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I'm doing my background chemistry for a redox titration to determine the concentration of copper ions using potassium iodide. I know the ionic equation I need is:
 
2Cu2+(aq) + 4I-(aq) -> 2CuI(s) + I2(aq)
 
I'm having problems explaining why this reaction occurs though because my two half-equations are:
 
Cu2+(aq) + e- ->Cu+(aq) - Eo = 0.15 V
I2(aq) + 2e- -> 2I-(aq) - Eo = 0.54 V
 
The Eo values would normally mean I would reverse the Cu half-cell as it has the more negative Eo value. But to get my overall ionic equation I actually need to reverse the iodine half-cell. So I'm confused why the reaction occurs.
 
Vikki

Corrie writes ....
 
Let's look at the two half-reactions involved here again:
 
Cu2+(aq) + e <=> Cu+(aq) - Eo = +0.15 V
 
I2(aq) + 2e- <=> 2I-(aq) - Eo = +0.54 V
 
On this basis I2 is a stronger oxidising agent than Cu2+ (more positive Eo value). Therefore the reaction should go in the direction: 2Cu+ + I2 -> 2Cu2+ + 2I-, as you have noted.
 
Instead it actually goes, as we know: 2Cu2+ + 2I- -> 2Cu+ + I2
 
The reason for this is that one of the products is insoluble CuI. So the [Cu+(aq)] is very low indeed, certainly no where near the 1 M value that the standard Eo values above are based on.
 
Lowering the [Cu+(aq)] will have the effect of making the Cu2+ + e <=> Cu+ halfcell potential much more positive, i.e. much more oxidising. So much so that in fact Cu2+ becomes a stronger oxidising agent than I2, and the reaction goes in a direction not predicted by just considering standard electrode potentials - a not uncommon situation in test-tube reactions where conditions are not standard.

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updated: 29 November 2007

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