Beruflich Dokumente
Kultur Dokumente
Thermodynamic functions including free energy, enthalpy, entropy, and specific heat,
are given for the compounds butadiene, benzene, cyclonexane, etnane, etnylene, etnyl
alcohol and water and for the elements carbon (graphite), hydrogen and oxygen. From
these are calculated and tabulated values of equilibrium constants for reactions of interest
in connection with the production of 1,3-butadiene for synthetic rubber. Comparisons
are made between table values and available experimental data on equilibrium constants,
gaseous specific heats and entropies. The cracking of hydrocarbons is discussed and the
importance of reaction rates in determining the amounts of reaction products is noted.
I. Introduction
In an earlier publication the measured thermal
properties of 1,3-butadiene including heat capaci-
ties down to 15 0 K were used to determine the Contents
Page
entropy and enthalpy of butadiene to 300 0 K I. Introduction __ ______ ______ _____________ ___ 263
[1,2] .3 With these calorimetric data and the most
II. Butadiene _____ __ ___ ________ ______________ 264
recent spectroscopic data, the thermodynamic
functions for butadiene were then extended to III. Benzene _________ ___ _______ _______ _______ 265
higher temperatures. These were combined with IV. Cyclohexane ____ __________________________ 266
the thermodynamic functions for n-butane and V. Ethane __ _______ _____ __ ___ ___ ___ .. ___ ______ 267
the n-butenes to calculate the equilibrium con- VI. Ethylene ___ _________ __ _________ _____ ___ ._ 268
stants for the dehydrogenation reactions of n- VII. Acetylene ____ ___ ___ ___ _________ ___ ___ __ .___ 269
butane and n-butenes used in the manufacture of
VIII. Ethyl alcohoL _ _ ____ _____ ____ ___ _ __ __ ____ _ 270
butadiene from petroleum and natural gas. [3, 4].
In the pres en t paper are given values for ther- IX. Water ___ ___ ____ ______ ___ _______ .. __ ______ .. 271
modynamic functions and properties of a number X. Graphite __ __ __ . _ ___ _ __ ____ __ ___ _ __ __ ___ _ _ 272
of other compounds for use in calculations of XI. Hydrogen __ _____ . ____________ ___ _________ 273
equilibria occurring in other reactions involved in XII. Oxygen ____ __ ________ ______ ____ __ ____ ____ 273
the commercial production of 1,3-butadiene for
XIII. Heats of formation at 0° K __ _________ __ __ __ 274
synthetic rubber. These compounds are benzene,
XIV. Equilibrium constants ____ _______ __ _________ 274
cyclohexane, ethane, ethylene, ethyl alcohol, and
water. Tables for the elements graphite, hydro- XV. Comments on cracking reactions ___ ______ ____ 277
gen, and oxygen also have been included. Tables XVI. References __ .. _____________________________ 278
I TiliR paper is "revision of a report entitled, "EquilibriulD constan ts of some reactions involved in the production of I ,3·bul adiene," submitted to the
Offi ce of the Rubber Director, March 24, 1944.
, Director, Cryogenic Laboratory, Pennsylvania State College.
, Figures iu brackets indicate literat ure references at the end 0 f this paper.
II. Butadiene
Thermodynamic functions for 1,3-butadiene mainly that of Bradacs and Kahovec [5]. It
from reference [4] are given in tables 1 and 2. differs in the following. The observed Raman
As indicated in that publication, it is concluded line 340 cm- 1 that Bradacs and Kohovec assigned, I
that 1,3-butadiene has more than one form, since, with expressed doubt, to the fundamental of the
for any vibration assignment that seemed reason- middle C-C torsional vibration was assigned by
able, the specific heat calculated did not agree
us to the first overtone of this vibration. For
with the experimental when it was assumed that
double-bond torsions the observed 520 cm- 1 and
only a single form existed. Agreement with the
experimental calorimetric data was obtained by a calculated 667 cm- I based on ethylene have been
the use of a cis and a trans form. used. For the skeletal deformation frequency Ws,
Except for the frequency of torsion about the the 520 cm- 1 used by Bradacs and Kahovec has
central C-C bond, the distribution of energy been replaced by 326 cm- 1 on the basis of force-
levels has been assumed to be statistically the constant calculations and the calorimetric data.
same for the cis as for the trans variety. The The barrier h eights are 5,000 cal mole- I for the
frequency assignment for the trans variety is trans form and 2,575 cal mole- I for the cis form.
