BRIGGS G POPPER-SPECIFIC HEAT OF T A R DISTILLATES 401

would be occupied by the C1- ions, assuming that they constitute a closely packed monolayer on
the surface of the solid, each ion occupyinge ll.4A2;this area is close to the maximum area
obtained from nitrogen adsorption measurements.

Acknowledgments
The authors record their thanks to Peter Spence and Sons Ltd. for the award of a research
scholarship (to M.R.H.) and to the Imperial Chemical Industries Ltd. Research Fund for the
loan of apparatus.

Royal Technical College

Salford
and
College of Technology
Liverpool
Received 26 July, 1956
References
1 Harris, M. R., & Sing, K. S. W., J . appl. Chem., 1955, * Gregg, S. J., J . chem. SOC.,1953, p. 3940
5, 223 Weiser, H. B., Milligan, W. 0.. & Purcell. W. R..
* Brunauer, S., 'The Adsorption of Gases and Industr. Engng Clem. (Industr.), 1941, 33, 669
Vapours ', 1945, Val. I (London: Oxford Univer- Emeleus, H. J., & Anderson, J. S., ' Modern Aspects
sity Press) of Inorganic Chemistry ', 1952, 2nd ed., p. 74,
3 Kolthoff, I. hf., .-lnnlyst, 1952, 77, 1000 (London: Routledge and Kegan Paul)

THE SPECIFIC HEAT OF COAL TAR DISTILLATES

By D. K. H. BRIGGS and F. POPPER

Specific heats of a large number of coal tar distillate fractions have been measured and the
following relationship, which will predict values to an accuracy of -f 5% for the temperature range
20-180", has been derived by means of statistically designed experiments:
+
Cp = l/d,,, (0,1758 0.2138 d,,+ +
0.000861 t ) x (0.00216 - 0.00000528 tb)
where C, is the specific heat, cal./g." c
d,, is the density of the sample a t 20°, g./ml.
t is the temperature, ' c
tb is the volumetric average boiling point of the sample, O c
x is the tar acid content, yo by volume.

Introduction
Extensive data on the specific heats of petroleum oils are available, and correlations between
such data and more simply determined constants, such as density, have been derived; these
however are not applicable to tar dsti1lates.l The few data that are available are reviewed by
Edler, who proposes a relationship between specific heat and density of the form
C, = l / d (A Bt) +
and gives values of the constants A and B for various types of raw material. The fact that Edler
gives constants for phenols which differ markedly from those for tar oils suggests that any
equation for tar oils, which may contain up to 40% of tar acids (i.e., phenols), should take into
account the tar acid content.
The present work consists of a designed statistical study of the effects of possible variables
on the specific heats of tar oils, and the development of an equation which will give a minimum
error when applied to data derived experimentally from a wide range of tar oils.

J. appl. Chem., 7, July, 1957

402 BRIGGS & POPPER-SPECIFIC H E A T O F T A R DISTILLATES

A simple calorimeter, consisting of a Dewar flask, thermometer, heater and stirrer, is

claimed to give the specific heats of liquids with an accuracy of about &€7&,.3 This type of
calorimeter was used by Forrest et aL4 for work on diphenyl, by Fortsch & Whitman5 on
petroleum products, and, with refinements, by Hyman & Kay* on tars and pitches, and was
adopted for the present work.

Experimental
Apparatus
The calorimeter and auxiliary equipment are shown in Fig. 1. The calorimeter body consists
of a ,one-1. Dewar flask A in its tin container B, silver-painted to reduce radiation losses. This is
mounted in a lagged box C and a lagging ring D placed on top after
fitting the cork E. The cork E bears the electrical leads, a standard
thermometer G and a recycle stirrer H. The heater F, situated a t
the bottom of the flask, consists of 8 in. of 27 s.w.g. nichrome wire
wound on a glass former. Power is supplied by a 12-v. 120 ampere-
hour accumulator adjusted by variable resistance R and measured
by ammeter I and voltmeter V. The ammeter was calibrated
against a standard instrument and the voltmeter against a standard
cell using a potentiometer.
The heat equivalent of the calorimeter was determined a t
several temperatures with 700-800ml. of water in the flask. The
quantity of water had, within these limits, no significant effect 011
the heat equivalent, and showed that no correction was necessary to
allow for expansion of liquid during the course of a series of runs a t
increasing temperature. From the heat equivalents determined, the
weights of Pyrex glass having the same heat capacity as the calori-
meter were calculated using the specific heat value 0.17 + 0.00036 t
cal./g.O c supplied by the manufacturer. The average equivalent
weight of Pyrex was then obtained, and this, when multiplied by the
specific heat of Pyrex, gives the average heat equivalent of the
calorimeter and its variation with temperature. Since most of the
.cI' '* The caz07imetev
apparatus which directly absorbs heat is constructed of glass the
above calculation will not give rise to any significant error.
Procedure
Determinations were carried out on 750 ml. of sample, cooling data being obtained before
and after each run in order to allow for heat 10sses.~
The specific heat at the average temperature of the experiment is given by

where C, is the specific heat at constant pressure (ca1.lg.O c), E is the voltage, I the current
(amp.), T the time (sec.),J the mechanical equivalent of heat (joules/cal.),t the corrected tempera-
ture rise (" c), W the heat equivalent of the calorimeter (ca1.l" c), MI the weight of the material
under test before the experiment (g.) and M , the final weight (g.).
Should there be a significant loss of weight due to evaporation the experiment is repeated
at a lower temperature.
The accuracy of the calorimeter was checked by tests on benzene and naphthalene (Table I).

