Chemical Thermodynamics of Tin - Volume 12 - OECD Nuclear ...

A Discussion of selected references
409
the value from the electrochemical measurements is added, log10
K from activities lies
within the prediction limits from concentration measurements, which casts some doubts
on the activity measurements also.
Figure A-48: Stoichiometric solubility constant for Sn 3 (OH) 2 OSO 4 .
-3.0
-3.5
-4.0
log 10
K s
-4.5
-5.0
-5.5
log 10
K s
from electrochemical
measurements
-6.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
(I / m) 0.5
[1996PLY/GRE]
This is the key paper elucidating the application of the Pitzer as well as the Brønsted-
Guggenheim-Scatchard specific ionic interaction models to the extrapolation of
enthalpies of reaction in electrolyte systems to infinite dilution. The methods described
in this paper became standard methods in the TDB projects.
For this review it is particularly important that the Vasil’ev [1967VAS] as well
as the Vasil’ev and Yasinskii [1978VAS/YAS] approaches are criticised on the grounds
ο
ο
that H2, I = H2,I + Φ L,i is used instead of H2,I = H2,I + L 2,i , where Φ L,i is the relative
apparent molar enthalpy and L 2,i the relative partial molar enthalpy. Although the
enthalpy of reaction at infinite dilution will probably not change very much, Vasil’ev et
ο
al.’s Δ H have to be revised.
r
m
CHEMICAL THERMODYNAMICS OF TIN, ISBN 978-92-64-99206-1, © OECD 2012