Sepon School of Hydrometallurgy

Assignment 1. Aqueous Ionic Equilibria

Assigned: February 22, 2006

Due: March 22, 2006
Submit by email to: drei@interchange.ubc.ca

Ionic Equilibria between Solids and Solution

1. Ferric sulfate, Fe2(SO4)3, is a yellow compound that is used as a coagulant in

water treatment. Write a balanced chemical equation and a solubility product
expression for it’s dissolution in water.
2. Lead antimonite, Pb3(SbO4)2, is used as an orange pigment in oil-based paints and
in glazes. Write a balanced chemical equation and a solubility product expression
for its dissolution in water.
3. Thallous iodate (TlIO3) is only slightly soluble in water. Its Ksp at 25 C is 3.07 X
10-6. Estimate the solubility of thallous iodate in water in units of grams per 100
mL of water.
4. Potassium perchlorate, KClO4, has a Ksp at 25 C of 1.07 X 10-2. Compute its
solubility in grams per liter of solution.
5. Ammonium hexachloroplatinate (IV), (NH4)2PtCl6, is one of the few sparingly
soluble ammonium salts. Its Ksp at 20 C is 5.6 X 10-6. Compute its solubility in
grams per liter of solution.
6. The solubility product constant of mercurous iodide is 1.2 X 10-28 at 25 C.
Estimate the concentration of Hg22+ and I- in equilibrium with solid Hg2I2.
7. The solubility product constant of Hg2Cl2 is 2 X 10-18 at 25 C. Estimate the
concentration of Hg22+ and Cl- in equilibrium with solid calomel (Hg2Cl2) at 25 C.
8. The solubility of silver chromate (Ag2CrO4) in 500 mL of water at 25 C is 0.0129
g. Calculate its solubility product constant.
9. At 25 C, 400 mL of water can dissolve 0.0896 g of lead iodate (Pb(IO3)2).
Calculate the Ksp for lead iodate.
10. At 100 C, water dissolves 1.8 X 10-2 g of AgCl per liter. Compute the Ksp of
AgCl at this temperature.
11. A mass of 0.017 g of silver dichromate (Ag2Cr2O7) will dissolve in 300 mL of
water at 25. Calculate the solubility product constant Ksp of silver dichromate.

Precipitation and the Solubility Product

12. A solution of barium chromate (BaCrO4) is prepared by dissolving 0.0063 g of

this yellow solid in 1.00 L of hot water. Will solid barium chromate precipitate
upon cooling to 25 C, according to the solubility product expression? Explain.
13. A solution is prepared by mixing 250 mL of 2.0 X 10-3 M Ce(NO3)3 and 150 mL
of 10 X 10-2 KIO3 at 25 C. Determine whether Ce(IO3)3(s) (Ksp = 1.9 X 10-10)
tends to precipitate from this mixture.
14. Suppose 100 mL of a 0.0010 M CaCl2 solution is added to 50 mL of a 6.0 X 10-5
M NaF solution at 25 C. Determine whether CaF2(s) (Ksp = 3.9 X 10-11) tends to
precipitate from this mixture.
15. Silver iodide (AgI) is used in place of silver chloride for the fastest photographic
film because it is more sensitive to light and so can form an image in a very short
exposure time. A silver iodide emulsion is prepared by adding 6.0 L of 0.10 M
NaI solution to 1.50 L of 0.08 M AgNO3 solution at 25 C. Calculate the
concentration of silver remaining in solution (Ksp = 9.55 X 10-17).
16. When 50 mL of 0.100 M AgNO3 and 30 mL of 0.0600 M Na2CrO4 are mixed, a
precipitate of Ag2CrO4 is formed. The solubility product of silver chromate in
water at 25 C is 2.8 X 10-9. Calculate the concentrations of silver and chromate
remaining in solution at equilibrium.
17. Calculate the solubility (in mol/L) of CaF2 (s) at 25 C in a 0.040 M aqueous
solution of NaF. Ksp for CaF2 is 4.03 X 10-11.
18. The solubility product of nickel hydroxide, Ni(OH)2, at 25 C is Ksp = 1.6 X 10-16.
a. Calculate the molar solubility of Ni(OH)2 in pure water at 25 C.
b. Calculate the molar solubility of Ni(OH)2 in 0.100 M NaOH.
19. A saturated solution of Mg(OH)2 at 25 C is prepared by equilibrating solid
Mg(OH)2 with water. Concentrated NaOH is then added until the solubility is
0.0010 times that in water alone. (Ignore the change in volume resulting from the
addition of NaOH). The solubility product Ksp of Mg(OH)2 is 1.2 X 10-11 at 25 C.
Calculate the concentration of hydroxide ion in the solution after the addition of
the NaOH.

