Arenes: Pressure up to 0.2 MPa 493 COHPONENTS: (1) Methane; CH 4 ; [74-82-8] (2) Arenes Benzene Methylbenzene Dimethylbenzenes l,l'-Methylenebisbenzene l-Methylnahthalene Decahvdronaphthalene EVALUATOR: H. Lawrence Clever Chemistry Department Emory University Atlanta, GA 30322 USA 1984, January CRITICAL EVALUATION: The Solubility of Methane in Arenes at Partial Pressures up to 200 kPa (aa. 2 atm). The solubility of methane in arenes at methane partial pressures up to 200 kPa is reported in nine papers. With one exception all of the solubilities were measured by volumetric methods at a total pressure near 101 kPa (aa. 1 atm). The exception (ref. 5) used a GLC system to analyze the saturated solution. The partial molal enthalpy change on solution is less exothermic for the arenes than for the alkanes. For the methane + benzene it is -1.23 kJ mol- 1 while for the other methyl substituted benzenes it ranges from -2.6 to -4.3 kJ mol- 1 • Most of the methyl substituted enthalpy change values are intermediate between the benzene and alkane values. Enthalpy changes based on the temperature coefficient of solubility are probably not reliable enough to base any far reaching conclusions on when they show as little difference as do these values. Methane + Benzene; C 6 H 6 ; [71-43-2] McDaniel (ref. 1) reports four solubility values between 295.25 and 323.05 K; Horiuti (ref. 2) reports four values between 286.25 and 333.15 K, Lannung and Gjaldbaek (ref. 3) report six values between 291.15 and 310.15 K and Hayduk and Buckley (ref. 4) report one value at 298.15 K. The smoothed McDaniel data are smaller by 9 percent at 293 K and 35 percent at 323 K than the data in (ref. 2,3). MCDaniel's data are rejected. The smoothed data of Horiuti and of Lannung and Gjaldbaek agree within 0.5 to 1.5 percent between 288 and 308 K with the Lannung and Gjaldbaek solubility values the larger. Hayduk and Buckley's single value at 298.15 K is between 1 and 2 percent smaller than the values from the other two papers. The data of Horiuti, Lannung and Gjaldbaek, and Hayduk and Buckley were combined in a linear regression to obtain the equation In xl = -6.66791 + 1.47786/(T/IOO K) with a standard error about the regression line of 1.7 x 10- 5 • The temperature independent thermodynamic changes calculated from the constants of the equation are AYi/kJ mol- 1 = -1.23 and ASi/J K- 1 mol- 1 = -55.4 Smoothed values of the mole fraction solubility and partial molal Gibbs energy of solution are given in Table 1.
H. Lawrence CleverChemistry DepartmentEmory UniversityAtlanta, GA 30322 USA
1984, January
CRITICAL EVALUATION:
The Solubility of Methane in Arenes at Partial
Pressures up to 200 kPa (aa. 2 atm).
The solubility of methane in arenes at methane partial pressures upto 200 kPa is reported in nine papers. With one exception all of thesolubilities were measured by volumetric methods at a total pressure near101 kPa (aa. 1 atm). The exception (ref. 5) used a GLC system to analyzethe saturated solution.
The partial molal enthalpy change on solution is less exothermic forthe arenes than for the alkanes. For the methane + benzene it is -1.23kJ mol- 1 while for the other methyl substituted benzenes it ranges from-2.6 to -4.3 kJ mol- 1
• Most of the methyl substituted enthalpy changevalues are intermediate between the benzene and alkane values. Enthalpychanges based on the temperature coefficient of solubility are probablynot reliable enough to base any far reaching conclusions on when theyshow as little difference as do these values.
Methane + Benzene; C6H6 ; [71-43-2]
McDaniel (ref. 1) reports four solubility values between 295.25 and323.05 K; Horiuti (ref. 2) reports four values between 286.25 and 333.15 K,Lannung and Gjaldbaek (ref. 3) report six values between 291.15 and310.15 K and Hayduk and Buckley (ref. 4) report one value at 298.15 K.
The smoothed McDaniel data are smaller by 9 percent at 293 K and35 percent at 323 K than the data in (ref. 2,3). MCDaniel's data arerejected.