• /lFo and K are the free-<lnergy chango and equilibrium constant, reo
'/lHO is the enthalpy of formation of 1,3·hutadiene from its elements in spectively, for tbe reaction forming I, 3-butadiene Crom its elements in their
their standard states at the temperature T . standard states at T"K.
III. Benzene
The frequencies assigned to the fundamental 1.39 A and distances between carbon and hydrogen
modes of vibration of the benzene molecule by atoms of 1.09 A. The symmetry number is 12.
K. S. Pitzer and D. W. Scott were used for this The principal moments of inertia about the
paper [6]. These frequencies in centimeters- 1 are center of mass are 292.9X10- 40 g cm2, 146.5XlO-40
as follows: g cm2, and 146.5XlO-40 g cm2 • Their product is
Oarbon skeleton frequencies: 6.28 X 10- 114 g3 cm6•
Calculated values of thermodynamic functions
Vibrations in the plane of the molecule:
and properties are given in tables 3 and 4. The
WI=W2=606, w3=1011, w4=992, w5=w6=1485,
moderate departures of calculated values of
W7=W8= 1596, and W9= (1693).
-(~-EOo)/T, HO-Eoo, and OOD from those of
Vibrations out of the plane of the molecule:
reference [6] are thought to be due to the use of
= (685) and ')'2=')'3=400.
')'1
the latest values for the fundamental physical
Frequencies due to CR groups: constants in the present calculations. The source
'Y(CH) waving motions out of the plane of the of the value for EO 0 used in this paper is given in
molecule: (1016),849(2),671, and (985)(2). section XII.
o(CH) waving motions in the plane of the Table values of 0° D are in agreement to within
molecule: (1298), 1178(2), (1170), and 1037(2). experimental accuracy with values of 0° D derived
}L(CH) stretching motions: 3062, 3047(2), 3046, from the calorimetrically measured heat capaci-
and 3080(2). The frequencies in parentheses ties, which extend over the range 360° to 480 0 K.
have not been observed because the vibrations to This may be seen in figure 7 in the paper by
which they correspond are optically inactive. Pitzer and Scott, since the sets of calculated
The benzene molecule is planar, a regular hexagon values of O D D in the two papers are in agreement
with distances between carbon atoms equal to to within less than the experimental error.
T
HO-EO
-T- HO aASO c; T _(F";;EO) So -F" otlF O "log" K
o AFo and K are the free-energy change and equilibrium constant, respec-
OAR ° is the enthalpy of formation of benzene from its elements in their tively, for the reaction forming benzene from its elements in their standard
standard states at tbe temperature T. states at T OK.
IV. Cyclohexane
The frequency assignment used in the calcula- The distance between carbon atoms was taken
tions for cyclohexane is essentially the same as one as 1.54 A and between carbon and hydrogen atoms
given previously [7]. A value of 673 em-I, which as 1.09 A. Using tetrahedral angles, the principal
was used in a previous form of t.his paper for one moments of inertia are 335.1 X 10-40 g cm2 , 193.8X
frequency, has now been replaced by 864 em-Ion 10- 40 g cm2, and 193.8X 10- 40 g cm 2, giving for the
the ground that the band report.ed at 673 cm- 1was product of the three 12.58X 10- 114 g3 ems.
