(a)
Interpretation:Overall cell reaction from half cell reactions of Au and Tl should be determined. Also, standard electrode potential of reaction is to be determined.
Concept introduction:Study of interchange between electrical and chemical energy falls under branch of chemistry called
Reactions that occur in galvanic cells can be broken down into two half-cell reactions. One half-cell reaction is that of reduction whereas another half-cell reaction is that of oxidation.
(a)

Answer to Problem 55E
Value of E°cell is 1.84 V .
Explanation of Solution
The reduction half cell reaction for Au is as follows:
Au+2+2e−→Au E°=1.50 V
The reduction half cell reaction for Tl is as follows:
Tl++e−→Tl E°=−0.34 V
Reduction potential is the ability of species to get reduced. More value of reduction electrode potential determines the tendency of species to get reduced. Since, reduction electrode potential of Au is higher than Tl . Therefore, Au undergoes reduction and Tl undergoes oxidation.
The half cell reaction at anode is as follows:
Tl→Tl++e−
The half cell reaction at cathode is as follows:
Au+3+3e−→Au
To equalize number of electrons half cell reaction of Tl is multiplied by 3. Hence, half cell reaction for Tl at anode is as follows:
3Tl→3Tl++3e−
On addition of above two reactions overall cell reaction is obtained and is as follows:
Au+3+3Tl→Au+3Tl+
Expression for E°cell is as follows:
E°cell=E°(cathode)−E°(anode)
Where,
- E°cell is standard electrode potential for cell.
- E°(cathode) is standard reduction potential for cathode.
- E°(anode) is standard oxidation potential for anode.
Value of E°(cathode) is 1.50 V .
Value of E°(anode) is −0.34 V .
Substitute the values in above equation.
E°cell=E°(cathode)−E°(anode)=1.50 V−(−0.34 V)=1.84 V
Hence, value of E°cell is 1.84 V .
(b)
Interpretation:Value of ΔG° and K for galvanic cell is to be calculated.
Concept introduction:Study of interchange between electrical and chemical energy falls under branch of chemistry called electrochemistry. It includes occurrence of oxidation and reduction reactions. This includes production of electric current from chemical reaction and vice-versa.
Reactions that occur in galvanic cells can be broken down into two half-cell reactions. One half-cell reaction is that of reduction whereas another half-cell reaction is that of oxidation.
(b)

Answer to Problem 55E
Value of ΔG° is −533 kJ and that of K is 2.52×1093 .
Explanation of Solution
The reduction half cell reaction for Au is as follows:
Au+2+2e−→Au E°=1.50 V
The reduction half cell reaction for Tl is as follows:
Tl++e−→Tl E°=−0.34 V
Reduction potential is the ability of species to get reduced. More value of reduction electrode potential determines the tendency of species to get reduced. Since, reduction electrode potential of Au is higher than Tl . Therefore, Au undergoes reduction and Tl undergoes oxidation.
The half cell reaction at anode is as follows:
Tl→Tl++e−
The half cell reaction at cathode is as follows:
Au+3+3e−→Au
To equalize number of electrons half cell reaction of Tl is multiplied by 3. Hence, half cell reaction for Tl at anode is as follows:
3Tl→3Tl++3e−
On addition of above two reactions overall cell reaction is obtained and is as follows:
Au+3+3Tl→Au+3Tl+
Expression for E°cell is as follows:
E°cell=E°(cathode)−E°(anode)
Where,
- E°cell is standard electrode potential for cell.
- E°(cathode) is standard reduction potential for cathode.
- E°(anode) is standard oxidation potential for anode.
Value of E°(cathode) is 1.50 V .
Value of E°(anode) is −0.34 V .
Substitute the values in above equation.
E°cell=E°(cathode)−E°(anode)=1.50 V−(−0.34 V)=1.84 V
Expression for ΔG° is as follows:
ΔG°=−nFE°cell
Where,
- ΔG° is standard Gibbs free energy change.
- n is moles of electrons involved in reaction.
- E°cell is standard electrode potential for cell.
Value of n is 3 mol e− .
Value of E°cell is 1.84 V .
Value of F is 96485 C/mol e− .
Substitute the values in above equation.
ΔG°=−nFE°cell=−(3 mol e−)(96485 C/mol e−)(1.84 V)(10−3 kJ1 J)=−533 kJ
Expression for E°cell is as follows:
ΔG°=−nRTlnK
Where,
- ΔG° is standard Gibbs free energy change.
- R isgas constant.
- T is temperature of reaction.
- K is equilibrium constant for reaction.
Rearrange above equation for lnK .
lnK=−ΔG°nRT
Value of R is 8.314 J /K mol .
Value of T is 298 K .
Value of ΔG° is −533 kJ .
Value of n is 1 mol .
Substitute the values in above equation.
lnK=−ΔG°nRT=−(−533 kJ)(1 mol)(8.314 J /K mol)(298 K)(1000 J1 kJ)=215.13
Value of K is calculated as follows:
K=2.52×1093
Hence, value of ΔG° is −533 kJ and that of K is 2.52×1093 .
(c)
Interpretation:Value of Ecell at 25 °C is to be calculated.
Concept introduction: Nernst equation represents relation between potential of electrochemical reaction, standard cell potential, activities of species and temperature.
Expression of Nernst equation at room temperature is as follows:
Ecell=E0cell−0.0591nlog(Q)
Where,
- Ecell is the cell potential.
- E0cell is the standard cell potential.
- n is total electrons transferred.
- Q is reaction quotient.
(c)

Answer to Problem 55E
Value of Ecell of electrochemical cell is 2.04 V .
Explanation of Solution
Given Information:Value of [Au+3] is 1×10−2 M , that of [Tl+] is 1×10−4 M and that of temperature is 25 °C .
Given equilibrium reaction is as follows:
Au+3+3Tl→Au+3Tl+
Expression of reaction quotient for above chemical equation is as follows:
Q=[Tl+]3[Au+3]
Where,
[Tl+] is concentration of Tl+ .
[Au+3] is concentration of Au+3 .
Value of [Tl+] is 1×10−4 M .
Value of [Au+3] is 1×10−2 M .
Substitute the values in above equation.
Q=[Tl+]3[Au+3]=(1×10−4)3(1×10−2)=10−10
The half cell reaction at anode is as follows:
3Tl→3Tl++3e−
The half cell reaction at cathode is as follows:
Au+3+3e−→Au
On addition of above two reactions overall cell reaction is obtained and is as follows:
Au+3+3Tl→Au+3Tl+
Expression for E°cell is as follows:
E°cell=E°(cathode)−E°(anode)
Where,
- E°cell is standard electrode potential for cell.
- E°(cathode) is standard reduction potential for cathode.
- E°(anode) is standard oxidation potential for anode.
Value of E°(cathode) is 1.50 V .
Value of E°(anode) is −0.34 V .
Substitute the values in above equation.
E°cell=E°(cathode)−E°(anode)=1.50 V−(−0.34 V)=1.84 V
Expression of Nernst equation for above net reaction of electrochemical cell at room temperature is as follows:
Ecell=E0cell−0.0591nlogK
Where,
- Ecell is the cell potential.
- E0cell is the standard cell potential.
- n is total electrons transferred.
- Q is reaction quotient.
Value of E0cell is 1.84 V .
Value of n is 3 .
Value of Q is 10−10 .
Substitute the value in above equation.
Ecell=E0cell−0.0591nlogK=1.84−0.05913log(10−10)=1.84−0.020(−10log10)=2.04 V
Hence, Ecell of electrochemical cell is 2.04 V .
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