ESTIMATION OF HEATS OF FORMATION

OF ORGANIC COMPOUNDS
K. K. VERMA AND L. K. DORAISWAMY
National Chemical Laboratory, Poona, India

A procedure based on group contributions has been developed for estimating the heat of formation of
organic compounds as a function of temperature. The temperature dependence of any group can be ex-
pressed as a straight-line relationship, and two such equations are required to cover the entire temperature
range of 300"to 1500' K. The values of the two constants appearing in these equations for the two regions
of temperature have been tabulated for a variety of hydrocarbon and nonhydrocarbon groups, In the
temperature rlange 300' to 1500" K. the proposed method predicts the heat of formation of hydrocarbons
with an average error of 0.35 kcal. and of nonhydrocarbon compounds with an average error of 0.26 kcal.
per gram-mole.

HE standard heat of formation of a compound in its ideal variety of hydrocarbon and nonhydrocarbon structures (which
gaseous state relative to the component elements, all in would not require the value of AH,' a t any base temperature).
their standard state of unit activities at any temperature, is ex-
pressed by the equation Method
T h e symmetry effect is absent for the heat content function.
(AH~')T = -
[(HT" &Bo) + (AHf')oIcompd - Therefore, from Equation 1, it should also be absent for
c (HT' - Ho')ele (1)

Expressing the enthalpy function ( H T o - H,') in terms of C',

and using 298' K. as base temperature,

= (AHfo)298$- C," (Compd) dT - 48t "2CP.C-c<H

(ENDOTHERMIC)

Methods for estimating, -

(HTo H,"),
40 t >c=c(

and C ', of organic compounds as additive functions of the

composing groups of any given molecule include those of
Anderson, Beyer, and Watson (7), Franklin (9),and Souders,
Mathews, and Hurd ( 2 7 ) . These (and a few others) have been
critically reviewed by Reid and Sherwood (27) and Janz (74).
None of these methods can be used for estimating the heat of
formation as a continuous function of temperature, and those
that enable estimation a t different temperatures are restricted
to certain discrete temiperatures only. O n the other hand,
methods are available ((22, 28) for estimating the other two
important thermodynamic properties, AGf' and C,', a t any
desired temperature in the range 300' to 1500' K.
It is possible to obtain an expression for AH,' as a function
of T from Equation 2, using the group methods for Cp' de-
veloped by Johnson and Huang (75) or Rihani and Dorais-
wamy (22) together with the C', values of the elements, pro-
vided that (AH,'),98 (or AH; a t any other base temperature)
is known. T h e object of the present paper is to develop a
relationship between heat of formation and temperature, Figure 1. Temperature dependence of heat of formation
based directly on the principle of group additivity, for a of representative hydrocarbon groups

VOL. 4 NO. 4 NOVEMBER 1 9 6 5 389

 Table 1. Aliphatic Hydrocarbon Groups
300-850 ' K. 850-7500° K. Highesj
Group A B X lo2 A B X lo2 Temp., K.
-CHI -8.948 -0.436 - 12.800 0.000 1500
1
-CH2 -4.240 -0.235 - 6.720 0.090 1500
I
-CH -1.570 0.095 - 2.200 0.172 1500
I
-0,650 0.425 0.211 0,347 1500

7.070 -0.295 4.599 -0,0114 1500

27.276 0.036 27.600 -0.010 1500
27.242 -0.046 27.426 -0,077 1500
33.920 -0.563 33.920 -0.563 1500

\
C=CH2 16.323 -0.437 12.369 0.128 1500
/
\
16.725 -0.150 15.837 0.038 1500
/C=CHz
\ /
c=c 29.225 0.415 30.129 0,299 1500
/ \

c=c
'
20.800 -0.100 19.360 0,080 1500
\H

20.100 0.000 19.212 0.102 1500

H
\c=c
/" 19.088 -0.378 17.100 0.000 1500
/ \
(cis)
H
\ /
c=c 18.463 -0.211 16.850 OIO0O 1500
/ \
H
(trans)
\
C=C=CHz 51,450 -0.050 50,200 0.100 1500
/
\
C=C=CH2 50.163 -0.233 48.000 0.000 1500
/
H
\ /
54,964 0.027 53.967 0.133 1500
H /c=c=cH'
5 Temperature ranges: 300-7700° K. and 7100-7500aK. Temperature ranges: 300-600" K. and 600-7500° K.

