Detonation Characteristics of Some of the Fuels Suggested as Standards of Antiknock

Quality
Author(s): John M. Campbell, Wheeler G. Lovell and T. A. Boyd
Source: SAE Transactions , 1930/1931, Vol. 25/26 (1930/1931), pp. 126-131
Published by: SAE International

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 Detonation Characteristics of Some of
the F uels Suggested as Standards
of Antiknock Quality
By John M. Campbell1, Wheeler G. Lovell2 and T. A. Boyd3

Annual Meeting Paper Illustrated with Photograph, Drawing and Charts

sion ratio for incipient knock over the entire range

WHATEVER the detonation
the detonationmethod characteristics is employed of of
characteristics for fuels,
fuels,measuring
somesome
of composition from zero to 100-per cent concentra-
reproducible reference fuel or scale of fuels is needed. tion, as determined in admixture with normal heptane.
Reference fuels are needed to assure dependability Normal heptane seems to be the only one of the
of results and to provide a common basis of compari- several fuels included in this survey that has a suffi-
son between different laboratories. The fuels should cient degree of tendency to knock to make it suitable
be of definite chemical composition so that they can the lower limit of a scale of antiknock qual-
to form
be reproduced with certainty at any time. ity consisting of two pure fuels mixed in various
It is not the function of this paper to recommend proportions, one of low and one of high antiknock
the specific fuels that should be selected as standards quality. Of the fuels from which a selection might
of antiknock quality, but rather to present quantita- be made for the upper limit of such a scale, there
tive data on the detonation characteristics of some are cyclohexane, iso-octane, benzene, toluene and alco-
of the individual fuels that have been suggested. hol, each having certain advantages and disadvan-
Such data are here presented in terms of compres- tages, some of which are discussed.

Another use for a standard fuel is found in connec-

tem of measuring the antiknock quality of a gaso- tion with those methods of measurement which express
THE line tem of THREE
line are measuring
are (a)(a)
a principal
a standard the antiknock requirements
standard engine, engine, quality
( b ( b ) of) a aof standard
standardany a gaso- sys- antiknock quality directly in terms of the chemical com-
procedure, and ( c ) a standard fuel. Items (a) and (ò) position of some reference fuel. Thus, the antiknock
are necessary because the tendency of ą given fuel to quality of a fuel is sometimes expressed in terms of
knock may depend in a large measure upon the design the amount of some knock suppressor or knock inducer
of the engine in which the fuel is burned and the con- that must be added to a reference gasoline to produce
ditions under which the engine is operated. Even the a fuel having the same tendency to knock under definite
relative tendency of one fuel to knock with respect to conditions as has the fuel under examination. But the
that of another may depend to some extent upon the only definite and positively reproducible means of check-
factors of design and the conditions of operation. ing the antiknock quality of the reference fuel, after
Whatever method of knock rating is employed, a long periods of storage and as new stocks are added to
standard fuel is required both to provide a common replace those exhausted, is by means of some standard
basis of comparison between the observations of dif- fuel of definite chemical composition which can be ex-
ferent laboratories and to furnish a definite means of actly duplicated at any time.
keeping the knock ratings of any individual laboratory Still another use for a standard fuel is found in those
on a uniform basis. If, for instance, antiknock quality methods of knock rating in which the antiknock quality
is measured in terms óf compression ratio for a definite of a fuel is expressed in terms of changes in the com-
degree of knock in a certain engine and under given position of the standard fuel itself. Such a standard
conditions, a standard fuel offers the only definite or fuel is really of variable composition and may consist
altogether reproducible basis for checking the mechani- of a mixture of two fuels of widely different antiknock
cal condition of the engine from time to time. Like- qualities that can be mixed in the right proportions to
wise, if antiknock quality is measured in terms of oper- match the antiknock quality of any fuel which it may
ating variables, such as throttle opening or spark be desired to rate. The particular advantage of this
advance for a definite degree of knock in a certain en- method of expressing antiknock quality is that, when
gine under given conditions, a standard fuel offers the the two components of the standard fuel are pure sub-
only means of definitely standardizing the mechanical stances, it is possible to establish antiknock specifica-
condition of the engine. tions which are reproducible to an exact degree by any-
one and at any time or place, provided the equipment
1 Research chemist, General Motors Corp. Research Laboratories,
Detroit. and operating conditions are maintained reasonably
2 Assistant head of fuel section, General Motors Corp. Research uniform. This is true irrespective of whether measure-
Laboratories, Detroit.
3 M.S. A.D. - Head of fuel section, General Motors Corp. Research ments of detonation are made by ear or by means of
Laboratories, Detroit. some form of instrumentation.
126

