Solubility of Ethylene in Several Polar

and NomPolar Solvents

A. SAHGAL, H . M . L A and W . HAYDUK
Department of Chemical Engineering, University of Ottawa, Ottawa, Ontario, K I N 9B4

Solubilities of ethylene at atmospheric pressure and tempera- On rapporte les solubilitks de l'kthylhne, 1 la pression
tures ranging from -9°C to 70°C are reported in solvents atmosphtrique et A des tempkratures bchelonn6es entre -9°C
ranging from the non-polar ones, heptane, dodecane, carbon et 70"C, dans des solvants non polaires (heptane, dodecane,
tetrachloride, carbon disulfide and chlorobenzene to the highly tktrachlorure de carbone, bisulfure de carbone et chloroben-
polar ones, isopropanol, butanol and ethylene glycol. A useful z h e ) et dans des solvants fortement polaires (isopropanol,
relation was observed between ethylene solubilities in non-polar butanol et glycol khylhique). On a nott une relation utile
solvents and those of methane, ethane and propane, along entre les solubilitks de l'kthylhe dans des solvants non polaires
with the corresponding energy of vaporization at the normal et celles du methane, de l'ethane et du propane, ainsi que
boiling for those gases. In the highly polar solvents on the l'hergie de vaporisation correspondante aux points normaux
othex hand, hydrogen bonding (H-bonding) factors were found d'kbullition de ces gaz. Par contre, dans les solvants fortement
more useful in relating solubilities in one hydrogen bonding polaires, on a constat6 que les facteurs relatifs A la liaison
solvent to those in other hydrogen bonding solvents. d'hydroghe (liaison H) btaient plus utiles pour 6tablir une
relation entre les solubilitks entre les solubilitk dans un
solvant 1 liaison d'hydroghe et celles dam d'autres solvents
A lthough ethylene is a commercial gas of consider-
able importance, solubility data for it appearing
in the literature are sparse. The early work of
possedant la m&me liaison.

Horiuti"' provided solubilities in benzene, chloroben- On the other hand, a chemical reaction between the
cene, carbon tetrachloride and acetone. Solubilities gas and solvent would be expected to yield a high
were measured a t high temperatures in octadecane solubility sometimes exceeding the ideal solubility.
and higher molecular weight paraffins by Ng et al(*' For these purposes the ideal solubility was defined
using a chromatographic technique. Ethylene solu- as :
bilities in heptane and toluene were reported by
Waters et a P . Ethylene solubilities in ethanol were pz / Pi.,. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
x; = . (1)
originally reported by Winkler'4'. More recently The H-b'onding factor was defined as:
solubilities of ethylene along with other gases a t
Lya0lUcn) = x2 / x;. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (2)
26°C have been reported in a sequence of alcohols '

from methanol to octanol, by Boyer and Bircher'". It was found that the H-bonding factors for a num-
It is frequently necessary to predict gas solubilities, ber of unreaetive gases were lowest in water, tending
and variations with temperature when experimental to increase for normal alcohol solvents with increas-
data are not available. Predictions have been partially ing carbon context. In chlorobenzene, only slightly
successful particularly for solubilities in non-polar polar and non-hydrogen bonding, gas solubilities
solvents. Such predictions have often been based on tended to approach ideal solubilities, and the H-bond-
comparisons of solubilities of several gases, prefer- ing factors tended to approach unity. It was therefore
ably of similar properties, in the same solvents, It possible to compare H-bonding factors of gases in
bas been confirmed by Wilhelm and Battino"' that a number of chemically similar hydrogen bonding
the energy of vaporization of the gas at its normal solvents and to deduce the effects of molecular asso-
boiling point (AEb) is the preferred gas parameter ciation or hydrogen bonding in the solution on gas
for such solubility comparisons in non-polar solvents, solubility.
the use of this parameter having been pointed out
originally by Hildebrand e t al"'. The temperature Experimental
variation of gas solubility in non-polar solvents has The solubility apparatus used was similar to that
been empirically correlated by Hayduk and Buckleu"'. described earlieF4'. An apparatus utilizing a gas
The correlation was subsequently re-examined by burette, and solution burette, of 20 em', and 10 cm'
Gotoh's' using the free-volume theory. Several other in volume, respectively, was used for most experi-
theories for gas solubilities and effects of temperature ments, whereas a second apparatus having 6-cm',
variation may be found in the literature"O*ll~la'. and 10-cms, gas and solution burettes, respectively,
Gas solubility predictions in hydrogen bonding sol- was used when the solubility was relatively low. De-
vents are most difficult mainly because of the diver- aerated solvent was introduced a t a constant rate by
sity of possible molecular interactions, whether as- means of 10 ems and 20 em8 Gas-Tight Hamilton
sociation between solvent molecules, between solute syringes and a Harvard Apparatus syringe pump
and solvent molecules even to the extent of reversible using motor speeds of yz and 1 rpm in suitable
chemical reaction between them, or a combination of combinations. Constant temperature ( & 0.05"C) gly-
both. For these types of complex behaviour, a semi- col-water solution (or just tap water a t normal tem-
quantitative prediction method has been proposed by peratures) was circulated through the jackets sur-
Hayduk and Laudie"'' based on H-bonding factors. rounding the solubility apparatus and solvent syringe.
A strong association between solvent molecules was It was also necessary to insulate the syringe head
postulated to result in a reduced solubility for all and needle to obtain consistent results when experi-
gases in that solvent well below the ideal solubility. ments were performed above or below ambient tem-