T h e following empirical equation can then be written: (AHf')T = A + BT (4)

(AH,'), compound = (AH,")* of composing groups 9 (AH,"), is plotted as a function of temperature in Figures 1
corrections if any (3) and 2 for representative hydrocarbon and nonhydrocarbon
An examination of the estimated values for a variety of groups groups!, respectively. I t is evident that the two temperature
at different temperatures has shown that the plot of AH," us. T ranges over which straight-line relations are obtained are not
for any group can be divided into two portions in the tem- the same for all the groups. For the majority of groups,
perature range 300' to 1500' K., the general form of the however, the approximate ranges are: 300' to 850', 850" to
equations being 1500'; and 300' to 750°, 750' to 1500' K.

390 I&EC FUNDAMENTALS

 ~-

Table II. Aromatic Hydrocarbon Groups

Highest
300-750" K. 850-7500" K. ~ ~ ~ p , ,
Group A B X 702 A B X 702 K.

H
C
( 3.768 -0.167 2.616 -0.016 1500

-c< 5.437 0.037 5.279 0.058 1500

d< 4.208 0.092 4.050 0.100 1500

Table 111. Branching in Paraffin Chains

Highest
300-750' K . 750-7500° K. ~ ~ ~ p . ,
Group A B X 102 A B X lo2 K.
Side chain with 2 or
more C-atoms 0.800 0.000 0.800 0.000 1500
I
3 adjacent -CH groups - 1 ,200 0.000 .,. ... 1500
I -NH
- -
(ALIPHATIC) I
I - - - - e - .__
-
-
-
- - - I
- NO2 (EXOTHERMIC) Adjacent -CH
I
I
- : I
and -C- 0.600 0.000 0.600 0.000 1500
-m - s-
(E,XOTHE?MIC) I I
- 2
300 100 500 $00 700 ew sw icca iiw 12w i3w 1400 1500 Table IV. Branching in Cycloparaffins
TEMP., ' K .
Highest
Figure 2. Temperature dependence of heat of formation 300-850" K. 850-7000° K. ~emp.,
of representative nonhiydrocarbon groups Group A B X 702 A B X lo2 ' K.
BRANCHING IN SIX-MEMBERED RINGS
Single branching 0.00 0.00 2.85 - 0.40 1500
Double branching
1,l position 1.10 0.45 -0.40 0.00 1500
T h e procedures by which the values of A and B have been cis-l,2 position 3.05 - 1 .09 1 .46 - 0.13 1500
trans-1,2 position -0.90 -0.60 -1.50 0.00 1500
evaluated for a variety of hydrocarbon and nonhydrocarbon ~i~-1,3-d 0 . 0 0 -1.00 -2.60 0.00 1500
groups and the temperai:ure ranges over which these are gener- trans-l,3 -1 0.00 -0.16 2.80 -0.32 1500
ally valid are briefly described below. CIS-^,^ 0 . 0 0 -0.16 2.80 -0.32 1500
trans-1,4 0 . 0 0 -1.00 -2.60 0.00 1500
BRANCHING IN FIVE-MEMBERED RINGS
