CHEM 18.

University Chemistry
Problem Set 4

SOLUBILITY EQUILIBRIA

1. Write the solubility product constant expression of the following salts:

a. AgCl d. Ag2CO3 g. ZnC2O4

b. BaSO4 e. PbF2 h. Ag2CrO4
c. Al(OH)3 f. Ca3(PO4)2 i. Mn3(PO4)2

2. Arrange the following salts in order of increasing solubility:

Salt Ksp
CaF2 4.0 x 10
–11

Fe(OH)2 1.6 x 10
–14

Ag2S 6.0 x 10
–51

BaCO3 8.1 x 10
–9

CuI 5.1 x 10
–12

AgI 8.3 x 10
–17

SnS 1.0 x 10
–26

–15 o
3. Calculate the Ksp value for bismuth sulfide (Bi2S3) which has a solubility of 1.0 x 10 mol/L at 25 C.
4. The solubility of silver bromate, AgBrO3, in water is 0.0072 g/L. Calculate the Ksp.
–7 o o
5. The Ksp value for copper (II) iodate is 1.4 x 10 at 25 C. Calculate the solubility at 25 C.
–6
6. The molar solubility of MnCO3 is 4.2 x 10 M. What is the Ksp for this compound?
7. A solution saturated in calcium hydroxide (limewater) has a pH of 12.35. What is the Ksp for calcium
hydroxide?
–8
8. The Ksp for lead iodide (PbI2) is 1.4 x 10 . Calculate the solubility of lead iodide in each of the
following:

a. water
b. 0.10 M Pb(NO3)2
c. 0.010 M NaI

9. Calculate the molar solubility of BaSO4 in

a. water.
2–
b. a solution containing 1.0 M SO4 ions.

10. A 50.00 mL sample of 0.00200 M AgNO3 is added to 50.0 mL of 0.0100 M NaIO3. What is the
+ –8
equilibrium concentration of Ag in solution? Ksp for AgIO3 is 3.0 x 10 .
 –4 + –2 2+ –
11. A solution contains 1.0 x 10 M Cu and 2.0 x 10 M Pb . If a source of I is added to this solution
–8 –12
gradually, will PbI2 (Ksp = 1.4 x 10 ) or CuI (Ksp = 5.3 x 10 ) precipitate first? Specify the
–
concentration of I necessary to begin precipitation of each salt.
+ +
12. Solid NaI is slowly added to a solution that is 0.010 M in Cu and 0.010 M Ag .

a. Which compound will begin to precipitate first?

+
b. Calculate the Ag concentration when CuI first begins to precipitate.
+
c. What percent of Ag remains in solution at this point?

13. Write the net ionic equation in which the slightly soluble salt magnesium oxalate, MgC2O4, dissolves in
dilute hydrochloric acid.
14. Which salt would you expect to dissolve readily in acidic solution, calcium phosphate, Ca3(PO4)2, or
calcium sulfate, CaSO4?
2+ 2+ 2+
15. Describe how you would separate the following mixture of metal ions: Cd , Pb , and Sr .
+ 2+ 2+
16. Describe how you could separate the following mixture of metal ions: Na , Hg , and Ca .

REDOX

1. Complete and balance the following half-reactions. In each case, indicate whether oxidation or
reduction occurs.

a. Sn2+(aq) → Sn4+(aq)
b. HOCl(aq) → Cl2(aq) (acidic solution)
c. NO3-(aq) → NO2-(aq) (basic solution)

2. Balance the following reactions thru the change in oxidation number method:

a. Cl2 +NaOH→NaCl+NaClO+H2O
b. P4 +NaOH+H2O→PH3 +NaH2PO2
c. As2O3 +MnO4- +H+ +H2O→H3AsO4 +Mn2+

3. Balance the following equation thru the half-reaction method:

a. B2Cl4 + -OH → BO2- + Cl- + H2O + H2 (basic solution)

b. CrI3 + H2O2 → CrO42- +. IO4- (acidic solution)

ELECTROCHEMISTRY

1. Write the cell notation for the voltaic cell with the following half reactions:

Cd(s) → Cd2+(aq) + 2e-

Pb2+(aq) + 2e- → Pb(s)
2. Calculate the standard cell potential for the following reactions:
a. Sn2+ + Ni → Sn + Ni2+
b. Zn + 2H3O+ → Zn2+ + H2 + 2H2O
c. Fe3+ + Sn → Fe2+ + Sn2+
d. Mg2+ + Al → Mg + Al3+

3. A voltaic cell is constructed from the following half-cells: a zinc electrode in zinc sulphate solution and a
nickel electrode in nickel sulfate solution. Sketch the cell, labeling the anode and cathode (and the electrode
reactions), and show the direction of electron flow and movement of ions.

4. A voltaic cell utilizes the following reaction and operates at 298K: 3Ce4+(aq) + Cr(s) → 3Ce3+(aq) + Cr3+(aq)

1. What is the Eocell?

2. What is the ΔGo and Keq?
3. What is the Ecell when [Ce4+] = 1.5M, [Ce3+] = 0.010M and [Cr3+] = 0.010M?

Cr3+ +3e- → Cr Eo = -0.74 V

Ce4+ + e- → Ce3+ Eo = +1.61 V

CHEMICAL KINETICS

1. A chemical kinetics assay is carried out to determine the rate law expression for the reaction:
K + 2M → KM2. Using the following data:

Expt no. [K], mM [M], mM Rate, mM/min

1 1.50 2.50 0.21
2 3.00 2.50 1.67
3 1.50 7.50 0.64

a. Determine the order of reaction with respect to K.

b. Determine the order of reaction with respect to M.
c. Determine the rate law expression.

2. The reaction, 2NO(g) + Cl2(g) → NOCl(g) was carried out at -10oC. The following results were obtained.

Expt no. [NO], M [Cl2], M Rate, M/min

1 0.08 0.08 0.092
2 0.08 0.16 0.184
3 0.16 0.16 0.736

a. What is the rate law expression?

b. What is the value of the rate constant?
3. Given the following three experimental data:

Experiment 1 Experiment 2 Experiment 3

Time, s [A], M Time, s [A], M Time, s [A], M
0 1.00 0 1.00 0 1.00
25 0.78 25 0.75 25 0.80
50 0.61 50 0.50 50 0.67
75 0.47 75 0.25 75 0.57
100 0.37 100 0.00 100 0.50
150 0.22 150 0.40
200 0.14 200 0.33
250 0.08 250 0.29

a. Which of these experiments corresponds to a (i) zero-order, (ii) first-order, and (iii) second-order
reaction?
b. What is the value of the rate constant k of the second-order reaction?
c. What is the approximate half-life of the first-order reaction?
d. What is the approximate initial rate of the second-order reaction?
e. What is the approximate rate of reaction at t=75 s for the (i) zero-order, (ii) first-order, (iii) second-
order reaction?
f. What is the approximate concentration of A remaining after 110 s in the (i) zero-order, (ii) first-order,
(iii) second-order reaction?

4. The first-order rate constant for the reaction of a particular organic compound with water varies with
temperature as follows:

Temperature, K Rate constant, (s-1)

300 3.2 x 10-11
320 1.0 x 10-9
340 3.0 x 10-8
355 2.4 x 10-7

From these data, calculate the activation energy in kJ/mol.