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 Vol. 25 Detonation Characteristics of Some Antiknock Standards 127

Requirements for Standard Fuels which meet some or all of these requirements for a
standard of antiknock quality, .no comprehensive data
It is apparent that, as already said, any fuels which on the relationships that they bear to one another have
are used as standards of antiknock quality should be been published ; consequently, it has been thought
of definite chemical composition so that they can be worthwhile to present some quantitative data on the
reproduced at any time. One way of meeting this re- detonation characteristics of several of the more com-
quirement definitely is to make the standard fuels out of
mon individual compounds that have been considered,,
pure substances that can be mixed in known quantities. and to make these data cover the entire range of com«
A gasoline is not a suitable standard because it cannot
be reproduced in antiknock quality to an accuracy
greater than the experimental error in matching fuels.
This process involves the possibility of a cumulative
error to such an extent that, after several successive
restandardizations, the reference gasoline might con-
ceivably have a knock rating appreciably different from
the original.
Further, gasolines, and especially cracked gasolines
of high antiknock quality, are not suitable for standard
fuels because of their tendency to change their knock
rating in storage. It is desirable, however, that the
standard fuel be as nearly like gasoline as possible in
its physical and chemical properties. It should be com-
posed of definite materials that are available in suffi-
cient quantities to meet the widespread demand for a
standard fuel. Finally, to serve as a standard of varia-
ble composition, it should be composed of substances
which, when combined in various relative percentages,
can be made to duplicate the antiknock quality of the
entire range of gasolines that have to be rated.
Although a number of chemical compounds exist

Fig. 2 - Cross-Section of the Engine Shown in Fig. 1

position from zero to 100-per cent concentration of

Fig. 1 - Single-Cylinder Variable-Compression Engine
Used for Determining the Relative Detonation Char-
acteristics of Fuels
each. Such data are presented in this paper, and the
principal compounds are discussed from the viewpoint
of their suitability for preparing a standard fuel-mix-
ture of variable composition that can be made to match
the antiknock quality of any commercial fuel.
Experimental Equipment Described
The detonation characteristics of these fuels were
determined in the one-cylinder variable-compression en-
gine shown in Fig. 1. This engine was designed and
built in the research laboratories of our company, fol-
lowing a general design made by Henry M. Crane. The
engine is of the valve-in-head type with a 314-in. bore

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 128 S. A. E. Transactions Vol. 25

and a 41/2-in. stroke. The compression ratio can be It has a fixed jet and two float-bowls independently
changed, even while the engine is running, by raisingadjustable for height, so that the mixture ratio for
or lowering the entire cylinder-head and valve mechan- each of the two fuels can be controlled as desired by
ism. This is accomplished by turning with a crank twoadjusting the level of each float-bowl with respect to the
collars which are threaded to the skirt of the cylinder.common fuel- jet. A three-way cock inserted in the fuel
The collars are placed on either side of a supporting line between the float-bowls and the jet makes it possi-
shoulder so that the cylinder-head can be clamped ble to change quickly from one fuel to another without
rigidly in place by turning down the upper collar sepa- interrupting the operation of the engine. The venturi
rately against the shoulder, which is a part of the tube of the carbureter is in a horizontal position and
crankcase. This variable-compression feature of the discharges the fuel mixture directly into the inlet port
engine is especially desirable for knock testing because of the engine. No heat is supplied to the mixture be-
it provides a convenient means of adjusting the engine fore it enters the cylinder. The carbureter has no
to conditions favorable for testing any particular fuel throttle, hence the engine is always operated with the
whether its antiknock quality be high or low. The same inlet opening. A muffler was attached to the in-
valves are actuated by rocker-arms through a vertical take of the carbureter during these experiments to
camshaft which is splined to allow for the up-and-down reduce to the minimum the sucking noise during the
movement of the cylinder-head when the compression intake stroke.
ratio is varied. Fig. 2 shows the general details of this
construction. Method of Making Knock Measurements
The engine is connected to an electric dynamometer Comparisons of the detonation characteristics of the
for absorbing the load and controlling the speed. An fuels and fuel mixtures used were made on the basis
evaporative cooling-system that provides ample room of the compression ratio for borderline detonation or
for water circulation around the entire cylinder-head incipient knock. This critical compression-ratio is de-
automatically maintains the jacket-water temperature fined as that at which detonation becomes just audible
at about 212 deg. fahr. The spark timing is observed under the following specified conditions of operation:
by the flash in a small neon tube, attached to the fly- full load; engine speed, 600 r.p.m.; jacket-water boil-
wheel, as it passes a stationary protractor which is ing, 212 deg. fahr.; mixture ratio for maximum power;
insulated from the ground and connected to the high- and spark advance for maximum power.
tension wire leading to the spark-plug. This procedure is similar to that employed by H. R.
The carbureter was especially built for knock testing. Ricardo several years ago4, the chief differences being
that he chose 1500 r.p.m. as his working speed. We
4 See Report of Empire Motor Fuels Committee (1923-1924),
Institution of Automobile Engineers (London), vol. 18, part I, have used a low speed in this work for the following
p. 77. reasons :