354 The Canadion Iournal of Chemical Enginem'ng, Vol. 56, rune, 1978
 " I

8
F
2
E
Y 0.01
8
>"
-
I-
-
-1
m
2 .
In

0.OOI
3.002
2.40 2.50 2.60 0.0007
LOG TEMP., T'I' 7 to 16 18
AE,,, kJ/rnol
Figure 1 - Ethylene solubilities as a function of temperature.
Figure 2 - Ethylene solubilities at 25' compared with those
of the paraffin gases in solvents:
perature. A Neslab Instruments refrigeration unit 1-perfluoroheptane, 2-hexadecane, 3dodecane, 4-hesane, 5-
provided cooling for measurements below ambient cyclohexane, 6-carbon tetrachloride, 7-benzene, %carbon disul-
temperature. Most results were obtained in triplicate fide, 9-butanol, 10-acetone, ll-ethanol, 12-methanol.
yielding reproducible values, the average of which
was estimated to be accurate to a t least 2%.
C P grade ethylene having a specified purity of sources. The methods for calculating solubilities were
99.6 mol % was purchased from Matheson of Canada. as reported e ~ r l i e r " ~ ' .
The gas molar volumes were taken from International
Thermodynamic Tables""; the equivalent value Results and discussion
a t 25°C and atmospheric pressure was 24.326 dm3/mol. Ethylene solubilities for temperatures ranging from
The solvents were obtained from variqus sources. -9°C t o 70°C and calculated for a gas partial pressure
Hexane, ethylene glycol, butanol, and chlorobenzene, of one atmosphere are listed in Table 1and graphically
were supplied by Fisher Chemicals and were specified indicated in Figure 1. Comparative solubilities are
to have minimum purities of 99.0 mol %, 99.8 mol %, available from the literature for a number of sol-
99.0 mol %, and 99.9 mol %, respectively. Chromato- vents. Solubilities in carbon tetrachloride and chloro-
graphic grade heptane and carbon disulf ide, were benzene a t 25°C compare favourably (within 1%)
supplied by Matheson Coleman and Bell, both with a with those of Horiuti"'. Solubilities in butanol differ
minimum specified purity of 99.0 mol %. Carbon from those of Boyer and Bircherc5' by 4.4% with no
tetrachloride and isopropanol were supplied by J. T. apparent reason for the discrepancy. Solubilities in
Baker both with a minimum specified purity of hexane by Waters et 511"' appear not to be reliable
99.9 mol %. Research grade dodecane was supplied especially a t temperatures near the ambient. Mole
by Phillips Petroleum a t a specified minimum purity fraction solubilities of hydrocarbon gases in hexane
of 99.0 rnol %. Solvent densities'16~'T~'8'and vapour are usually very similar to those in heptane which i n
pressure^"^*"'^^^' were taken from standard literature turn are less than those in dodecane or also in hexa-

