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RECEIVED
for review July 10, 1970. Accepted October 1 2 , 1970.
DONALD G. MILLER
Lawrence Radiation Laboratory, University of California, Livermore, Calif. 94550
Hittorf transference numbers have been determined at 25 C for aqueous CuSOi
solutions from 0.046rn to 1.4171
(saturation). All solutions were first equilibrated with
Cu metal. The results, except a t 0.046m,can be well represented by the equation:
t- =
0.4010 - 0.1426m
+ 0.0186m
(u
= 0.005)
The results are in satisfactory agreement (<0.01)with Fritz and Fugets moving
boundary results over a more limited concentration range.
2 Cu'
2 2 cu-
+ H202 C u 2 0 + 2 H'
(1)
(2)
wo = 1 + 1 0W- ~ m ~ 4 ,
(4)
(a
= 0.005)
(5)
Table I. Hittorf Transference Numbers in Copper Equilibrated Aqueous CuSO4 Solutions at 25" C
PH
(+0.05)
0
0.046345
3.28
0.046336 (3)
0.08350
3.17
0.08347 (4)
m,
...
m,,
mom
...
...
0.11480
3.18
0.11483 (2)
0.17955
3.14
0.17955 (3)
0.27756
3.02
0.27756 (4)
0.42603
2.98
0.42632 (4)
0.54000
0.541,
2.92
2.86
0.54421 (2)
0.69979
2.89
0.69999 (4)
0.8975
2.86
0.8986 (4)
0.9060
2.85
0.9063 (2)
0.9792
2.76
0.9791 (2)
1.1690
2.84
1.168, (2)
1.314,
...
...
0.08350 (2)
0.11479 (2)
0.11487 (1)
0.17950 (1)
0.17954 (1)
0.27752 (2)
0.27762 (2)
0.42563 (2)
0.4260, (2)
0.54007 (2)
0.54425 (1)
0.54418 (1)
0.69919 (2)
0.6999, (1)
1.399,
2.70
...
0.8977 (2)
0.9064 (1)
0.9053 (1)
0.9791 (2)
0.9792 (2)
1.1697 (1)
1.1697 (1)
1.3139 (2)
1.313, (2)
1.3994 (2)
1.399, (2)
...
1.399, (2)
...
...
0.046342 (2)
0.046&i9 (2)
0.08352 (2)
0.08353 (2)
0.11479 (1)
0.11474 (2)
0.17960 (1)
0.17960 (1)
0.2775, (2)
0.27759 (2)
0.42577 (2)
0.42608 (2)
0.53992 (2)
0.54406 (1)
0.54421 (1)
0.69976 (2)
0.6999, (2)
0.8954 (2)
0.8972 (2)
0.9062 (1)
0.9053 (1)
0.9791 (2)
0.9793 (2)
1.1692 (1)
1.1686 (1)
1.3139 (2)
1.3142 (2)
1.399, (2)
1.399, (2)
0.046344 (2)
0.046373 (1)
...
m,
0.036947 (2)
0.03666, (2)
0.07333 (2)
0.07333 (2)
0.09374 (2)
0.10414 (2)
0.15480 (2)
0.15379 (2)
0.2217, (2)
0.22162 (2)
0.34011 (2)
0.34172 (2)
0.43675 (2)
0.4722, (3)
0.47065 (3)
0.62362 (3)
0.61975 (2)
0.7030 (2)
0.7060 (2)
0.7829 (3)
0.7806 (3)
0.8069 (3)
0.8106 (3)
1.0331 (3)
1.0345 (3)
1.0468 (2)
1.0339 (2)
1.171, (3)
1.1898 (3)
1 0 ~ ~
...
0.4257
0.4352
0.4340
0.4334
0.9041
0.4550
1.0353
1.0772
2.305
2.326
3.486
3.364
4.081
2.869
2.935
2.972
3.120
7.150
7.306
4.712
4.850
6.501
6.415
5.094
5.076
10.03,
10.43,
8.335
7.424
t,
0.401"
0.392
0.389
0.357
0.351
0.360
0.355
0.346
0.349
0.331
0.334
0.313
0.314
0.308
0.298
0.301
0.302
0.297
0.278
0.279
0.282
0.281
0.276
0.275
0.264
0.267
0.269
0.269
0.258
0.260
t- (calcd)
0.401
0.371
0.371
0.361
0.361
0.355
0.355
0.344
0.344
0.331
0.331
0.316
0.316
0.306
0.306
0.306
0.295
0.295
0.283
0.283
0.282
0.282
0.278
0.278
0.269
0.269
0.262
0.262
0.258
0.258
'
'
'
'
'
'
-,
-
0.34-
'+
0'321
8
0.30o,28
\tY
(IO) at
temperature t
:\
',"0.24-
v Hopfgartner ( 1 1 ) 6-15'
A kin
,'5 O
a
;\
:<*I
( 3 ) 16-19'
228
APPENDIX
RECEIVED
for review July 22, 1970. Accepted November 23, 1970.
This work was performed under the auspices of the U.S. Atomic
Energy Commission. Portions of the work of M. J. Pikal were
done at Lawrence Radiation Laboratory during the tenure of an
LRL postdoctoral fellowship.
229