IUPAC-NIST Solubility Database
NIST Standard Reference Database 106

Glass Ball as Bullet Solubility System: Ethene with Solvents containing nitrogen
Components:
   (1) Solvents containing nitrogen; ; []  NIST Chemistry WebBook for detail
   (2) Ethene; C2H4; [74-85-1]  NIST Chemistry WebBook for detail
Evaluator:
   Peter G.T. Fogg, School of Applied Chemistry, University of North London, Holloway Road, London, N7 8DB, U.K.
Novermber, 1993

 Critical Evaluation:
   Critical evaluation of the solubility of ethene at a partial pressure not greater than 101.3 kPa in solvents containing nitrogen.

In general solubility in compounds containing nitrogen that have been studied is lower than solubility in halogen or oxygen compounds measured under the same conditions. It is considerably lower than solubility in hydrocarbons.

1-Methyl-2-pvrrolidinone; C5H2NO; [872-50-4]

Solubility in 1-methyl-2-pyrrolidinone at, or below 101.3 kPa was measured by Wu et al.1, Shenderei and Ivanovskii2 and by Lenoir et al.3. Measurements by Shenderei from 273.15 K to 288.15 K and pressures from about 13 kPa to 101.3 kPa indicate that mole fraction solubility is, within the limits of the experimental accuracy, proportional to pressure to at least 101.3 kPa. Lenoir et al. measured Henry’s constant at 298.15 K and low pressure by gas chromatography. The corresponding mole fraction solubility at a partial pressure of 101.3 kPa, calculated on the basis of a linear variation with change in pressure, is within about 5% of the value corrected to 101.3 kPa from direct measurements by Wu at 100 kPa. The six data points for a partial pressure of 101.3 kPa from the three sources fit the equation
          ln x1 = –503.92 + 22206/(T/K) + 74.519 ln(T/K)
          standard deviation in values of x1 = 1.65 × 10–4
This can be accepted on a tentative basis for the temperature range 273 K to 298 K.

Nitrobenzene: C6H5NO2; [98-95-3]

The solubility in nitrobenzene was measured by Choudhari and Doraiswami4 at a total pressure of 94.23 kPa in the temperature range 286 K to 333 K. Lenoir et al.3 measured Henry’s constant at low pressure by gas chromatography. The corresponding mole fraction solubility at 101.3 kPa, calculated on the assumption of a linear variation of mole fraction solubility with variation of pressure, is 0.00794. The corrected and interpolated value from Choudharai’s measurements is 0.00543. Measurements of gas solubility by gas chromatography are subject to some uncertainty because of effects due to surface adsorption. Some of the values of solubility of other gases reported in Lenoir’s paper are appreciably higher than values reported by other workers. The evaluator considers that Choudhari’s measurements are likely to be the more reliable although further work on the system is required. The five-mole fraction solubility from Choudhari, corrected to a partial pressure of gas of 101.3 kPa, fit the equation
          ln x1 = –233.51 + 12038/(T/K) + 32.982 ln(T/K)
          standard deviation in values of x1 = 6.6 × 10–5
Temperatures range 386 K to 333 K.

Ammonia; NH3 [7664-41-7]

Hannaert et al.5 reported the solubility of ethene in liquid ammonia in a paper in which the solubility of various hydrocarbons in liquid ammonia and other solvents were reported. In each case solubility are reported as coefficients of a two constant equation giving the variation of Henry’s constant with temperature. The equation can be written in the form
log H = A – B/(2.3 RT)

The authors identify the constant B with a heat of solution of the gas in the solvent. Mole fraction solubility can be calculated from values of H if it is assumed that solubility vary linearly with partial pressure of gas. The equation for solubility of ethene in ammonia is reported to be valid for the temperature range of 208 K to 318 K. What is unusual about the equation for ethene in ammonia is the very low value of B or heat of solution compared with values for other systems that were studied by the authors. The value is 0.23 kcal mol–1 compared with 2.72 kcal mol–l for ethyne in ammonia and 1.215 kcal mol–1 for propene in ammonia. The low value for ethene corresponds to a very small variation of solubility with change in temperature and contrasts markedly with the behavior of ethene in nitrobenzene and in 1-methyl-2-pyrrolidinone. The evaluator is of the opinion that the solubility equation for ethene in ammonia should be treated with caution until it is confirmed by other measurements.