TABLE
1
ETHYLENE
SOLUBILITY AT ATMOSPHERIC PRESSURE ; LITERATURE
VALUES ARE SHOVJN WITH SOURCES IN BRACKETS

1
Solvent
Dodecane -9.2 4.08 402 25.0 2.35 216
48.0 1.81 159 66.0 1.55 ,131
Heptane 0.0 4.56 284 25.0 3.35 198
50.0 2.51 143
Hexane 25.0 3.91 207 25.0 - 230(3)
Carbon Tet. 0.0 5.02 208 25.0 3.72 146
25.0 - 145(1) 50.0 2.74 103
Chlorobenzene 0.0 3.92 173 25.0 2.90 I20
25.0 - 120.5(1) 50.0 2.27 89.3
Butanol -9.2 3.62 149 25.0 2.23 83.4
25.0 - 87.1(5) 49.0 1.67 59.6
70.0 1.50 51.1
Isopropanol 0.0 3.02 101 25.0 2.14 67.3
50.0 1.58 47.3
Carbon Disulfide 25.0 2.61 64.6
Ethylene Glycol 25.0 0.312 7.15

The Canadian Journal of Chemical Engineering, VoZ. 56, June, 1978 3 55

 TABLE2
9 U R C E S OF SOLUBILITY DATA FOR ETHYLENE AND PARAFFIN GASES

~~
Solvent I Methane 1 Ethylene I Ethane 1 Fropane
Hexane 8 this work 14 21
Dodecane 8 this work 14 23
Hexadecane 8 - 14 23
Cyclohexane 22 - 24 21
Benzene 8 1 1 21
C&&n tetra-
chloride 1 this work 14 21
Carbon disulfide 25 this work 26 21
Fluoroheptane 25 - 26 -
Acetone 1 1 1 27
Butanol 28 this work - 27
Ethanol 5 5 5 29
Methanol 5 5 5 29

003 0.1 1.0

H- BONDING FACTORS IN METHANOL TABLE3
-
Figure 3 Gas solubilities at 25°C in homologous polar sol-
vents as a function of their H-bonding factors.
SOURCES FOR SOLUBILITIES AT 25°C IN POLAR SOLVENTS

Butanol : CdHIo, C3Ha (27); 02, Nz,.A (29);

