Sublimation Pressure Data for Organic Compounds. A. HAMILTON JONES,' The Edward Davies Chemical Laboratories, University College of Wales, Aberystwyth, Wales
c
ONSIDERING T H E valuable information which may be derived either directly or indirectly from sublimation data, it is rather surprising that there is so little quantitative information available in the literature on the sublimation process. Apparently, no compilation of such data has been attempted. This summary of most of the available data, although not exhaustive, is the first serious attempt a t a tabulation for organic compounds. The variation of sublimation pressure with temperature may be represented to a first approximation by Loglop B - A / T where p is the pressure of the saturated vapor in millimeters of mercury a t the absolute temperature T(T = to C. + 273.18). The constants A and B are related to the heat of sublimation and the entropy of sublimination (assuming these to be constant) in the following way: H
= 2.303 R A 2.303R ( B - 2.881) R is the gas constant, 1.986 cal. per gram mole.
S
=
The values of A and B are quoted to an accuracy a t least sufficient to reproduce sublimation pressures over the quoted temperature ranges to within the accuracy of the original observations. The AH and A S values derived from A and B are less certain if only because of the limitations in the relations used. Table I contains all the compounds for which full details are available. I n cases where the authors have given an equation but have not deduced values for the heat and entropy of sublimation such values have been calculated and appear in bold face. The constants A and B are valid for the temperature ranges quoted for each compound. I t is obviously difficult to assess the quality of many of the results quoted, but an assessment has been attempted and the data considered most acceptable are footnoted. I n arriving a t these conclusions the following facts were taken into account: I n recent years there has been a considerable advance in the quality of the equipment available for the measurement of sublimation pressures. The adverse effect of impurities on the accuracy of the measurements was not fully appreciated by a considerable number of authors. I n cases where doubts exist as to the validity of the results published, the data has been ignored. Failure by certain authors to ensure complete saturation in the air-flow method would invalidate their results. The effusion method is less sensitive to impurities than methods involving the use of a gauge. The fact that comparatively few measurements which have been described survive a critical appraisal, results in the paucity of reliable data. Table I1 contains a list of compounds for which limited sublimation pressure data are available. I n the references given no heats or entropy values have been calculated for these compounds. ACKNOWLEDGMENT
The author thanks Mansel Davies for his help and guidance. A grant from the Ministry of Education is also gratefully acknowledged. LITERATURE CITED (1) Aihara, Ariyuki, J . Chem. Soc. Japan, Pure Chem. Sect. 73, 855 (1952). 'Present address, Newport and Monmouthshire College of Technology, Newport (Mon.), England.