Hydrocarbon Groups Single branching 0.00 0.00 1 .40 - 0.20 1500
Double branching
T h e heats of formation of the composing groups of paraffin 1,l position 0.30 0 00 1.90 -0.25 1500
hydrocarbons in the temperature range 300' to 1500' K. cis-1,2 0.70 0.00 0.00 0.00 1500
trans-1,2 -1.10 0.00 -1.60 0.00 1500
have been established from published data (74, 23, 25). For cis-1,3 -0.30 0.00 0.15 0.00 1500
the olefins the basic structural groups described earlier (74,22) trans-1,3 -0.90 0 . 0 0 -1.40 0 00 1500
have been used, since they have the advantage of accounting for
hyperconjugation and cis-trans isomerism. The introduction Table V. Branching in Aromatics
of the -C= and =CH groups makes it possible to apply this Highest
method for several acetylenes as well. T h e values of A and B 300-850 K. 850- 1500O K.
~- 2mp.,
for each of these groups (are summarized in Table I. Group A B X 702 A B X lo2 K.
T h e usual aromatic groups have been retained, and the Double branching
1,2 position 0.85 0.03 0.85 0.03 1500
values of A and B for these groups are summarized in Table 11. 1.3 uosition 0.56 -0.06 0.56 -0 06 1500
~..
Corrections due to branching were found to be necessary in 114 bosition 1.00 -0.14 1.40 -0.12 1500
paraffin chains, cycloparaffins, and aromatic rings, and were Triple branching
1,2,3position 2.01 -0.07 1.50 0.00 1500
calculated from reported data (24, 25). T h e estimated con- 1,2,4position 1.18 -0.25 1.50 -0.10 1500
stants are listed in Tables 111, IV, and V, respectively. 1,3,5 position 1.18 -0.25 1.80 -0.08 1500
While dealing with cycloalkanes, it is necessary to calculate
corrections for the formation of rings. T h e corrections due to Table VI. Ring Correction
ring formation for three-, four-, five-, and six-membered rings Highest
were calculated from the data assembled by Janz ( 7 4 , and the 300-750' K . 750-7500'K. ~:~p.,
constants A and B for these corrections are listed in Table V I . Group A B X lo2 A B X lo2 K.
Ca-cycloparaffin
ring 24.850 -0.240 24.255 -0.174 1500
Nonhydrocarbon Groups C4-cycloparaffin
ring 19.760 -0.440 17.950 -0,231 1500
Contributions for the important oxygen-containing groups, Cs-cycloparaffin
ring 7.084 -0.552 4.020 -0.140 1500
-0-, C=O, O J I ---CHO, and -COOH, were calculated C6-cycloparaffin
*I' ring 0.378 -0.382 -4.120 0.240 1500
from the values of dimethyl ether (2, 29) and diethyl ether ( Z ) ,

