3 _______________ _ 15t. _____ _____ ____ _ 130.
B oili ng poi n L ___________ ____ ___ o F _ 405______ ___ ___ ___ _ 41.5 _______ _______ _ :J23 _____ _______ _ 22 1.
Sulph u r co n tcoL .. __________ _____ % __ 0.20 ____ ____ ______ _ 0.23 ___ __ 0.10 __ ___________ __ 0.l4.
SIT ___ _________________________ ' C __ 233 _____ ___ _______ _ 230 ______ _____ ____ 225 ___ ________ . __ _ _ 226.
19nition lag ___________ ______ min-see __ 3:00 ___ ___ ______ ___ 2:30 ________ ___ __ 2:30 __ ____ _______ __ 1:45.
Evidence R _____ _ L ________________ _ 5 __ _______ ___ _____ _ 4 __ __ _______ ___ __ _ 3.

11 Key for eviden ce of ign itio n : 1, :1tIild flame; 3, flame; 4, mild explosion ; 5, ex plosion .

58
 z50 ~o ~'~'7----'----~ 420 rA------~
,,'\ \
'4 \
I, \
\\
I, \ \.

330 ,',' ,," _ 3Z6' c - - - - I 410 I-h-\-- - - ---I z

"I '-- - - - 3Z3'c o
• >=
OIL Z
>10 55 CE rAN£.
S.I .r. =Z30oC 3Z0~------~----~ "
,.,'
<.)
o

"'":J
\ =::-::- : \
310 t--,-C----'-c,-, -
,I '
'
--+- - - - -1

xr ~:~- ,,
I

..
I-
c:/ /) "
23 1"C
' 22 9'C
I
: ' - -- 299' c u
,
~ 2 w~~'-~'--~'~~~--------~
~ 1'-2;6'c
-~r
l I ' t:i " I
- - - _ __ 292 ' ( z:
III
I--
I'
I

,
-225'C
..
::J
I-
tt •
,

,
,'
~_-= J67'C !!'
o
372 'c >=
368'c Z
~ .
~290~'---------+--------~
S5 CETANE OIL AND
:E ..... ~~ - --- - ,, '' z:
I 'Yo e THYL NITRATE It! / :;;,
I- I-
S,'.T.~Z.2."oC , :r\
1 "\

2 20 ZOO t--- - - --+- - - - ----i 3601-',;--

' \-
' \-'- - - -I '"
u 'z"
" \ \ ::>
~: \ \
1 350:: \~>':_ 346'ct
o 2 4 6 8 I' )4S'CT
TIME, min 1\ Z
Q
,,
I \
,
/'"' - "
260'( \ ~
FIGURE 11. E:treet of ethyl nit,'ate on the 3 17' of diesel oil. ~~, ~---------+----------- .340 /,. \ !,!)
I,I" z:
Hiler fl ns k, cha rge equa ls 0.2 m!.
-- - - - - _ ...... _- 250°c '1 \ \ ~
/ ,---
. :: \
25&- '( 330 'I ,
o 5 10 0 5
f. Furnace Oil No.2 TIME , m,n TIME,m ln

FiGURE 12. Time-temperatm'e curves f01' maim' lubl'icati ng oil.

The general ignition characteristics of furnace oil
No.2 were substantially the sam e as those of Diesel
fuels of 41 and 55 cetan e numb er , i. e., single-stage
reaction with m edium self-heating b efore ignition,
which occurred at 233 0 C, with mild flame after
2 min 40 sec.
g. Lubricating Oils
Lubricating oils generally represent a complex
mixture of different h ydrocarbon components hav-
ing different affinity for oxygen. B ecause of this,
th e self-ignition of oil vapor does no t always proceed
in a defini te ordcr, or as consistently as in the case
of other combustible liquids. Oils having a com-
paratively low ignition temperature, such as U. S.
Navy Nos. 2075 and 8190, ignited in a more or less
definite and reproducible manner. However, chlori-
nated paraffin oils and motor lubricating oils used
for internal-combustion engines usually showed
irregular ignition in the zone of minimum ignition
temperatures. Above this zone, ignition was ob-
served regularly, and below it the oil vapors wer e
definitely not ignitible. For chlorinated paraffin
oil this doubtful zone covered a range of about
10 deg C, but for motor oil it amounted to about
35 deg C, as indicated in figure 12.
The reasons for this irregularity of ignition were
not establish ed. However , from observation of the
reacting mixture under a strong light directed
through the pyrex cover over the neck of the flask ,
it appeared that poor distri.bution of the char~e may
have been largel y r esponSIble. As th ese olls were
sprayed into the reaction chamber , they formed
den se clouds that r equired an appreciable time to
become well mixed 'w ith the air throughout the
59
l ·liter £Insk , charge equ als 0,2 1111.
ch amb er. In this nonuniform mixture there was a
tenden cy for igni tion to take place in small local
areas, At relatively high initial temperatures, su ch
local ignition was commonly followed by mul tiple
ignitions in other parts of the ch amber , but at lower
initial temperatures, a partial ignition frequen tly
occurred without suf£cien t violen ce to affect the
remainder of the mixture. ]Ivforeover , th e dense
clouds of unburned oil tended to obscLlre th e evidence
of a mild ignition, even when viewed under dark-
room conditions, and detection was sometimes un-
certain. These variable conditions could be ex-
pected to produce irregular ignition results in th e
temperature range near th e SIT. It was noted,
furth ermore, that th e irregularities became more
pronounced as richer reaction mixtures or larger
flasks were used , a situation par ticularly susceptible
to nonuniform distribution of th e charge.
h. Benzene
The time-temperature curves obtained for pure
benzen e (C 6H 5 ) are shown in figure 13. Appreciable
self-h eatin g of th e reacting mixture was observed
50 deg C below the self-ignition temperature. At
the initial temperature of 557 0 C, the mixture se1£-
heated to 690 0 C. However , at the initial tem-
perature of 565 0 C, actual ignition was observed
at 603 0 C, or about 87 deg C b elow the maximum
temperature of the preceding test. H ere, again,
evidence is presented of the fact that the initial
temperature from which the exothermic reaction
proceeds to ignition is more significant than the
 temperature of the reacting mLxture at the instant
of ignition. It is interes ting to note that th e maxi-
m um temperatures for each reaction fall on a smooLh
curve. The shape of the nonignition r eaction ti:rnc-
temperat ure cur ve is similar to , but not identical
I
700
6690'C
with, that of single-stage reactions of other materials.
~ Although both t he ignition and nonignition reactions
were characterized by rapid increases in temperature,
il\: igni tion was indicated by a barely audible exp ulsion
,: ,I

