Coeficientes de Selectividad Potenciometricos Cationes Inorg IUPAC 2000

Pure Appl. Chem., Vol. 72, No. 10, pp. 18512082, 2000.
2000 IUPAC INTERNATIONAL UNION OF PURE AND APPLIED CHEMISTRY ANALYTICAL CHEMISTRY DIVISION COMMISSION ON ELECTROANALYTICAL CHEMISTRY*
POTENTIOMETRIC SELECTIVITY COEFFICIENTS OF ION-SELECTIVE ELECTRODES PART I. INORGANIC CATIONS

(Technical Report)
Prepared for publication by 1 1 2 1 YOSHIO UMEZAWA , PHILIPPE BHLMANN , KAYOKO UMEZAWA , KOJI TOHDA , 1 AND SHIGERU AMEMIYA
1
Department of Chemistry, The University of Tokyo, Hongo, Tokyo, Japan; Department of Chemistry, Ochanomizu University, Otsuka, Tokyo, Japan
*Membership of the Commission during the preparation of the report (19951999) was as follows: Chairman: R. P. Buck (USA, 19911999); Secretary: K. Tth (Hungary, 19911995); S. Rondinini-Cavallari (Italy, 19951997); W. Kutner (Poland, 19981999); Titular Members: M. F. Cames (Portugal, 19961999); M. LHer (France, 19911995); W. Kutner (Poland, 19961999); E. Lindner (Hungary, 19981999); S. Rondinini-Cavallari (Italy, 19921999); K. Stulk (Czech Republic, 19891997); Y. Umezawa (Japan, 19921999); Associate Members: A. M. Bond (Australia, 19891997); K. Cammann (Germany, 19891995); M. F. Cames (Portugal, 19871995); A. G. Fogg (UK, 19871997); L. Gorton, (Sweden, 19941999); W. R. Heineman (USA, 19911995); S. Kihara (Japan, 19921999); W. F. Koch (USA, 19911995); W. Kutner (Poland, 19891995); E. Lindner (Hungary, 19951997); R. Naumann (Germany, 19961999); K. W. Pratt (USA, 19961999); K. Stulk (Czech Republic, 19981999); K. E. Wang (China, 19871995); J. Wang (USA, 19921999); National Representatives: D. Bustin (Slovakia, 19941999); A. Covington (UK, 19881999); D. R. Groot (Republic of South Africa, 19941999); I. R. Gutz (Brazil, 19941999); S. S. M. Hassan (Egypt, 19941999); J-M. Kauffmann (Belgium, 19921999); F. Kadirgan (Turkey, 19941997); H. Kim (Republic of Korea, 19941999); H. B. Kristensen (Denmark, 19881999); T. Mussini (Italy, 19901999); B. Pihlar (Slovenia, 19941999); P. Spitzer (Germany, 19981999); H. P. van Leeuwen (The Netherlands, 19941999); Y. Vlasov (Russia, 19961999). Names of countries given after Members names are in accordance with the IUPAC Handbook 19981999 (Blackwell Science, Ltd).
Republication or reproduction of this report or its storage and/or dissemination by electronic means is permitted without the need for formal IUPAC permission on condition that an acknowledgment, with full reference to the source along with use of the copyright symbol , the name IUPAC, and the year of publication, are prominently visible. Publication of a translation into another language is subject to the additional condition of prior approval from the relevant IUPAC National Adhering Organization.
1851
1852
Y. UMEZAWA et al.
Potentiometric selectivity coefficients of ion-selective electrodes Part I. Inorganic Cations

