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S. DEPARTMENT
or COMMERCE
For ethylene, propylene, the four butenes, the six pentenps, and the 17 hexenes,
and all the higher I-alkene hydrocarbons, in the gaseous sta te at 25 C, values
are given for the heats of formation (from the elements solid carbon (graphite)
and gaseous hydrogen), the heats of hydrogenation in the gaseous state, and the
heats of combustion (in oxygen to form gaseous carbon dioxide and liquid water).
The values for 2 of the pentenes, 14 of the 17 hexenes, and all the higher I-alkene
hydrocarbons, were calculated by a method involving correlation of the heat of
hydrogenation with structure and the use of constants evaluated from the available experimental data on 4 butenes, 4 pentenes, 3 hexenes, and 1 hcptene.
CONTENTS
I.
II.
III.
IV.
V.
VI.
Page
269
270
270
271
273
275
1. INTRODUCTION
In a previous report [11 2 values were given for the heats of formation of the monoolefin hydrocarbons from ethylene through the pentenes in the gaseous state. At that time, the data on the heats of
hydrogenation of the higher monoolefins [2, 3] could not be utilized
for calculating heats of formation because of the lack of reliable
experimental data on the corresponding paraffin hydrocarbons.
Since then new data on the paraffin hydrocarbons above the pentanes
have become available [4, 5, 6, 7, 8]. The present paper presents
(a) revised values for the monoolefins through the pentenes, changed
on account of slight revisions in the selected "best" values for heats
of formation of water and carbon dioxide [9, 10] and of improved
values of specific heat [11, 121 for converting to 25 C the heats of
I This investigation was performed at the National Bureau of Standards jointly by the Thermochemical
Laboratory and the American Petroleum Institute Research Project 44 on the "Collection, Analysis, and
Calculation of Data on the Properties of Hydrocarbons."
, Figures in brackets indicate the literature references at tbe end of tbis paper.
269
The unit of energy upon which the values presented in this paper
are based is the international joule determined by standards of resistance (international ohms), electromotive force (international
volts), and time (mean solar seconds) maintained at this Bureau.
Oonversion to the conventional thermochemical calorie is made by
means of the relation [13]
4.1833 international joules= 1 calorie.
The molecular weights of hydrogen, oxygen, and carbon were
taken as 1.0080, 16.0000, and 12.010, respectively, from the 1941
table of International Atomic Weights [14].
The uncertainties assigned to the various quantities dealt with
were derived, where possible, by a method previously described [15].
In other cases, reasonable estimates of the uncertainties were made.
III. DATA USED IN THE CALCULATIONS
271
0.40 kcal/mole,
(la)
(lb)
which is a rounded average of the following four values based on experiment: I-butene, -30.092 0.081; 3-methyl-l-butene, -29.995
0.082j3,3-dimethyl-l-butene, -30.103 0.153; I-heptene, -29.876
0.100, kcalJmole.
684201-46--5
Structure
Type
H
1______________
AHho.',1I
Kcal/molt
H
R
IIt ____________
C=C
IV _________ ___
H/
-30.00 Oo4O
H
/
C=C
-28.40 0.50
H
-27040 0.50
"- R
H
H
~C=C/
H/
IIL ___________
C=C
R
-28.10 0.50
R
C=C
-26.70 0.50
R
"-C=C/
V _____________
R
For type lIe, RHO=OHR (cis), the value of the heat of hydrogenation at 25 0 was taken as
(RHO=OHR) (cis)(gas) +H2(gas) = (RH20-OH2R) (gas), (2a.)
i l l 021lS 18
(2b)
273
For type lIt, RHO=OHR (trans), the value of the heat of hydrogenation at 25 0 was taken as
(RHO=OHR) (trans) (gas) + H2(gas) = (RH 20-OH2R) (gas)
AH0298.16=-27.40 0.50 kcal/mole,
(30.)
(3b)
(40.)
(4b)
(50.)
(5b)
(60.)
>
>5
(70.)
(7b)
--
--------~-------
OnH~ ..
!l
3; O
(gas) +
(8a)
H0 298.16=-19.592-157.443n (O.3248-0.03884n+O.003102n2)1/2
>
kcal/mole; n
5
(8b)
Equations 7a and 7b correspond to eq la and Ib of this report. Equations 6a and 6b were obtained by combining eq 7a and 7b of this report
with eq 5 and 6 from [8). Equations 8a and 8b were obtained by
appropriately combining with eq 6a and 6b the equations for the
heats of formation of water and carbon dioxide.
2.-Heats of formation, hydrogenation, and combustion of the mono olefin
hydrocarbons through the hexenes, and of the higher i-alkene hydrocarbons, in the
gaseous stale al 25 C
TABLE
Compound (gas)
Formula
Heat of
formation I
11HjO
Keallmole
+ 12. 496 O. 066
+4.879 . 122
+0. 280 .196
-1.362 .196
-2.405 . 196
- 3.343 .182
-5.00 .43
-6.51 .26
-7.59 . 26
-8.68 .23
-6.92 .22
-10.17 . 22
-9.96 .44
-11.56 .53
-12.56 .53
-11. 56 .53
-12.56 .53
-13.56 .56
-11.02 .46
-11.66 .47
-14.96 .56
-14.32 .55
-14.32 . 55
-13.26 .56
-14.26 .56
-12.92 .55
- 14.78 .27
-14.25 .28
-15.91 .27
-14.89 .44
-19.82 .45
-24.74 .46
-29.67 .48
-34.60 .50
-39.52 .52
-44.45 .56
-40. 38 .59
OUH:!8
C.,H" - 54.31 .62
CuH" - 59. 23 .66
CI7H" - 64.15 .70
C.,R" - 69.08 . 75
C.,H" -74.00 .80
C"H .. -78.93 .84
-CH,- -4.926
C,H,
C,H.