; I~ of dense smoke and mild flame.

650
i. Toluene

The self-h eating and ignition characteristics of

toluene were similar to t hose of benzene, and time-
temperature curves of s ubstantially the same type
600
U
were obtained.
4.3. Petroleum Compounds
Three groups of hydrocarbon com pounds derived
.. l , .. --.,_,"
from petroleum , were supplied by the di vision of
,, thermo chemistry. The ignition characteristics of
. ",' 1',
Lhese hydrocarbons were determined in the I-li ter
- -~-
--..::..::..:: --- - 506' C apparatus, anel are given in table 7.

500
.. ,.,"
, ,.- --- - - - ---- ---- -~-
_ __ - - - - - - - - ---~ :: - -- 494'C
a. Normal Paraffins
....
v'
F igure 14 gives representative time-temperature
curves for fractions of the chain type, which showed
substantially the same behavior, with the exception
I I I I I I I I I I I I I I I I of dodecane and cetane , the nonignition reactions of
450
o 5 \0 15 ZO which h ad a rctarding portion sim ilar to a two-
TIM~, min stage reaction. The rate of the inducing reaction
FIGURE 13. T ime-temperature cu rves for benzene. preceding igni tion gradually decreased, and the
1·lile r flask , charge equals 0. 2 ml. ignition lag increased with the carbon content.

T ABLE 7. Physical properties and ignition chaTacteristics of petroleum compounds

Ignition ch a racteristics ( I-liter flas k )

Compound a Formula R atio Boiling
point
H /C
SIT Lag IEviden ce b

(a) Normal paraffins

n-Pentanc ____________________ _ C,H ,, ____ ____ _ 3.60

'C
35. I
'C
258
I mi~ 8ec
00 1
n- H CXan{L ___________________ _ C. H ,, ________ _ 2. 33 ti8. i 240 J 30 1
n- H e ptanc __________ ___ ______ _ C,H ,, _____ ___ _ 2.28 98.4 223 0 45 5
n-No nanf' _____________ _______ _
n- Decanc ___________ __ ________ _
C' H 20 ___ . ____ _
C'OH 22 ____ ____ _
2.22
2.20
150.
1i4. 0
i 211
206
I 1
2
25
10
3
1
n- D odccanc ___ _____ _ C 12II 26 _____ _ __ _ 2. 17 21 6..5 203 2 Ii
n -Cetane ___________ _ C16H 34 _____ _ __ _ 2. 12 287.5 202 2 35
I
(b) C ycloparaffins

Cyclohexane __ -.--- -- _-- __ -- -- _I C,H j, _- --- -- --I 2.0 81. 4 246 17 15

Meth ylcyclohexanc __________ _ C,H I4 ____ ____ _ 2.0 163.0 218 20 10

(c) Branched-chain paraffins

l'rimeth ylbutanc _____________ C,H j6_ 1

I soDcta nc_____ ____ _____ ___ _____ CSH iS ________ _
--------1 2. 28
2.25
80.9
99.3
421
420
26
20
2
2

• T he ti me-temperature cur ves for the above liquids arc given in figu res 23 to 29.
b Key for e vidence of ignition: 1, mild fl ame; 2, blue flame; 3, flame; 5, explosion.