Spark Advance for Maximum Power

,r0 10 Z0 30 40 50
15 fi
+
r6
rļ X
7 I 15 r

15 I

,4
'4 r

U
,3 * 15

1 12 * g 12
X $ ."'/I
X i,
c /' Ï 11 ;
:'==^5=== ,3 I io
•s c 10

I 9
~ / X
O 9

è 8 - -i-y
i 8 - -y~r I e
** 7 ' '

I Ä
~c
* <q -Premium Grade
^
o Ani i knock Gasolines
Upper Li
** i 7 77I ' ' M
mii of

S.
1 o 5 Ani ii i knock TT Gasolines i
O 5 - f-i-
^ h' "
i" 4
j o 3 . - - - -Norme i Heptāni ?
g y
o
2 -Lower Limit of Ordinary- Z
Commercial Oaso/ines .
. i.l
I

0 100 Z00 300 400 ^ 500 0 10 Z0 30 40 50 60 70 80 90 100 l0

Compression Pressure, Ib. per sq. ^ in Percentage By Volume in Heptane
2.0 2.5 3.0 3.5 4.0 4.5 P

Brake Horsepower
Fig. 4 - Graphical Representation of
Fig. 3 - Showing Brake-Horsepower
Output, Spark Timing for Maximum
Power, and Compression Pressure
Plotted against Compression Ratio
These Curves Apply to This Engine Only
When It Is Operated According to the Pro-
cedure Outlined
Data in Table 2
Showing Relative Detonation Characteris-
tics of Several Fuels in Admixture with
Normal Heptane at Concentrations from
Zero to 100 Per Cent by Volume. The
Shaded Band Represents the Range of
Compression Ratios within Which Most of
the Gasolines That Are Being Marketed
Today Begin To Knock
Fig. 5 - Composition of Fuel Mix-
tures Based upon Parts by Volume
Added to 10 Parts of Heptane
Plotted against Compression Ratio
for Incipient Knock
On This Basis the Composition of Benzene-
Heptane Mixtures Have Nearly a Straight-
Line Relationship to the Comnression Ratio

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Vol. 25 Detonation Characteristics of Some Antiknock Standards 129

