Некоторые аспекты термодинамики ионного обмена
Ключевые слова:
ионный обмен, термодинамика, константа равновесия, термодинамические функции.
Аннотация
Обсуждаются вопросы терминологии, используемой и рекомендуемой в области
термодинамики ионного обмена. Обращается внимание на важность обоснованного выбора
концентрационных шкал при определении термодинамических характеристик. Разбираются причины,
по которым коэффициенты селективности, выраженные через эквивалентные доли ионов, не относят
к термодинамическим характеристикам. Анализируются проблемы, возникающие при определении
коэффициентов активности обменивающихся компонентов в ионите, термодинамической константы
равновесия и термодинамических функций реакции ионного обмена. Также уделено внимание
анализу тех выводов, которые обычно делают из рассчитанных термодинамических функций
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Литература
1.Lopatkin A.A. Dialog fizikokhimika i
khromatografista o termodinamike [The
dialogue between the physicist and
chromatographica about thermodynamics],
Иванов и др. / Сорбционные и хроматографические процессы. 2015. Т. 15. Вып. 1
33
Ross. khim. Zhurn, 1997, V. 41, No 3,
pp. 85-95 [in Russian].
2.Soldatov V.S. Prostye ionoobmennye
ravnovesiya [Simple ion-exchange equilibrium].
Minsk: Nauka i tekhnika Publ., 1972, 224 p. [in
Russian]
3.Soldatov V.S., Bychkova V.A. Ionnyi
obmen v mnogokomonentnykh sistemakh (Ion
exchange equilibria in multicomponent
systems). Minsk: Nauka i tekhnika Publ., 1988,
359 p. [in Russian]
4.Kokotov Yu.A., Pasechnik V.A.
Ravnovesie i kinetika ionnogo obmena,
Leningrad: Khimiya Publ. 1970l 336 p. [in
Russian]
5.Sposito G. The thermodynamics of soil
solutions. Clarendone press: Oxfordl 1981l 223
p.
6.Ionnyi obmen v khimicheskoi tekhnologii
(Ion exchange in chemical technology). Pod.
Red. B.P. Nikol'skogo. Leningrad: Khimiya
Publ. 1982, 416 p.[in Russian]
7.Kokotov Yu.A., Zolotarev P.P., El'kin G.E.
Teoreticheskie osnovy ionnogo obmena
(Theoretical bases of ion exchange). Leningrad:
Khimiya Publ., 1986, 270 p. [in Russian]
8.Soldatov V.S. 6. Theory of Ion Exchange.
6.1. Thermodynamics, In: Ion
Exchangers.(Konrad Dorfner, Ed.). Berlin, New
York: De Gruyter, 1992, pp. 1243-1275.
9.Grant S.A., Fletcher P. Thermodynamics of
cation exchange. In: Ion Exchange and Solvent
Extraction. A Series of Advances. J.A.
Marinsky and Y. Marcus Eds. V. 11. Marcel
Dekker, New York, 1993, pp. 1-108.
10. Hoell W., Franzreb M.Z., Horst J.,
Eberle S.H. Description of ion-exchange
equilibria by means of the surface complexation
theory, In: Ion Exchange and Solvent
Extraction. A Series of Advances. J.A.
Marinsky and Y. Marcus Eds., V. 11, Marcel
Dekker, New York. 1993, pp. 151-236.
11. Marinsky J.A. A Gibbs-Donnan-based
analysis of ion exchange and related
phenomena., In: Ion Exchange and Solvent
Extraction. A Series of Advances. J.A.
Marinsky and Y. Marcus Eds. Vol. 11. Marcel
Dekker, New York, 1993, pp. 237-334.
12. Reshenie I Vsesoyuznogo simpoziuma
po termodinamike ionnogo obmena (The
decision of the first all-Union Symposium on
the thermodynamics of ion exchange), Zhurn.
fiz. Khimii, 1967, V. 41, No 4, pp. 942-944. [in
Russian]
13. IUPAC. Analytical Chemistry Division.
Comission on Analytical Nomenclature.
Recommendations on ion exchange
nomenclature (1972), Pure Appl. Chem., 1972,
V. 29, pp. 619-624.
14. IUPAC. Analytical Chemistry Division.
Commission on Chromatography and other
analytical separations. Commissions on
analytical nomenclature. Nomenclature for
Chromatography (1993), Pure Appl. Chem.
1993, V. 65, No. 4, pp. 819-874.