The smoothed data of Horiuti and of Lannung and Gjaldbaek agreewithin 0.5 to 1.5 percent between 288 and 308 K with the Lannung andGjaldbaek solubility values the larger. Hayduk and Buckley's single valueat 298.15 K is between 1 and 2 percent smaller than the values from theother two papers.
The data of Horiuti, Lannung and Gjaldbaek, and Hayduk and Buckleywere combined in a linear regression to obtain the equation
In xl = -6.66791 + 1.47786/(T/IOO K)
with a standard error about the regression line of 1.7 x 10- 5 •
The temperature independent thermodynamic changes calculated fromthe constants of the equation are
Smoothed values of the mole fraction solubility and partial molal Gibbsenergy of solution are given in Table 1.
494 Arenes: Pressure up to 0.2 MPa
Table 1. Solubility of methane in benzene. Tentative mole fractionsolubility at 101.325 (1 atm) methane partial pressure andpartial Gibbs energy of solution as a function of temperature.
T/K Mol Fraction IIG]/kJ mol- 1
283.15293.15
298.15
303.15313.15323.15333.15
2.142.10
2.05
2.072.042.011.98
14.46915.023
15.300
15.57816.13216.68617.241
Methane + Methylbenzene; C7H8 ; [108-88-3]
McDaniel (ref. 1) reports four values of the solubility of methane inmethylbenzene between 303.15 and 333.15 K and Field, Wilhelm and Battino(ref. 7) report three values of temperatures between 284.28 and 313.17 K.
The McDaniel data are 10 percent smaller than the Field et a~. dataover the temperature interval of common measurement. Although both datasets are classed as tentative the data of Field, Wilhelm and Battino arepreferred and the tentative values below are based on their data.
A linear regression of the data of Field et a~. gives the equation
In xl = -7.79695 + 5.22l44/(T/IOO K)
with a standard error about the regression line of 1.66 x 10- 4 •
The thermodynamic changes for the transfer of one mole of gas fromthe gas phase to the infinitely dilute solution are
We are concerned that this is larger by about 25 percent than any of theother enthalpies of solution in benzene and methyl substituted benzenes.
Smoothed values of the mole fraction solubility and partial molalGibbs energy of solution are in Table 2.
Table 2. Solubility of methane in methylbenzene. Tentative values of themole fraction solubility at 101.325 kPa methane partial pressureand partial molal Gibbs energy of solution as a function oftemperature.
EVALUATOR:H. Lawrence CleverChemistry DepartmentEmory UniversityAtlanta, GA 30322
1984, January
USA
CRITICAL EVALUATION:
Methane + 1,2-Dimethylbenzene; C8HIO ; [95-47-6J
Methane + 1,3-Dimethylbenzene; C8HIO ; [108-38-3]
Methane + 1,4-Dimethylbenzene; C8HIO ; [106-42-3]
Byrne, Battino and Wilhelm (ref. 9) report between 5 and 7 solubilityvalues each for these systems over the 283 to 313 K temperature interval.McDaniel reports four solubility values for the methane + 1,3-dimethylbenzene system at temperatures between 294.25 and 333.15 K.
All of the data are classed as tentative. For the methane +1,3-dimethylbenzene system McDaniel's smoothed data are 5.2 to 5.4 percentsmaller than the smoothed results of Byrne, Battino and Wilhelm. Theagreement is within the experimental error. However, the Byrne et a~.
data are preferred and their data are the basis of all the smootheddata presented here. The data were fitted to the following equations bya linear regression.
Methane + 1,2-dimethylbenzene
In xl = -7.03873 + 3.13979/(T/IOO K)
Methane + 1,3-dimethylbenzene
In xl = -7.06540 + 3.44764/(T/IOO K)
Methane + 1,4-dimethylbenzene
In xl = -7.20727 + 4.01581/(T/IOO K)
with standard errors about the regression lines of 7.9 x 10~ ,9.7 X 10-6 , and 18.2 x 10-6 , respectively.
The temperature independent thermodynamic changes for the transferof one mole of methane from the gas phase to the infinitely dilute solution are given in Table 3.
Table 3. Thermodynamic values for the transfer of methane from the gasto the infinitely dilute solution in dimethylbenzenes.
a The partial molar Gibbs energy values are for a temperature of 298.15 K.
The smoothed solubility values are given in Table 4.