60
 275 -.---+---- - - ,
DOTRI - CO NTAt-JE-
ABov~ 3 00°(,. f
(C-,. >-I •• )

260 r-----
I L
270-H'HI-------1 Pt;.I\lTANE' (C.-H,. )

I
~260ov 200
2G5 - I-{l+t--------1

U
Z40
I-I&XAN !;.- (c" ~14) I/
°
u
'#(' "" 2100(..
W
ri Z30 \
~'") I
tl> 2 15 - 1rJ---.1-+--J-L-----1 '- '- : tll0(. ::J

r1
:>
~
NON ANI; 01 \ f.<I;O P TA"E' (c,
t: W
0. 'Zzo
~
~lTANI;O (L~,o)
210 -'=III-IL--i-=':":' I
0- 2
~ ~
ill
t-
205 - Ir+----/-/
:z
0210
;::
\
~ONAN!;
DECCA ,"""
(c g H :0)
(C-,o ~,,) /
/
2
~ ~ANE- (C'''~ '.)
-O-C~TAI\JG (G ", H 3...)
zoo

I I I I
19°0 15 20 25 30
235 195
i/ CARBON ATO M S'"

)"
I I I I FlG UnE 15. R elation between S I T and cm'bon content of normal
2~0 190
0 5 0 5
parajJins.
TIME-, min T IM ~ , min ].I i tCl" flask.

FI CU HE 14. Tim e-temperaIUl'e cur ves for some nOT?nal parajjins.

j ·litcr flask. Z80 I
275°C I I
The self-ignition tem peraLure of liquids of the 275
chain type consistently diminished with an increasing
number of ca rbon atoms up Lo 16 (C 16H s4), as shown
in fig ure 15. The curve for fra ctions of larger ZlO

~Jl
carbon content was not deLerminecl because of
limited quantities of rare fraclions . However , tests 1
of very small amounts of dotriacontane (C"2H6tl) 265 I - I
indicated the self-ignition temperature to be some- »- I
251°1
where above 300 0 C. In other words, it would v I,
appear that the curve must turn upward after 0 ... 260
I I
I \

)
I
carbon 16. Additional tests will be necessary to LiI
()' I I ,
I \
confirm the shape of this curve. " 255
~ ~ I \

[71yi
Z-55°(..
;;<
II! /
"':!
0-
\
\

b . Cycloparaffins "'
>-
;;-
~
L/ 249°C
\
\
147.5°C

--
2-50

~
I

The time-temperature curves for cyclohexane and '(:;- -- - - - - ----- ----- /

methylcyclohexane, the two ring type fractions

tested, were similar. Curves for methylcyclohexane 245
- I
I
1/ ....... ./ ... - -
r-
- - - ...... - ---- ----- -
- - - - -- -- --- --
---- ----
14 10°C
-

1,'(,-/ - - - - - - ---- - -'--

arc shown in figure 16. It will be noted that the ~

1/
Z43°c
reaction appeared to be of a t\vo-stage type, with an 240
1
ex tended period of constant temperature before the
~
rapid heating of the second stage began . Ignition 1
took place during the second stage, and, as the 255
1 11 1 I II III ~ I I 1 I 1 11 1 1 1 1j
initial temperature was raised , the dela~T between o 5 10 15" 20 25 30 35
TIMG mIn
stages was gradually eliminated. The two-stage t

pattern of reaction for c~Tclohexane is nearl.\Tidentical F I GU HE 16. Time-temperatuTe CUTveS fOT m ethylcyclohexa ne
with the patterns obtained for motor and aviation (C7 H 14 ) •
gasolines in the same region of ini tial temperatures. l ·liter flask, charge eql1als 0.2 Illl

