Compilation - Carbon dioxide with Ammonium chloride and Water (IUPAC SDS Volume 62)

SDS Volume (2833)

Volume 62. Carbon Dioxide in Water and Aqueous Electrolyte Solutions, p None

Original Measurements

Rumpf, B.; Nicolaisen, H.; Maurer, G.; Ber. Bunsenges. Phys. Chem. 1994, 98, 1077-81.

Variables:

Room Temp: 313.14 - 433.10 $\pu{K}$
Pressure: 0.482 - 9.692 $\pu{MPa}$
Molality (2): m2/mol kg-1 = near 4.00 and 6.00 mol/kg

Prepared by:

P. Scharlin

Method/Apparatus/Procedure:

The experimental equipment has been described in [1]. It consists of a high pressure optical cell, thermostat, magnetic stirrer, thermocouples, and $\ce{Pt}$ resistance thermometer, pressure transducers and tanks for aqueous solutions, rinse water and solute gas.
The thermostated about 30 mL high pressure optical cell is filled with carbon dioxide. Pressure and temperature of the gas are measured after equilibration. A known amount of aqueous solvent is added which is slightly greater than that needed to completely dissolve the gas. The pressure in the cell is reduced stepwise by removing very small amounts of the liquid until the first stable bubble appears.
The mass of carbon dioxide is calculated from the Bender equation (3). The volume of the cell is known within 0.06 mL. The solvent density is from the literature.

Source and Purity of Materials:
  1. Carbon dioxide. Messer Griesheim, Ludwigshafen, > 99.995 mol%, used as received.
  2. Ammonium chloride. Riedel de Haen AG, Seelze, > 99.5 mass%. Degassed and dried under vacuum.
  3. Water. Deionized and degassed by vacuum distillation.
Estimated Errors:

Ambient temperature: δT/K = ±0.1
Pressure: δp/p < ±0.04 (at p up to 6 Mpa)
δp/p < ±0.05 (at higher pressure)

References

1 Rumpf, B.; Maurer, G.; Ber. Bunsenges. Phys. Chem. 1993, 97, 85-97.
2 Rumpf, B.; Nicolaisen, H.; Öcal, C.; Maurer, G.; J. Solution Chem. 1994, 23, 431-48.
3 Bender, E.; 5th Proc. Symp. Thermophys. Prop., ASME, NY, 1970, 227-35.

Components:
  1. Carbon dioxide, $\ce{ CO2 }$; [124-38-9] NIST WebBook
  2. Ammonium chloride, $\ce{ NH4Cl }$; [12125-02-9] NIST WebBook
  3. Water, $\ce{ H2O }$; [7732-18-5] NIST WebBook
Experimental Data

The authors used Pitzer's semiempirical model to correlate the data. The model has been described in detail in Ref. 1. The dissociation of CO2 can be neglected at the concentrations here. The system was treated as containing a non-dissociating gas, G and a completely dissociating electrolyte, MX. A temperature dependent interaction parameter, B°CO2, NH4Cl, and a temperature independent interaction parameter, ΓCO2, NH4Cl, NH4Cl, were derived from the experimental data.

For the CO2 + NH4Cl + H2O system the values are:
B°CO2, NH4Cl = 0.2834 - 123.27(T/K)-1 + 1551.29(T/K)-2 + 3543·103(T/K)-3
and ΓCO2, NH4Cl, NH4Cl = - 0.0010.

The interaction parameters were also predicted from earlier measurements on the solubility of CO2 in aqueous solutions of Na2SO4, (NH4)2SO4 (Ref 1.) and NaCl (Ref. 2). The predicted values are:

B°CO2, NH4Cl = 0.4206 - 187.48(T/K)-1 + 691.287(T/K)-2 + 6312 · 103(T/K)-3
and ΓCO2, NH4Cl, NH4Cl = - 0.0035.

Solubility of carbon dioxide in aqueous ammonium chloride. (m2 = 3.994 mol/kg)
$T$ ($\pu{K}$) m1 (mol/kg) $P$ ($\pu{MPa}$)
313.33 0.09800.482
313.22 0.23581.157
313.21 0.50862.648
313.21 0.76004.320
313.22 0.90505.523
313.21 1.07447.354
313.33 1.15198.823
333.12 0.09730.689
333.10 0.29182.173
333.11 0.48783.897
333.11 0.49063.920
333.11 0.68795.997
333.08 0.88568.803
353.13 0.00.0426
353.08 0.09951.018
353.10 0.25022.504
353.11 0.50345.547
353.13 0.75839.692
393.00 0.00.173
393.09 0.12731.970
393.07 0.22753.433
393.13 0.40646.487
393.12 0.51128.458
413.05 0.00.314
413.09 0.10051.921
413.06 0.25254.413
413.05 0.40367.276
413.08 0.50469.276
433.08 0.00.537
433.07 0.09982.137
433.07 0.09992.212
433.04 0.25104.937
433.10 0.34986.676
433.08 0.45168.792

(a) m2 = molality of NH4Cl

(b) m1 = solubility of CO2

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