M-Q
496 Arenes: Pressure up to 0.2 MPa
Table 4. Tentative values of the solubility of methane in the dimethylbenzenes. Mole fraction solubility at 101.325 kPa partialpressure methane as a function of temperature.
Cukor and Prausnitz (ref. 6) report Henry's constant values at25 degree intervals from 300 to 475 K. The solubility values were converted to mole fraction values at a 101.325 kPa methane partial pressureassuming ideal gas behavior and Henry's law to be obeyed. The resultsare classed as tentative.
The solubility shows a minimum in the temperature range. The valueswere fitted to a three constant equation by a linear regression to obtain
with a standard error about the regression line of 1.26 x 10- 5 •
Values of the thermodynamic changes for the transfer of methane fromthe gas phase at 101.325 kPa to the infinitely dilute solution at severaltemperatures are as follows:
Smoothed values of the solubility of methane and the partial molal Gibbsenergy as a function of temperature are given in Table 5. The temperatureof minimum solubility is 391 K.
Table 5. Tentative values of the solubility of methane inl-methylnaphthalene. Mole fraction solubility of 101.325 kPa(1 atm) methane partial pressure and partial molal Gibbs energyas a function of temperature.
Lenoir, Renault, and Renon (ref. 5) report solubility values at twotemperatures of 298.2 and 323.2 K. The values are classed as tentative,but there is some concern regarding the results because of the largemagnitude of the enthalpy of solution relative to similar solvents.
The solubility data are reproduced by the equation
ln Xl = -8.7721 + 8.7034/(T/100 K)
which gives temperature independent thermodynamic changes for thetransfer of methane from the gas at 101.325 kPa to the infinitely dilutesolution of
and
The values are of larger magnitude than normally observed for eitheralkane or arene solvents.
Smoothed values of solubility and partial molal Gibbs energy ofsolution are given in Table 6.
Table 6. Tentative values of the solubility of methane in decahydronaphthalene or decalin. Mole fraction solubility at 101.325 kPamethane partial pressure and partial molal Gibbs energy ofsolution as a function of temperature.
References
T/K
298.15
303.15313.15323.15
Mol Fraction
2.87
2.742.502.29
AGj/kJ mol- 1
14.513
14.87715.60716.336
1. McDaniel, A. S. J. Phys. Chem. 1911, 15, 587.
2. Horiuti, J. Sai. Pap. Inst. Phys. Chem. Ees. (JPN)~ 1931/32, 17, 125.
3. Lannung, A.; Gjaldbaek, J. C. Aata Chem. Saand. 1960, 14, 1124.
4. Hayduk, W.; Buckley, W. D. Can. J. Chem. Eng. 1971, 49, 667.
5. Lenoir, J-Y.; Renault, P.; Renon, H. J. Chem. Eng. Lata~ 1971, 16, 340.
6. Cukor, P. M.; Prausnitz, J. M. J. Phys. Chem. 1972, 76, 598.
7. Field, L. R.; Wilhelm, E.; Battino, R. J. Chem. Thermodyn. 1974,6, 237.
8. Chappelow, C. C.; Prausnitz, J. M. Am. Inst. Chem. Engnrs. J. 1974,20, 1097.
9. Byrne, J. E.; Battino, R.; Wilhelm, E. J. Chem. Thermodyn. 1975,7, 515.
498 Arenes: Pressure up to 0.2 MPa
COMPONENTS:(1) Methane: CH4 : [74-82-8]
(2) Benzene: C6H6 : [71-43-2]
ORIGINAL MEASUREMENTS:McDaniel, A. S.
J. Phys. Chern. 1911, 15, 587-610.
VARIABLES: PREPARED BY:T/K = 295.25 - 323.05 H. L. Clever
Pl/kPa = 101.3 (1 atm)
EXPERIMENTAL VALUES:
Temperature Mol Fraction Bunsen a Ostwald bCoefficient Coefficient
bListed as absorption coefficient in the original paper.Interpreted to be equivalent to Ostwald coefficient by compiler.
COstwald coefficient (absorption coefficient) estimated as298.15 K value by author.
dMole fraction and Bunsen coefficient values calculated bycompiler assuming ideal gas behavior.
EVALUATOR'S COMMENT: MCDaniel's data should be used with caution.His values are often 20 percent or more too small when comparedwith more reliable data.