VOL. 4 NO. 4 NOVEMBER 1 9 6 5 391

 Table VII. Oxygen-Containing Groups
300-850 K. 85O-150Oa K. Highest
Group A B x 702 A B X loz Temp., O K .
\
-31.505 0,007 -32.113 0.073 1500

-0- -24.200 0.000 -24.200 0.000 1000

-0- - 30.500 0.000 -30.500 0.000 1000

-21.705 0.030 -21.600 0.020 1500

- CHOO -29.167 -0.183 - 30.500 0.000 1000
0 0

//
-C -94.488 -0.063 - 94.880 0.000 1500
O
'H
OF -OH
CONTRIBUTION GROUP
HO - -- - CHs -37.207 -0.259 -37.993 -0.136 1000
HO - -- - CH2- -40.415 -0.267 - 41.265 -0.116 1000
I
HO---CH -43.200 -0.200 -43.330 -0.143 1000
I
I
HO---C- -46.850 -0.250 - 47 ,440 -0.146 1000
I
H O - - - C yf
"4
-44.725 -0.125 - 45 ,220 -0.021 1000
a Temperature ranges: 300-700° K. and 750-7500O K .

Table VIII. Nitrogen- and Sulfur-Containing Groups

300-750" K. 750-750O0 K. Highest
Group A B X lo2 A B X lo2 Temp., K.
--NO2 (aliphatic) - 7.813 -0.043 -9.250 0.143 1500
-C=N 36.580 0.080 37.170 0.000 1000
3.832 -0.208 2.125 0.002 1500
a 13.666 -0.067 12.267 0.133 1500
18.050 0.300 18.050 0.300 1500
- 0.713 -0.188 -1.725 0.000 1000
9.240 -0.250 8.460 -0.140 1000
=N 18.890 0.110 16.200 0.250 1000
SHb -10.580 -0.080 ... ... 1000
-S-b - 4.725 0.160 *.. ... 1000
a Temperature ranges: 300-600° K. and 600-1000° K. Temperature ranges: 300-1000° K.
Standardstate of sulfur is SZ(gas) at 298' K. For conversion to S (crystal, rhombic) at 298' K., the factor is 75.42 kcal./mole ( 78).

acetone (76), furan ( 7 7 ) , acetaldehyde ( 6 ) , and acetic acid from nitromethane (77) ; of the -C=N group from the data
(30), respectively, and the corresponding values of A and B of cyanogen (76); of the primary, secondary, and tertiary
are shown in Table V I I . T h e contribution of -0- was aliphatic amino groups from the values.of methylamine (76),
found to be dependent on the nature of the carbon atom dimethylamine (76), and trimethylamine (76), respectively;
attached to the two bonds. Values for -0- when the and of the primary, secondary, and tertiary aromatic amino
adjacent groups are -CHa and -CH2 are given in the table. groups from the values of aniline (72), monomethylaniline
The contribution of the -OH group was not found to be (29),and dimethylaniline (29),respectively.
independent of position. T h e values of A and B for several The contributions of the sulfur-containing groups, -SH and
positional contributions of -OH appear in Table VII. These -S-, are also listed in Table V I I I . They were obtained
were calculated from the values of methanol ( 3 ) ,ethanol (3), from the values of methanethiol and dimethylsulfide (7).
isopropyl alcohol (5),tert-butyl alcohol (4),and phenol (4). I n the case of halogen-containing groups, data are available
The principal nitrogen-containing groups are listed in Table for the -C1 group only. As in the case of -OH, the position
V I I I . The contributions of the nitro group were obtained of -C1 in the organic molecule was found to have a profound

392 I h E C FUNDAMENTALS
 pounds at 300', 600', lOOO', 1200',-and 1500' K. T h e
Table IX. Halogen-Containing Groups values for the hydrocarbons are shown in Table X. On the
Highest basis of 148 points for 32 hydrocarbons tested at the five tem-
___.
300-;'50° K. 750-7500'K. ~~,,p., perature, listed, the average error was estimated as 0.35 kcal.
Group A B X 102 A B X lo2 K. per gram (1.87G).
H LYhere very low heats of formation are involved, the error is
I high-i.e., 32.3yG for o-xylene and -23.44% for rn-xylene,
H-C---Cl - 9.322 -0.045 - 9.475 -0,025 1000
I both a t 600' K. I t is therefore evident that this method
H should be used n i t h caution where the heat effect is small.
H T h e calculated and reported values for several nonhydro-
1 carbon compounds are summarized in Table XI. The average
H3C-C---Cl -10.007 -0.033 -10.438 0.029 1000
I error for 86 points covering 26 compounds a t the five tempera-
H tures listed amounts to 0.26 kcal. per gram-mole.
e1 The positional effect in the case of AH," appears to be more
significant than in the case of C,', and this has been adequately
Hac-C-H -14.780 -0.040 -14.780 -0.040 1500
accounted for in the tabulated contributions. T h e method
(51 is not applicable to esters, anhydrides, fluorides, bromides,
H iodides, and conjugated compounds.
I I t is interesting to compare this method with existing methods
H-C---C1 -13,222 -0.029 -13.222 -0.029 1500
which permit estimation of AH,' at different temperatures.
C1 For hydrocarbons, AH,' was calculated for 15 compounds a t
c1 four temperatures (300', GOO', lOOO', and 1500' K.) covering
a total of 60 points; for nonhydrocarbons, for 10 compounds
H-C---Cl - 6.684 -0.033 - 6.684 -0.033 1500 at the same four temperatures covering a total of 40 points.
C1 The results are tabulated below.
c1
- 6.400 -0.050 - 6.400 -0.050 1500
Av. Error (Absolute D i f . ) ) ,
61 Kml. IG.-Mole
H c1 Hydro-
Method Ref. carbons Nonhydrocarbons
\ ,I'