C,H,
C.H,
C.H,
C.H,
C,H"
C,H"
C,H"
C,HI'
C,H"
C,HI'
C,Hu
C,H"
C,Hn
C,Hn
C,H"
C,H"
C,H.,
C,H.,
C,Hn
C,H"
C,H"
C,Rn
C,H"
C,Hn
C,Hn
C,H"
C,Hn
C,Hu
C,H.,
C,R"
C R"
CuH"
C.,H,.
C.,H"
H eat of
hydrogenation'
11Hho
Heat of
combustion'
-11Heo
Kcallmole
- 32. 732 0.133
-29.699 181
- 30. 092 .081
-28.450 .080
-27.407 .080
-28.109 .080
- 30.00 .400
- 28.491 .201
-27.410 .201
-28.240 . 182
-29.935 .082
-26.745 .082
-30.00 .40
- 28.40 .50
-27.40 .50
-28.40 .50
-27.40 .50
- 28.10 . 50
-30.00 . 40
-30. 00 .40
-26.70 .50
-26.70 .50
-26.70 .50
- 28.40 .50
-27.40 .50
-28.10 .50
- 27.713 .124
-30.103 .153
-26.5i6 .124
-30.00 .40
-30.00 .40
-30.00 . 40
-30.00 .40
-30.00 . 40
- 30.00 .40
- 30.00 . 40
-30.00 .40
-30.00 .40
-30.00 .40
-30.00 .40
-30. 00 . 40
- 30.00 . 40
-30.00 . 40
0.00 . 40
Keallmole
337.234 0.072
491. 987 .129
649. 757 . 204
648. 115 . 204
647.072 .204
646.134 .191
806.85 .44
805.34 .27
804.26 .27
803.17 .24
804.93 .23
801.68 .23
964. 25 .45
962.56 .54
961.66 . 54
962.66 .54
961.66 .54
960.66 .57
963.20 .47
962.56 . 48
959.26 .57
959.90 . 56
959.90 .56
960.96 .57
959.96 .57
961. 30 .56
959.44 .28
959.97 .29
958.31 .28
1121. 69 .45
1279.13 .46
1436.58 .48
1594. 02 .50
1751. 46 .52
1908. g1 .55
2066.35 .59
2223. i9 .62
2381. 23 .66
2538.68 .70
2696.13 . i4
2853.57 .79
3011. 01 .85
3168.45 .89
157.443
I AHr"s . , represents the lllcrement III the heat content or enthalpy of the process of formlllg the given
hydrocarbon in the state indicated, from its elements, a: 25 C, with all r eactants and products in their
appropriate standard reference states.
, 11Hho,,, . represents the increment in heat content or enthalpy of the reaction of h ydrogenation of the
monoolefin to form the corresponding paraffin hydrocarbon, in the gaseous state at 25 C, with all reactants
and products in their appropriate standard reference states .
11Hco,,,.u represents the heat evolved in the combust ion of the given hydrocarbon, in gaseous oxygen to
form gaseous carbon dioxide and liquid water, at 25 C and constant pressure, with all reactants and products
in their appropriate standard reference states.
275
VI. REFERENCES
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Chem. Soc. 58, 137 (1936) .
[3] M. A. Dolliver, T. L. Gresham, G. B. Kistiakowsky, and W. E. Vaughan,
J . Am. Chem. Soc. 59, 831 (1937).
[4] E. J. Prosen and F . D. Rossini, J. Research NBS 27, 289 (1941) RP1420.
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RP1620.
[10] D. D. Wagman, J . E. Kilpatrick, W. J . Taylor, K. S. Pitzer, and F. D.
Rossini, J. Research NBS 34, 143 (1945) RP1634.
[11 ] J. E. Kilpatrick and K. S. Pitzer, National Bureau of Standards. American
Petroleum Institute Research Proj ect 44. Unpublished.
[1 2] J. E . Kilpatrick, E. J. Prosen, K. S. Pitzer, and F. D . Rossini, National
Bureau of Standards. American Petroleum Institute Project 44. Unpublished .
[1 3] E. F. Mueller and F. D. Rossini, Am. J . Physics 12, 1 (1944).
[14] G. P. Baxter, M. Guichard, O. Honigschmid, and R. Whytlaw-Gray, J. Am.
Chern. Soc. 63, 845 (1941).
[1 5] F. D. Rossini and W. E. Deming, J. Wash. Acad. Sci. 29,416 (1939).
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[17] G. B. Kistiakowsky, H. Romeyn, Jr., J. R. Ruhoff, H . A. Smith, and W. E .
Vaugh an, J. Am. Chern. Soc. 57, 65 (1935).
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Chern . Soc. 57, 876 (1935) .
[19] W. J. Taylor, J . M . Pignocco, and F. D. Rossini, J. Research NBS 34, 413
(1945) RP1651.
[20] C. E. Boord, Petroleum Refmer 21, 371 (1942) .
[21] K. S. Pitzer, Ind. Eng. Chem. 36, 829 (1944).
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[23] K. S. Pitzer. Chern. Rev. 27,39 (1940) .
WASHINGTON,