61

c. Branched-Chain Paraffins
Trimethylbutane (Triptane). As the mmImum
self-ignition temperature of this compound was
approached, the visible and audible evidences of
ignition became weak, and precise determination of
the SIT was difficult. Furthermore, the time-
temperature curves for ignition and nonignition re-
actions had substantially the same shape. However,
at an initial temperature of 421 0 C the reaction
definitely proceeded to ignition with a blue-violet
flame. At lower temperatures light produced by
the reacting mixture appeared to be that of a cool
flame reaction.
Isooctane (2,2,4-Trimethylpentane). The ignition
characteristics of isooctane (and difficulties of ignition-
temperature determination) were similar to those for
trimethylbutane. The observed reproducibility of
blue flame, or cool flame, was very poor and was
affected by deposits on the flask wall, by direction of
the charge stream, and by relative humidity of the
air. Injection of the charge along the side of the
neck wall usually stimulated ignition at slightly
lower temperatures than injection directly to the
bottom of the flask. Self-ignition temperatures
obtained at different times ranged from 408 0 to
425 0 C. The value of 420 0 C (with corresponding
ignition lag of 1 min 20 sec) recorded in table 7 was
fairly reproducible.
Although these difficulties were encountered with
all sizes of flasks used, reproducibility of the deter-
minations was slightly better in the 0.2 and 12-liter
flasks than in the I-liter flask. The band of un-
certainty in the 0.2-liter flask was no more than
12 deg C , and in the 12-liter flask it was reduced to
4 deg C.
4.4. Reference Fuels
The reference fuels commonly used in determining
the knock ratings of motor fuels comprise variously
proportioned mixtures of isooctane and n- heptane.
Essentially the rating procedure consists in deter-
mining what mixture most closely matches the per-
formance of the fuel under study, using a standard
CFR (Cooperative Fuel Research Committee) engine
operated under specified conditions. The percentage
of isooctane in this mixture is taken as the octane
number of the fuel being tested. Details of the
procedure differ with the purpose of the fuel, and the
ASTM has established four different methods (motor,
research, aviation , and supercharged) for gasolines,
and one for Diesel fuels. The rating of a particular
fuel may vary appreciably with the method used,
and it is therefore necessary to consider the method
of determination when lmock ratings are used as a
basis of comparison.
The ignition characteristics of these primary refer-
ence-fuel mixtures were studied in the regular I-liter
test apparatus, and time-temperature curves for a
number of them are shown in figure 17. In addition
two other typ es of mixtures, formerly used as
62
-~ -
I
secondary reference fuels were also tested. These
secondary reference fuels were prepar~d from three
specific fuels, and consisted of (1) mlxtures of fuel
A6 with fuel C 12 , and (2) mixtures of fuel C 12 with
fuel F 3 . Although improved methods of manufac-
ture and reduced cost of the primary reference fuels
have now eliminated th e need for intermediate
standards, investigation of the well-defined secondary
reference fuels were of interest at the time the tests
were performed.
In figures 18 and 19 the data obtained for primary
and secondary reference-fuel mixtures, respectively,
have been plotted to show the effect of change m
composition on different ignition characteristics.
With increasing isooctane con tent, up to about
70 percent, the SIT of the primary .reference-fuel
mixtures increased gradually and contmuously , and
the ignition was marked by the characteristic red
flame of n -heptane. The intensity of ignition changed
gradually from explosion to mild flame as the iso-
octane content increased. With isooctane concen-
trations of 50 percent and higher an audible exp ul-
sion of gases without flame was observed at tempera-
tures below ignition, and this " puff" also diminished
in intensity as the concentration of isooctane in-
creased. At 70 percent isooctane, the SIT -composi-
tion curve showed a break; mixtures containing more
than 70 percent of isooctane igniting only at decid-
edly higher temperatures, af!.d ~~nerally with th~ blue
flame and considerable vanabIhty noted prevIOusly
for pure isooctane. Ignition was somewhat err~tic
also in mixtures of slightly less than 70 percent ]SO-
octane content, forming a so-called "secondary
nonignition zone" similar to those observed by
Prettre [15] with pentane and hexane by Townend
[16] with hexane, by Sortman and Beatty [:5] wit~
heptane and cetane, and by many other mvestl- i
gators. The fact that nonignition zones with these
latter liquids were not observed in the present
investigation suggests that the appearance of such
zones may be a function of the test apparatus and
conditions rather than of the material under study.
The series of secondary reference-fuel mixtures
prepared from fuels A6 and C12 showed a continuous
linear increase in ignition temperature with increasing
C 12 content as indicated in curve II of figure 19 .
The series of mixtures of fuels C 12 and F a, however,
gave a pattern of ignition behavior (curve III)
similar to th at obtained for the primary rcference- I
fuel mixtures, including a secondary nonignition
zone and the "puff" without flame at temperatures
below ignition for mixtures rich in the component
having the higher ignition temperature.
In order to indicate th e degree of correlation
between self-ignition temperature and motor-method
octane number, SIT- octane-number curves were
plotted for both the primary and secondary refer-
ence-fuel mixtures. In addition, self-ignition tem-
perature determinations were made on three other
gasolines of known octane number. Of the second-
arv reference fuels, only the end fuels A6 and F 3
showed substantiall y the same SIT values as the
primary reference "fuels of corresponding octane
 ~
26 0 ~ 70 OCTAN E FUEL