(1) An engine runs more quietly at lower speeds and
the accuracy of determinations made by ear is
correspondingly greater.
(2) From the practical viewpoint, knocking in auto-
mobiles is most objectionable at low speeds and
full load.
(3) At low speeds an engine requires less fuel, of
which sometimes only a limited quantity is
available.
(4) At the lower speeds the temperature within the
combustion-chamber, especially of the spark-
plug and exhaust valve, is lower, therefore
more uniform operation of the engine can be
expected.
(5) The tendency of any fuel to knock is greater at
low speeds than at high speeds, hence it be-
comes possible to obtain knock measurements
on some fuels which could not be made to knock
at high speeds.
Experiments were made which indicate that the spark
advance for maximum power at compression ratios
close to the detonation point is not appreciably affected
by the chemical composition of the fuel whether the lat-
ter be a hydrocarbon or an alcohol. For this reason the
spark timing was adjusted for maximum power at each carbon of low antiknock quality, and iso-octane (2, 2,
compression-ratio in conformity with a previously de-
termined curve, such as that shown in Fig. 3. This fig-
ure shows also the gage compression-pressure and the
5 See S.A.E. Transactions, vol. 22, part 1, p. 55.
6 See Journal of Industrial and Eiigineering Chemistry; Ana-
lytical, vol. 1, p. 98.
7 See Paper No. N6, Transactions of the Fuel Conference, World
Power Conference (London), 1928, vol. 3, p. 662.
TABLE I- FUELS ON WHICH DATA ARE PRESENTED
brake horsepower of the engine at various compression
ratios extending from 3:1 up to 15:1 under the stand-
ard operating conditions.
The mixture ratio was adjusted in each case for
maximum power as indicated on the beam of the dyna-
mometer scale. This adjustment was much easier to
make experimentally than that for maximum knock, al-
though the two were identical as nearly as could be de-
termined by ear.
The compression ratio was determined by measuring
with a micrometer the distance between two fixed an-
vils, one fastened to the cylinder-head and the other
mounted on the crankcase. The compression ratio cor-
responding to this distance was then obtained from a
calibration curve previously prepared.
Fuels Available
The fuels on which detonation data are presented are
listed, together with their structural formulas, densi-
ties, boiling-points, and sources, in Table 1. Some of
these fuels have been proposed definitely as standard
fuels. Dr. Graham Edgar proposed for this purpose
the use of mixtures of normal heptane, a paraffin hydro-
4-trimethyl pentane), a hydrocarbon of high antiknock
quality5.
R. Stansfield and F. B. Thole have suggested a modi-
fication of Edgar's plan, consisting in the substitution
of benzene for iso-octane6. Toluene with heptane has
also been used by H. R. Ricardo and 0. Thornycroft to
produce reference fuels with a range of antiknock
quality7.

Density at Boiling-Point,
Structural 20 Deg. Cent. Uncorrected
Fuel Formula (68 Deg. Fahr.) Deg. Cent. Deg. Fahr.
Normal Pentane CH3- CH2- CH2- CH2- CH3 0 . 631 34 . 7- 41 . 0 94 . 5-105 . 8
Normal Heptane CH3- CH2- CH2- CH2- CH2- CH2- CH3 0.686 96.8- 99.4 206.6-211.0
Iso-Octane CH3 CH3 0.691 97.6- 99.8 208.1-212.0
I I
CH3- C- CH2- CH- CH3
I
ch3
Cyclohexane H2 0.779 79.5- 81.0 175.5-178.0
C

HaC^ 'iH2
I I
h2c ch2

V
h2
Benzene H 0.878 79.0- 79.0 174.5-174.5
C
S '
HC CH
I H
HC CH

C
H

Toluene CH, 0.866 108.0-109.0 226.8-228.6

I
C
^ '
HC CH

Jo ¿'h
V
H

Ethyl Aleoho CH, - CH2OH 0.789 78.1- 78.1 173.0-173.0

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 130 S. A. E. Transactions Vol. 25