due to an impurity.6 The molecule has a chair Tables 5 and 6 give the calculated values of
form with Dad symmetry, for which the symmetry
number is 6. The frequencies in cm- 1 used were TABLE 5.-Heat capacity and constant pressure, heat con-
as follows: tent, and related quantities of cycZahexane in the ideal gas
state
Oarbon skeleton frequencies: lEO= 19,950 cal moi ~-'l
1,200 97.06 145.39 136,420 132,690 -24.166 cal deg- l cal defTI
151. 96 151,290 146,820 oJ( mole- l mole- l
1,300 101.03 -24.683
1,400 104. 90 158.21 166,800 160,920 -25.121 370 32. SO 33.0 (8)
1,500 108.65 164.17 182,930 175,000 -25.498 390 34.86 35.0 (8)
410 36.88 36.8 (8)
4lO 36.88 37.0 (9)
.tJ.r and J( are the free-energy change and equilibrium constant, respec·
tlvely, for tho reaction forming cycJohexane from its elements in theirstandard
states at TOK. ' (8) J . B. Montgomery and T. DeVries, (9) K. Bennewitz and W. Rossner,
V. Ethane
The frequency assignment used for ethane was determined by Kistiakowsky, Lacher, and Stitt
taken from a paper by Stitt [10]. The frequencies (12] from low-temperature specific-heat measure-
in centimeters- I were: ment on gaseous ethane.
Frequency due to 0 -0 vibration: The ethane molecule has a symmetry number
of six. With 1.54 A for the carbon-carbon dis-
w=993.
tance and 1.09 A for the carbon-hydrogen dis-
Frequencies due to OH3 vibrations: tances, the principal moments of inertia are found
,,(OHa) rocking motions: 827 (2) and 1170 (2) . to be 10.60 X lO- 40 g cm 2 , 41.84XI0- 40 g cm 2 , and
IJ(HOH) bending motions: 1375, 1380, 1460(2), 41.84 X lO- 4O g cm 2 , whereas the reduced moment
and 1465(2). for the internal rotation is 2.65 X 10- 40 g cm 2 •
,u(O-H) stretching motions: 2925(2),2960(2), The product of the principal moments of inertia
and 2980 (2). is 18.56 X 10-117 g3 cm6•
Stitt's value of 1,170 cm- I for the "uncertain fre- The values calculated for the various thermo-
quency" of ethane is based upon Dad symmetry dynamic functions of ethane are given in tables
and an application of the product rule to the 8 and 9.
spectra of 02H6 and 02D6' Table 10 gives a comparison of calculated
As Kemp and Pitzer [11] have shown and others values of a;
with experimental values based on
have confirmed, there is a mode of hindered rota- the work of Thayer and Stegeman [13], Dailey and
tion corresponding to rotation of one methyl Felsing [14] and Eucken and Parts [15].
group with respect to the other. For low ener- The calorimetric entropy, So, at 25° 0 is given
gies the motion is vibration, whereas for large by Witt and Kemp [16] as 54.85 cal deg- l mole-I.
energies it is complete rotation. The height used The corresponding statistically calculated So for
for the barrier, 2,750 cal mole-l, is the value 298.16° K is 54.83 cal deg- I mole-I.
W-Eo HO a~ a~
T --T- -t;W ~ T Observers -
(calculated) (experimental)
700 14. ()7 -6,250 -23,980 23.71 387.56 15.30 15.27 (14)
800 15.93 -3,780 -24,530 25.82 451.96 17.26 17.31 (14)
900 17.13 -1,100 -24,960 27.68 520.56 19. 24 19.14 (14)
1,000 18.27 +1,750 -25,280 29.31 561.66 20.36 20.62 (14)
1,100 19.34 4, 750 -25,500 30.75 603.26 21.42 21.62 (14)
at;FO and K are the freeo{lnergy change and equilibrium constant, reo
spectively, tor the reactiou forming ethane trom its elements in their standard
Itates at T OK.
