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Fundamentals of Electrolysis

17 - 6.The cell in Figure 17 - 4 is:

Cu|1.0MCuSO4(aq)|KCL(aq,3M)|AgCI(s)|Ag(s)

Write half-reactions for this cell. Neglecting activity coefficients and the junction potential betweenCuSO4(aq)and KCI(aq), predict the equilibrium (zero-current) voltage expected when the Lugging capillary contacts the electrode. For this purpose, suppose that the reference electrode potential is 0.197Vvs. S.H.E. Why is the observed equilibrium potential+109mV, not the value you calculated?

How would the over potentials change if>1.000Vwere imposed by the

Potentiostat?

Short Answer

Expert verified

(a) The Potential is E = 0.142 V

(b) The over potentials would increase because current is increased. The anode is intercepted when > 0.122 V , while the cathode when < 0.085 V

Step by step solution

01

Fundamentals of electrolysis

  • Electrolysis is a fundamental process in chemistry that involves the breakdown of an electrolyte (a solution) and the creation of positive and negative ions.
  • This is the underlying concept of electrolytic cells.
  • The procedure may appear hard, yet it is as simple as a walk in the park.
02

Determine the potential

a)

The half-reactions for this cell is:

Cathode:Cu2++2e-→CuSO4Anode:AGCL+e-→Aq+Cl-

The Potential is E = E ( cathode ) - E ( anode )

So, we first calculate E of cathode:

E(cathode)=E°-0.05916.log(CuSO4)E(cathode)=0.339V-0.339VE(cathode)=0.339V

And, the E of reference electrode (anode) is:

E(cathode)=0.339VE(anode)=0.197V

The Potential is

E=0.339V-0.197VE=0.142V

The predicted potential is 0.142V , while the observed potential is 0.109V is from Cu2+activity coefficient and using the 3MKCI instead of saturated KCI.

Step 2: Determine the over potential by the potentiostat

b)

If > 1.000V were imposed by the potentiostat, the over potentials would increase because current is increased.

The anode is intercepted when > 0.122V , while the cathode when .

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