196
Ibid., 74,437 (1953). Ibid., p. 631. Allen. R. W.. J . Chem Soc. 77.400 (1900). Andrews, M. R., J.Phys. Chem. 30,1497 (1926). Ani, Kimio, Bull. Inst. Phys. Chem. Research (Tokyo) 8, 714 (1929). Balson, E. W., Trans. Famduy Soc. 4 3 , 5 4 (1947). Bergstrom, F. W., J . Phys. Chem. 26,358 (1922). Boer, J. H. de, Trans. Famday Soc. 32, 10 (1936). Boer, J. H. de, Dippel, C. J., Z. physik. Chem. 921, 273 (1953). Bradley, R. S., Care, A. D., J . Chem. Soc. 1953, p. 16Pd. Bradley, R. S., Cleasby, T. G., Ibid., 1953, p. 1681. Ibid., p. 1690. Bradley, R. S., Cotson, S., Ibid., 1953, p. 1684. Bradley, R. S., Shellard, A. D., Proc. Roy. Soc. (London) 198A. 239 (1949). Bright. N. F. H.. J . Chem. Soc. 1951. D. 624. Bright; N. F. H.; Carson, T., Dyson; T. A., Research (London) 3,185 (1950). Broadway, L. F., Fraser, R. G. J., J . Chem. Soc.,1953, p. 429. Brown, C. A., Laubengayer, A. S., J . Am Chem. Soc. 77, 3699 (1955). Brown, H. C., Sujishi, Sei, Ibid., 70, 2878 (1948). Bruylants, A., Memoires en-8O de la c l a w des Sciences de 1'Academie royale de Belgique, tome XVIII, fasc. 7, 1939. Bywater, S., J . Polymer Scz. 9, 417 (1952). Coolidge, A. S., J . Am. Chem. SOC. 53, 1874 (1930). Coolidge, A. S., Coolidge, M. S., Ibid., 49, 100 (1927). Crooks, D. A., Feetham, F. M., J . Chem. Soc. 1946, p. 899. Crowell, T. I., Jones, G. L., J . Phys. Chem. 58, 666 (1954). Darkis, F. R., Vermillion, H. E., Gross, P. M., Ind. Eng. Chem. 32,946 (1940). Davies, Mansel, Jones, J. I., Trans Faraday Soc., 50, 1042 (1954). Deitz, V. R., J . Am. Chem. Soc. 55,472 (1933). Dennis, L. M., Corey, R. B., Moore, R. W., Ibid., 46, 657 (1924). Dickinson, W., Trans. Famday Soc. 52,31 (1956). Dunken, H., dissertation, Physikalisch-Chemischen Institut der Universitat Halle, Germany, 1938. Dunn, S. A,, J . A m . Chem. SOC.76,6196 (1954). Edwards, G., Trans. Faraday Soc. 46,423 (1950). Ibid., 49, 152 (1953). EmelBus, H. J., Maddock, A. G., Reid, C., J . Chem. Soc. 1941, p. 353. Eucken, A., Karwat, E., Z. physik. Chem. 112, 467 (1927). Ewald, A. H., Trans. FamduySoc. 49,1401 (1953). Fischer, Werner, Blitz, W., Z. anorg. allgem. Chem. 176, 81 (1928). Granovskaya, A. A., J . Phys. Chem. ( U . S . S . R.) 21, 967 (1947). Handbook of Chemistry and Physics, 37th ed., Chemical Rubber Publ., Cleveland, Ohio, 1955. Hara, R., Shinozaki, H., Tech. Repts. Tohoku Imp. Uniu. 4, 145 (1924). Heilbronner, E., Wieland, K., Helu. Chim. Acta 30, 947 (1947). Henglein, F. A., Rosenberg, G. V., Mulchinski, H., Z. Physik. 11, l(1922). Heycock, C. T., Lamplough, F. E. E., Proc. Chem. SOC. (London)28, 3 (1912). Hirsbrunner, Hans, Helu. Chim. Acta. 17, 477 (1934). Holborn, L., Baumann, A., Ann. Physik. (4), 31, 945 (1910). Inokuchi, Hiroo, J . Chem. Soc. Japan Pure Chem. Sect. 72, 552 (1951). Inokuchi, Hiroo, Shiba, S., others, Bull. Chem. Soc. Japan 25, 299 (1952). Ivin, K. J., Dainton, F. S., Trans. Faraduy Soc. 43, 32 (1947). King, F. E., Partington, F. R., J . Chem. Soc. 129, 925 (1926). Klosky, Simon, Woo, L. P. L., Flanigan, R. J., J . Am. Chem. Soc. 49, 1280 (1927). Knudsen, Martin, Ann. Physck (4) 29,179 (1909). Kuhn, Werner, Massini, Peter, Helu. Chim. Acta 32, 1530 (1949). JOURNAL OF CHEMICAL AND ENGINEERING DATA
Table I.