- 7.622 0.029 - 7.390 0.000 1500 1. Franklin (9) 0.31 2.50

H=
' c\H 2. Souders, Mathews,
and Hurd (27) 0.34 Not applicable
H c1 3. Present method ... 0.34 0.24
\
c=c - 6.171 0.029 - 6.171 -0,029 1500
/ "Cl
H T h e method of bond energies (21) is an approximate one,
H H giving an error of the order of 4 kcal. per gram-mole, while
\
c=c/ - 5.916 0.071 - 5.386 -0.007 1500
that of Anderson, Beyer, and Watson (7) is applicable a t one
temperature only (298' K.). These methods were therefore
c1' Cl not used in the comparative evaluation of the present method.
(cis-1,2) From the table presented and the particular features of the
c1 H proposed method, the following general conclusions may be
'\.C=C / - 6.532 0.233 - 5.480 0.106 1500 drawn :
/ "'cl For hydrocarbons the method is as reliable as that of Franklin
H
(trans-1,2) or Souders, Mathews, and Hurd. I t is particularly advan-
tageous since it permits the evaluation of AH," as a continuous
e1 c1 function of temperature, which the other methods do not.
For nonhydrocarbons the proposed method is distinctly
'C=C
, \
- 6.047 0.236 - 6.047 0.236 1500
superior to any of the available procedures.
c1' 'c1
In some cases where this method cannot be applied because
of lack of data for certain structures, AH,' can be calculated
as a continuous function of temperature from Equation 2,
using the Cp' equations formulated by the method of Rihani
effect on the heat of formation. T h e positional effect was and Doraiswamy (22). if the value of AH,' at any one tempera-
calculated from the values of the following compounds (76) : ture (usually 298' K.) is known.
CH3C1, CSHsC1, CzH4C12, CHzClz, CHC13, cc14, CzH3C1, When the results obtained from Equation 2 were compared
1,1-CzHzC12,1,2-C2HK12 (cis), 1,2-CzH&12 (trans), and C2C14. with those by the present method for 15 different compounds
T h e corresponding values of A and B are presented in Table a t 1000' K., it was observed that the average error by the
IX. present method was 0.25 as against 0.26 kcal. per mole by the
use of Equation 2. This clearly shows that the two methods
Discussion
are almost equally accurate.
Two examples have been worked out in Table X I 1 to
T o test the validity of the proposed method, AH,' was cal- illustrate the use of the proposed method for the estimation of
culated for several hydrocarbon and nonhydrocarbon com- AH,'.

VOL. 4 NO. 4 NOVEMBER 1 9 6 5 393

 Table XII. Illustrative Examples
m
N O N
00-
3 -
*o
0 0
m -
0 - N
w m m Group No. A B x 702
. .. .. .o . .:' 0 : : : :"?':

(i-0
.
,
. . e .
?" : ? 7 :oh!
0 . 3 0 . 0 0 ' . . ,000 CH3
I I I I I I
LOWTEMP.
(TOLUENE), RANGE

HC <
If
5 18.840 -0.835

-c\ 1 5.437 0.037

-CH3 1 - 8.948 -0.436
Compounda 15.329 -1.234
CHI
@:-CH~--C-CSCH (3-METHYL-I-BUTYNE),L O W TEMP.
RANGE
I
H
CHI 2 - 17,896 -0.872
I
-CH 1 - 1.570 -0.095
I
-C- 1 27.276 0.036
HC= 1 27.242 -0.046
Compound* 35.052 -0.787
(AH,"), =
a 15.329 - 1.234 X T. * (AH,")T = 35.052
- 0.0787 X T.