(Technical Report)
pot Abstract: Potentiometric selectivity coefficients, KA,B, have been collected for ionophore-based ion-selective electrodes (ISEs) for inorganic cations reported pot from 19881997. In addition to numerical values of KA,B, together with the methods and conditions for their determination, response slopes, linear concentration ranges, chemical compositions, and ionophore structures for the ISE membranes are tabulated.
INTRODUCTION
pot An earlier IUPAC data compilation of potentiometric selectivity coefficients, KA,B, for ion-selective pot electrodes (ISEs) was published in 1979 in Pure and Applied Chemistry [1]. It covered KA,B data reported during 19661977 and was later followed by another extensive compilation of such data in a handpot book from CRC Press [2]. The latter covered most of the KA,B data reported during the years 19661988. An updated compilation reported in 1998 was limited to a number of particularly selective ionophores [3], which are lipophilic complexing agents that are incorporated into ISE membranes to selectively and reversibly bind analyte ions. pot This paper presents the latest compilation of KA,B data for liquid-membrane, inorganic-cation ISEs based on neutral and charged ionophores, reported between 1989 and the end of 1997. Moreover, this new compilation also contains some older data that had not been included in the CRC handbook. pot The presented KA,B data are listed together with the methods and conditions for their determinations; also tabulated are response slopes, linear ranges, chemical compositions, and ionophore structures for the corresponding ISE membranes. This report constitutes the first part in a series. The second and third part, which will be published separately in forthcoming issues of Pure and Applied Chemistry, will cover ISEs for inorganic anions and organic ions, respectively.
METHODS FOR THE DETERMINATION OF POTENTIOMETRIC SELECTIVITY COEFFICIENTS [47] Potentiometric selectivity coefficients can be measured with different methods that fall into two main groups, namely (1) mixed solution methods, and (2) separate solution methods. The most commonly used approach is the fixed interference method, which is a mixed solution method. This method was recommended by IUPAC in 1975 [4], but other approaches have also been frequently employed. The details of the definition of each method are given below. The potentiometric selectivity coefficients are expressed according to the NicolskyEisenman equation as z /z pot E = E0 + R T / (zA F) ln [aA+ KA,B (aB) A B] (1)
B
where E is the measured potential; E0 is a constant that includes the standard potential of the electrode, the reference electrode potential, and the junction potential; zA and zB are charge numbers of the primary ion, A, and of the interfering ion, B; aA and aB are the activities of the primary ion, A, and the 2000 IUPAC, Pure and Applied Chemistry 72, 18512082
Potentiometric selectivity coefficients of ion-selective electrodes
1853
pot interfering ion, B; and KA,B is the potentiometric selectivity coefficient for the primary ion A against the pot interfering ion, B. R, T, and F have the usual meanings. If KA,B is larger than 1, the ISE responds to the pot interfering ions more selectively than to the primary ions. In most cases, KA,B is smaller than 1, which means that such ISEs respond to the primary ions more selectively than to interfering ions. The NicolskyEisenman equation assumes a Nernstian response not only for the primary ion but pot also for the interfering ion. Obviously, KA,B is assumed to be constant. Several experimental methods for the determination of potentiometric selectivity coefficients are based on this equation. These methods will be explained in some detail in the following section. Notably, the NicolskyEisenman equation does not correctly describe responses in the activity range in which primary and interfering ions of a different charge significantly contribute to the potential. More complex equations must be applied to describe correctly such mixed ion responses [8]. Among the four mixed solution methods, the matched potential method is unique in that it depends neither on the NicolskyEisenman equation nor on any of its modifications; this method was recommended in 1995 by IUPAC as a method that gives analyticalpot ly relevant practical KA,B values [6].