decane. Hence, an ethylene solubility in hexane which C2H6 (28) C H I , C2H4. This work.
is greater than that in dodecane appears unlikely. Isopropanol: CzH4 This work; CIHIO,CaHa (32); 02,
The supposedly inconsistent data of Waters e t al. N2 (33).
have not been shown in Figure 1. I t is noted that
ethylene mole fraction solubilities in benzene are es- Ethanol: 02,N2, H z , He, Ne, A , NzO, COz. SOZ,
sentially the same as those in chlvrobenzene as meas- NHS, CHI, CzH4, C3Hs, C ~ H I(29);
O
NO (28); CaHe (30).
ured by Horiuti'l), hence the former data are not
shown in Figure 1.Benzene and chlorobenzene appear Ethylene glycol: N z , A, C2He (30) ; C2H4 This work;
to have a similar solvent power for other gases, such COz (31).
as for example, propane'") In Figure 1, the solid lines Methanol : 02,N2,
H2, He, Ne, A. NzO, NO, COZ,
for each solvent indicate the temeprature range for S02,NH3, Kr, CH4, C2H4, c3H0, CI Hlo
which that solvent is a liquid, the ends of the lines (29) ; CzHa (30).
indicating the solvent freezing point and normal boil-
ing point, where applicable. As for other hydrocarbon
gases, the order of decreasing ethylene solubility ap-
pears to be: in paraffin solvents, other non-polar or associating tendency of the solvent molecules. Hydro-
slightly polar solvents, and finally in hydrogen-bond- gen bonding solvents which tend to undergo exten-
ing solvents. sive molecular association have a tendency to prevent
In Figure 2 are shown solubility data a t 25°C for solute gas molecules from entering the solvent and
ethylene a s well as for methane, ethane and propane hence exhibit a lowering of the gas solubility"". A
in a range of solvents plotted against the energy of reference for comparison is the ideal gas solubil-
vaporization a t the normal boiling point for the dis- ity, xi, In some highly associated solvents such as
solving gas, Ah?,. The excellent consistency on such water, ethylene glycol and methanol, gas solubilities
a plot for the solubilities of paraffin gases has been are reduced by factors of u p to 10000 below the
observed previously'21).It is apparent, however, that ideal solubilities. On the other hand in some few
'
solubilities of ethylene differ significantly from that instances where the gas itself is highly polar, tending
relation which describes solubilities of the paraffin to associate o r even react with the polar solvents,
gases. It would appear that ethylene solubilities are solubilities in excess of the ideal solubility occa-
comparable to those for the paraffin gases in certain sionally occur, such as for example, for NHs in water
non-polar solvents, as determined from the AEb for or methanol. An observed fact is that in non-polar
the gases, but significantly higher than might be ex- solvents, gas solubilities usually range metween 0.5
pected in benzene aod the hydrogen bonding solvents, and 1.5 of the respective ideal solubilities. It is useful
acetone, butanol, ethanol, and particularly in methanol. then to compare solubilities, or more particularly,
It can be observed that for the non-polar solvents, H-bonding factors of a number of gases in one hydro-
extrapolations for solubilities a t 25°C using the solute gen bonding solvent with equivalent H-bonding fac-
gas property AEb for the paraffin gases would be tors in other solvents. This comparison is shown in
generally successful, yielding a maximum deviation Figure 3 where H-bonding factors in methanol are
of about 20% in benzene. As might have been ex- compared with those in butanol, ethanol and ethylene
pected, however, utilizing solubilities in paraffin gases glycol. On such a diagram solubilities for most gases
to predict solubilities of ethylene in hydrogen bonding in nortrpohr solvents would usually appear as an
solvents, would yield large deviations, suggesting that approximately horizontal line with H-bonding factors
such extrapolations are of limited use in estimating ranging between 0.5 and 1, excluding the paraffin
solubilities in hydrogen bonding solvents, particularly solvents. It may be observed that a very distinct
when the gases whose solubilities are being compared relation exists between H-bonding factors in methanol,
have different chemical properties. Sources of the and the other hydrogen bonding solvents, ethanol,
solubilty data shown in Figure 2 are listed in Table 2. isopropanol, butanol and ethylene glycol, These rela-
The gas solubility behaviour in hydrogen bonding tions appear consistent in that solubilities are most
solvents may be considered to depend on the molecular reduced in ethylene glycol and progressively less in

356 The Canadian lournal of Chemical Engineering, Vol. 56, June, I978
 (4) Winkler L. W 2. phpsik, Chem. 66. 850 (1906).
ethanol, isopropanol and then butanol, in that order. (6) Boyer. k. L. a2d Bircher, L.. J Phm Chem. 64 1880 (1960).
Although, only a few points are shown for H-bonding (6) Wilhelm E. and Battino R., Chem. Rev. 73, l’(1978).
(7) HildebrLnd J H., Prauabitz. J. M. and Scott. R. L..
factors in isopropanol, these appear consistent when ff!mARelat;?d ’ Solutions”, , Van Nostrand-Reinhold, Ne?%$
compared with those of the homologous alcohols, (IJIUJ.
(8) Hayduk. W. and Buckley, W. D., Can. J. Chem. Eng. 49, 667’
ethanol and butanol. Such a plot would appear to be (1971).
(9) Gotoh K., Ind. Eng. Chem. Fundam. 15, 269 (1976).
useful for estimating solubilities in hydrogen bond- (10) Piemiti, R. A.. J. Phys. Chem. 67. 1840 (1968).
(11) $?
&
I?
: P. M. and PrausnitZ. J. M.. J. Phys. Chem. 76, 601
ing solvents, although its utility is of course limited ,AcV‘.2,.