15. Harjula R., Lehto J. The international
workshop on uniform and reliable
nomenclature, formulations and
experimentation for ion exchange, Helsinki,
Finland, May 30-June1, 1994. // React. Func.
Polymers. 1995. V. 27. P. 147 – 153.
16. Harjula R., Lehto J. Memorandum of
the International Symposium on Unification
Ion-Exchange Nomenclature, Terms and
Experimental Methods, Russian Journal of
Physical Chemistry A. 1996. V. 70, No. 9,
pp. 1604-1606.
17. Tolmachev A.M., Gorshkov V.I.
Nekotorye voprosy termodinamiki ionnogo
obmena (Some questions of thermodynamics of
ion exchange), Zhurn. fiz. Khimii, 1966, V. 40,
No 8, pp. 1924-1928. [in Russian].
18. Vorontsova O.N. Izuchenie ravnovesiya
obmena ionov raznoi valentnosti na
sul'fokationitakh (The study of the equilibrium
exchange ions of different valency on the
sulfonic cation). Diss. … kand. khim. nauk
(PhD thesis). Moscow, Lomonosov Moscow
State University. 1965, 121 p. [in Russian]
19. Gaines G.L., Thomas H.C. Adsorption
studies on clay minerals. II. A formulation of
the thermodynamics of exchange adsorption, J.
Chem. Phys., 1953, V. 21, No 4, pp. 714-718.
20. Selemenev V.F., Slavinskaya G.V.,
Khokhlov V.Yu. Praktikum po ionnomu
obmenu: Uchebnoe posobie (Tutorial on ion
exchange: a Training manual). Voronezh:
Voronezh. State University Publ., 2004, 160 p.
[in Russian]
21. Ivanov V.A., Timofeevskaya V.D.,
Drozdova N.V., Gorshkov V.I. Effect of
temperature on the exchange equilibrium of ions
with different charges on insoluble cross-linked
polyelectrolytes: An experimental study,
Russian Journal of Physical Chemistry A, 2000.
V. 74, No. 4, pp. 641-645.
22. Ivanov V.A., Timofeevskaya V.D.,
Gorshkov V.I., Drozdova N.V. Determination
Иванов и др. / Сорбционные и хроматографические процессы. 2015. Т. 15. Вып. 1
34
of the thermodynamic functions for the
exchange of differently charged ions on
insoluble cross-linked polyelectrolytes, Russian
Journal of Physical Chemistry A, 2000, V. 74,
No. 4, P.812-815.
23. Ivanov V.A., Timofeevskaya V.D.,
Gorshkov V.I. Enthalpy of ion exchange
reaction on the cross-linked polyelectrolytes: a
theory, Russian Journal of Physical Chemistry.
2007, V. 74, No. 10, pp. 637-640.
24. Ivanov V.A., Gorshkov V.I., Gavlina
O.T., Ilyukhina E.A. The differential enthalpy
of ion exchange on selective ionites, Russian
Journal of Physical Chemistry, 2007, V. 81,
No. 10, pp. 1776-1780.
25. Vasil'ev V.P. Termodinamicheskie
svoistva rastvorov elektrolitov (Thermodynamic
properties of electrolyte solutions), Moscow:
Vyssh. Shkola Publ., 1982, 320 p. [in Russian]
26. Boyd G.E. Thermal effects in ionexchange
reactions with organic exchangers:
enthalpy and heat capacity changes, In: Ion
exchange in the process industries. Society of
Chemical Industry, London, 1970, pp. 261-269.
27. Ivanov V.A., Gorshkov V.I., Gavlina
O.T., Ilyukhina E.A. Effect of the temperature
on the thermodynamic characteristics of the ionexchange
separation of substances on ionites. //
Russian Journal of Physical Chemistry, 2006,
V. 81, No. 11., pp. 1826-1831.
28. Ivanov V.A., Gavlina O.T., Ilyukhina
E.A., Gorshkov V.I. The temperature
dependence of the exchange enthalpy of
calcium and sodium ions on polymethacrylic
and polyacrylic cationites, Russian Journal of
Physical Chemistry, 2007, V. 81, No. 11,
P, 1723-1727.
29. Hogfeldt E. A three parameter model
for summarizing data in ion exchange. // In: Ion
Exchange and Solvent Extraction. Vol. 11.
Dekker_ New York. 1993. P. 120 – 150.