AH,Kcal Compound Temp. Range, C. Acetic acid -95-+1U p- Acet ylanisole 10-60 Acetylene - 140- - 82 130-157 p-Aminophenolb ... Anthanthrene Anthracene 106-i 60 Anthracene Anthracene 65180 Anthracene' ... Anthracene Anthracene 1231i48 Anthracene 105-125 Anthracene ... Anthracene ... Anthraquinone Anthraquinone 30160 cis-Azobenzeneb 30-60 trans-Azobenzeneb ... Azulene ... Benzanthrone - 30-5 Benzene 58- 30 Benzene ... Benzene ... Benzil ... Benzoic acid Benzoic acid" 70-114 60-121 Benzoic acid Benzoic acid 104-116 ... 3,4-Benzophenanthrene Benzophenone ... Benzophenone ... Benzophenone ... .... Benzophenone" ... Benzophenone' Benzoquinone ... Betaine of p-aminobenzoic acid ... Betaine of'sulfanilic acid ... 9,9'-Bianthryl ... 9.9-Biphenanthryl sblioo Butyramide 0-25 Camphor Camphor 0-180 Camphor 2i-41 (-Caprolactam Carbon tetrachloride - 64- - 48 5-50 Chloroacetophenone' o-Chlorohenzoic acid ... m-Chlorobenzoic acid ... p-Chlorobenzoic acid 36150 p-Chloroiodo benzene' m-Chloronoitro benzene ... m-Chlorophenol ... p-C hlorophenol ... ... C h rynene 10-5,i Cinnamic acid Citronellol 10-60 Coronene 20180 Coumarin 2-44 m-Cresyl acetateh Cyclamen aldehyde 10-60 Cycloheptadecanone ... Cvclohexadecannne ... Cyclohexane - 5 +5 Cyclohexanone ... C yclononadecanone ... ... C yclo-octadecanone ... C yclopentadecanone ... Cvclotetradecanone Cyclo-trimethxlene 110-138 trinitramine 25 -30 p-Dibromobenzene ... 1,2-Dihrnmoethane 10-50 p-Dichlorohenzene 25-30 p - Dichlorobenzene 30-50 p-Dichlorobenzene l,l,p.p-Dichloro50-90 diphenyltrichloroethane 1.1,p.p-Dichlorodititi 100 phenyltrichloroethaneb 1,l.p,p,-Dichlorodi40 -90 phenvltrichloroethane 2.6-Di~hlorohydro... quinone ~
~
~
VOL. 5 , No. 2, APRIL 1960
Mole 9.9 22.4 5.2 22.0 32.3 22.3 17.2 22.8 24.4 21.9 22.0 23.3 23.4 22.3 26.3 25.0 17.9 17.9 16.2 27.6 10.6 10.3 10.7 19.8 20.1 21.8 20.1 19.5 25.4 21.3 18.7 18.8 22.7 22.0 15.0 34 16 35.4 36.2 20.8 15.7 12.8 12.1 19.9 9.2 21.7 19.0 19.3 21.0 14.6 17.9 12.7 12.4 28.1 26.2 15.8 35.5 20.6 14.5 17.3 18.1 19.6 8.9 11 8
Sublimation Data
AS,Cal. 1 Mole Deg 25.7 51.9 27.7
A 2177 4892 1144
B
Method"
Ref
8.502 14.217 8.933
... E
1411 82 I 141
'K
(331
45.8
7060
12.889
...
...
...
E
I
...
49)
! 57,
(41) i 661 131 1491 49 8& 76 1 93, 95 41 149 I17 17 \ 43 ,49) i411 (41) 9 ! 95) 9.3, 95 1
27.6 39.7 44.7 39.1 40.0
3760.6 4980 5320 4790 4820
igio 11.549 12.638 11.420 11.611
41.7
5102
...
12.002
...
43.1 43.8 30.9 31.2
5747 5470 3914 3911
12.305 12.437 9.652 9.721
48.1 31.9 30.5
6030 2309 2241
13.416 9.846 9.556
...
...
...
...
...
... ...
4776 4409 4277
...
...
...
12.8699 11.956 11.620
43.7
4654
12.i34
'E
...
... ...
65.46 40.6 32.5
4966 4818 3280
17.46 17.19 10.00
E E C
(59 [ 24
...
...
...
... ...
...
... ...
...
1951 195, 1571 57
45.5 38.8 27.1
4539 3439 2797
ii.8i6 11.352 8.799
... ... ... ...
40.9 28.5 49.9
4339 2027 4740 ...
1i.839 9.089 13.779
3200
9.819
...
...
...
45.5 41.5 39.9
...
...
...
... ...
...
31.7 ...
...
...
... ...
...
... ...
... ... ...
... ... ... ...
62.6 31.5
5723 3447
...
... 31.5 35.1
... ...
26.1 29.3
... ...
3170 3794
...
... 1953
...
...
...
... ...
... ... ... ...
16.569 9.757
...
9.7.59 1 0 ;1'l
...
... 8.594
'E
E E E J F
... 'E
E E 'E
... ... ... ... ...
w,
(281
A B
...