by the availability of solubility data in other hydrogen (12) Field, L. R., Wilhelm, E. and Battino, R.. J. Chem. “ h e m d m .
6 237 (1974)
bonding solvents of similar chemical nature. The (13) &duk W. and Laudie H., AIChE J. 19 1233 (1978).
(141 Hasduk: W. and Chew.’ 9. C.. Can. J. Chem. Ew. 48, 98
predictive accuracy appears to be of the order of (1970).
+- 25%. One might extrapolate the H-bonding factors Angus S., Armstronz B and d e Beuck K. X., Eds. “Inter-
nstion;l Thermodynsdic Table. of the h i d State, Ethylene”
line for ethylene glycol to estimate very low solubil- Butterwortha, London (1972).
Timmermans, J., “Physieo-Chemical Coastants of Pure OrPaniC
ities of propane and butane in that solvent, for Compounds” Elsevier, New York (1960),.c
example, compared with solubilities in ethanol. With ASTM Corn.’ D-2. API Re% Project 44 Physical Constant8 Of
Hydrocarbons Ci to Cio”. ASTM Phhadelphh Pa. (1971).
due consideration for the grossly simplified treatment Rossini F. D., “Selected Values or‘ Phyaicaf and’Thermodunamfe
Properbes of Hydrocarbons and Related Compounds”. C a r n d e
of complicated molecular interactions between associat- Press (1963).
ing solutes and solvents, the relatively good relation Zwolinski B. J. and Wilhoit, p . C.. “Bandbook of Vapor
Pressures’ and Heats of Vaponeation of EYdroearbona and
between H-bonding factors in various solvents is Related ComDounds”. Thermodynamics Research Centre, TeKas
A & M University,. Collepe Station. Texas (1971).
noteworthy. Sources for solubility data shown in F5g- Perry, R H and Chilton C €I “Chemfeal
., Engineers’ Hand-
ure 3, are listed in Table 3. book” Fifth’Ed 8-49 MiG&w-Hill New York (1978).
FleuG. D. and Haydud, W., Can. J.’Chem Eng. 68, 196 (1976
Lannung, A. and Gjaldbaek, J. C.. A& Chem. S a n d .
1124 (1960).
d;
Acknowledgment (28) Hayduk, W., Walter, E. B. and Simpson, P., J. Chem. Enn.
The authom acknowledge with thanks financial support from the Data 17. 69 (1972).
(24) Drmond J. H J. P ~ E Chem. .
National Research Council of Canada in the form of an operating
grant.
71, 1829 (1967
(25) Kobatke: Y. aGd Hildebrand, J. H., J. Phps.
(1961).
dk. 66. 881
(26) Thomsen. E. 5. and Gjaldbaek, J. C.. Acta Chem. Sand. X l r
Nomenclature 127 (1963).
(27) Hayduk, W. and Castaneda, R.. Can. J. Chem. Eng. 61. 868
Ostwald coefficient, m3 gas/m3 solvent. (1978 .
energy of vaporization at the normal boiling point, (28) Seideh, A. and Lfnke, W. F., “Solubilities of Inorprnic and
Metal-Organic Compound#’. Am. Chem. Suc., Washfnpton, D.C.
kJ/mol. (1966).
partial pressure of dissolvinggas a t equilibria, atm. (29) Stephen. H. and Stephen, T., Eds., “Solubilities of Inorpanio
vapor resure of liquefied gas, atm. and Organic Compounds” Vol. 1, MaelYIillan, New York (1968).
mole iaction dissolved gas for a partial pressure of 1 (30) Gjaldbaek. J. C. and Ni&rmn, H.. Acta Chem. Sand. 8. 1898
11OKA\
,A””=,.

atmosphere. (81) Hayduk, W. and M a l i V. K, J. Cham. Ens. Data X6. 148

ideal solubility of gas in mole fraction, based on (1971)
Raoult’s law. (82) Kretarhmer. C. B. and Wiebe, R.. J. Am. Chem. Soc. 74, 1816
(1952)
hydrogen- bonding factor. (88) Kretaihmer.0. B., Nowakiw~ka, J. and Wiebe. R, Ind. Eng.
Chem. 38. 606 (1946).
References
(1) Horiud J J. 8ci. Papers Imt. Phm. Chem. Rea. (Tob‘o) 11. Manuscript received Jnly 20. 1077: accepted for publieation Feb
182 cid8ii: mm 7. 1978.
(2) Ng. S., Barria H. G. and Pransnitz, J. Y., J. Chem. Eng.
Data 14. 482 (1969).
(8) Waters. J. A. Yortkner, G. A. and Clements, H. E., J. Chem.
E m . Data Id, 174 (1970). * * *

The Canadian Iournal of Chemical Engineering, Vol. 54, lune, 1978 357