VI. Ethylene
The fundamental frequencies used for ethylene oCHCH) bending motions: 1342.4 and 1443.9.
are those given by Galloway and Barker [17]. JLeC-H) stretching motions: 3019.3, 2989.5,
The frequencies in centimeters- 1 are: 3105.5, and 3069. The frequency 825 cm- 1
Frequency due to C=C vibration: corresponds to the torsional twist of the C=C
bond.
1623.3
The molecule is planar and has a symmetry
Frequencies due to CH z vibrations: number of 4. The principal moments of inertia
-yCC-H) rocking motions: 995, 1055, 949.2, derived from the ethylene spectra by Galloway and
950, and 825. Barker were used. They are 33.84X10- 4O g cm2,
~ 298.16°K is 52.454 cal deg- I mole-I. 700 52.51 64. 70 22,230 22,680 -7.082
800 M . 20 67.31 28,830 24,500 -6.693
S n.-Heat capacity at constant pressure, heat content
900 55.79 69.76 35,680 26,350 -6.400
1 TABLE
and related quantities of ethylene in the ideal gas state
1,000
1,100
57. 31
58.75
72.09
74.29
42,780
50,100
28,240
30,150
-6.172
-5.990
°11F" and K are the frec-<lnergy change and equilibrium constant, respec-
eal deg-' cal deo- I
oK mole-' cal mole-' cal mole' I mole-I tively, for the reaction forming etbylene from Its elements in their standard
298. 16 8.47 17,060 12,510 10.41 states at T"K.
300.00 8.49 17.080 12.490 10.46
400 9.28 18,240 11,780 12.91 TABLE 13.-Comparison of the calculated and experimental
500 10.24 19,650 11,150 15.18 values fOT the heat capacity of ethylene in the ideal gas state
600 11.23 21,270 10,610 17.12 above 300 0 K
700
800
900
12.19
13.11
13.97
23,070
25,020
27,110
10,170
9,800
9,490
18.78
20.23
21. 49
T
C'. C~
(calculated) (experimental) Observers .1
1,000 14.78 29,310 9,250 22.60
1,100 15.54 31,620 9,060 23.58 cal dtg- I cal deo- I
OK molr' mole-I
298.16 10.41 9.97 (18)
1,200 16.25 34,020 8,920 24.43
310. 16 10.08 10.40 (18)
1,300 16.90 36,500 8,810 25.18
339.96 11. 46 10.98 (18)
1,400 17.52 39,050 8,740 25.83
300.0 10.46 10.39 (19)
1, 500 18.09 H,670 8,690 26.41
320.7 11.00 10.99 (19)
-I1W is tbe enthalpy of formation of etbylene from its elements In their 368.2 12.15 11.897 (15)
standard states at tbe temperature T. 464.0 14.39 14.16 (15)
VII. Acetylene
For acetylene, the thermodynamic functions tiooal-vibrational coupling, rota~ional stretching,
used are those given in a l'ecen t paper by Wagman, and an Euler-Maclaurin series summation correc-
Kilpatrick, Pitzer, and Rossini [21]. Their values tion term. They have been used in preference to
l
o are based largely upon an assignment by Wu
[22] and include the effects of anharmonicity, rota-
our earlier tables, which were based on a table
by Gordon [23].
1
a AW is the enthalpy o( (ormation o( ethyl alcohol (rom its elements in their
minimum of 1,560 cal mole- 1 at 104°, to another
standard states at the temperature T. maximum of 5,970 cal mole- I at 180 0 , in which
l
mole- l mole- l
0.96 A for the O-H distance, 105° for the O-O-H 363. 16 19. 76 18. 49 (32)
370.26 20. 00 19.86 (33)
angle and tetrahedral angles for all other angles, 407.16 21.24 18. 75 (33)
the product of the three principal moments of 410.16 21.34 19.6 (9)
437.16 22.20 20.8 (34)
inertia is found to be 2.249x10- l15 g3 cm6 for the 623.16 27.38 28.2 (34)
molecule in the straight form and 2.292x10- 115 g3
cm6 for the molecule in the bent form. The • (32) H. B . Dixon and G. Greenwood, (33) S. K. K. Jatkar, (9) K. Benne-
reduced moment of inertia for the OH3 group is wltz and W. Rossner, (34) H. V. Rcgnault.
