Specific anion effects on glass electrode pH measurements of buffer solutions:: Bulk and surface phenomena

被引:100
作者
Salis, A
Pinna, MC
Bilanícova, D
Monduzzi, M
Lo Nostro, P
Ninham, BW
机构
[1] Univ Calgary, Dipartimento Sci Chim, CSGI, I-09042 Monserrato, Italy
[2] Univ Florence, Dipartimento Chim, CSGI, I-50019 Sesto Fiorentino, Italy
[3] Australian Natl Univ, Dept Appl Math, Canberra, ACT, Australia
关键词
D O I
10.1021/jp0546296
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The effect of electrolytes on pH measurements via glass electrodes is explored with solutions buffered at pH 7 (phosphate and cacodylate). Salt and buffer concentrations are varied. Direct and reverse Hofmeister effects are observed. The phenomena are significant for salt concentrations above 0.1 M and for buffer concentrations below 20 mM. Changes in measured pH show LIP Most strongly with anions. They can be related to the usual physicochemical parameters (anion molar volumes, molar refractivity, and surface tensions) that are characteristic of Hofmeister series. They correlate strongly with anionic excess polarizabilities; this suggests the involvement of non-electrostatic, or dispersion, forces acting on ions. These forces contribute to ionic adsorption at the glass electrode surface, and to the liquid junction potential.
引用
收藏
页码:2949 / 2956
页数:8
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