COPPERBELT UNIVERSITY

SCHOOL OF MINES AND MINERAL SCIENCES

METALLURGY DEPARTMENT
MT420/MT520 ASSIGNMENT 1 Due on: 20.03.2023

POTENTIAL – pH DIAGRAMS – PROBLEMS

(R = 8.314 J K-1 mol, 1 Faraday = 96500 coulombs mol-1,ln X = 2.303 log10X, 273K = 0oC)

Please use graph paper.

Problem One
Noah Mulenga, John Chiyabi and Martha Kaunda

(a) Draw a potential – pH diagram for the Fe – H2O system at 25oC and 1 atmospheric pressure. Consider
only the species given in table 1. Take Fe2+ = 10-4M, Fe3+ = 10-4M. Show also the upper and lower stability
limits of water.

Table 1. Gibbs energy of formation data.

Species ΔGof (KJ mol-1)
Fe (s) 0
Fe(OH)2 (s) - 484
Fe(OH)3 (s) - 695
Fe2+ (aq) -85.0
Fe (aq)
3+ -10.5
H2O (l) - 237
OH (aq)
- - 157
H+ (aq) 0
H2 (g) 0

(b) Use your diagram to answer the following questions:

(i) Is Fe stable in the presence of water at any pH values?
(ii) What is the lowest pH value at which Fe(OH)3 is stable in the presence of Fe3+ (aq) at a
concentration of 10-4 mole/litre?
(iii) What is the lowest pH value at which Fe(OH)2 is stable in the presence of Fe2+ (aq) at a
concentration of 10-4 mole/litre?
(iv) If the pH were lowered, what would actually happen to Fe(OH)3?
(v) Considering the redox couple Fe2+/Fe3+ on your Fe-H2O system, predict the behavior of
dissolved iron at (i) anode (ii) cathode of an electrolytic system.
Question Two
Simenda Daisy, James Kachiwende and Suwilanji Simunyola

(a) Draw the potential- pH diagram for the three species Co2+ (aq), Co(OH)2 and Co(s) at 25oC and 1
atmosphere total pressure. Show also the equilibrium line between H2 (gas) at 1 atmosphere and water.
Give the equations of all the lines involved.

Concentration of Co2+ = 10-3 mole litre-1.

Use the following standard free energies of formation:-
Species ∆ Gof (kJ mol-1)
Co2+ (aq) - 53.5
Co(OH)2 (s) - 456
H2O (l) - 237
OH - - 157.0
H+ 0
Co 0
H2 0

(b) With the help of the answer in Question One, compare the Fe-H2O and Co-H2O systems and explain
the best way to remove iron from cobalt leach liquor in a cobalt purification circuit.

Problem Three
Bethel Changani, Danny Chipampe and Chinyanta Ndhlovu

(R = 8.314 J K-1 mol, 1 Faraday = 96500 coulombs mol-1,ln X = 2.303 log10X, 273K = 0oC)

Please use graph paper.

Ignoring dissolved species, draw an Eh – pH diagram to represent the equilibrium among magnetite,
siderite, metallic iron and water, at a partial pressure of CO2 of 10-2, 1 atmosphere total pressure and 25oC.
Indicate metastable equilibria (if any) by a dashed line. From the diagram answer Yes or No to the following
questions:
(i) Can iron and magnetite co-exist?
(ii) Can water and siderite co-exist?
(iii) Can oxygen and siderite co-exist?
(iv) Can hydrogen and magnetite co-exist?

Species ∆ Gof (kJ mol-1)

Iron 0
Magnetite (s) - 1015
Siderite (s) - 667
Water (l) - 237
CO2 (g) - 394
H2 0
H+ 0
Question Four
Ryan Kashulwe, Karen Namukanzye and David Yotamu

Calculate the pressure at 25oC at which 1M Ca2+ (aq) and 1M ZnO22- (aq) would be 99% reduced by
hydrogen at pH 14. Would it be possible to separate (theoretically) the two metals by hydrogen reduction at
this pH ?
Data: 1 Faraday = 96500 C mol-1
R = 8.314 Jk-1mol-1
Species ∆Gof (kJ mol-1)
Ca (aq)
2+ - 553.0
ZnO22- (aq) - 389.2
H2O (l) - 237.2
OH- (aq) - 157.0
H (aq)
+ 0

Problem Five
Chimponda Mulenga, Cecilia Katongo and Richard Abel Phiri

(1) Calculate the equilibrium pH values for the three reactions given below. Take equilibrium
concentrations [Zn2+] = [Fe2+] = [Fe3+] = 10-3 mol/litre.
a) Zn2+(aq) + 2H2O(l) = Zn(OH)2(s) + 2H+(aq)
b) Fe2+(aq) + 2H2O(l) = Fe(OH)2(s) + 2H+(aq)
c) Fe3+(aq) + 3H2O(l) = Fe(OH)3(s) + 3H+(aq)

(2) Use the pH values you have calculated in (1) to suggest an effective way of removing iron from
zinc in aqueous solution.