30. Leites I.L. Vtoroi zakon i ego
dvenadtsat' zapovedei. Populyarnaya
termodinamika i khimicheskaya
energotekhnologiya (The second law and its
twelve commandments. Popular
thermodynamics and chemical energy
technologies). Moscow: Moscow State
University Publ., 2002, 176 p. [in Russian]
khromatografista o termodinamike [The
dialogue between the physicist and
chromatographica about thermodynamics],
Иванов и др. / Сорбционные и хроматографические процессы. 2015. Т. 15. Вып. 1
33
Ross. khim. Zhurn, 1997, V. 41, No 3,
pp. 85-95 [in Russian].
2.Soldatov V.S. Prostye ionoobmennye
ravnovesiya [Simple ion-exchange equilibrium].
Minsk: Nauka i tekhnika Publ., 1972, 224 p. [in
Russian]
3.Soldatov V.S., Bychkova V.A. Ionnyi
obmen v mnogokomonentnykh sistemakh (Ion
exchange equilibria in multicomponent
systems). Minsk: Nauka i tekhnika Publ., 1988,
359 p. [in Russian]
4.Kokotov Yu.A., Pasechnik V.A.
Ravnovesie i kinetika ionnogo obmena,
Leningrad: Khimiya Publ. 1970l 336 p. [in
Russian]
5.Sposito G. The thermodynamics of soil
solutions. Clarendone press: Oxfordl 1981l 223
p.
6.Ionnyi obmen v khimicheskoi tekhnologii
(Ion exchange in chemical technology). Pod.
Red. B.P. Nikol'skogo. Leningrad: Khimiya
Publ. 1982, 416 p.[in Russian]
7.Kokotov Yu.A., Zolotarev P.P., El'kin G.E.
Teoreticheskie osnovy ionnogo obmena
(Theoretical bases of ion exchange). Leningrad:
Khimiya Publ., 1986, 270 p. [in Russian]
8.Soldatov V.S. 6. Theory of Ion Exchange.
6.1. Thermodynamics, In: Ion
Exchangers.(Konrad Dorfner, Ed.). Berlin, New
York: De Gruyter, 1992, pp. 1243-1275.
9.Grant S.A., Fletcher P. Thermodynamics of
cation exchange. In: Ion Exchange and Solvent
Extraction. A Series of Advances. J.A.
Marinsky and Y. Marcus Eds. V. 11. Marcel
Dekker, New York, 1993, pp. 1-108.
10. Hoell W., Franzreb M.Z., Horst J.,
Eberle S.H. Description of ion-exchange
equilibria by means of the surface complexation
theory, In: Ion Exchange and Solvent
Extraction. A Series of Advances. J.A.
Marinsky and Y. Marcus Eds., V. 11, Marcel
Dekker, New York. 1993, pp. 151-236.
11. Marinsky J.A. A Gibbs-Donnan-based
analysis of ion exchange and related
phenomena., In: Ion Exchange and Solvent
Extraction. A Series of Advances. J.A.
Marinsky and Y. Marcus Eds. Vol. 11. Marcel
Dekker, New York, 1993, pp. 237-334.
12. Reshenie I Vsesoyuznogo simpoziuma
po termodinamike ionnogo obmena (The
decision of the first all-Union Symposium on
the thermodynamics of ion exchange), Zhurn.
fiz. Khimii, 1967, V. 41, No 4, pp. 942-944. [in
Russian]
13. IUPAC. Analytical Chemistry Division.
Comission on Analytical Nomenclature.
Recommendations on ion exchange
nomenclature (1972), Pure Appl. Chem., 1972,
V. 29, pp. 619-624.
14. IUPAC. Analytical Chemistry Division.
Commission on Chromatography and other
analytical separations. Commissions on
analytical nomenclature. Nomenclature for
Chromatography (1993), Pure Appl. Chem.
1993, V. 65, No. 4, pp. 819-874.
15. Harjula R., Lehto J. The international
workshop on uniform and reliable
nomenclature, formulations and
experimentation for ion exchange, Helsinki,
Finland, May 30-June1, 1994. // React. Func.
Polymers. 1995. V. 27. P. 147 – 153.
16. Harjula R., Lehto J. Memorandum of
the International Symposium on Unification
Ion-Exchange Nomenclature, Terms and
Experimental Methods, Russian Journal of
Physical Chemistry A. 1996. V. 70, No. 9,
pp. 1604-1606.