Correlation for tar oils

The specific heat of a tar fraction is dependent upon temperature and the composition of
the mixture. In addition to hydrocarbons, which constitute the bulk of petroleum oils, tar oils
also contain acidic and basic organic compounds with comparatively high specific heats. Thus,
whilst simple relationships have been evolved between the specific heat of petroleum oils and
their density, correlations for tar oils may be expected to be more complex. I n order to assess
the effect of temperature, and of tar acids and bases, on the mixtures, two statistically designedlOa
series of experiments were carried out.

J. sppl. Chem., 7, July, 1957

 BRIGGS G POPPER-SPECIFIC HEAT OF T A R DISTILLATES 408
Table I
Specific heat data f o r benzene and naphthalene
Compound Temperature, Specific heat, cal./g.' c
OC
Present Literature values
work
Benzene 33.0 0.418 0-4127, 0.422*
Naphthalene 110.1 0.439 0.439%
150.7 0.467 0.470%
188.7 0.501 0.4998

In the first series, dry tar acids and bases were added in controlled amounts to the dry,
neutral, vertical retort heavy naphtha from which they had been extracted. In the second series
a vertical retort heavy anthracene oil was used.

Results
First series
The experimental results are given in Table 11, and statistical evaluation of these results
by the method of Yateslob is shown in Table 111.

Table 11
.<pecLfic heats of test iriixtzivrs
Coniposition of Temperature, Specific heat,
mixture OC cal./g." c

loo, Tar acids

200 Tar bases
88", Naphtha

Zoo; Tar acids

I 30
6o

30
0 ' 4567
0.4882

0.4710
2 7 , Tar bases
7So/, Naphtha 0.5039

45; Tar bases JU 0.4636

86;; Naphtha 60 0.4904

20% Tar acids 30 0.4738

76%
496 Tar bases)J
Naphtha 60 0 ' 5063

Table III
Effects of vaviables
Effect Value Significance
level

Tar acids (A) +0.0561 0.1%

Tar bases (B) $0.0143 -
Temperature (C) $0.1237 0.1%
Interaction AB -0.0039 -
Interaction AC +0.0071 -
Interaction BC -0.0051 -
Interaction ABC +0.0039 -

The results show that none of the interactions is significant at the 5% level. The variation
of concentration of tar bases between 2 and 4% alters the result insignificantly; a variation of
0 to 4% would have an effect significant a t the 5% level, assuming linearity of effect with con-
centration. The tar bases are present in only very small amounts in normal tar distillate fractions
and, in view of the decrease in effect found later with the higher-boiling range of the fraction,
they may be ignored. The effects of tar acids and temperature are highly significant.

J. appl. Chem., 7, July, 1957

404 BRIGGS G POPPER-SPECIFIC HEAT OF T A R DISTILLATES

In view of the absence of interactions between factors, specific heats of tar oils should be
additive functions of the tar acid content and temperature. The effect of temperature is linear
over the experimental range and a further series of experiments showed the effect of tar acids
t o be linear also up to about 25%. Therefore the specific heat of the naphtha can be represented
by an equation of the form
+ +
C, = a bx ct ........................................................* ( I )
where C, is the specific heat (cal./g. c), x is the tar acid content ( v 0 1 . - ~ t~ is
O ) , the temperature
(" c) and a, b and c, are constants.
Using all available data to evaluate the constants by the method of least squares, the follow-
ing expression for this naphtha can be derived
+ +
C, = 0.4112 0 * 0 0 1 2 8 ~ 0.00113t ..................................... .(2)
which predicts results with an accuracy of f 1 -3%in 95% of the experiments.

Second series
The interactions between variables and the effect of tar bases were again negligible; the
effect of tar acids was significant only at the 5% level; the effect of temperature was, however,
still highly significant.
Again using all the results obtained for mixtures of the anthracene oil, the method of
least squares gives
+ +
C, = 0.3739 0 * 0 0 0 3 1 ~ 0.00094t ......................................(3)
which predicts results with an accuracy of & 1.8% in 95% of the experiments.
Results from determinations on a vertical-retort wash oil treated in a similar fashion gave
the equation
+ +
C, = 0.3881 0 * 0 0 0 7 3 ~ 0.00100t ......................................(4)
The values for the constants a, b and c of equations 2-4 are given in Table IV as evaluated
for the three oils studed.
From the data in Table IV it is apparent that the constants a, b and c decrease as the
average molecular weight of the material increases. This decrease is small in the case of the
constants a and c but very marked in the case of b.
The above illustrates the effects of the variables on the specific heat of tar oils for specific
samples. In order to produce a general equation for tar distillates the variation of the effects
with change in sample must be studied.
The effect of tar acid content is evaluated solely from the statistical design data rather than
from results on commercial samples, since in the designed experiments the tar acid content of the
samples was accurately known, whereas for the commercial samples only estimates of tar acid
content are available. A plot of the values of b (Table IV) against the volumetric average boiling
points of the corresponding original unwashed oils is linear within experimental error and the
least squares relationship is
b= 0 * 0 0 2 1 6 - 0*00000528tb ............................................. * (5)

where t,, is the average boiling point (" c ) .