Table 2. Gibbs Energies of formation data.

Species ΔGof (KJmol-1)
Zn2+(aq) -174.06
Zn(OH)2(aq) -555.9
Fe2+(aq) -85.0
Fe3+(aq) -10.5
Fe(OH)2 (s) -484.0
Fe(OH)3 (s) -695.0
H2O -237.0
H+ 0

Problem Six
Bwalya Karen, Chasha Collins, Namukanzya Drusilla and Kunda Tashani
Calculate the pressures at 200oC at which 20gpl Ni2+ and 20gpl Cu2+ would be 99% reduced by hydrogen
gas at pH 1. Would it be possible to separate (theoretically) the two metals by hydrogen at this pH ?

Species ∆Gof (kJmol-1)

Ni 0
Ni2+ -46
Cu 0
Cu2+ -66
H+ 0
H2 0
Question Seven
Busiku Muleya, Richard Shawn Tembo and Manfred Mwaba

Consider the equilibrium: Fe3+ +3H2O = Fe(OH)3 + 3H+

(1) Calculate the equilbrium concentrations of Fe3+ at the pH values of 1, 2, 3, 4, 5, 6 and 7.

(2) Plot a graph of Fe3+ concentration against pH
(3) From your graph, how does the pH affect the concentration of Fe3+ in an aqueous solution?

Table 2. Gibbs Energies of formation data.

Species ΔGof (KJmol-1)
Zn2+(aq) -174.06
Zn(OH)2(aq) -555.9
Fe2+(aq) -85.0
Fe3+(aq) -10.5
Fe(OH)2 (s) -484.0
Fe(OH)3 (s) -695.0
H2O -237.0
H+ 0

Question Eight
Phiri Chibamu, Erick Mulenga and Exildah Namukoko

(a) Calculate the equilibrium pH for the reaction:

3Fe2O3 (s) + 2H+ + 2e- = 2Fe3O4 (s) + H2O (l)
(b) Calculate the Nernst potential at pH = 2 for the reaction:
Fe3O4 (s) + 8H+ + 8e- = 3Fe (s) + 4H2O (l)

Data:
T = 298K, R = 8.314 kJmol-1, F = 96500 C mol-1
Species ΔGfo (kJmol-1)
Fe2O3(s) -741.2
Fe3O4 (s) -1014.4
Fe(s) 0
H2O (l) -237.2
H+ 0

QUESTION NINE
Angolwishe Nesi, Ngosa Kalunga, Joseph Nkosha and Alfred Mphande

(a) Calculate the solubility of CaF2 in;

(i) Water
(ii) 0.1M Ca(NO3)2 solution
(iii) 0.1M NaF solution

Where Ks(CaF2) = 4x10-11 at 25oC

(b) By referring to the equilibrium constants listed below, find the equilibrium constants for each of the
following:
(i) Fe(OH)3 (s) + 3H3O+ = Fe3+ + 6H2O
(ii) PbSO4 (s) + CrO42- = PbCrO4 (s) + SO42-
 (iii) Mg(OH)2 (s) + 2CH3CO.OH = Mg2+ + 2CH3CO.O- + 2H2O

Data:
Ks{Fe(OH)3} = 4x10-38 Ks(PbCrO4) = 2x10-14
Kw = 10-14 Ks(PbSO4) = 2x10-8
Ka(CH3CO.OH) = 1.7x10-5 Ks{Mg(OH)2} = 1.2x10-11

Question Ten
Stephen Mate, Mwinsa Chileka, Richard Mulindwa and Moses Brown

1. Assume Co2+ = 10-3 mol/litre in solution, temperature at 25 oC and H2 & O2 partial pressures = 1
atm, Calculate:
1.1 The EH for the equilibrium Co – Co2+at pH = 1.8.
1.2 The EH for the equilibrium Co – Co(OH)2 at pH = 1.8
2. Assuming that Co2+ = 10-2 mol/litre, calculate the logPO2 at pH = 1.5 for the reaction
2Co + 4H+ + O2 = 2Co2+ + 2H2O

Species ∆ Gof (kJ mol-1)

Co2+ (aq) - 53.5
Co(OH)2 (s) - 456
H2O (l) - 237
OH- - 157.0
H+ 0
Co 0
H2 0