4.83xlO- 40 g cma and for the OH group is 1.40xlO-40
!. g cm2 • In table 16 the calculated values of 0; The entropy, So, at the boiling point, 351.5° K,
I are compared with the experimental values by based on calorimetric measurements below 298.16°
Dixon and Greenwood [32], Jatkar [331, Bennewitz K by Kelley [35] and at higher temperatures by
and Rossner [9], and Regnault [34], The calcu- Fiock, Ginnings, and Holton [36] is 69.7 cal deg- 1
lated values are higher than the experimental . mole-I. The value interpolated from table 15
H
values except for the value of Regnault at 623 0 K. is 69.42 cal deg- 1 mole-I, agreeing to the uncer-
This one value may be doubted because of its tainty of the calorimetric value. A similarly
antiquity and the experimental difficulties at the obtained calorinletric value of So at 403.2° K is
elevated temperature. It is entirely possible 72.1 cal deg- l mole-I, while the corresponding
that the present treatment will require reVISIOn value from table 15 is 72.28 cal deg- l mole-I.
IX. Water
The thermodynamic functions of table 17 and 18 accepted values of the fundamental physical con-
for water are based on tables published by Gordon stants has also been made.
[37] . Gordon took into account the anharmoni- The entropy, So, of water at 25° 0, was given by
cities of the H 20 vibrations. For the tables of Giauque and Archibald [40] as 45.10 cal deg- 1
this paper Gordon's values have been adjusted for mole-Ion the basis of an investigation of the
rotational stretching by using Wilson's theory equilibrium of MgO, Mg(OH)2, and H 20, and
[381, with a value of the stretching constant deter- the calorimetrically determined entropies of MgO
mined by Stephenson and McMahon [39]. An and Mg(OH)2. The value from table 18 is
adjustment for the change in the generally 45.109 cal deg- l mole- l at 298.16° K.
TABLE 17.-Heat capacity at consta'Tit pressure, heat con- TABLE IS.-Entropy, free energy and related quantities of
tent, and related quantities of water in the ideal gas 3tate water in the ideal gas state at 1·atmosphere pressure
[E8 =-57,106 cal mole-I]
[EO=-57,106 cal mole-i]
o t::. HO is the enthalpy of formation of water from Its elements In their of). F" and K arc the free-energy cbange and equilibrium constant. re-
spectively, for the reaction forming water from its elements In their stand·
"'1
standard statos at the temperature T.
,
ard states at TOK.
X. Graphite •i
The thermodynamic functions for graphite are TABLE 20.-Entropy, free energy, and the free-energy
function for graphite
given in tables 19 and 20. They were obtained by
tabular integration of the specific heat of graphite [EO-O] II
which has been measured [41, 42, 43, 44, 45]
within the range -244 to 1,200°0. The values T _( F";EO) SO -F"
used for specific heats at the higher temperatures
were also based in part on specific-heat measure-
cal derrl cal derrl
ments [46] on a carbon filament from 1,200° to OK mol.-! mole-' cal mole-!
2,100° O. 298.16 0.525 1.367 157
300. 00 0.529 1.379 159
400 .830 2.088 332
TABLE 19. -Heat capacity at constant pressure, heat con-
500 1.153 2.795 577
tent, HO, and (HO-E 8)/T for graphite 600 1. 484 3.477 890
[EO=O]
700 1. 815 4. 124 1,271
800 2.142 4.732 1,714
T
HO-EO Co
-T- W 900 2.462 5.303 2,216
• 1.000 2. 774 5.838 2.774
1,100 3.075 6.337 3,382
cal defT! cal defT!