AUXILIARY INFORMATION
METHOD/APPARATUS/PROCEDURE:The apparatus is all glass. It consists of a gas buret connected to acontacting vessel. The solvent isdegassed by boiling under reducedpressure. Gas pressure or volume isadjusted using mercury displacement.Equilibration is achieved at atmpressure by hand shaking, and incrementally adding gas to the contactingchamber. Solubility measured byobtaining total uptake of gas byknown volume of the solvent.
SOURCE AND PURITY OF MATERIALS:(1) Methane. Prepared by reaction
of methyl iodide with zinccopper. Passed through waterand sulfuric acid.
The mole fraction and Bunsen coefficient values were calculated by the compiler with the assumption the gas is ideal and that Henry's law is obeyed.
Smoothed Data: For use between 286.25 and 333.15 K.
1n :1:1 = -6.6908 + 1.5351/(T/100K)
The standard error about the regression line is 6.44 x 10- 6 •
T/K Mol Fraction10 3 :1:1
288.15298.15308.15318.15328.15
2.1162.0792.0442.0131. 983
AUXILIARY INFORMATION
METHOD/APPARATUS/PROCEDURE:The apparatus consists of a gas buret,a solvent reservoir, and an absorption pipet. The volume of the pipetis determined at various meniscusheights by weighing a quantity ofwater. The meniscus height is readwith a cathetometer.
The dry gas is introduced into thedegassed solvent. The gas and solventare mixed with a magnetic stirreruntil saturation. Care is taken toprevent solvent vapor from mixingwith the solute gas in the gas buret.The volume of gas is determined fromthe gas buret readings, the volumeof solvent is determined from themeniscus height in the absorptionpipet.
SOURCE AND PURITY OF MATERIALS:(1) Methane. Aluminum carbide was
prepared from aluminum and sootcarbon. The aluminum carbide wastreated with hot water. The gasevolved was scrubbed to removeimpurities, dried and fractionated. Final product had adensity,p/g dm- 3 = 0.7168±0.0003at normal conditions.
(2) Benzene. Merck. Extra pure andfree of sulfur. Ref1uxed withsodium amalgam, distilled.Boiling point{760 mmHg) 80.18°C.
ESTIMATED ERROR:oT/K = 0.05
0:1: 1/:1: 1 = 0.01
REFERENCES:
500 Arenes: Pressure up to 0.2 MPa
COMPONENTS:(1) Methane; CH4 ; [74-82-8]
(2) Benzene; C6H6; [71-43-2]
VARIABLES:T/K = 291.15 - 310.15
P1/kPa = 101.325 (1 atm)
ORIGINAL MEASUREMENTS:Lannung, A.; Gjaldbaek, J. C.
Aota Chem. Soand. 1960, 14,1124 - 1128.
PREPARED BY:
J. Chr. Gja1dbaek
EXPERIMENTAL VALUES:T/K
291.15291.15298.15298.15310.15310.15
Mol Fraction
10 3 x1
2.132.112.092.092.052.08
BunsenCoefficient
a/cm 3 (STP)cm- 3 atm- 1
0.5370.5330.5230.5230.5060.514
OstwaldCoefficient
L/cm 3 cm- 3
0.5720.5680.5710.5710.5740.584
Smoothed Data: For use between 291.15 and 310.15 K.
1n Xl = -6.5770 + 1.2198/{T/100 K)The standard error about the regression line is 1.37 x 10- 5
•
T/K Mol Fraction
10 3 x1
298.15 2.095308.15 2.07
AUXILIARY INFORMATION
METHOD/APPARATUS/PROCEDURE:A calibrated all-glass combinedmanometer and bulb containingdegassed solvent and the gas wasplaced in an air thermostat andshaken until equilibrium (1).
The absorbed volume of gas iscalculated from the initial andfinal amounts, both saturated withsolvent vapor. The amount ofsolvent is determined by the weightof displaced mercury.
The values are at 101.325 kPa(1 atm) pressure assuming Henry'slaw is obeyed.
SOURCE AND PURITY OF MATERIALS:(1) Methane. Generated from
magnesium methyl iodide.Purified by fractional distillation. Specific gravitycorresponds with mol wt 16.08.