IA\ ....--+"
400

,.
,,~

~~~I'G ):t RED FL"ME L.-- krrl V ~"'~ f . -

25 t
1--, ~~oC
t--P\M~fl:~'''' iDS
PUFF I""
+
)(
. BLUE FL A.t.AE
puFF
NON · IGNIlION
t(

t(
~i/ Y SE-CO N DARY NON IG N IT IO N
ZOINE
Yo
~J/
50 · 0CTA.NE f UEL 0 FLUCTUATIO N Of ):t 1
~
~£ 24907 -...t45 t EMPERA..TURe:
3 50
):t l

246 C
50 · 0c.r .... NE fUE. L
~\ )(

If ~1"""~Blc
HP.lmB. T
.......... PUff 246°C=--
z
0
;:
z
0
u
oJ,
t(
'i
It'\
)1 I,::_.J< 1/
I
I
I

\1 Z
!;!
Z
'2 OC It ",oJ F
U24
~
239C
40 OCTANE FUR
~ ILIa:
~

~300
w
t(
.)(- - ---
"j
/ 239°C z z~

.
v ..... ..
lJ
t<
...':::l"
>- o~
'"< ", ,,"'
~V
W
~x'P. 1m 30s.
« "0z '"'!: ~

I~
-
c.:
w
0..
~
~ 23
~ II
"\122~~
200CTA"£: fUEL
1' __
~
V) "«
Z >-'"

250
FUEL Cit C u,,""1. ~

Cu~~ f.--
V
- ~
-
fUEl CI2-

/ 1'' I+ ~EXP.. . . +-,,,,23;-....

......... Z290C
~.
1 22 1°C

~1~2 20C

22 0
~

I#'
f n - HEPTA NE
---zzzo-C-- - -+--_.l-...2!67oC
Z700C

200
o 10 20 30
CONCENTRATION Of FUEL MIXTURE, '/.
40 50 60 70 BO 90 100

II FJ(1uR,, 19. R elation between S I T and composition oj secondary

refeTence fuels.
I-liler Oas k .

2 10
I I I I
o 2 4 6 8 8
TIME , min
1-,,
FIGU RE: 17. Time-temperature curves Jor primary "eJe"ence 3 I 011-----"",- -- -+-------+------4--------1
fu els. '" ........ ·30 6 o C
( ......,
1·li ter fl as k.
305 II ,~"";"
ift-",~,
l . . --~'~:::' 30 IoC
1;-_, ','~ i~~:~ ______-I-_______-+______~
~~:a:~J
300
I " ../ \ .... "" 2geOC
//L -~' ....
t--t--+--+-+--+---+--+--j-HZ~~ -
296°C
400 ,', \ '.... I
1.
f/ 1 ' c-r,',~'-",..-c-'-~-----_+------+------___I
29 5I."+'- i-',,
1 / ...... ' , ......... ·2 94 °C
k:( - RE D FL A.M E
W
jf"'·
t -,
,I
/' ,,/ r'::,,' ~oC
/ -,,','
Z8
Z92°C

r ..,
" - BLUE- FLAME
• - PUFF
~ 2 9 olt!++--f-...:.."".,.....+--'------+~-----..L-----__+
• - NON. - IGNIT ION

350r--+---t--+---r-~~-4--r-4~,Lr-+-4--r-+~
L1.J if / "~' 2 8 7 °C NON - IGNITION REACTIONS OF
rr "ll / " ' ~~~~~·t)~i~~~T~t: :ER
~/ I
GAL
;: \i+!4-'-:I'_',,/, -__"---=,+<;:-2_B_4_ _C-:-_ _+ IS. I.T. 0
c .0:1 Q3-C. LA.G .. 3 SEC. _

M, ~ ~ 285 " l'--- -_ "zezoc /V \

J/' / ....
..... .-i,S r:COND"RV NOH lGNlflON
:' .. ( "" ZONE 2 ' 00 ~ Z. 79;C
~ t .. \\ I I - SO 2 1 / / 1\
~
~30 0r---r--t--+/~~~~'~~~-~~~'~-r-t-4-+-~1/~' \ ' 40
/r.-", I '" 28 0
...
~'£-------H-\----+-\----+------+------I
,I -; "-_.' \
~
, / F-->.....~- 2750C
.,/; \ \ - 30
(r..,
~ ~o~ " V ~~~
..../ / /1
~ __ - - ,r_~\"\
_- .... \ I __
w...... ........-~ fo.....
"20: •
275~/~~_~C----
~
" 27 40C
~~--------~--------~+-~~----~
V I __ V.~\'OI,) I ;/~-/----- ::~~
\ \

.//
r-
or v \ \ "10 r:
l \Xvi;\}f'f' . . / , - 00 .E.
~
~\ c:+- ~
_/
2 7 Of--/-c_..,
c-...--
--=±l~_"'-----===I===----+--------I
250 r---r--t--+----,---j--
~V
\ 1 ......, 'I~o
\ ,~ <
I I
so
.J
/
J
'-~-r' f"
40",

'<~Jt / ::' t ' - - 262°C

265~----~L---+----------+----------+---------~
, J - IG NITI ON RE.4.CTlON OF-
[ FUEL (c.z) RATED '18.9 OCTANE
2000~--.J10~--~20~--3~0~---,-4~0--~5LO--~
60~L-7~0~~8~O-.l---,-90~~~,OO 0 S. LT." 26Z"C. LAG" 3m S4S.

(n-H'PTANE) 'Yo ISO ' OCTANE (OCTANE NUMBERS) (l so·ocrAO')

TIM E , mln

F IGURE 18. Relation between S IT and composition of pTimary FIGUHE 20. Effect of a combustion accelerator on the time-
reference fu els. temperature curves of f uel C ,2.
I-liter fl ask. l·liter flask, charge equals 0.2 1ll1.

63
numbers. Only one of t he three additional gasolines 540 ---.-----~

tested gave an SIT value approximately the same

as that of the primary reference fuel of corresponding
octane number. Similar poor correlation between 530 ---if/t--------j

ignition characteristics and octane-number ratings

have been noted by other investigators with other 520 -tirl--- -- S.II =491'0
test apparatus (Jentzsch Eckert Zerbe and Carhart). lAG=Z3S<G
The effects of a small amount of ethyl flu id addi-
tive on the ignition characteristics of a fuel were also
studied. A typical time-temperature curve for the
ignition of fuel C 12 (78.9 octane number) is shown in u
o
the lower part of figure 20. The broken-line curves in _ 500---1f1---'c-- - - - - 1
the upper part of the figure are time-temperature u
cY
curves for nonignition reactions, at increasing initial
temperatures, of the same fuel with 1.25 ml of tetra- ~
~ 490
ethyl lead added per gallon. The shape of these 0.
~
curves changed entirely, and many additional stages "'
f-

of reaction developed before the reaction finall y ,

accelerated to ignition. _ f ,' . . . ~\" -- 475°("

4 .5. Miscellaneous Compounds '" ' ........ I

470 ---i+,---"'-~--=-=---'4" 7 'c