OK mole-! cal mole-! mole-! 1.200 3.367 6. 804 4,040
298. 16 0.842 251 2. 055 '" 1,300 3.648 7. 241 4,742
300.00 . 850 255 2.071 • 1,400 3.919 7.653 5,487
400 1. 258 503 2. 852 1,500 4.181 8.043 6,272
500 1.642 821 3. 488
600 1. 993 1, 196 3.991
4
1, 200 3.437 4,124 5.422
1,300 3. 593 4, 671 5. 520
1,400 3. 734 5,227 5.609
1,500 3.862 5.793 5.699
T _(Ji'O;EO) SO -Ji'O
HO-E1,
T -T- W C~ cal deg-I cal deq-I
OK mole-I mole -I cal mole-I
eal deq-I cal deq-I 298. 16 24.420 31.207 7.281
oK mole -1 cal mole-I mole- 1 300.00 24.462 31. 250 7, 339
298.16 6.787 2023.8 6. 891 400 26.420 33.247 10,568
300.00 6.788 2036.4 6.894 500 27.947 34.806 13,974
400 6.827 2731. 0 6.975 600 29.200 36.083 17,520
500 6.859 3429.5 6.993
700 30.263 37. 165 21,184
600 6. 883 4129.5 7.009
800 31.187 38. 109 24.950
700 6.902 4831. 7 7.036 900 32. 003 38.946 28.803
800 6. 922 5537.3 7. 081 1,000 32.735 39.701 32,735
900 6.943 6248.3 7.142 1, 100 33. 400 40.393 36,740
1,000 6. 966 6966.2 7.219
1,200 34, 010 41. 033 40,812
1,100 6. 993 7,692 7. 307
I~ 1.200 7. 023 8,428 7.406
1,300
1,400
34.572
35.096
41. 629
42.189
44,944
49,134
1,300 7. 057 9,174 7. 511 1,500 35.588 42.719 53,382
1, 400 7.093 9,930 7.617
1,500 7. 131 10, 697 7.720
"The nuclear spin entropy bas been suhtracted so tbat tbese values may
be used directly in connection witb chemical rcaclions.
XII. Oxygen
Thermodynamic functions for oxygen are given relative to the lowest vibrational level (v=O) by
in tables 23 and 24. These are based on the tables the formula
of Johnston and Walker [48] but have been ad-
justed to be consistent with a more recent value (1568.33v-11.993v2+0.0517v3-0.00143v 4) •
of Curry and Herzberg [49] for the vibrational fre-
The earlier, or 1933, tables of Johnston and
quency and with present generally accepted values
Walker, from which the tables of this paper were
of the fundamental physical constants. Curry
obtained by adjustment, were based on the formula
and Herzberg represented the term values in cm- 1
of the vibrational levels, with quantum number v, (1565.37v-ll.37v 2) •
TABLE 23.-Heat capacity at constant pressure, heat content TABLE 24.-Entropy, fr ee energy, and related quantities of
and related quantities of oxygen in the ideal gas state oxygen in the ideal gas state at i-atmosphere pressure
[Eo-OJ [Eo~OJ
where flY' is the difference between the sums of 700 5.66XIo-· 1. 95XID-4 0.916
the free energies of the products and of the re- BOO 4.94XlO-' 0.113 24.5
900 1. 23XlO-· 15.7 3. lOXlOl
actants of the reaction to which Kp applies, the 1, 000 6.49XIo-" 8. 03XI0' 2. 30XIOI
free energies being those of pure substances in the 1,100 5.89XIo-lI 1. 97XIO' 1. 16XIO'
