Abstract
Thermodynamic characteristics are determined for supersaturated (8÷28m) aqueous ammonium chloride solutions at 298.15 K: activity as well as partial molar enthalpy, volume, and excess entropy of water, osmotic coefficients, density, and salt hydration numbers. The relative humidity above the solution decreases from 75.6% (8m solution) to 44.7% (28m solution). A directly proportional dependence is found between the enthalpy and entropy characteristics. The negative values of the nonideal portion of the Gibbs energy are due to structural effects (excess entropy). The excess entropy of water has the same value 1.8 J/(mol·K) in supersaturated 12m NaCl and 28m NH4Cl. The ratio 12/28 = 3/7 is also valid for other “isoentropic” molalities of the said salts.
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References
Y. Marcus, J. Chem. Soc. Faraday Trans., 89, 713–718 (1993).
K. P. Mishchenko and A. A. Ravdel’ (eds.), Concise Handbook of Physicochemical Quantities, 4th ed. [in Russian], Khimiya, Leningrad (1965).
V. P. Korolev, G. I. Egorov, and G. A. Krestov, Zh. Fiz. Khim., 56, 437–439 (1982).
H. S. Frank and A. L. Robinson, J. Chem. Phys., 8, 933–938 (1940).
V. P. Korolev, J. Struct. Chem., 54, No. 4, 797–800 (2013).
Gy. Jákli, J. Chem. Thermodyn., 39, 1474–1483 (2007).
H. E. Wirth, J. Phys. Chem., 71, 2922–2929 (1967).
Y. Marcus, J. Sol. Chem., 23, 831–848 (1994).
M. V. Kaulgud and W. K. Pokale, J. Chem. Soc. Faraday Trans., 91, 999–1004 (1995).
K. Fajans and O. Johnson, J. Am. Chem. Soc., 64, 668–678 (1942).
K. P. Mishchenko and G. M. Poltoratskii, Aspects of the Thermodynamics and Structure of Aqueous and Non-Aqueous Electrolyte Solutions [in Russian], Khimiya, Leningrad (1968).
S. L. Clegg and A. S. Wexler, J. Phys. Chem. A, 115, 3393–3460 (2011).
D. W. Hu, J. M. Chen, X. N. Ye, et al., Atmos. Environ., 45, 2349–2355 (2011).
V. P. Korolev, J. Struct. Chem., 55, No. 3, 463–469 (2014).
J. N. Pearce and G. G. Pumplin, J. Am. Chem. Soc., 59, 1219/1220 (1937).
E. M. Kuznetsova, Zh. Fiz. Khim., 67, 1765–1775 (1993).
W. E. Thiessen and J. M. Simonson, J. Phys. Chem., 94, 7794–7800 (1990).
O. Redlich and P. Rosenfeld, Z. Electrochem., 37, 705–711 (1931).
O. Redlich and P. Rosenfeld, Z. Phys. Chem. A, 155, 65–74 (1931).
D. G. Archer and P. M. Wang, J. Phys. Chem. Ref. Data, 19, 371–411 (1990).
V. P. Korolev, J. Struct. Chem., 54, No. 3, 534–540 (2013).
P. A. M. Walker, D. G. Lawrence, and G. W. Neilson, J. Chem. Soc. Faraday Trans. I, 85, 1365–1372 (1989).
L. Degréve and F. L. B. da Silva, J. Chem. Phys., 110, 3070–3078 (1999).
D. S. Viera and L. Degréve, J. Mol. Struct.: Theochem., 580, 127–135 (2002).
I. J. Zsigrai, R. M. Nicolić, and I. J. Gal, J. Chem. Soc. Dalton Trans., 879–883 (1976).
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Original Russian Text © 2014 V. P. Korolev.
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Translated from Zhurnal Strukturnoi Khimii, Vol. 55, No. 4, pp. 695–699, July–August, 2014.
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Korolev, V.P. H2O-NH4Cl system: Thermodynamics and structure of supersaturated (8÷28m) solutions at 298.15 K. J Struct Chem 55, 660–665 (2014). https://doi.org/10.1134/S0022476614040106
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DOI: https://doi.org/10.1134/S0022476614040106