Mixed solution methods Fixed interference method (FIM) The electromotive force (emf) of a cell comprising an ion-selective electrode and a reference electrode (ISE cell) is measured for solutions of constant activity of the interfering ion, aB, and varying activity of the primary ion, aA. The emf values obtained are plotted vs. the logarithm of the activity of the primary ion. The intersection of the extrapolated linear portions of this plot indicates the value of aA that pot is to be used to calculate KA,B from the following equation: z /z pot KA,B = aA / (aB) A B (2) where both zA and zB have the same signs, positive or negative. Fixed primary ion method (FPM) The emf of a cell comprising an ion-selective electrode and a reference electrode (ISE cell) is measured for solutions of constant activity of the primary ion, aA, and varying activity of the interfering ion, aB. The emf values obtained are plotted vs. the logarithm of the activity of the interfering ion. The intersection of the extrapolated linear portions of this plot indicates the value of aB that is to be used to calpot culate KA,B from the following equation: z /z pot KA,B = aA / (aB) A B (3) Two solution method (TSM) This method involves measuring potentials of a pure solution of the primary ion, EA, and a mixed solution containing the primary and interfering ions, EA+B. The potentiometric selectivity coefficient is calculated by inserting the value of the potential difference, E = EA+B EA, into the following equation: E zA F / (R T) z /z pot 1) / (aB) A B KA,B = aA(e (4)
Matched potential method (MPM) This method does not depend on the NicolskyEisenman equation at all. In this method, the potentiometric selectivity coefficient is defined as the activity ratio of primary and interfering ions that give the same potential change under identical conditions. At first, a known activity (aA') of the primary ion solution is added into a reference solution that contains a fixed activity (aA) of primary ions, and the corresponding potential change (E) is recorded. Next, a solution of an interfering ion is added to the 2000 IUPAC, Pure and Applied Chemistry 72, 18512082
1854
Y. UMEZAWA et al.
reference solution until the same potential change (E) is recorded. The change in potential produced at the constant background of the primary ion must be the same in both cases.
pot KA,B = (aA' aA) / aB
(5)
Separate solution methods Separate solution method (aA = aB) (SSM) The potential of a cell comprising an ion-selective electrode and a reference electrode is measured with two separate solutions, one containing the ion A at the activity aA (but no B), the other one containing the ion B at the same activity aA = aB (but no A). If the measured values are EA and EB, respectively, the value of is calculated from the equation: (EB EA ) zA F pot lg KA,B = _________________ + (1 zA/zB) lgaA R T ln 10 which is equivalent to (1 zA/zB) (EB EA) zA F / (R T ) pot e KA,B = aA (7) (6)
Separate solution method (EA = EB) [SSM (EA = EB)] The loga vs E relations of an ISE for the primary and interfering ions are obtained independently. Then, pot the activities that correspond to the same electrode potential value are used to determine the KA,B value. z /z pot KA,B = aA / (aB) A B ABBREVIATIONS A complete list of abbreviations that are used in the following tables is given below. AcCh+ acetylcholine BBPA BEHS cdl CHEMFET CP CWE DBE DBS DBP 2,3-DMNB DOA DOP DOPP DOS DPE emf ETH 500 ETH 5373 bis(1-butylpentyl) adipate bis(2-ethylhexyl) sebacate detection limit chemically modified field effect transistor chloroparaffin coated wire electrode dibenzyl ether dibutyl sebacate dibutyl phthalate 2,3-dimethylnitrobenzene bis(2-ethylhexyl) adipate bis(2-ethylhexyl) phthalate {dioctyl phthalate} dioctyl phenylphosphonate bis(n-octyl) sebacate diphenyl ether electromotive force tetradodecylammonium tetrakis(4-chlorophenyl)borate o-nitrophenyl dihydrophythyl ether 2000 IUPAC, Pure and Applied Chemistry 72, 18512082 (8)
Potentiometric selectivity coefficients of ion-selective electrodes FIA FIM FNDPE FPM ISE ISFET KTFPB KTmClPB KTPB KTpClPB M MPM MSM N NaTFPB NaTpClPB nN pNP oNPOE oNPPE Po/w PTLC PVC PVC-COOH PVC-NH2 r.o.o.g. SSM SSM (EA = EB) tresp t90, t95
1855
TDDMA+ TDDMACl TEHP TOPO TSM
flow-injection analysis fixed interference method 2-fluorophenyl 2-nitrophenyl ether fixed primary ion method ion-selective electrode ion-sensitive field effect transistor potassium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate potassium tetrakis(2-chlorophenyl)borate potassium tetraphenylborate potassium tetrakis(4-chlorophenyl)borate mol dm3 matched potential method mixed solution method Nernstian sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate sodium tetrakis(4-chlorophenyl)borate near-Nernstian 4-nonylphenol 2-nitrophenyl octyl ether 2-nitrophenyl phenyl ether partition coefficient, P, of the ionophore between 1-octanol and water Po/w as estimated experimentally by use of thin-layer chromatography poly(vinyl chloride) poly(vinyl chloride) carboxylated poly(vinyl chloride) aminated read-out of graph (where data in original paper were in graphical rather than numerical form) separate solution method (to be used for aA = aB method) separate solution method (to be used for EA = EB method) life time response time time that elapses between the instant at which an ISE and a reference electrode are brought into contact with a new sample solution and the instant at which the potential has changed to a value corresponding to 90% or 95%, respectively, of the activity change tridodecylmethylammonium tridodecylmethylammonium chloride tris(2-ethylhexyl) phosphate trioctylphosphine oxide two solution method