ideal gaseous state at 1 atmosphere pressure and 1,200 B.09XlO-1I 2.79XHl' 4. 40XIO'
at temperature TOK. The values of Kp in tables 1,300 1. 53XlO-1I 2.56XIO' 1. 33XlO'
700 5.86 8. 57 1. 39XlO 2. 83XlO 700 1. 54X I0-' 3.27XlO-1I 9.08XlO' 5. 35XIO'
800 6.55X I()-1 7.80XI()-1 1. 21 2.54 SOO 7. 84XlO-' 3. 61 X 10-8 1. 79XlO' 7. 43XI08
900 1. 20XIO-1 1. 2IXI()-1 1. 81X I()-1 4.22XlO-1 900 1. 69 X I()-' 8. 59XIO'" 5.l5XI0' 1. 58XI08
1,000 3. 11 X I()-' 2.74X l()-· 4.00Xl()-' 9. 85XI()-' 1,000 1. 98XlO-3 6.92XIO-l 1. 92Xloe 4. 57XIO'
1,100 1. 04XIO-' 8.20XIO-' 1.18XIO-' 3.04XI0-' 1,100 1. 49 X I()-' 2.53XlO-' 8.6I XIO' 1. 64XIO'
1,200 4. 17X I ()-' 3.0IXI()-3 4. 26XIO-3 1. 14XI()-' 1, 200 8.00XlO-' 0.507 4.44XIO' 7.00XIO'
1,300 1. 95Xl()-3 1. 30X l()-' 1. 82XIO-3 5.07XJO-3 1,300 0.333 6. 40 2.54XlO' 3.37XI06
1,400 1. 02 X 1()-3 6. 32XI()-' 8. 85XlO-' 2. 54XlO-3 1,400 1.12 56.0 1. 57XlO' 1. 80X IO'
1,500 5.82XIO-' 3.40XI()-' 4. 69XI()-' 1. 39XJO-3 1,500 3.21 290.0 1. 04X IOI 1. 05XI06
I
TABLE 30.-A comparison of calculated and experimental C 6H12 (cyclohexane)~C4H6 (1, 3-butadiene)+C2H 6
values for the equilibrium constant Kp for the reaction:
Ethane is not formed to any appreciable extent
as a primary product in the thermal cracking of
cyclohexane. The equilibrium indicated by the
T K. (ealeu- K. (exper!· Observers·
equation heading this subsection is probably the ~
lated) mental) I
result of the two reactions:
oK atm-' atm-'
503.1 134.0 135. 0 (55) CsH12~C~6+C2H4+H2
503.3 132. 0 104. 0 (55)
503.5 129. 0 77.0 (55)
C2H, + H2~C2H6
522.6 19.5 11. 0 (55)
522. 6 19.5 10.7 (55)
With increase of pressure on the gaseous system ;:
523.1 (55) the concentration of ethane will increase relative
J
18. 6 12.6
523. 4 18. 1 11. 7 (55)
623.4 18. 1 16.0 (55) to the concentration of ethylene in accordance
523.6 17. 8 15.4 (55) with the law of mass action.
540.0 3.92 5.10 (54)
TABLE 31.-A comparison of calculated and experimental complex formed by C 2H 4 and C 4H 6, possibly the
values for the equilibrium constant J(~ for the reaction: triolefin C 6H s, which breaks down, giving C 6H 6.
C2H8~C2H4+ H2
2C~6 (1,3 -butadiene) ~C6H6 (g) +C 2H 4 + H 2
K K. K.
(axperi- Observers-
Schneider and Frolich [56] suggest that benzene
(calculated) mental) may be formed as a result of a coalescence of two
butadiene molecules.
oK atm atm
653 3.68XIQ-' 4.04XIQ-' (57)
) 673 7.98XI0-' 8.2XlO-' (58) TABLE 32.- A comparison of calculated and experimental
723 4.63XlO-4
p.16XIQ-4 (57) values for the equilibrium constant J(~ of the reaction:
.5.6XI0-· (58)
773 2. 16XIQ-' e· 2XlO-'
2. 4XIO-·
(59)
(58)
C2H4+H20~C2H50H
XVI. References
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