~
, ,

The SIT values obtained in the I-liter flask for I

seven miscellaneous l iquids are given in table 8. 460

o
The effect of varying th e flask size is shown for several
of them in table 3.
For all except methyl alcohol, both th e ignition and FICURE 2l. Tim e-tempemtuTe curves for acetone.
nonignition reactions were characterized by an im- I-liter flask, charge equals 0.2 m1.
mediate rapid acceleration, as illustrated by the
curves for acetone shown in figure 21. With methyl
alcohol (fig. 22) , the acceleration was somewh at
delayed, and the curves for ignition and nonignition
r eactions differed distinctly in shape. Additional ,
450
commen ts on the reaction characteristics of the ,,
individual liquids follow. .,!
TABLE 8. Ignition chamcteristics of miscellaneous compounds 445 ~
determined in the i -liteT flask u
o ff\ ,
Uo
/
,,
I
,
~ 440
I
, 43<0 ~c I--
Compound SI1' Lag
'> -~
~

/-

Acetone _________ _____ ___________________________ _

'C
491
min
0
sec
40
<
cY
~
;: ~I / /' 43"7 o C ' ,
4 4 3eOc ,,
4 3 "oC
'S.I :T.
Acetic acid ______________________________ . ________ _
Ethyl "lcohoL ___________________________________ _
488
391
0
0
13
-10
L
u-
f-
435
~ YII - 4 33 °C
1
I
Ethylene glycoL __ _________________________ __ ____ _
Methyl formate ____________________________ ______ _
:I[ethyl a lcohoL _________________________________ _
G lyccrinc ________________________________________ _
398
467
428
0
0
1
23
25
30 430
\1/
\11, /
/ ~~

- -- -
~
4Z9°C.
/
389 0 31 ~ /
"II /
,'I
425
II
Q. Acetone
0\ T\M~
5
, min
Io

At the minimum self-ignition temperature, acetone

ignited with a blue-violet light, often initiated at and
spreading from a small, red, glowing center of carbon-
ized deposit of acetone on the flask wall. The light
usually appeared without audible manifestation and
continued to be visible for about 20 seconds at 491 0 C
and about 15 seconds at 505 0 C. The nature of
t his light gradually changed from dull blue-violet at
491 0 C to blue-pink at 515 0 C and to a pink-violet
flash with an audible explosion at higher tempera-
tures. The initial blue-violet light was similar to
FI GURE 22. Time-temp erature curves for methyl alcohol_
Hiter flask, charge equals n.2 m1.
that of a cool flame, and when first observed it was
questioned whether this could be taken as an indica-
tion of ignition. However, in consideration of the
very sharp increase in the time-temperature curve
(fig. 21) at 491 0 C, this temperature was taken as
the self-ignition temperature.

64
 b. Acetic Acid
Ignition of acetic acid occurred so irregularly that
it was difflcult to define t he lowest self-ignition tem-
perature. One possible explanation of such irregu-
larity may lie in the ability of acetic acid to exist in
two interchangeable states, "dimeI''' and "monomer",
expressed by the relationship
(CH3 COOH)2P2CH,COOH.
Th e two forms may have different ignition tempera-
tures, and uncontrolled variables might have caused
a shift from one form to the other.
Ignition of acetic acid, in spite of the irregularity
of occurrence, was distinctly defined by audible and
visible evidence, and usually occmred about 8 seconds
after inj ec tion of th e charge. Ignition was initiated
with a blue flame , which , at the end of the ignition
period, changed to a pink color. Th is p ink color,
however, might have been due to reflection of the
dull-red furnace walls from fog formed within the
chamber. Although the mixtme remained clear and
transparent throu ghout most of the r eaction , there
was some eviden ce of the development of fo g toward
the end of the exo thermic r eaction .
c . Ethyl Alcohol
Due to the rapid increase of press ure at the time
of evaporation, an audible expulsion of gases was
observed before ignition. The actual ignition, at
391 0 C after 40 seconds, was accompanied by blue
flame with a second expulsion of gases.
Ethyl alcohol-water mixtures were also found to
be readily ignitible. Th e self-ignition temp erature
increased from 39 10 to 444 0 C as the water content
of th e mixture approached 70 p er cent. Very weak
flame was observed at 467 0 C even with 80 p ercent
water.
of both liquids occurred suddenly with a violent
explosion wh en the th ermocouple indicated a temp er-
ature only 3 clcg C ab ove the initial temper ature.
e. Methyl Formate
I gnition of methyl formate was indicated r egu-
larly by a mild explosion and rapid rise in tempera-