3Calculated by compiler from the following equation:
~Go/J mol- 1 = -RT In Xl
AUXILIARY INFORMATION
HETHOD/APPARATUS/PROCEDURE:
A volumetric method using a glassapparatus was employed. Degassedsolvent contacted the gas whileflowing as a thin film, at aconstant rate, through an absorptionspiral into a solution buret. Aconstant solvent flow was obtainedby means of a calibrated syringepump. The solution at the end ofthe spiral was considered saturated.Dry gas was maintained at atmospheric pressure in a gas buret bymechanically raising the mercurylevel in the buret at an adjustablerate. The solubility was calculatedfrom the constant slope of volumeof gas dissolved and volume ofsolvent injected.
Degassing was accomplished using atwo stage vacuum process describedby Clever et ale (1).
SOURCE AND PURITY OF MATERIALS:
1. Matheson Co. Specified asultra high purity grade of99.97 per cent.
2. Canlab. Chromatoquality gradeof specified minimum purity of99.0 per cent.
a Bunsen coefficient, ex/cm 3 (STP) cm- 3 atm- I •
b Listed as absorption coefficient in the original paper.Interpreted to be equivalent to Ostwald coefficient by compiler.
c Ostwald coefficient (absorption coefficient) estimated as298.15 K value by author.
d Mole fraction and Bunsen coefficient values calculated bycompiler assuming ideal gas behavior.
EVALUATOR'S COMMENT: MCDaniel's data should be used with caution.His values are often 20 percent or more too small when comparedwith more reliable data.
AUXILIARY INFORMATION
HETHOD/APPARATUS/PROCEDURE:
The apparatus is all glass. It consists of a gas buret connected to acontacting vessel. The solvent isdegassed by boiling under reducedpressure. Gas pressure or volume isadjusted using mercury displacement.Equilibration is achieved at atmpressure by hand shaking, and incrementally adding gas to the contactingchamber. Solubility measured byobtaining total uptake of gas by know~
volume of the solvent.
SOURCE AND PURITY OF MATERIALS:
(1) Methane. Prepared by reactionof methyl iodide with zinccopper. Passed through waterand sulfuric acid.
(2) Methylbenzene.
ESTIMATED ERROR:
is L/L > -0.20
REFERENCES:
Arenes: Pressure up to 0.2 MPa 503
COMPONENTS:(1) Methane; CH4 ; [74-82-8]
(2) Methy1benzene or toluene; C7H8 ;[108-88-3]
ORIGINAL MEASUREMENTS:Field, L. R.; Wilhelm, E.;Battino, R.
J. Chem. Thermodyn. 1974, 6,237 - 243.
VARIABLES:T/K:
P/kPa:284.28 - 313.17101.325 (1 atm)
PREPARED BY:H. L. Clever
EXPERIMENTAL VALUES:T/K Mol Fraction
10 3 z1
284.28297.80313.17
2.6562.2402.240
BunsenCoefficient
a/cm 3 (STP)cm- 3 atm- 1
0.5670.5070.464
OstwaldCoefficient
L/cm 3 cm- 3
0.58990.55340.5315
The gas solubility values were adjusted to an oxygen partial pressure of101.325 kPa (1 atm) by Henry's law.
The Bunsen coefficients were calculated by the compiler.
Smoothed Data: For use between 284.15 and 313.17 K.
ln zl = -7.7969 + 5.2214/(T/100 K)
The standard error about the regression line is 1.66 x 10- 4 •
T/K
283.15293.15
298.15
303.15313.15
Mol Fraction10 3 z
1
2.602.44
2.372.302.18
AUXILIARY INFORMATION
METHOD/APPARATUS/PROCEDURE:The solubility apparatus is based onthe design of Morrison and Billett(1) and the version used is describedby Battino, Evans, and Danforth (2).The degassing apparatus is thatdescribed by Battino, Banzhof, Bogan,and Wilhelm (3).
Degassing. up to 500 cm 3 of solventis placed in a flask of such sizethat the liquid is about 4 cm deep.The liquid is rapidly stirred, andvacuum is applied intermittentlythrough a liquid N2 trap until thepermanent gas residual pressuredrops to 5 microns.
SolUbility Determination. The degassed solvent is passed in a thinfilm down a glass spiral tube containing solute gas plus the solventvapor at a total pressure of one atm.The volume of gas absorbed is foundby difference between the initial andfinal volumes in the buret system.The solvent is collected in a taredflask and weighed.
