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

A Discussion of selected references
299
ο
overlaps with that given by the authors ( E = − (0.1375 ± 0.0005) V). Due to the
limited range of m −
ClO considered, no reliable Δε value could be extracted from these
4
measurements. When the slope was fixed to – 0.09 RT ln(10)/2F, as predicted by
ε(Sn 2+ , ClO − 4
) selected by this review and ε(H + , ClO − 4
) given in Appendix B, Table B-4,
ο
a value of E = − (0.1399 ± 0.0006) V was arrived at, see Figure A-19. This value falls
just outside the confidence limits of the one accepted for statistical analysis.
Table A-12: Standard potential
HClO 4 /M Sn(ClO 4 ) 2 /M
ο
E /V
air-free
ο
E of the reaction Sn 2+ + H 2 (g) β-Sn + 2 H + .
ο
E /V
recalc.
HClO 4 /m Sn(ClO 4 ) 2 /m I/m ClO − 4
/m
0.005 0.00021 − 0.1376 − 0.11400 0.005016 0.000213 0.00565 0.00544
0.005 0.00042 − 0.1374 − 0.10501 0.005016 0.000425 0.00629 0.00587
0.005 0.00085 − 0.1378 − 0.09672 0.005016 0.000852 0.00757 0.00672
0.010 0.00085 − 0.1375 − 0.11500 0.010035 0.000852 0.01259 0.01174
0.010 0.00170 − 0.1377 − 0.10659 0.010036 0.001705 0.01515 0.01345
0.010 0.00340 − 0.1378 − 0.09830 0.010037 0.003412 0.02027 0.01686
0.050 0.00425 − 0.1370 − 0.13879 0.050286 0.004273 0.06311 0.05883
0.050 0.00850 − 0.1370 − 0.13061 0.050306 0.008551 0.07596 0.06741
0.050 0.01700 − 0.1373 − 0.12359 0.050347 0.017117 0.10170 0.08458
Figure A-19: SIT analysis of the data of [1957WAK/SAL] (: experimental data
recalculated by this review; solid line: linear fit; dotted lines: 95% confidence limits;
dashed line: slope predicted by Δε = 0.08 kg·mol –1 ).
-0.138
Sn 2+ (aq) + H 2
(g) Sn(s) + 2 H + (aq)
{E° m
' + [RT·ln(10) / 2·F ]·2·D} / V
-0.139
-0.140
-0.141
-0.142
T = 298.15 K
0.00 0.02 0.04 0.06 0.08 0.10
m (ClO - 4 ) / mol·kg-1
CHEMICAL THERMODYNAMICS OF TIN, ISBN 978-92-64-99206-1, © OECD 2012