Nomenclature
A constant of Equation 4
=
B constant of Equation 4
=
GPO heat capacity, cal./gram-mole/' K.
=
Compd compound =
ele = element(s)
AG j" = free energy of formation, kcal./gram-mole
AH,' = heat of formation, kcal./gram-mole
(AH,")o = heat of formation a t 0" K., kcal./gram-mole
(AHfO)T = heat of formation a t any temperature T ,
kcal ./gram-mole
(HT" - Hoe) = enthalpy function, kcal./gram-mole
T = temperature, ' K.
I n using Equation 2, cal. may be used and the final result
converted to kcal.

literature Cited
(1) Anderson, J. W., Beyer, G. H., Watson, K. M., Natl. Petrol
News 36, R476 (1944).
(2) Banerjee, S. C., Doraiswamy, L. K., Brit. Chem. Eng. 9, 311
I1
\-, -
964)
'I'
( 3 ) Chermin, H. A. G., Petrol. Refiner 40, No. 3, 181 (1961)
14) Zbid.. No. 4. 127 11961).
(5j Zbid.;40, N'o. 5, 236 (i961).
(6) Zbid.,No. 6, 179 (1961).
(7) Zbid.,No. 9, 261 (1961).
(8) Dyatkina, M. E., Zh. Fit. Khim. 28, 377 (1954).
(9) Franklin, 3. L., Znd. Eng. Chem. 41, 1070 (1949).
110) Green. J. H. S.. Chem. Znd. (London) 1960. D. 1215.
(11) Guthrk, G. B.', Jr., et all, J . Am. Chem. Soc. 74, 4662
11952).
,----,
(12) Hatton, W. E., Hildenbrand, D. L., Sinke, G. C., Stull,
D. R., J . Chem. Eng. Data 7, 229 (1962).
(13) Hubbard, W. N.,et al., J. Am. Chem. Soc. 80, 3547
(1958).
114) Ja&. G. J.. "Estimation of Thermodvnamic ProDerties of
' Organid Compounds," Academic Press, Ndw York, 195'8.
(15) Johnson, A. I., Huang, C. J., Can. J . Technol. 34, 405 (1957).
(16) Kobe, K. A., Crawford, H. R., Petrol. Refiner. 37, No. 7, 125
I1 958\
\-,--/.
(17) McClellan, A. L., Pimentel, G. C., J . Chem. Phys. 23, No. 2,
245 (1955).
(18) McCullough, J. P., Good, W. D., J . Phys. Chem. 65, 1430-2
(1961).
(19) McCullough, J. P., Scott, D. W., Pennington, R. E., Hossen-
lopp, I. A,, Waddington, Guy, J . Am. Chem. Soc. 76, 4791
(1954).

VOL. 4 NO. 4 NOVEMBER 1 9 6 5 395

(20) Perry, P. H., “Chemical Engineering Handbook,” p. 238, (26 Skinner, H. A,, Snelson, A,, Trans. Faraday Soc. 56, 1776
McGraw-Hill, 1950. 019601.
(21) Reid, R. C., Sherwood, T. K., “Properties of Gases and (27) Sohders, M., Mathews, C. S., Hurd, C. O., 2nd. Eng. Chem.
Liquids,” McGraw-Hill, New York, 1958. 41, 1037, 1048 (1949).
(22) Rihani, D. N., Doraiswamy, L. K., IND.ENG.CHEM.FUNDA- (28) van Krevelen, D. W., Chermin, H. A. G., Chem. Eng. Sci.
MENTALS, 4, 17 (1965). 1, 66 (1951).
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(1949). Methanol and Aniline to Dimethylaniline,” M. Sc. (Tech.)
(24) Rossini, F. D., et al., “Selected Values of Physical and thesis, Bombay University, 1964.
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Hydrocarbons,” Natl. Bur. Standards Circ. C464 (1947). National Chemical Laboratory Communication 714.