M-Q'
SOURCE AND PURITY OF MATERIALS:(1) Methane. Either Matheson Co.,
Inc. or Air Products andChemicals, Inc. Purest gradeavailable, minimum purity greaterthan 99 mole per cent.
(2) Methy1benzene. PhillipsPetroleum. Pure Grade.Distilled.
ESTIMATED ERROR:oT/K = 0.03
oP/mmHg = 0.5ox
1/x
1= 0.005
REFERENCES:1. Morrison, T. J.; Billett, F.
J. Chern. Soc. 1948, 2033.2. Battino, R.; Evans, F. D.;
Danforth, W. F. J. Arn. OilChern. Soc. 1968, 45, 830.
(2) 1,2-Dimethy1benzene or o-xy1ene;CSH10 ; [95-47-6]
ORIGINAL MEASUREMENTS:Byrne, J. E.; Battino, R.;Wilhelm, E.
J. Chem. Thermodyn. 1975, 7, 515-522.
VARIABLES:T/K:
Pl/kPa:283.24 - 313.17101.325 (1 atm)
PREPARED BY:H. L. CleverA. L. Cramer
EXPERIMENTAL VALUES:T/K
283.24283.40
298.16
313.08313.17
Mol Fraction
10 3 x1
2.6672.651
2.507
2.3962.390
BunsenCoefficient
a/cm3 (STP)cm- 3 atm- 1
0.50160.4985
0.4647
0.43780.4367
OstwaldCoefficientL/cm3 cm- 3
0.52010.5172
0.5073
0.50180.5007
The Bunsen coefficients were calculated by the compiler. The solubilityvalues were adjusted to a methane partial pressure of 101.325 kPa (1 atm)by Henry's law.
Smoothed Data: For use between 283.15 and 313.17 K.
1n xl = -7.0387 + 3.1398/(T/100 K)
The standard error about the regression line is 7.91 x 10- 6 •
TIK Mol Fractionl03 xl
283.15293.15
298.15
303.15313.15
2.6592.560
2.515
2.4712.391
AUXILIARY INFORMATION
0.030.50.005
REFERENCES:
Morrison, T. J.; Billett, F.J. Chem. Soa. 1945, 2033.
2. Battino, R.; Evans, F. D.;Danforth, W. F. J. Am. OiZChem. Soa. 1968, 45, 830.
SolUbility Determination. The degassed solvent is passed in a thinfilm down a glass helical tube containing solute gas plus the solventvapor at a total pressure of oneatm. The volume of gas absorbed isfound by difference between theinitial and final volumes in theburet system. The solvent is collected in a tared flask and weighed.
METHOD/APPARATUS/PROCEDURE: SOURCE AND PURITY OF MATERIALS:The solubility apparatus is based on (1) Methane. Either Air Products &the design of Morrison and Billett Chemicals, Inc., or Matheson Co.,(1) and the version used is described Inc. 99 mol per cent or better.by Battino, Evans, and Danforth (2). (2) 1,2-Dimethylbenzene. PhillipsThe degassing apparatus is thatdescribed by Battino, Banzhof, Bogan,~~~p~e~t~r~o~l~e~u~m~c~o~.__~p~u~r~e~g~r~a~d~e~.~-- ~and Wilhelm (3). ESTIMATED ERROR:
e5 T/K =Degassing. Up to 500 cm 3 of solvent oP/mmHg =is placed in a flask of such size e5x
l/x
l=
that the liquid is about 4 cm deep.The liquid is rapidly stirred, andvacuum is intermittently appliedthrough a liquid N2 trap until thepermanent gas residual pressure dropsto 5 microns. 1.
b Listed as absorption coefficient in the original paper.Interpreted to be equivalent to Ostwald coefficient by compiler.
c Ostwald coefficient (absorption coefficient) estimated as298.15 K value by author.
d Mole fraction and Bunsen coefficient values calculated bycompiler assuming ideal gas behavior.
EVALUATOR'S COMMENT: McDaniel's data should be used with caution.His values are often 20 percent or more too small when comparedwith more reliable data.
AUXILIARY INFORMATION
HETHOD/APPARATUS/PROCEDURE:
The apparatus is all glass. It consists of a gas buret connected to acontacting vessel. The solvent isdegassed by boiling under reducedpressure. Gas pressure or volume isadjusted using mercury displacement.Equilibration is achieved at atmpressure by hand shaking, and incrementally adding gas to the contactingchamber. Solubility measured byobtaining total uptake of gas byknown volume of the solvent.