The Effects of pH on Solubility

20. Compare the molar solubility of Mg(OH)2 in pure water with that in a solution
buffered at pH = 9.00. Note that the difference between the two: when Mg(OH)2
is dissolved in pure water, the pH does not remain at 7. The Ksp for Mg(OH)2 is
1.2 X 10-11 at 25 C.
21. For each of the following ionic compounds, state whether the solubility will
increase, decrease or remain unchanged as a solution at pH 7 is made acidic.
a. SrCO3
b. Hg2Br2
c. MnS

Selective Precipitation of Ions

22. An aqueous solution at 25 C is 0.10 M in Ba2+ and 0.5 M in Ca2+ ions. We wish to
separate the two by taking advantage of the different solubilities of their fluorides,
BaF2 and CaF2. Ksp for BaF2 = 1.039 X 10-6. Ksp for CaF2 = 4.026 X 10-11.
a. What is the highest possible fluoride ion concentration that allows only
one solid fluoride salt to be present at equilibrium? Which ion is present
in the solid – Ba2+ or Ca2+?
b. What fraction of the less soluble ion still remains in solution under the
conditions of part (a)?
23. The cations in an aqueous solution that contains 0.150 M Ba(NO3)2 and 0.0800 M
Ca(NO3)2 are to be separated by taking advantage of the difference in the
solubilities of their sulfates. Ksp (BaSO4) = 1.1 X 10-10 and Ksp (CaSO4) = 2.4 X
10-5. What should be the concentration of sulfate for the best separation?
24. Calculate the Zn2+ concentration in a solution that is in equilibrium with ZnS(s)
and in which H+ concentration is 1.0 X 10-5 and the H2S (dissolved species)
concentration is 0.10 M. (Note: ∆Gf values: ZnS = -198.514 kJ/mol; Zn2+ = -
147.252 kJ/mol; H+ = 0 kJ/mol, H2S = -28.6018 kJ/mol). For calculation
purposes; ∆Greaction = -RTlnK = -2.303RTlogK, where R = 8.314 J/mol/K.

Complex Ions and Solubility

25. The overall formation constant of TlCl4- (thallic tetrachloride) complex ion is 1 X
10-18. Suppose 0.15 mol of Tl(NO3)3 is dissolved in 1.00 L of a 0.5 M solution of
NaCl. Calculate the concentration at equilibrium of TlCl4- and Tl3+. Ignore the
concentrations of other species that may form (TlCl3 (aq), TlCl2+, TlCl2+).
26. Calculate the pH of the following solutions (ignore activity coefficients):
a. 0.01 M HCl
b. 0.01 M oxalic acid (H2C2O4) Ka1 = 0.056; Ka2 = 5.42 X 10-5 (Hint: Write
out all relevant reactions. Write equilibrium constant expressions for each.
Write a charge balance equation. Write a mass balance equation.)
27. Calculate the pH of a saturated lime suspension. (Ksp for Ca(OH)2 = 6.5 X 10-6 at
25°C).
28. Problem: A solution contains 0.1 molar Hg(NO3)2, 0.1 molar Cu(NO3)2, 0.1 molar
Pb(NO3)2, 0.1 molar Zn(NO3)2. A solution of 0.1 molar Na2S is added in order to
precipitate all of the metals. Which metal will precipitate first? Ans.: Calculate
the [S2–] required to precipitate each metal.
Sulphide salt Ksp
HgS 4 x 10–53
CuS 6 x 10–36
PbS 1 x 10–28
ZnS 2 x 10–24
FeS 5 x 10–18

29. Calculate the Ksp value for AlF3 from the following data. Use the Ksp to
determine how much fluoride will be in a solution of water saturated with AlF3.

Species ∆Gf (kJ/mol)