The specific heats of tar samples5 '4 have been shown to vary in a linear manner with
temperature over a limited range. The results of 137 individual specific heat determinations
have confirmed this, and the data have been used to obtain the following generalized equation
predicting values with the minimum error:
. +
C, = l/dzo (0.1758 0.2138d2, + +
0.000861t) ~(0.00216- 0.00000528tb) ... .(6)
where C, is specific heat at temperature 1" c (cal./g."c), d,, is the density a t 20" c (g./ml.),
t b average boiling point (" c) and x the tar acid content (yoby volume).

Table IV
Constants for specific heat equations
Mixture a b C

Naphtha 0.4112 0.00128 0.00113

Wash oil 0.3881 0.00073 0.00100
Anthracene oil 0.3739 0.00031 0.00094

J. appl. Chem., 7, July, 1957

 BRIGGS & POPPER-SPECIFIC HEAT OF T A R DISTILLATES 405

Equation (6) predicts results with an accuracy of &0-0162ca1.lg.l" c for 95% of experiments,
or an average error of about &3.5% over the experimental temperature ranges.

Discussion
The correlation presented here for tar distillates (equation 6) will give satisfactory data for
most chemical engineering purposes. A comparison of values calculated from Edler's equation
+
C, = l/d (0.339 0.00124t) with values calculated from the equation now recommended is
given in Table V.
Table V
Comparison of calculated and experimental specific heat data
Sample Density, Tar acid, 7; Temperature, Specific heat cd./g."c
g./ml.. by volume O C

Experimental Calculated Calculated

from present from Edler's
equation (6) equation
Light naphtha 0.868 5 20 0.431 0.443 0.420
100 0.525 0 * 522 0.534
180 0.618 0.601 0.648
Heavy naphtha 0.943 27 20 0.463 0.451 0.386
100 0 * 539 0.524 0.491
180 0.615 0.597 0.596
Naphthalene oil 1.002 34 20 0.432 0.441 0.363
100 0.501 0.510 0 * 462
180 0.570 0.579 0.561
Wash oil 1.037 15 20 0.398 0.411 0.352
100 0.469 0,477 0.448
180 0.540 0.543 0.544
Anthracene oil 1.120 18 20 0.364 0.385 0.325
100 0.441 0.447 0.414
180 0.518 0 * 509 0.503

The experimental data show the necessity for a tar acid factor which alters the pattern of
decrease of specific heat with increase in density, and the inclusion of such a factor in equation (6)
gives predicted values within f5y0 of the experimental values in 95% of cases over the range
20-180". Edler's equation, which was developed from German tar data, gives values with a
corresponding accuracy of &16y0, the lower accuracy being due mainly to the comparatively
high value of his temperature coefficient.

Acknowledgment
The authors wish to express their thanks to the Council of The Coal Tar Research Association
for its permission to publish this work.

The Coal Tar Research Association

Oxford Road
Gomersal, nr. Leeds
Yorks.
Received 27 June, 1956; amended manuscript, 4 September, 1956
References
Ryabov. L. I., K o k s u. Khim., Ir'harkov, 1936, (9), Williams, J. W., & Daniels, F., J . Amer. chem. Soc.,
47 1924, 46, 903
Edler. E., Erdol u. Kohle. 1953, 6, 543
Sturtevant, J. M.. ' Physical Methods of Organic Oliver, G. D., Eaton, M., & Huffman, H. M., J . Amer.
Chemistry ', 1945, Vol. 1, p. 365 (New York: chem. Sac., 1948, 70, 1502
Interscience Publishers Inc.) @Spaght,M. E., Thomas, S. B., & Parks, G. S.,
4 Forrest, H. O., Brugmann, E. W., & Cummings, J . phys. Chem., 1932, 36, 882
L. W. T., Industv. Engng Chem., 1931, 23, 37
6 Fortsch, A . I<., & Whitman, W. G., Industr. Engng l o Bennett, C. A., & Franklin, N. L., 'Statistical
Chem., 1926, 18, 795 Analysis in Chemistry and the Chemical
Hyman, D., & Kay, W. B., Industr. Engng Chem., Industry ', 1954, (4 Chapter 8; (b) p. 499
1949, 41, 1764 (London: J. Wiley and Sons, Inc.)

J. appl. Chem., 7, July, 1957