SOURCE AND PURITY OF MATERIALS:(1) Methane. Prepared by reaction
of methyl iodide with zinccopper. Passed through waterand sulfuric acid.
(2) 1,3-Dirnethylbenzene.
ESTIMATED ERROR:
/) L/L > -0.20
REFERENCES:
506 Arenes: Pressure up to 0.2 MPa
COMPONENTS:
(1) Methane; CH4 ; [74-82-8J
(2) 1,3-Dimethylbenzene or rn-xylene;C
8HlO ; [108-38-3]
VARIABLES:
ORIGINAL MEASUREMENTS:
Byrne, J. E.; Battino, R.;Wilhelm, E.
J. Chern. Therrnodyn. 1975, 7, 515-522.
PREPARED BY:283.13 - 313.21101.325 (1 atm)
H. L. CleverA. L. Cramer
EXPERIMENTAL VALUES:T/K
283.13283.21
298.09298.17
313.14313.14313.21
Mol Fraction103x
1
2.8852.891
2.7092.713
2.5562.5842.569
BunsenCoefficient
a/cm 3 (STP)cm- 3 atm- 1
0.53300.5341
0.49280.4935
0.45810.46310.4603
OstwaldCoefficient
L/cm 3 cm- 3
0.55250.5538
0.53780.5387
0.52520.53090.5278
The Bunsen coefficients were calculated by the compiler. The solubilityvalues were adjusted to a methane partial pressure of 101.325 kPa (1 atm)by Henry's law.
Smoothed Data: For use between 283.15 and 313.21 K.
In Xl ::: -7.0654 + 3.4476/(T/IOO K)
The standard error about the regression line is 9.72 x 10- 6 •
T/K Mol Fraction103x
1
283.15293.15
298.15
303.15313.15
2.8862.769
2.715
2.6632.568
REFERENCES:
1. Morrison, T. J.; Billett, F.J. Chern. Soc. 1948, 2033.
2. Battino, R.; Evans, F. D.;Danforth, W. F. J. Arn. OiZChern. Soc. 1968, 45, 830.
METHOD/APPARATUS/PROCEDURE: SOURCE AND PURITY OF MATERIALS:The solubility apparatus is based on (1) Methane. Either Air Products &the design of Morrison and Billett Chemicals, Inc., or Matheson Co.,(1) and the version used is described Inc. 99 mol per cent or better.by Battino, Evans, and Danforth (2). (2) 1,3-Dimethylbenzene. PhillipsThe degassing apparatus is that Petroleum Co. Pure grade.described by Battino, Banzhof, Bogan,I-E~S=T=I~MA~T=E=D~E~R~R~O~R~:~~~~~~~~------4and Wilhelm (3). oT/K::: 0.03Degassing. Up to 500 cm 3 of solvent oP/mmHg::: 0.5is placed in a flask of such size ox
1/x
1::: 0.005
that the liquid is about 4 cm deep.The liquid is rapidly stirred, andvacuum is applied intermittentlythrough a liquid N2 trap until thepermanent gas residual pressure dropsto 5 microns.
Solubility Determination. The degassed solvent is passed in a thinfilm down a glass helical tube containing solute gas plus the solventvapor at a total pressure of one atm.The volume of gas absorbed is foundby difference between the initial andfinal volumes in the buret system.The solvent is collected in a taredflask and weighed.
Arenes: Pressure up to 0.2 MPa 507
COMPONENTS:(1) Methane; CH
4; [74-82-8]
ORIGINAL MEASUREMENTS:Byrne, J. E.; Battino, R.;Wilhelm, E.
(2) 1,4-Dimethylbenzene or p-xylene;C8HIO ; [106-42-3] J. Chem. The'I'modyn. 1975, 7, 515-522.
The Bunsen coefficients were calculated by the compiler. The solubilityvalues were adjusted to a methane partial pressure of 101.325 kPa (1 atm)by Henry's law.
