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PROBLEM SET IN PHYSICAL CHEMISTRY 2

A.Y. 2015-2016
How many faraday of charge is required for conversion of C6H5NO2 into C6H5NH2?
Explain why Zn dissolves in dil. HCl to liberate H2(g) but from conc.H2SO4, the gas evolved is SO2.
Cu does not dissolve in HCl but dissolves in nitric acid. Explain why?
Fluorine has a low electron gain enthalpy compared to chlorine, yet it is a more powerful oxidant. Explain why?
If Zn2+/Zn electrode is diluted 100 times, then what will be the change in emf?
You are aquainted with the construction and working of a lead-storagebattery. Give the plausible reasons for
these facts:
1. There is only a single compartment unlike other electrochemical cells.
2. Replacement of water is necessary for maintenance.
For what concentration of Ag+(aq.), will the emf of given cell be zero at 25 oC , if the concentration of Cu(s) |
Cu2+(0.1M) || Ag+(aq.) | Ag(s)?Given , E0 Ag+/Ag=0.80V; E0 Cu2+/Cu=0.34V.
In a small town along the coastal area, it is observed that iron objects rust easily. Being an industrial town, it also
faces air pollution problem. Identify any 4 factors which are contributing to rusting phenomenon.
Iodine(I2) and Bromine(Br2) are added to a solution containing iodide(I-) and bromide ions(Br-). What reaction
would occur if the concentration of each species is 1M? The electrode potentials are E0 I2/I-=0.54V and E0
Br2/Br-=1.08V.
The continued electrolysis of each of the following solutions at pH 7.0 and 25C, predict the main product at
each electrode if there are no (irreversible) electrode polarization effects: (a) 1M NiSO4 with palladium
electrodes; (b) 1M NiBr2 with inert electrodes; (c) 1MNa2SO4 with Cu electrodes.
An electrolytic cell contains a solution of CuSO4 and an anode of impure copper. How many kilograms of copper
will be refined (deposited on the cathode) by 150A over 12.0 h? The copper deposited on the cathode comes
fromthe solution; however, that copper deposited is replaced from the anode. This is a technique of separating
the copper from the impurities in the anode (refining).
Hydrogen peroxide, H2O2, can be prepared by the successive reactions below:
2NH4HSO4 H2 + (NH4)2S2O8
(NH4)2S2O8 + 2H2O 2NH4HSO4 + H2O2
The first reaction is an electrolytic reaction; the second is a steam distillation. What current would have to be
used in the first reaction to produce enough (NH4)2S2O8 to yield 100 g of pure H2O2 per hour from the second
reaction? Assume 50% anode current efficiency.

13. An important measure of the efficiency of a battery is the energy density, the amount of energy delivered
divided by the mass of reactants consumed. For comparison purposes, calculate the energy density of (a) the
2.00V (approximate) lead storage battery that discharges by the following reaction: Pb + PbO2 + 2H2SO4
2PbSO4 + 2H2O (b) and calculate the energy density of a 1.30 V (approximate) NiCad battery, which discharges
by Cd + 2NiOOH + 2H2O Cd(OH)2 + 2Ni(OH)2 Note that these calculations do not take into account such
practical factors as the cost of the chemicals required, fraction of reactants not utilized, or nonreactive structural
materials. These factors and others add to the cost of the batteries.
14. The cell in the preceding problem is, in a sense, a pH meter. Suppose one half-cell contained 1.00MH+, the
standard state. Describe the relationship (at 25C) between the pH of the other half-cell and the observed
voltage (connecting the positive terminal of the meter to the standard half-cell).
15. A cell has a silver electrode at the left, in contact with a solution containing Ag+ ions, and a silversilver chloride
electrode at the right, in contact with a solution containing Cl ions. Write the cell symbol for the cell. Is a salt
bridge needed? If a salt bridge is needed, what can the usual electrolyte be used? Explain. Propose another
electrolyte if one is needed. b. Write the two half-reaction equations and the cell equation. c. Find E for the cell
at 298.15 K. d. Find the cell voltage at 298.15K if the Ag+ activity is 0.250 and the Cl activity is 0.199. Is the cell
reaction spontaneous as written?

16. Find the reversible cell voltage at 298.15K of a concentration cell in which both half-cells have calomel
electrodes and HCl solutions. In one solution the molality is equal to 2.50 mol kg1 and in the other solution the
molality is equal to 0.100 mol kg1.
17. THE cell reaction of the lead storage battery is Pb(s) + PbO2(s) + 2H2SO4(aq)2PbSO4(s)+2H2O(l) a. Find the
value of E at 25C. b. Find the value of H at 25C. c. Find the value of E at 18C (approximately 0F)