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# PRINCIPLES OF PYROMETALLURGY (CHMT4012A/CHMT5005A)

## Due 24 July 2019, 1700hrs

Instructions: Answer all questions on a clean sheet of paper. Illegible work will not
be graded. Only hand written work will be accepted.

1) Compared to two decades ago, modern blast furnaces are characterized by low coke
rates (ca. 350kg/tHM compared to 450-500kg/tHM historic) due to the adoption of
pulverized coal injection practices. Based on this statement, critically reflect on the
practice of pulverized coal injection in the blast furnace operation [5 marks]
2) Discuss the three main objectives/advantages of hot metal treatment [3 marks]
3) Based on the possible chemical reactions and the physicochemical conditions
favorable for the removal of sulphur in the iron and steelmaking, explain why
sulphur removal is better carried out in the blast furnace and not in the oxygen
steelmaking processes [5 marks]
4) With respect to energy efficiency, briefly discuss the principle of slag foaming in
electric arc furnace [5 marks]
5) Consider the following reaction for the production of stainless steel:
FeCr2O4(s) + 4[%C] = [Fe](l) + 2[%Cr] + 4CO(g)
Assuming that the slag is saturated with chromite (FeCr2O4), calculate the
minimum carbon that can be achieved at 1600ºC and 1700ºC. Assume that aFe =0.95;
[%Cr] = 5; pCO = 1; aFeCr2O4 = 1. State all assumptions [10 MARKS].
Data
Fe(s) + 2Cr(s) + 2O2(g) = FeCr2O4(s); ΔG01 = -333 550 + 74.2Tcal
C(s) + 0.5O2(g) = CO(g); ΔG02 = -27 700 -20.95Tcal
C(s) = [%C] in Fe; ΔG03 =5 400-10.1Tcal
Cr(s) = [%Cr] in Fe; ΔG04 =5 000- 11.31T cal
Fe(s) = [Fe]; ΔG05 = 3 587 – 1.995Tcal
6) Pig iron containing 0.1 wt. % S, 0.3 wt. % Si, 3.4 wt. % C, 0.8 wt. % Mn and 1.8 wt. %
P is desulphurized at 1300ºC according to the following reactions:
[S]1wt % + (CaO)(s) + [C] = (CaS)(s) + CO(g); ΔG01=23 090- 25.14T cal.
[S] 1wt % + 2(CaO)(s) +0.5[Si] = (CaS)(s) + 0.5(2CaO·SiO2)(s); ΔG02=-53 945 + 17.85T cal.
Assuming that iron is saturated with carbon and all solid compounds are pure and
pCO = 1 atm, show that desulphurization is favoured in the presence of silicon,
given that fS = 3.6 and fSi = 4.5. [10 MARKS]
7) In the basic open hearth process, the reaction of manganese in the bath with iron
oxide (FeO) in the slag attains condition very closely approximating true
equilibrium. The steel contains 0.065 atom % manganese and the slag analysis (by
weight) is: FeO: 76.94%; Fe2O3: 4.15%; MnO: 13.86%; MgO: 3.74%; SiO2: 1.06%; and
CaO: 0.25%. Calculate the value of the equilibrium constant and the standard free
energy change for the reaction at 1655oC, assuming that the slag and Fe-Mn system
behave ideally at that temperature. Neglect the effect of other metalloids present in
the steel [15 MARKS].
8) With the aid of equations, discuss the typical conditions employed in the ladle
desulphurization of Al-killed steels [4 MARKS]
9) Depending on their sources, non-metallic oxide inclusions can be classified as either
exogenous or indigenous inclusions. Discuss the four (4) possible sources of
exogenous non-metallic inclusions and two possible sources of endogenous non-
metallic inclusions [6 MARKS]
10) Carbon in the liquid iron can reduce silica in the refractory by the reaction: 2[%C] +
SiO2(l) = [%Si] + 2CO(g). This is an important reaction in acid steelmaking
processes. The standard free energy formation of silica is given as [%Si] + 2[%O] =
SiO2(l); ΔGo = -594 100 +230T J. You are also given that [%C] + [%O] = CO; ΔGo =-
22 400 -39.6T
a) What are the equilibrium concentrations of carbon and oxygen in the metal at
1600ºC and pCO = 1atm when %Si = 0.16? [12 marks]
b) What will happen to the composition of the metal in part (a) if the temperature of
the system is raised to 1800ºC? [8 marks]
Assume that the activities of species in the metal are equal to their compositions in
wt. %.
TOTAL MARKS 

## ©University of the Witwatersrand, Johannesburg 2019

Useful information
Atomic masses of elements (g/mol):
Iron (Fe) 55.85; Copper (Cu) 63.55; Calcium (Ca) 40.08; Aluminium (Al) 26.98;
Silicon (Si) 28.09; Magnesium (Mg) 24.305; Sulfur (S) 32.07; Oxygen (O) 16.00;
Manganese (Mn) 54.94; Chromium (Cr) 51.996; Carbon (C) 12.01; Nitrogen (N) 14.00;
Phosphorus (P) 30.97

1 cal = 4.184J

## Conditions at STP: T = 0°C, P = 100 kPa

Conditions at NTP: T = 20°C, P = 1 atm = 101.325 kPa