ACKNOWLEDGMENTS This work was financially supported by Monbusho (Ministry of Education, Science and Culture, Japan) for Publication of Scientific Research Results. We thank Kang Ping Xiao, Noriaki Kato, Hiroshi Okuyama, Qin Hang Jin, Tsuyoshi Amano, and Yuhki Uchiya for their help in this data compilation. REFERENCES 1. E. Pungor, K. Tth, A. HrabczyPll. Pure Appl. Chem. 51, 19131980 (1979). 2000 IUPAC, Pure and Applied Chemistry 72, 18512082
1856
Y. UMEZAWA et al.
2. Y. Umezawa (Ed.). Handbook of Ion-Selective Electrodes: Selectivity Coefficients, CRC Press, Boca Raton, FL (1990). 3. P. Bhlmann, E. Pretsch, E. Bakker. Chem. Rev. 98, 15931687 (1998). 4. G. G. Guilbault, R. A. Durst, M. S. Frant, H. Freiser, E. H. Hansen, T. S. Light, E. Pungor, G. Rechnitz, N. M. Rice, T. J. Rohm, W. Simon, J. D. R. Thomas. Pure Appl. Chem. 46, 127132 (1976). 5. R. P. Buck and E. Lindner. Pure Appl. Chem. 66, 25282536 (1994). 6. Y. Umezawa, K. Umezawa, H. Sato. Pure Appl. Chem. 67, 508518 (1995). 7. J. Inczdy, T. Lengyel, A. M. Ure. Compendium of Analytical Nomenclature, Blackwell Science, Oxford (1998). 8. M. Ngele, E. Bakker, E. Pretsch. Anal. Chem. 71, 10411048 (1999).
2000 IUPAC, Pure and Applied Chemistry 72, 18512082
1857
continues on next page
1858
Y. UMEZAWA et al.
1859
1860
Y. UMEZAWA et al.
1861
1862
Y. UMEZAWA et al.
1863
1864
Y. UMEZAWA et al.
1865
1866
Y. UMEZAWA et al.
1867
1868
Y. UMEZAWA et al.
1869
1870
Y. UMEZAWA et al.
1871
1872
Y. UMEZAWA et al.
1873
1874
Y. UMEZAWA et al.
1875
1876
Y. UMEZAWA et al.
1877
1878
Y. UMEZAWA et al.
1879
1880
Y. UMEZAWA et al.
1881
1882
Y. UMEZAWA et al.
1883
1884
Y. UMEZAWA et al.
1885
1886
Y. UMEZAWA et al.
1887
1888
Y. UMEZAWA et al.
1889
1890
Y. UMEZAWA et al.
1891
1892
Y. UMEZAWA et al.
1893
1894
Y. UMEZAWA et al.
1895
1896
Y. UMEZAWA et al.
1897
1898
Y. UMEZAWA et al.
1899
1900
Y. UMEZAWA et al.
1901
1902
Y. UMEZAWA et al.
1903
1904
Y. UMEZAWA et al.
1905
1906
Y. UMEZAWA et al.
1907
1908
Y. UMEZAWA et al.
1909
1910
Y. UMEZAWA et al.
1911
1912
Y. UMEZAWA et al.
1913
1914
Y. UMEZAWA et al.
1915
1916
Y. UMEZAWA et al.
1917
1918
Y. UMEZAWA et al.
1919
1920
Y. UMEZAWA et al.
1921
1922
Y. UMEZAWA et al.
1923
1924
Y. UMEZAWA et al.
1925
1926
Y. UMEZAWA et al.
1927
1928
Y. UMEZAWA et al.
1929
1930
Y. UMEZAWA et al.
1931
1932
Y. UMEZAWA et al.
1933
1934
Y. UMEZAWA et al.
1935
1936
Y. UMEZAWA et al.
1937
1938
Y. UMEZAWA et al.
1939
1940
Y. UMEZAWA et al.
1941
1942
Y. UMEZAWA et al.
1943
1944
Y. UMEZAWA et al.
1945
1946
Y. UMEZAWA et al.
1947
1948
Y. UMEZAWA et al.
1949
1950
Y. UMEZAWA et al.
1951
1952
Y. UMEZAWA et al.
1953
1954
Y. UMEZAWA et al.
1955
1956
Y. UMEZAWA et al.
1957
1958
Y. UMEZAWA et al.
1959
1960
Y. UMEZAWA et al.
1961
1962
Y. UMEZAWA et al.
1963
1964
Y. UMEZAWA et al.
1965
1966
Y. UMEZAWA et al.
1967
1968
Y. UMEZAWA et al.
1969
1970
Y. UMEZAWA et al.
1971
1972
Y. UMEZAWA et al.
1973
1974
Y. UMEZAWA et al.
1975
1976
Y. UMEZAWA et al.
1977
1978
Y. UMEZAWA et al.
1979
1980
Y. UMEZAWA et al.
1981
1982
Y. UMEZAWA et al.
1983
1984
Y. UMEZAWA et al.
1985
1986
Y. UMEZAWA et al.
1987
1988
Y. UMEZAWA et al.
1989
1990
Y. UMEZAWA et al.
1991
1992
Y. UMEZAWA et al.
1993
1994
Y. UMEZAWA et al.
1995
1996
Y. UMEZAWA et al.
1997
1998
Y. UMEZAWA et al.
1999
2000
Y. UMEZAWA et al.
2001
2002
Y. UMEZAWA et al.
2003
2004
Y. UMEZAWA et al.
2005
2006
Y. UMEZAWA et al.
2007
2008
Y. UMEZAWA et al.
2009
2010
Y. UMEZAWA et al.
2011
2012
Y. UMEZAWA et al.
2013
2014
Y. UMEZAWA et al.
2015
2016
Y. UMEZAWA et al.
2017
2018
Y. UMEZAWA et al.
2019
2020
Y. UMEZAWA et al.
2021
2022
Y. UMEZAWA et al.
2023
2024
Y. UMEZAWA et al.
2025
2026
Y. UMEZAWA et al.
2027
2028
Y. UMEZAWA et al.
2029
2030
Y. UMEZAWA et al.
2031
2032
Y. UMEZAWA et al.
2033
2034
Y. UMEZAWA et al.
2035
2036
Y. UMEZAWA et al.
2037
2038
Y. UMEZAWA et al.
2039
2040
Y. UMEZAWA et al.
2041
2042
Y. UMEZAWA et al.
2043
2044
Y. UMEZAWA et al.
2045
2046
Y. UMEZAWA et al.
2047
2048
Y. UMEZAWA et al.
2049
2050
Y. UMEZAWA et al.
2051
2052
Y. UMEZAWA et al.
2053
2054
Y. UMEZAWA et al.
2055
2056
Y. UMEZAWA et al.
2057
2058
Y. UMEZAWA et al.
2059
2060
Y. UMEZAWA et al.
2061
2062
Y. UMEZAWA et al.
2063
2064
Y. UMEZAWA et al.
2065
2066
Y. UMEZAWA et al.
2067
2068
Y. UMEZAWA et al.
2069
2070
Y. UMEZAWA et al.
2071
2072
Y. UMEZAWA et al.
2073
2074
Y. UMEZAWA et al.
2075
2076
Y. UMEZAWA et al.
2077
2078
Y. UMEZAWA et al.
2079
2080
Y. UMEZAWA et al.
2081
2082
Y. UMEZAWA et al.