ture similar to that for acetone (fig. 21).
f. G lycerine
Glycerine ignited with a vioknt explosion accom-
panied by long flame and smoke expelled from t he
n eek of the ignition apparatus. Th e rise in tempera-
ture of the gas mLxture imm ediately after injection
of th e charge was particularly extreme for bo th igni-
tion and nonignition reac tions.
Observation of the flask interior showed that,
immediately after injection of the charge, viscous
glycerine dropl ets accumulated on the bottom sur-
face of the flask and rapidly produced a dense white
fog. After about 20 seconds, this fog b ecame clear
either clue to superheating or par tial oxidation.
This was follovved , usually in about 5 seconds, by
the appearance of a small blue flame with a pink
center. Due to rapid propagation of flame , gases
were exp elled from the neck of the flask with con-
siderable force.
g . Methyl Alcohol
M ethyl alcohol showed a mild form of igniLion
characteriz ed by a dull blu e flam e and a weak expul-
sion of clear gas, but the differen ce in shape of th e
tim e-temper ature curves for ignition and nonigni-
tion reac tions (fig. 22 ) provided supplem ental evi-
dence of the definite location of t he SIT.
4.6. Miscellane ou s C ommer cial Materials

d. Ethylene Glycol A number of commercially produced combustible

materials wer e tested in the I-liter ignit ion apparatus
The ignition of ethylen e glycol in the I-liter flask and t h eir ignition characteristics are given in table 9.
was indicated at 398 0 C by orange-blue flame and a The time-temperature curves typical of many of
hardly audible expulsion of gases. HO'wever, the these materials were similar to those for acetone
same liquid containing 3 percent of an antirusting (fig. 21 ) .
ingredient (triethanolamine phosphate) ignited at
395 0 C with a violent explosion. T ests on ethylene
glycol-water solutions showed ignition of mixtmes TABLE 9. Ignition characteristics of miscellaneous commercial
materials
containing up to 90 percent of water (for which an
ignition temperature of 460 0 C was obtained),
although with more than 40 percent of water the Material Grade SI T Lag Evi-
dence a
flame became very weak. --- - -
Two o ther antifreeze liquids, R - 19 and R - 19d, °C min sec
were tested, and the results indicated that these Black enameL .... .... . SynthetiC (601) ... ... 478 0 06 4
Pine taL .............. OommerciaL....... 439 0 ]0 3
liquids were highly ignitible. Both liquids were Pine oiL ................... do............... 316 0 07 4
Linseed oi l (ra\\") ............ do.. . ............ 425 0 04 3
p etroleum distillates (kerosine type), liquid R- 19 Oasto r oiL ................. do ..... .......... 409 0 24 3
b eing th e product without additive and R- 19d being Varnish (interior) . ..... TT- V- 7L . . ......... 359 0 02 6
Varnish (spar) . ........ TT-V-121a. ......... 350 0 03 3
a mixture of the produ ct with an ingredien t reported Lacquer (red ) .......... N itrocellulose .......
L acq uer (clear) . ......... . .. do. . ... ......... .
349
342
0 25 3
0 14 3
t o prevent the softening of rubber hose in enp:ine L acq uer (thimler) ...•.. OommerciaL..... .. 298 0 12 5
installations. Th e self-ignition temperature of R- 19 T urpentine ................. do........ . . ..... 250 0 40 3
was 211 0 C, with an ignition lag of 3 min 50 sec;
a ICey for e\~ i dcnce of ignition: 3, Flam e; 4, mild explosion; 5, explosion: 6
R- 19e1 ignited at 223.0 C after 1 min 30 sec. Ignition violent cxplosioil.

65
 a . Black Enamel
Noticeable decomposition of synthetic black auto-
mobile enamel (601) was indicated at 270 0 C by the
appearance of smoke. At a temperature of about
445 0 C, carbonized residue of the charge self-heated
to the glow state. However, self-ignition occurred
at 478 0 C with a large flame and audible expulsion of
gas and smoke. As a result of ignition, all the carbon
residue was burned out and the flask surface becamf'
clear.
b . Pine Tar
Pine tar of commerical grade, dUG to its low
"{luidity", was preheated in boiling water before in-
jection with a hypodermic syringe. The exothermic
reaction began far below the ignition temperature
and ignition was indicated by flame and a mild
expulsion of smoke. The flask surface, after igni-
tion , was usually covered by a brownish coating and
tar residue, baked to a hard carbon deposit removable
only with a scraper. However, with pine oil the
residue after ignition was soft and easily removable
from the surface.
