Chapter 17

17.2

Bubbles of gaseous hydrogen are released to rise through the solution in contact with the platinum electrode. When the two electrodes are then connected by a wire, electrons flow from left to right through the wire. Negative ions migrate to the left in the salt bridge, and positive ions migrate to the right. The overall reaction is

17.4 The quantity of electricity is 0.9600 mol of electrons, as shown by dividing the number of coulombs by the Faraday constant. Dissolving 1 mol of Ni to give Ni2+(aq) requires passage of 2 mol of electrons, so the maximum amount of Ni dissolved is 0.4800 mol.

17.6 (a) The balanced equation is .

(b) The product of the (steady) current in amperes and the time in seconds is the charge in coulombs. It is amount of electrons, 0.141 mol. (c) Every 1 mol of electrons that passes through the cell oxidizes mol of zinc. Hence 0.0703 mol of zinc is oxidized. This is 4.60 g of zinc and is the mass lost by the zinc electrode. (d) Every 1 mol of electrons that passes through the cell reduces mol of cadmium(II) . Dividing by the Faraday constant gives the chemical

ions. This is 0.0703 mol of Cd2+, or 7.91 g of Cd2+. This mass of cadmium metal is gained by the cadmium electrode.

17.10 (a) Anode: Cathode: Overall: (b)

17.12 Use the equation:

The

is 0.48 V, and F is 95,485 C mol-1. If 1 mol of zinc were oxidized, then n would

equal 2 mol, and welec, max would be -92.6 kJ. But 1.000 g of zinc is much less than 1.000 mol of zinc; it is only 0.0153 mol. Therefore n=0.0306 mol in the formula, and the maximum work done on the cell is -1.4 kJ. The maximum work done by the cell is the negative of this, or +1.4 kJ per gram of zinc consumed.

17.14

(a) The reduction of Fe3+ to Fe2+ has E0=0.770 V, and the reduction of Cd2+ to Cd has E0=-0.4026 V. In this galvanic cell with all species in their standard states, the half-reaction takes place at the cathode, and the oxidation takes place at the anode. Only in this way is (b) of the cell positive.

17.16 (a) The increase in the concentration of Cl- ions means that Cl2(g) is reduced as the cell operates spontaneously. The half-reaction at the cathode, where reduction occurs, is accordingly (b) The overall voltage is . At the anode, the half-reaction is .

and equals 1.918 V. It also equals the standard reduction

potential of the reduction hapf0reaction minus the standard reduction potential of the oxidation half-reaction. The reduction is the conversion of Cl2 to Cl-, which has E0 equal to 1.3583 V (Appendix E). Hence:

It follows that x, the reduction potential for the Ga3+/Ga half-cell, is -0.560 V.

17.20 The standard reduciton potentials for ClO3-, ClO-, and Cl2 in acidic aqueous media are 1.47, 1.63, and 1.3583 V respectively, according to Appendix E. This means that at a given concentration at pH 0, a solution of NaClO is the strongest bleach, despite the fact that the change in oxidation number its experiences is small. At pH 0, the ClO- ion, a fairly strong base, picks up a hydrogen ion. So the species in the half-equation is HClO. At pH 0

the reduction potential of O3 to O2 is 2.07 V (given in Appendix E). Therefore ozone is a stronger bleach than any of the chlorine bleaches. 17.24 (a)

(b)

= 2.87- (-0.37) = 3.24 V > 0

17.26 (a) ClO- tends to disproportionate spontaneously at pH 14 to give Cl- and ClO2-. The of the reaction is 0.90-0.59=0.31 V. (b) According to the reduction potentials given in the problem ClO- is oxidized to ClO2more readily than Cl- is oxidized to ClO- at pH 14; the ClO- is the stronger reducing agent under these conditions. However, neither of these is a very good reducing agent.

17.28 We calculate the standard potential difference of the cell from the data in Appendix E. At the anode is the Ag/Ag+ couple; at the cathode is the Cl2/Cl- couple for the overall cell reaction . The is

. This standard voltage must be corrected for the non-standard concentrations in this cell. At 25C:

17.32 We will write the Nernst equation for the redox reaction

at 25 C and use it to calculate the unknown concentration. The standard potential difference of the cell comes from the data in Appendix E. It is

The Nernst equation is then:

Inserting [Cu2+]=1.00 M and solving for [Br-] gives

17.36 The standard potential difference of the reaction is the standard reduction potential for the conversion of mercury(II) to mercury(I) minus the standard reduction potential for the conversion of gold(III) to gold(0): = 0.905 - 1.42 = -0.515 V.

The quantity n in the reaction as given in the problem is 6, so at 25C:

Log K =

n 0.0592 V

= 6 0.0592 V

(-0.515 V) = -52.2

The equilibrium constant for the reaction as given is K= 6 x 10^-53. The second question really concerns the reverse of the reaction written in the problem. The equilibrium constant of the reverse reaction is the reciprocal of the K just computed:

After

and Au3+ are mixed, but before the reaction starts, their concentration are

both 0.50 M. The equilibrium constant is very large, so the reaction proceeds until the ion, which is the limiting reactant, is essentially all consumed. Suppose all of the 0.500M reacted. The concentration of Hg2+ formed is then 1.00M, and the

concentration of excess Au3+ is 0.166M, by the stoichiometry of the reaction. Let the concentration of actually left at equilibrium equal x. Then [Au3+]= 0.166 + 2/3x

M, and [Hg2+]= 1.00 -x/2 M at equilibrium. We substitute these expression into the equilibrium law:

Because x is certainly very small compared to 0.166, this equation becomes

Solving gives x = 1 x 10^-17 M. This is the equililbrium concentration of

ion. The

equilibrium concentration of Au3+ ion is 0.166M, and the equilibrium concentration of Hg2+ ion is 1.00M.

17.44 The overall reaction is Zn(s) + HgO(s) + H2O(l) --> Zn(OH)2 (s) + Hg(l) for which

17.46 (a) The reaction is Zn(s) + HgO(s) + H2O(l) --> Zn(OH)2 (s) + Hg(l) The equation implies that the reduction of 1 mol of HgO in the battery occurs by passage of 2 mol of electrons through an outside circuit. The 0.50 g of HgO (M= 216.59 g mol-1) is 2.3 x 10^-3 mol of HgO. Hence, 4.6 x 10^-3 mol of electrons pass the circuit. Multiplying by the Faraday constant converts this to 4.5 x 10^2 C. (b) The work performed on the battery ( the "system") is

Thus the battery can perform at most 600 J of work.

17.50 The for the oxidation of 1.00 mol of CO(g) to CO2(g) is -257.21 kJ, regardless of

how the reaction is performed. If the reaction is performed with 100% efficiency at standard conditions, then kJ of work is obtained. = w and the cell absorbs -257.21 kJ of work, that is, 257.21