Coeficientes de Selectividad Potenciometricos Cationes Inorg IUPAC 2000

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Coeficientes de Selectividad Potenciometricos Cationes Inorg IUPAC 2000

Uploaded by

Copyright:

Available Formats

Pure Appl. Chem., Vol. 72, No. 10, pp. 18512082, 2000.

POTENTIOMETRIC SELECTIVITY COEFFICIENTS OF ION-SELECTIVE ELECTRODES PART I. INORGANIC CATIONS

Potentiometric selectivity coefficients of ion-selective electrodes Part I. Inorganic Cations

Potentiometric selectivity coefficients of ion-selective electrodes

TDDMA+ TDDMACl TEHP TOPO TSM

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

Potentiometric selectivity coefficients of ion-selective electrodes

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

Potentiometric selectivity coefficients of ion-selective electrodes

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

Potentiometric selectivity coefficients of ion-selective electrodes

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

Potentiometric selectivity coefficients of ion-selective electrodes

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

Potentiometric selectivity coefficients of ion-selective electrodes

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

Potentiometric selectivity coefficients of ion-selective electrodes

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

Potentiometric selectivity coefficients of ion-selective electrodes

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

Potentiometric selectivity coefficients of ion-selective electrodes

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

Potentiometric selectivity coefficients of ion-selective electrodes

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

Potentiometric selectivity coefficients of ion-selective electrodes

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

Potentiometric selectivity coefficients of ion-selective electrodes

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

Potentiometric selectivity coefficients of ion-selective electrodes

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

Potentiometric selectivity coefficients of ion-selective electrodes

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

Potentiometric selectivity coefficients of ion-selective electrodes

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

Potentiometric selectivity coefficients of ion-selective electrodes

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

Potentiometric selectivity coefficients of ion-selective electrodes

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

Potentiometric selectivity coefficients of ion-selective electrodes

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

Potentiometric selectivity coefficients of ion-selective electrodes

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

Potentiometric selectivity coefficients of ion-selective electrodes

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

2000 IUPAC, Pure and Applied Chemistry 72, 18512082

Potentiometric selectivity coefficients of ion-selective electrodes