17. Tolmachev A.M., Gorshkov V.I.
Nekotorye voprosy termodinamiki ionnogo
obmena (Some questions of thermodynamics of
ion exchange), Zhurn. fiz. Khimii, 1966, V. 40,
No 8, pp. 1924-1928. [in Russian].
18. Vorontsova O.N. Izuchenie ravnovesiya
obmena ionov raznoi valentnosti na
sul'fokationitakh (The study of the equilibrium
exchange ions of different valency on the
sulfonic cation). Diss. … kand. khim. nauk
(PhD thesis). Moscow, Lomonosov Moscow
State University. 1965, 121 p. [in Russian]
19. Gaines G.L., Thomas H.C. Adsorption
studies on clay minerals. II. A formulation of
the thermodynamics of exchange adsorption, J.
Chem. Phys., 1953, V. 21, No 4, pp. 714-718.
20. Selemenev V.F., Slavinskaya G.V.,
Khokhlov V.Yu. Praktikum po ionnomu
obmenu: Uchebnoe posobie (Tutorial on ion
exchange: a Training manual). Voronezh:
Voronezh. State University Publ., 2004, 160 p.
[in Russian]
21. Ivanov V.A., Timofeevskaya V.D.,
Drozdova N.V., Gorshkov V.I. Effect of
temperature on the exchange equilibrium of ions
with different charges on insoluble cross-linked
polyelectrolytes: An experimental study,
Russian Journal of Physical Chemistry A, 2000.
V. 74, No. 4, pp. 641-645.
22. Ivanov V.A., Timofeevskaya V.D.,
Gorshkov V.I., Drozdova N.V. Determination
Иванов и др. / Сорбционные и хроматографические процессы. 2015. Т. 15. Вып. 1
34
of the thermodynamic functions for the
exchange of differently charged ions on
insoluble cross-linked polyelectrolytes, Russian
Journal of Physical Chemistry A, 2000, V. 74,
No. 4, P.812-815.
23. Ivanov V.A., Timofeevskaya V.D.,
Gorshkov V.I. Enthalpy of ion exchange
reaction on the cross-linked polyelectrolytes: a
theory, Russian Journal of Physical Chemistry.
2007, V. 74, No. 10, pp. 637-640.
24. Ivanov V.A., Gorshkov V.I., Gavlina
O.T., Ilyukhina E.A. The differential enthalpy
of ion exchange on selective ionites, Russian
Journal of Physical Chemistry, 2007, V. 81,
No. 10, pp. 1776-1780.
25. Vasil'ev V.P. Termodinamicheskie
svoistva rastvorov elektrolitov (Thermodynamic
properties of electrolyte solutions), Moscow:
Vyssh. Shkola Publ., 1982, 320 p. [in Russian]
26. Boyd G.E. Thermal effects in ionexchange
reactions with organic exchangers:
enthalpy and heat capacity changes, In: Ion
exchange in the process industries. Society of
Chemical Industry, London, 1970, pp. 261-269.
27. Ivanov V.A., Gorshkov V.I., Gavlina
O.T., Ilyukhina E.A. Effect of the temperature
on the thermodynamic characteristics of the ionexchange
separation of substances on ionites. //
Russian Journal of Physical Chemistry, 2006,
V. 81, No. 11., pp. 1826-1831.
28. Ivanov V.A., Gavlina O.T., Ilyukhina
E.A., Gorshkov V.I. The temperature
dependence of the exchange enthalpy of
calcium and sodium ions on polymethacrylic
and polyacrylic cationites, Russian Journal of
Physical Chemistry, 2007, V. 81, No. 11,
P, 1723-1727.
29. Hogfeldt E. A three parameter model
for summarizing data in ion exchange. // In: Ion
Exchange and Solvent Extraction. Vol. 11.
Dekker_ New York. 1993. P. 120 – 150.
30. Leites I.L. Vtoroi zakon i ego
dvenadtsat' zapovedei. Populyarnaya
termodinamika i khimicheskaya
energotekhnologiya (The second law and its
twelve commandments. Popular
thermodynamics and chemical energy
technologies). Moscow: Moscow State
University Publ., 2002, 176 p. [in Russian]
Опубликован
2015-02-10
Как цитировать
Карпюк, Е. А., & Иванов, В. А. (2015). Некоторые аспекты термодинамики ионного обмена. Сорбционные и хроматографические процессы, 15(1), 19-34. https://doi.org/10.17308/sorpchrom.2015.15/251
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