AlF3 -1431.11
Al(+3a) -487.478
F(-a) -281.705

30. Estimate the pH of solutions of sodium formate (NaCOOH) at concentrations of

10-5, 10-4, 10-3, 10-2, 10-1 and 1 M.
31. Draw a distribution diagram for acetic acid (CH3COOH) as a function of pH. Ka
= 1.8 X 10-5. Present the fractional distribution on a linear and then a log scale.
32. Draw the distribution diagram for As(V) acid, H3AsO4 as a function of pH. pK1 =
2.258, pK2 = 6.772 and pK3 = 11.604.
33. Calculate the buffer point (pH) of a solution containing 0.1 M NH4Cl and 0.2 M
NH3. pKb for NH3 is 4.7.
34. Calculate the buffer point (pH) of a solution in which 0.2 M NH4Cl is combined
with 0.1 M NaOH.
35. Calculate the solubility of Zn from Zn(OH)2 and Fe from Fe(OH)3 as a function of
pH. Log Ksp for Zn(OH)2 = -16.077 and Log Ksp for Fe(OH)3 = -38.536
36. Calculate the solubility of MnCO3 and MgCO3 as a function of pH. Log Ksp for
MnCO3 = -10.637 and Log Ksp for MgCO3 = -5.306.
37. Calculate the distribution diagram for the copper (Cu2+) and ammonia (NH3)
system given the following values of stepwise and overall formation constants.
i 1 2 3 4
log Kci 4.33 3.598 3.022 2.193
log βi 4.33 7.928 10.95 13.143
Atomic Molecular Weight Atomic Molecular Weight
Number Element Name (g/mol) Number Element Name (g/mol)
1 H Hydrogen 1.0079 54 Xe Xenon 131.29
2 He Helium 4.0026 55 Cs Cesium 132.9055
3 Li Lithium 6.941 56 Ba Barium 137.327
4 Be Beryllium 9.0122 57 La Lanthanum 138.9055
5 B Boron 10.811 58 Ce Cerium 140.116
6 C Carbon 12.0107 59 Pr Praseodymium 140.9077
7 N Nitrogen 14.0067 60 Nd Neodymium 144.24
8 O Oxygen 15.9994 61 Pm Promethium 145
9 F Fluorine 18.9984 62 Sm Samarium 150.36
10 Ne Neon 20.1797 63 Eu Europium 151.964
11 Na Sodium 22.9898 64 Gd Gadolinium 157.25
12 Mg Magnesium 24.305 65 Tb Terbium 158.9253
13 Al Aluminum 26.9815 66 Dy Dysprosium 162.5
14 Si Silicon 28.0855 67 Ho Holmium 164.9303
15 P Phosphorus 30.9738 68 Er Erbium 167.26
16 S Sulfur 32.066 69 Tm Thulium 168.9342
17 Cl Chlorine 35.4527 70 Yb Ytterbium 173.04
18 Ar Argon 39.948 71 Lu Lutetium 174.967
19 K Potassium 39.0983 72 Hf Hafnium 178.49
20 Ca Calsium 40.078 73 Ta Tantalum 180.9479
21 Sc Scandium 44.9559 74 W Tungsten 183.84
22 Ti Titanium 47.867 75 Re Rhenium 186.207
23 V Vanadium 50.9415 76 Os Osmium 190.23
24 Cr Chromium 51.9961 77 Ir Iridium 192.217
25 Mn Manganese 54.938 78 Pt Platinum 195.078
26 Fe Iron 55.845 79 Au Gold 196.9666
27 Co Cobalt 58.9332 80 Hg Mercury 200.59
28 Ni Nickel 58.6934 81 Tl Thallium 204.3833
29 Cu Copper 63.546 82 Pb Lead 207.2
30 Zn Zinc 65.39 83 Bi Bismuth 208.9804
31 Ga Gallium 69.723 84 Po Polonium 209
32 Ge Germanium 72.61 85 At Astatine 210
33 As Arsenic 74.9216 86 Rn Radon 222
34 Se Selenium 78.96 87 Fr Francium 223
35 Br Bromine 79.904 88 Ra Radium 226.0254
36 Kr Krypton 83.8 89 Ac Actinium 227.0278
37 Rb Rubidium 85.4678 90 Th Thorium 232.0381
38 Sr Strontium 87.62 91 Pa Protactinium 231.0359
39 Y Yttrium 88.9059 92 U Uranium 238.0289
40 Zr Zirconium 91.224 93 Np Neptunium 237.0482
41 Nb Niobium 92.9064 94 Pu Plutonium 244
42 Mo Molybdenum 95.94 95 Am Americium 243
43 Tc Technetium 98 96 Cm Curium 247
44 Ru Ruthenium 101.07 97 Bk Berkelium 247
45 Rh Rhodium 102.9055 98 Cf Californium 251
46 Pd Palladium 106.42 99 Es Einsteinium 252
47 Ag Silver 107.8682 100 Fm Fermium 257
48 Cd Cadmium 112.411 101 Md Mendelevium 258
49 In Indium 114.818 102 No Nobelium 259
50 Sn Tin 118.71 103 Lr Lawrencium 260
51 Sb Antimony 121.76 104 Unq (Unnilquadium) 261
52 Te Tellurium 127.6 105 Unp (Unnilpentium) 262
53 I Iodine 126.9045 106 Unh (Unnilhexium) 263