Exercises for Potentiometry

1.

For each of the following cells, write a balanced equation for the half-cell reaction at each electrode and calculate the cell potential. Indicate whether the redox reaction in the cell is spontaneous under the given conditions. a) Fe(s) FeBr2 (0.010 M) NaBr (0.050 M) Br2(l) Pt(s)

b) Pt(s) Hg2Cl2(s) Hg(l) KCl(0.060 M) Cu(NO3)2(0.020 M) Cu(s)

2.

Consider the following redox reaction. I2(aq) + 2S2O32-(aq) a) b)

2I-(aq) + S4O62-(aq)

Write a balanced equation for the oxidation and reduction half reactions. Write the line notation for a cell based on this redox reaction.

3.

Is the redox reaction occurring in the following cell spontaneous under standard conditions? Explain. Pb(s) PbSO4(s) K2SO4(aq) H2SO4(aq) PbSO4(s) PbO2(s) Pb(s)

4.

Which of the following will be the strongest oxidizing agent under standard conditions? Explain your choice. HNO2 Se UO22+ Cl2 H2SO3 MnO2

Exercises for Potentiometry

5.

Cyanide ion causes E0 for Fe(III) to decrease. Fe3+(aq) + e-

Fe2+(aq) Fe(CN)64-(aq)

E0 = 0.771 V E0 = 0.356 V

Fe(CN)63-(aq) + ea) b)

Which ion is stabilized more by complexing with CN-? Explain. Which of the following half reactions would you expect to have the more favorable half-cell potential? Explain. Ag+(aq) + eAgCl(s) + e-

Ag(s) Ag(s) + Cl-(aq)

Using activities, calculate the potential for the following cell. Assume that the salts are completely dissociated.

Ni(s)

NiSO4 (0.0020 M)

CuCl2 (0.0030 M)

Cu(s)

7.

a)

For the following cell, write a balanced equation for each half reaction occurring at the electrodes and the Nernst equation for the overall cell reaction.

Pt(s)

H2 (g, 1.00 bar)

H+ (aq, pH = 3.60)

Cl- (aq, ?M)

AgCl(s)

Ag(s)

b)

If the cell potential is 0.485 V, what is the [Cl-] in the cathode solution?

Exercises for Potentiometry

8.

a)

E0Hg2Cl2/Hg (calomel electrode) = 0.268 V. How would you expect the potential for a KCl-saturated calomel electrode to compare? Explain. Calculate the activity of Cl- in a KCl-saturated calomel electrode.

b)

9.

What causes a junction potential? How does this potential limit the accuracy of potentiometric analyses. Why is a 0.1 M HCl - 0.1 M KCl junction potential of opposite sign and greater magnitude than a 0.1 M NaCl - 0.1 M KCl junction potential? Which side of the liquid junction 0.1 M KNO3 - 0.1 M NaCl will be negative? Explain.

10.

11.

12.

List two major sources of error associated with pH measurements.

13.

To determine the concentration of a dilute analyte with an ion-selective electrode, why do we use standards with a constant and large concentration of an inert salt? By how many volts would you expect the potential of a Mg2+ ion-selective electrode to change if the electrode is moved from a 1.00 x 10-4 M MgCl2 solution to a 1.00 x 10-3 M MgCl2 solution? When measured with a F- ion-selective electrode with a Nernstian response at 25 EC, the potential due to fluoride in an unfluoridated groundwater sample was 40.0 mV more positive than the potential of tap water reportedly maintained at the recommended level of 1.00 mg F-/L. What is the concentration of F- (in mg/L) in the groundwater?

14.

15.