c. Linseed Oil
The ignition characteristics of linseed oil were
similar to those of lubricating oils, and appreciable
self-heating of the vapor-air mixture was observed
at temperatures far below the ignition temperature.
d . Varnish and Lacquer
The reaction characteristics of varnish and lac-
q uers were substantially the same, particularly in
the nonignition region. Self-heating of the vapor-air
mixture was initiated far below' the self-ignition
temperature, and often amounted to 20 to 25 deg C
in nonignition reactions near the self-ignition tem-
perature. Ignition of these liquids, with the excep-
tion of interior varnish and lacquer thinner, was very
mild; both th e lacquer thinner and interior varnish
ignited with an audible explosion.
e. Turpentine
The time-temperature curves for turpentine were
similar to those for kerosine, having the same two-
stage nonignition reaction with ignition definitely in
the first stage.
5. Summary
The apparatus and method described for the
determination of self-ignition temperatures is prac-
tical and readily adaptable to combustible liquid s of
widely different physical and chemical properties.
Data on a considerable number of liquids are pre-
sented.
Time-temperature curves of a thermocouple junc-
tion in mLxtures of combustible liquid and air, offer
a convenient means of studying the preignition
reactions in such mixtures. Typical time-tempera-
ture curves are given.
66
The importance of careful standardization of
equipment and procedure in obtaining reproducible
results has b een demonstrated. Thus, for reaction
vessels of similar construction, the self-ignition tem-
perature was found to decrease with increase in size
of th e chamb er, over the capacity range studied,
with differences as high as 200 deg C being obtained
in vessels of 0.008-and 12-liter capacity. With Py-
rex reaction chambers of the same size but with
different exterior casings, variations up to nearly 30
deg C were observed in the determined self-ignition
temperature. In view of t h e effects produced by
these modifications of equipment within a single
method, the large discrepancies in ignition tempera-
tures reported by different investigators using
various methods are not surprising.
The ignition temperatures measured with t h e
apparatus described are lower than those reported
by most other workers.
The author is indebted to M. Sandholzer for assist-
ance in the preparation of this paper.
6. References
[1] T. T. S. Sebastian and M. A. Maye rs, Ind. Eng. Chern.
29, 1118 (1937) .
[2] C. R. Brown, The determination of the ignition tempera-
t ure of solid materials (Doctoral Thesis, Catholic
Univ. of Ame ri ca 1934) .
[3 ] H. Holm , Z. Angew. Chern. 26, 273 (1913) .
[4] H. Moore, J. S. C. 1. 36, 109 (1917) ; J. I. P. T. 6, 186
(1920) .
[5] C. W . Sortman and H. A. Beatty, Ind. Eng. Chern. 33,
357 (1941 ) .
[6] H. J entzsch, Z. Vel'. deut. Ing. 68,11 50 (1924) ; 69, 1353
(1925) .
[7] D. M. Newitt and D. T. A. Townend, The Science of
Petrole um, vol. IV, p . 2958 (1938) .
[8] H. B. Dixon and H . F. Coward , J. Chern. Soc. 98, 514
(1909) .
[9] H. B. Dixon and H. F. Coward , J. Chern. Soc. P . 1382
(1934) .
[10] W. Mason and R. V. Wheele r, J. Chem. Soc. 121, 2079
(1922) ; 125, 1869 (1924) .
[ll] H. L. Calle n dar, Engineering 123, 147 (1927) .
[12] C. Moureu, Chim. et Ind. 18, 3 (1927) ; Compt. rend.
185, 1545 (1927) .
[13] S. M. Estrad6re, Pub. Tech. of Mi nistry of Air (Paris) ,
No. 49 (1934).
14] S. J. Le wis, J. Chem. Soc. p. 1555 ( 1927) ; p. 58 and 2241
(1930) .
[15] M. Prettre, The Sci ence of Petroleum , vol. IV, p. 2951
(1938) .
[16] D. T. A. Townend, Proc. Roy. Soc. H1A, 484 (1933) ;
H3A, 168 (1933) ; H6A, 113 (1934) .
[17] L. M . Pidgeon and A. C. Egerton, J. Chem. Soc. p. 661,
676 (1932).
[18] Neumann, Z. Vel'. deut. Ing. 70, 1071 (1926) ; NACA
Tech. Mem. 391 (Dec. 1926) .
[19] H. T. Tizard and D. It. Pye, Auto. Eng. 13, 136 (1923).
[20] A. Pignot, Compt. rend. 182, 376 (1926) .
[21] ASTM Standard Method, ASTM Standards, pt. 5, 147
(1952) .
[22] L. F. Mareck and D. A. Hahn, Catalytic oxidation of
organic compounds in vapour phase, Chern. Soc.
Monograph Series (Chemical Catalog Co., N . Y. ,
1932) , p . 311.
[23] H. L. Callen dar, Engineering 125, 183 (1927).
[24] N. J. Thompson, Ind. Eng. Chern. 21, 134 (1929).
[25] A. F. Matson and R. E. Dufour, Underwriters' Labora-
tories, Inc., Bu!. of Research No. 43 (1950) .
WASHINGTON, March 5, 1954.