I performed the experiment yesterday.
For the cathode of the electrolytic cell I used a coiled piece of Copper wire.
For the anode of the cell, I used a small strip of Copper metal a few mm thick.
As the electrolyte I used a concentrated solution of Acetic Acid prepared by diluting glacial acetic acid down to about 50% (roughly estimated) by weight.
I used a current controllable (one with a knob which allows be to adjust the current to whatever I wish [within reason] at about 5 volts) power supply.
I performed two runs of the cell.
One run I used a constant current of about 500 mA for about 30 minutes.
The second run I used a current about 300 mA for a few hours, then I lowered it down to 50 or 100 mA overnight.
Both runs gave me to the same result (just one was faster than the other).
The anode corroded and a dark substance formed on the cathode. The electrolyte solution turned the characteristic blue color as one would expect from a Cu+2 (aq) solution. While the cathode was immersed in the blue solution, the substance forming on the cathode looked black, but when one lifts the electrode out of solution the substance looked green. Near the bottom of the cathode, the substance looks a little like Copper metal, it has a similar color and shine even though the actual Copper wire is not exposed at that point.
The green substance formed on the cathode was not water soluble, nor did it dissolve (or show any signs of a chemical reaction) when it was submerged into concentrated Hydrochloric acid.
However, a chemical reaction defiantly occurs when the substance is in the presence of concentrated Nitric acid. The substance reacts with Nitric acid to give off brown NO2 gasses and the solution turns blue as the substance dissolved in the acid.
If I had to guess what the substance formed on the cathode was, I would probably say it is Copper metal. However, the color makes me question that slightly. The color (greenish) does not look anything like Copper metal in the usually sense….but maybe that is just because of the way it is plated onto the surface. Also, I would have thought the HCl would (although it would not have dissolved the Copper) have perhaps cleaned off any Copper Oxide coating on the Cu to give it the usual Cu color if the green color is resulting from any oxidization which has occurred to the Cu, but the HCl seemed to have no effect.
I remember reading some time ago that one way to purify Copper metal is to electrolytically dissolve it and re-plate it out on to another surface. The Copper metal will be oxidized into solution and then be reduced back out at Cu metal, but the impurities will be left behind in a pile underneath the Copper anode. So this is what I think it occurring, you are basically plating over Copper from one electron to the other.
The Copper ions which have not yet been plated over are causing the blue color of the electrolyte solution as a aqueous solution of Copper(II) Acetate is forming.
Here are some pictures…
Electrodes after the electrolytic reaction:
http://i62.photobucket.com/albums/h104/mrjeffy321/PF-CopperAcetate/IMG_0611.jpg
Solution after electrolysis:
http://i62.photobucket.com/albums/h104/mrjeffy321/PF-CopperAcetate/IMG_0615.jpg