Smoothed Data: For use between 287.94 and 313.18 K.
ln xl = -7.2073 + 4.0158/(T/IOO K)
The standard error about the regression line is 1.82 x 10- 5 •
TIK Mol Fraction103 x
1
293.15
298.15
303.15313.15
2.916
2.850
2.7882.672
REFERENCES:
1. Morrison, T. J.; Billett, F.J. Chem. Soc. 1948, 2033.
2. Battino, R.; Evans, F. D.;Danforth, W. F. J. Am. Oi~
Chem. Soc. 1968, 45, 830.3. Battino, R.; Banzhof, M.;
Bogan, M.i Wilhelm, E.Ana~. Chem. 1971, 43, 806.
AUXILIARY INFORMATION
METHOD/APPARATUS/PROCEDURE: SOURCE AND PURITY OF MATERIALS:The solubility apparatus is based on (1) Methane. Either Air Products &the design of Morrison and Billett Chemicals, Inc., or Matheson Co.,(1) and the version used is described Inc. 99 mol per cent or better.by Battino, Evans, and Danforth (2).The degassing apparatus is that (2) 1,4-Dimethylbenzene. Phillipsdescribed by Battino, Banzhof, Bogan, Petroleum Co. Pure grade. Used
as received.and Wilhelm (3). t-;:;-ES=T~IMA~T~E;:;'D~E;:;'R;:;'R::::O;::;'R~:-----------1Degassing. Up to 500 cm 3 of solvent oT/K = 0.01is placed in a flask of such size op/mmHg = 0.5that the liquid is about 4 cm deep. o xl/xl = 0.005The liquid is rapidly stirred, andvacuum is intermittently appliedthrough a liquid N2 trap until thepermanent gas residual pressure dropsto 5 microns.
solubility Determination. The degassed solvent is passed in a thinfilm down a glass helical tube containing solute gas plus the solventvapor at a total pressure of one atm.The volume of gas absorbed is foundby difference between the initial andfinal volumes in the buret system.The solvent is collected in a taredflask and weighed.
508 Arenes: Pressure up to 0.2 MPa
COMPONENTS:
1. Methane; CH4; [74-82-8]
2. 1-l1ethylnaphthalene; CIIHIO;[1321-94-4]
VARIABLES:
Temperature
ORIGINAL MEASUREMENTS:
Chappelow, C.C.; Prausnitz, J.M.
Am. Inst. Chem. Engnrs. J. 1974,20, 1097-1104.
PREPARED BY:
C.L. Young
EXPERIMENTAL VALUES:
T/K
300
325
350
375
400
425
450
475
Henry's Constanta Mole fractionb of/atm methane at 1 atm. partial
pressure, xCH4
644 0.00155
676 0.00148
705 0.00142
728 0.00137
740 0.00135
738 0.00136
719 0.00139
680 0.00147
a. Authors stated measurements were made at several pressuresand values of solubility used were all within the Henry'sLaw region.
b. Calculated by compiler assuming linear relationship betweenmole fraction and pressure.
AUXILIARY INFORMATION
METHOD/APPARATUS/PROCEDURE:
Volumetric apparatus similar to thatdescribed by Dymond and Hildebrand(I). Pressure measured with a nulldetector and precision gauge. Detailsin ref. (2).
a. Quoted in supplementary material for original paper
b. Calculated by compiler for a partial pressure of 1 atmosphere
AUXILIARY INFORMATION
METHOD/APPARATUS/PROCEDURE:
Volumetric apparatus similar tothat described by Dymond andHildebrand (1). Pressuremeasured with a null detector andprecision gauge. Details in ref.(2) •
* Calculated by compiler assuming a linear function of PCH4
VS xCH4 'i.e., xCH (l atm) = l/HCH •
4 4
AUXILIARY INFORMATION
METHOD/APPARATUS/PROCEDURE:A conventional gas-liquid chromatographic unit fitted with a thermalconductivity detector was used. Thecarrier gas was helium. The value ofHenry's law constant was calculatedfrom the retention time. The valueapplies to very low partial pressuresof gas and there may be a substantialdifference from that measured at1 atm. pressure. There is alsoconsiderable uncertainty in the valueof Henry's constant since surfaceadsorption was not allowed foralthough its possible existence wasnoted.
SOURCE AND PURITY OF MATERIALS:(1) L'Air Liquide sample, minimumpurity 99.9 mole per cent.
(2) Touzart and Matignon orSerlabo sample, purity 99 mole percent.
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