The standard reduction potential of 
and 
are 0.226 V and 0.344 V respectively. A mixture of salts of Bi and Cu at unit concentration each is electrolysed at 25ºC. To what value can [Cu 2+ ] be brought down before bismuth starts to deposit during electrolysis.
Text Solution
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0001
Sol. We know,
Since initially
= 
+ 
log [Cu 2+ ]
= 0.344 + 
log 1 = 0.344 V
= 0.266 + 
log [Bi 3+ ]
= 0.266 + 
log 1 = 0.266 V
Thus, passage of current would initially deposit Cu 2+ till 
becomes 0.266 V because then only Bi 3+ will be deposited
Thus, 
+ 
+ 
log [Cu 2+ ]
0.266 = 0.344 + 
log [Cu 2+ ]
∴ [Cu 2+ ] = 10 –4 M
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