KINETICS OF THE PYROLYSIS OF

C H LO ROD I FLU0 RO METHAN E
JOHN W. EDWARDS AND PERCY A. SMALL
Plastics Division, Imperial Chemical Industries, Ltd., Welwyn Garden City, Herts, England

The thermal decomposition of chlorodifluoromethane has been studied at 1 -atm. pressure over the tempera-
ture range 533’ to 750’ C. The reaction i s essentially homogeneous and gives hydrogen chloride and
tetrafluoroethylene as main products. Reaction mechanisms are proposed and the Arrhenius parameters
for the main reaction steps obtained using a computer to integrate the kinetic equations and to make a least-
squares fit to the experimental results are given; an empirical correction term was used to take account of
side reactions. Values for the heats of formation in the gas phase at 25’ C. were derived for chlorodifluoro-
methane as - 1 12.3 kcal. per mole and for difluorocarbene as - 39.1 kcal. per mole.

PARK and coworkers (9) first described the pyrolysis of chloro- 620’ C. and the other of 4-cc. volume used in the range 620’
difluoromethane and the yields of the various products in to 750’ C. They were shaped like pipets with the central
zone (length 20 cm.) arranged in a tubular electric furnace
the temperature range 650’ to 800’ C. and the pressure range in a position corresponding to the central constant temperature
0.5 to 4.0 atm. The principal reaction, which is endothermic, zone of the furnace (constant to f 2 ’ C. a t 700’ C . over a
is represented by the over-all equation 2 CFzHCl + CZF4 + length of 25 cm.). Chlorodifluoromethane was passed a t a
known flow rate and pressure through a filter to the reaction
2 HCl; tetrafluoroethylene is made commercially by this route.
vessel in the furnace. The products then went through a
Norton (8) found that chlorodifluoromethane decomposed on control valve and were collected in a trap a t liquid nitrogen
silica in the range 425’ to 525’ C. in a reaction initially of the temperatures. The inlet a r m of the reaction vessel was fitted
first order with a n activation energy of 49 kcal. per mole. with a small electric preheater and a Pt-Pt, 13% R h thermo-
More recently, Gozzo and Patrick (4)have reported a n activa- couple was fitted inside the vessel with its hot junction a t the
tion energy of 51.4 =t2.5 kcal. per mole for the homogeneous vessel’s center. Similar thermocouples were fitted inside the
furnace tube and on the outside surface of the reaction vessel
reaction CFzHCl + CFz f HCI, and one of 15 =t5 kcal. per a t its middle. While gas was being passed, the preheater
mole for its inverse. voltage was adjusted so that the internal thermocouple in-
All products other than C2F4 and HC1 will be called collec- dicated the same temperature (to within =t2’ C. during a run)
tively “high boilers,” following Park (9). The main by- as the external one in the furnace tube; the thermocouple on
the surface of the vessel indicated the same close agreement in
products are cyclo-C4F8, CF2: CF.CF1, H(CF2)&1, and
temperature. While steady flow and preheater conditions
H(CF2)&1, though there are many others, often in trace were being set up the pyrolysis products were discarded to a
amounts; lists of these are given by Park (9) and Serpinet dummy trapping system. When all was steady, a tap was
(72). quickly turned and the products were collected in the main
We have studied the effects of temperature and pressure on trap for a known time. Mercury manometers fitted a t the
inlet and exit ends of the reactor showed a pressure drop of
this reaction and obtained plausible mechanisms and rate about 1 cm. along the reaction vessel. The contact time in
constant parameters for the more important steps, which seconds was calculated from the expression t = 2V1T1/(L‘2 +
reproduce our experimental results within analytical errors, V3)T2, where V1 is the volume of the central section of the
a t I-atm. pressure. reactor in cubic centimeters, T I is the CF2HCl inlet tempera-
ture (room temperature) in ’ K., Vz is the flow rate (cubic
centimeters per second) of CFzHCl into the reactor a t T I , Va
Experimental is the flow rate (cubic centimeters per second) of products out of
the reactor a t T I ,and Tz is the temperature a t the center of the
Flow System. To study the initial stage of the reaction a t reaction vessel in OK. This expression thus includes a n
high temperature, two flow reaction vessels were constructed in approximate correction for the expansion arising during the
platinum; one of 60-cc. volume was used in the range 500’ to reaction a t constant pressure.

396 l&EC FUNDAMENTALS