E II
52 I 461 ! 67
i
65 93, 95 i
90, 95
59 1
21 97 41 1941 13 i
621 7 95 1951 \ 95 38 90, 95 9.5 9.5 57 t
1.: (.
...
... 'E
81
E 'E E
E
... ... ...
82 149 80 7 82 I
41! 64 95 96
E
... ... ...
95
I 96 1
19.7 18.5 18.5 19.3
...
26.8 14.3 14.1 16.3
41.1 27.3
5850 3115
11.870 8.846
3570 2972 3771
1i.986
17.3
41.7 36.1 43.9
10.760 12.480
I.: I.: A E ...
27.5
49.9
6010
13.778
A
J1
28.2
51.7
6160
14.191
E
I37
20.0
30.7
4370
9.60
A
$54
22
25.8
4800
8.54
C
24
13.6
... ... ... ...
...
...
1.:
195 95
(
I35
98 1 64 I
27 70 41
197
Compound 2.6-Dichloroquinone Difnrmvlhvdrazine 9,10-Dihydroanthracene 5.12-Dihydrotetracene o- Dihydroxybenzene m-Dihydroxyhenzene p-Dihydroxybenzene trans-Diiodoethvlene~ 2,6-Dimethyl-3,5dinitro-4-tert-butylacetophenone Dimethyl fumaric ester Dimethvl glyoxime 3.4-Dimethyl hexadiene Dimethvl maleic ester Dimethyl racemic ester d-Dimethyl tartrateh d-Dimethyl tartrate meso-Dimethyl tartrate di-Dimethyl tartrateh o-Dinitrobenzene m-Dinitrobenzene p-Dinitrobenzene 4,4'-Dinitrobiphenyl 3.5-Dinitro-o-cresol Diphenyl Diphenyl Diphenyl Diphenyl Diphenylamine 9,1O'-Diphenylanthracene 9.10-Diphenylanthracenen Diphenylcyanoarsine* Diphenylethane Diphenylmethane Enanthamide meso-Erythritol Ethylene dibromide Fluoreneh Formic acid Fumaric acid 2-Fuoric acidh n-Heptadecane n-Hexachlorobenzeneh B-Hexachlorobenzene' r-Hezachlorobenzene" 6-Hexachlorobenzene' Hexachlorobenzene Hexachloroethane' cubic form Hexachloroethaneh triclinic form Hexachloroethane Hexachloroethane n-Hexadecane Hexamethylbenzene HexamethylcvclotrisiIoxaneh' Hydroquinone p-Hydroxybenzoic acid Indole Iodobenzene Iodoform m-Iodonitrohenzene Maleic acid Methane Methane o-Methoxybenzoic acid" N-Methyl acetamide Methyl anthranilate Methyl methacrylate 1-Methyl-4-tertbutyl methoxy-2. 6-dini trobenzene Monochlorohydroquinone Monochloroquinone Naph thacene Naphthalene Naphthaleneb Naphthalene Naphthalene Naphthalene meso-Naphthodianthrene 1
198
Temp. Range. 1-42 97-1:x
... ... ... ... ...
- 8-20
PO 80
... 35-44 4235
...
C.
Table I. Continued I H . Kca I. i s . Cal. Mole Mole Deg. 16.7 31.9 24.1 39.6 21.4 ... ... 28.8 ... 19.3 22.8 . . 23.7 ... 9.72 13.6 25.8 20.2 23.2 12.7 10.6 22.7 27.0 21.1 28.5 27.2 20.7 19.4 21.2 25.0 24.7 16.4 19.5 17.4 17.9 23.1
B
A 3670 ,5264
9.85 11.,53
... ...
...
2130
6.86 ...
...
... ... ... ... ...
62.8
5903.2
16.610
... ...
...
... ... ... ...
60.6
... ... ...
... ... ...
...
...
...
...
...
... ...
...
...
...
...
10.744 14.140
43.0 34.3 37.2 43.7
4262 3799 3918 4654
12.282 10.38 11.002 12.434
3'2.0
...
...
60.3 35.8
8213 4420
16.058 10.724
28.5 49.2
3341 5182
9.12 13.617
32.0 39.1 43.9
2606 4324 3160
9.i384 11.325 12.486
44-56 16 20