Tabulation and Discussion of Data Obtained ratios as low as 3:1 in the engine used for these deter-
The results of the investigation herein reported are minations; hence normal heptane, which has a limiting
tabulated in Table 2 and are shown graphically in Fig. compression-ratio of 2.75:1, under the conditions of
4, in which is presented the relationship between the these tests, is the only one of the hydrocarbons in-
composition of each of the various mixtures, expressed cluded in this survey the limiting compression-ratio of
as percentage by volume in normal heptane, and the which is low enough to form the base-line of the scale.
Selection of the most suitable substance for use to
compression ratio for incipient knock. In Fig. 4 the
compression ratio for incipient knock is measured on form the upper limit of the scale of antiknock quality
the vertical axis and the percentage of admixture withis not so easy to makeš Normal pentane is hardly suit-
normal heptane on the horizontal axis. The shaded able because its antiknock quality or limiting compres-
band represents the range of compression ratios withinsion-ratio is below that of many of the gasolines cur-
which most of the automobile fuels that are being mar- rently sold. The extremely high volatility of normal
keted today begin to knock. The upper limit of the pentane is also undesirable. Cyclohexane might be an
band corresponds to thè antiknock fuels and the lower excellent material to form the upper standard of anti-
limit to the regular automobile gasolines. Most regular knock quality if the range within which knock ratings
automobile gasolines come well above this lower limit. are to be made were to be confined to that covered by
A gasoline which was approximately equivalent in present-day automobile-fuels.
knock rating to the average of the Country, as found Fig. 4 shows that a convenient straight-line relation-
by the United States Bureau of Standards detonation ship exists between the compression ratio for incipient
survey of 1927 and reported upon by H. K. Cummings8, knock and the composition of cyclohexane and heptane
began to knock at a compression ratio of 3.6:1, or al- mixtures. This seems to be desirable from the view-
most midway between the limits of the shaded band. point of a standard fuel of variable composition, be-
The data show that normal heptane begins to knock cause it would provide a uniform change in standard-
at a compression ratio of 2.75:1. When a substance of fuel composition over all parts of the scale. Another
higher antiknock quality is added to normal heptane feature of mixtures of cyclohexane and heptane that
in increasing proportions, the compression ratio can be
increased without knock, along the curves of Fig. 4,
TABLE 2 - RESULTS OF THE INVESTIGATION
until the compression ratio is reached at which the
SEE FIG. 4 FOR GRAPHICAL ANALYSIS
fuel of higher antiknock quality itself begins to knock.
It is important to note that the numerical values as- Composition of Fuel, Compression
signed to the compression ratios for incipient knock in Percentage by Ratio for
this work apply only to this particular engine when it Volume in Heptane Incipient Knock
is operated under the conditions existing at the time 100.0 Normal Heptane 2.75
the experiments were made. The characteristics of this
engine are such that, in general, the limiting compres- 0.01 7 f 2.75
53.9 > Normal Pentane *( 3.40
sion-ratios reported here are about one ratio below 100.0 J I 3.80
those corresponding to conventional automotive-engine
experience. 0.0 ļ f 2.75
33.0 3.35
The compression ratio for incipient knock could be 47.7 3.60
determined, at the time the experiments were made,
within 0.05 of a compression ratio. By this it is irxeant 73 0 63.0
i Iso-Octane -r n _ -s ^ 2q I I
that detonation would be inaudible if the compression 82^0 4.65
were lowered 0.05 of a ratio below that determined for 91.5 5.40

incipient knock. This procedure constituted the experi-

100.0 J [ 6.90
mental technique employed for establishing the com- 0.0 ļ r 2.75
pression ratio for incipient knock. 20.9 3.15
47.7 3.65
At compression ratios above 10:1 the manifestation
of "roughness" made more difficult the distinct detec- 59.0
71.0 I
f
tion of the characteristic sound of detonation. This 85.0 7.05
roughness, however, should not be confused with pre- 92.3 10.00
100.0 J [above 15.00
ignition, which is an altogether different phenomenon.
Under the conditions of these tests preignition was 0.0Ì 2.75
never observed at a compression ratio below that at 23.8 3.23
which knocking began. The effect of normal varia- 52.5 4.10
tions of atmospheric conditions upon the determina- 74.6 * Toluene "ļ 6.50
87.2 9.50
tions was negligible, so far as was observed during the 93.5 11.60
period of these tests. 100.0 J 113.60

Some Factors Influencing the Selection of 0.01 r 2.75

Reference Fuels
52.1
100.0 )
r cyclo
I 4.50
The range of antiknock quality of the fuels to be
rated is an important factor to be considered in the
selection of the fuels which are to be the most suitable
0.0 Ì r 2.75
14.6 3.20
for use as standards of antiknock quality. Some gaso- 37.7 [ Absolute Ethyl Alcohol J 3.97
lines are known which begin to knock at compression 61.6 i I 5.60
78.8 8.50
8 See S.A.E. Transactions, vol. 23, p. 53. 100.0 J 11.60