N,N-Dimethylacetamide C4H9NO; [127-19-5]
N,N-Dimethylformamide C3H7NO; [68-12-2]
N-Methylformamide C2H5NO; [123-39-7]
Acetonitrile C2H3N; [75-05-81]

Bruckl and Kim6 measured the solubility in the above solvents at 298.2 K. There is no reason to doubt the reliability of the measurements but other workers have not confirmed them. In the case of the amides the mole fraction solubility at a partial pressure of 101.3 kPa increases with increase in the number of methyl groups present. Solubility in N-methylformamide is low compared with the solubility in nitrobenzene and in 1-methyl-2-pyrrolidinone and is close to the solubility in ammonia as reported by Hannaert5.

Benzenamine; C6H7N; [62-53-3]

Lenoir et al.3 measured Henry’s constant for dissolution in benzenamine by a chromatographic method. The mole fraction solubility at a partial pressure of 101.3 kPa, calculated on the assumption of a linear variation of mole fraction solubility with change in pressure, is close to the value for dissolution in nitrobenzene. However the value needs confirmation by further measurements because of unreliability of the chromatographic method.

Cyclohexylamine; C6H13N; [108-91-8]

Keevil et al.7 reported a value of the solubility in cyclohexylamine at 298.1 K and 101.3 kPa. The value is higher than that in other nitrogen compounds for which data is available. This can be explained by the presence of the alicyclic ring. There is no reason to doubt the reliability of the measurement but confirmation is needed.

N,N-Dimethylformamide; C3H7NO; [68-12-2] + Ethyne; C2H2; [74-86-2]

Shenderei8 measured the solubility of ethene in N,N-dimethylformamide, containing various proportions of ethyne, at 218.15 K over the pressure range 13.3 kPa to 101.3 kPa. The measurements indicate that the mole fraction solubility (moles C2H4/total moles of C2H4, C2H2 & DMF) does not change when the proportion of ethyne is increased from 33.8 to 249 cm3(STP)/g DMF. This is in contrast to the solubility of carbon dioxide in N,N-dimethylformamide containing various concentrations of ethyne. In this case the mole fraction solubility decreases with increase of ethyne concentration. The evaluator considers that the data for ethene needs to be confirmed before it can be accepted as reliable.



Experimental Data:   (Notes on the Nomenclature)

 References: (Click a link to see its experimental data associated with the reference)
   1  Wu, Z.; Zeck, S.; Langhorst, R.; Knapp, H., Proc. Int. Conf. Coal Gas and Air, Beijing, China, 1985, 1, 209-229.
   2  Shenderei, E.R.; Ivanovskii, F.P., Gaz. Prom. 1962, 7, 11-17. Same paper also in: Khim. Prom. 1963, 10, 91-97.
   3  Lenoir, J-Y.; Renault, P.; Renon, H., J. Chem. Eng. Data 1971, 16, 340-2.
   4  Choudhari, R.V.; Doraiswami, L.K., J. Chem. Eng. Data 1972, 17, 428-432.
   5  Hannaert, H.; Haccuria, M.; Mathieu, M.P., Ind. Chim. Belge 1967, 32, 156-164.
   6  Brückl, N.; Kim, J. I., Z. Phys. Chem. (Wiesbaden) 1981, 126, 133-150.
   7  Keevil, T.A.; Taylor, D.R.; Streitwieser, A.; J. Chem. Engng. Data. 1978, 23, 237-239.
   8  Shenderei, E.R.; Khim. Prom. 1966, 42, 514-516.