ChE 323 Problem Set 6: ELECTROCHEMISTRY March 12, 2014 Engr. May V.

Tampus

CONCEPTS:
1. What is the difference between a galvanic cell and an electrolytic cell?
2. Sketch a typical galvanic cell. Show direction of electron flow, the direction of ion migration through the porous disk, and identify the cathode and anode. Indicate in
which electrode oxidation and reduction occur. Will there be migration of ions in the absence of the porous disk? Next, sketch a galvanic cell with a salt bridge
showing the required features as in a typical galvanic cell. Is there a change in the direction of ion migration when a salt bridge is present? Explain.
3. Discuss the relationship between ionic mobility, molar conductivity, and transport number to ionic conduction. Does electronic conduction also involve the
measurement of these quantities? Explain.
4. You want to “plate out” nickel metal from a nickel nitrate solution onto a piece of metal inserted into the solution. Should you use copper or zinc or can you use
either)? Explain.
5. Explain the following relationships: ΔG and W, cell potential and W, cell potential and ΔG, cell potential and Q (reaction quotient). Using these relationships, explain
how you could make a cell in which both electrodes are the same metal and both solutions contain the same compound, but at different concentrations. How could
this cell run spontaneously?
6. What is the difference between ξ and ξo? When is ξ equal to zero? When is ξo equal to zero? (Consider “regular” galvanic cells as well as concentration cells.)
7. Why is the use of a salt bridge or porous disk in a galvanic cell necessary?
8. In making a specific galvanic cell, explain how one determines which electrodes and solutions to use in the cell.
9. Explain why cell potentials are not multiplied by the coefficients in the balanced equation.
10. You are told that metal A is a better reducing agent than metal B. What, if anything, can be said about A + compared with B+? Explain.

PROBLEMS:
1. The standard Gibbs energy for the hydrolysis of ATP in the reaction ATP (aq)  ADP(aq) + Pi(aq), where Pi is inorganic phosphate, is -31 kJ.mol-1 at 37oC. In a typical
bacterial cell the concentrations of ATP, ADP, and P i are 8, 1, and 8 mmol.L-1, respectively. What is the Gibbs energy under these conditions? [ANSWER:-48.80 kJ.mol-
1
]
2. A fuel cell designed to react grain alcohol with oxygen has the following net reaction:

C2H5OH(l) + 3O2(g)  2CO2(g) + 3H2O(l)

The maximum work one mole of alcohol can yield by this process is 1320 kJ. What is the theoretical maximum voltage this cell can achieve? [ANSWER:1.14 V]
3. In a common car battery, six identical cells each carry out the reaction:
Pb + PbO2 + 2HSO4- + 2H+ 2PbSO4 + 2H2O

For such a cell Eo is 2.04 V. Calculate ΔGo at 25oC. [ANSWER:-394 kJ]

4. An antique automobile bumper is to be chrome plated. The bumper, which is dipped into an acidic Cr 2O72- solution, serves as a cathode of an electrolytic cell. If
oxidation of H2O occurs at the anode, how many moles of oxygen will evolve for every 1.00 x 10 2 grams of Cr(s) deposited? M Cr = 51.996 g/mol [ANSWER:2.88 moles]
5. Refer to #4. If the current is 10.0 amperes, how long will it take to deposit 100 x 10 2 grams of Cr(s) onto the bumper? [1.29 d]
6. Given the reactions:
Fe2+ + 2e-  Fe(s) Eo = -0.440 V
2H+ + 2e-  H2(g) Eo = 0.000 V
In a galvanic cell, the iron compartment contains an iron electrode and [Fe 2+] =1.00 x 10-3 M. The hydrogen compartment contains a platinum electrode (P H2 = 1.00
atm) and a weak acid HA at an initial concentration of 1.00 M. If the observed cell potential is 0.333 V at 25 oC, calculate Ka for the weak acid HA at 25 oC.
[ANSWER:2.43 x 10-7]
7. A 4 molal solution of FeCl3 is electrolyzed between platinum electrodes. After the electrolysis the cathode portion, weighing 30 g, is 3.15 molal in FeCl 3 and 1.00 molal
in FeCl2. What are the transport numbers of Fe 3+ and Cl- ions, respectively?[ 0.647; 0.353]
8. For the oxidation-reduction reaction
S4O62-(aq) + Cr2+(aq)  Cr3+(aq) + S2O32-(aq)
The appropriate half reactions are
S4O62- + 2e-  2S2O32- o
= 0.17 V
3+ - 2+ o
Cr + e  Cr = -0.50 V
What is the value of the equilibrium constant K at 25 oC? [ANSWER:4.32 x 1022]
9. What fraction of the total current is carried by Cl- when current flows through an aqueous solution of NaCl at 25 oC? Limiting conductivities in water of Na+ and Cl- in
mS.m2.mol-1 are 5.01 and 7.63, respectively. [ANSWER:0.396]
10. The calomel electrode, Hg(l) l Hg2Cl2(s) l Cl-(aq), is a component of instruments used to measure pH. What is the half reaction of this electrode? What is the reaction
quotient? [ANSWER: Hg2Cl2(s) + 2e-  2 Hg(l) + 2 Cl- (aq); Q aCl ]
2

11. A hydrogen electrode can, in principle, be used to monitor changes in the molar concentration of weak acids in biologically active solutions. Consider a hydrogen
electrode in a solution of lactic acid (CH3CHOCOOH) as part of an overall galvanic cell at 25 oC and 1 bar. Estimate the change in the electrode potential when the
solution is charged from 5.0 mmol/L to 25.0 mmol/L. [ANSWER:64.2 mV]