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Vol. 25 Detonation Characteristics of Some Antiknock Standards 131

seems desirable is that an inaccuracy of 0.5 per cent in lines referred to in Fig. 4, a variation of 0.5 per cent
measuring out the respective volumes of cyclohexane of benzene in heptane is equivalent to about 0.04 of a
and of heptane would not introduce a large error in the compression ratio or to about 0.2 cc. of tetraethyl lead
knock rating of the mixture. This comes about because per gal. This variation in concentration of tetraethyl
of the narrow range in antiknock quality represented lead is greater than the tolerance desirable in some
by the entire scale, and it would make it unnecessary knock ratings. Accordingly, great care is necessary in
to use extremely accurate measuring vessels in prepar- measuring out the components of these mixtures when
ing mixtures of the two standard fuels, as is the case they are to be used as standard fuels. It is also essen-
with some of the materials discussed later; but the tial that the benzene used for this purpose be of a high
adoption of cyclohexane as a standard would place an degree of purity.
upper limit on the scale of antiknock quality that would Another apparent disadvantage of mixtures of ben-
be only slightly higher than that of some of the auto- zene or of toluene with normal heptane is the large
mobile fuels distributed today. variation in antiknock effect resulting from a given
Iso-octane is one of the first compounds proposed for change in composition on different parts of the scale.
use as a standard fuel in mixtures with normal heptane, For example, referring to Fig. 4, increasing the con-
and it has been used to some extent. One of the points centration of benzene in heptane from 30 to 40 per cent
mentioned in favor of mixtures of iso-octane and nor- permits an increase of 0.2 of a compression ratio ;
mal heptane as standards of antiknock quality is that whereas an increase in concentration of benzene from
the common physical properties of these two hydrocar- 80 to 90 per cent allows an increase of 2.8 compression
bons are almost identical, and thus the physical charac- ratios. So, over the latter range, a given change in con-
teristics of the mixtures remain practically unchanged centration of benzene produces nearly 15 times as large
over the entire range of composition. an effect on antiknock quality as over the former range.
One possible disadvantage of iso-octane is that some This objectionable feature is overcome somewhat by
fuels might be found that have a higher antiknock plotting the scale of knock rating on the basis of the
quality than iso-octane itself, which has a limiting com- amount of benzene added to a constant volume of nor-
pression-ratio of 6.9:1 under the conditions of this mal heptane, as shown in Fig. 5.
survey. However, it may be that for a time, as far as In Fig. 5, compression ratios for incipient knock are
automobile practice is concerned, such fuels may be plotted on the vertical axis, as in Fig. 4, but along the
used for blending purposes only. In such cases the horizontal axis the concentrations of benzene, of to-
antiknock quality of the fuel, in admixture with the luene, and of iso-octane in heptane are plotted on the
fuel with which it is to be blended, should be deter- basis of number of parts by volume of these substances
mined. The reason for this is that the knock rating of added to 10 parts by volume of normal heptane. This
a pure substance cannot be taken as a direct indication means that 10 on the horizontal scale of Fig. 5 corre-
of its effectiveness for improving antiknock quality in sponds to the 50-per cent point in Fig. 4, and that 30 in
a blend. This is another point which is evident from Fig. 5 corresponds to the 75-per cent point in Fig. 4.
the data presented in Fig. 4 ; for example, the antiknock The result is that, in Fig. 5, benzene and heptane pro-
quality of pure benzene is superior to that of iso-octane portions have a straight-line relationship to compression
although, in blends with normal heptane up to 50 per ratio up to 40 parts of benzene in 10 parts of heptane,
cent, iso-octane is just as effective by volume as benzene which corresponds to 80 per cent of benzene in heptane,
for increasing the antiknock quality of the mixture. or to a limiting compression-ratio of 6.0 : 1 under the
Benzene and toluene are both quite high in respect conditions of this work. A similar relationship exists
to antiknock quality when used alone, the limiting com- in the case of mixtures of toluene in heptane. Iso-oc-
pression-ratio for toluene under the conditions of these
tane does not lend itself to this method of plotting to
tests being 13.6:1, and that for benzene being more any advantage.
than 15.0:1. Both benzene and toluene have been used This latter method of constructing a scale of knock
as reference fuels in making knock ratings. One of the rating has been presented here to illustrate that, not
apparent disadvantages of these substances for use in only is there a choice as to the most suitable compound
mixtures with normal heptane is the relatively large to serve as a standard fuel, which definite selection it
variation in antiknock quality that is brought about byis not a function of this paper to make, but that the
a small change in the composition of the mixture on method of expressing results or of establishing the
certain parts of the scale. Thus, at the point corre- scale of antiknock quality in the best and most useful
sponding to the upper limit of the premium-grade gaso-
form is also a matter that needs consideration.

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