Q1

[a]
Given:

Pb conc Flux
CaCO3

Air Off gas

O2 SMELTER bullion

Slag
54 % PbO
15 % ZnO
18.5 % Fe2O3
CaO
=0.35
Si O2 12.5 % SiO2
PbO
=3.2
CaO+ SiO2

Required: mass CaCO3/kg slag to achieve target composition

Solution:
Basis: 100 g slag
CaO
Using =0.35
Si O2
CaO=0.35 Si O2
CaO=0.35∗12.5=4.375 g

Reaction: CaC O 3 → CaO+C O 2

g CaC O3
=
4.375 g CaO ( 1 mol CaO
56.1 g CaO )(
1mol CaC O3
1 mol CaO )( 100.1 g CaC O3
1 mol CaC O3 )
kg slag
100 g slag ( 1000
1 kg
)
g CaC O 3
=7 7.24
kg slag
[b]
Required: plot the target composition
Solution:
Basis: 100 kg slag
CaO=0.35 Si O2
CaO=0.35 ( 12.5 )=4.375 kg

Wt. Wt. %
PbO 54 51.7
ZnO 15 14.4
Fe2O3 18.5 17.7
SiO2 12.5 12.0
CaO 4.375 4.2
TOTAL 104.375 100

PbO+ CaO+ Si O2=67.9 %

ZnO=14.4 %
F e 2 O 3 =17.7 %
[c] Composition: Liquid = 75.9 % and Zinc ferrite = 24.1 %

3.5

11.0
[d]Bulk slag composition
Wt. Wt. % - bulk slag
composition
PbO 0 0
ZnO 14.4 30.97
FeO 15.9 34.19
SiO2 12.0 25.81
CaO 4.2 9.03
TOTAL 46.5 100

CaO+ Si O2=34.84 %
ZnO=30 . 97 %
F eO=34 . 19 %

Liquidus = 1200 ˚C
Primary phase = zincite
Q2.

[a] The form of the copper that can be removed from lead bullion by slow cooling of the bullion is solid, and
is almost pure. The minimum copper is 0.2 mol % (0.06 wt. %) near the eutectic point.

[b]
Assumption: All Cu reacts with S, excess S in the solution (2.81 mol %)

T=603 K

R1: 2Cu(l) + 0.5S2(g)  Cu2S(l)

R2: 0.5S2(g)  1 mol % S

ΔH ΔS ΔG (603 K)
R1 -140708 -43.35 -114568
R2 -84340
R1-R2 -30228

( )
a Cu S
∆ G=0=∆ Go603 K + RTln 2
2

a mol % S
Cu
a Cu S=1, since it is asusmed to be pure solid, mol % = 2.81
2

Then,

( )
o
2 1 ∆ G 603 K
a =
Cu exp
2.81 RT
a Cu=0.0293
a
x Cu= Cu =0.0225 mol %
γ Cu
x Cu M Cu
wt . %= =0.00707
x Cu M Cu + x Pb M Pb+ x S M S

The residual level of Cu is about 10 times less in the presence of S. Therefore, it is beneficial to add some S
to the solution.
Q4.
[a]
ΔH ΔS ΔG (1473 K)

Pb(l) + 0.5O2  PbO(l) -185080 -72.028 -78982.8

Pb(l)  1 wt % in Cu 36066 58.618 -50278.3

0.5O2(g)  1 wt% in Cu -85354 -18.535 -58051.9

Pb(1wt%) + O(1 wt%)  PbO(l) -135792 -112.111 29347.5

 To facilitate the transfer of PbO to slag, the activity of PbO must be reduced in the refining slag as
low as possible. This is done thru silica addition in excess, which will give a minimum a (PbO) = 0.08 at
silica saturation.

∆ G=∆ Go + RTln (
aPbO
wt % Pb ∙ wt % O )
∆ G=29347.5+8.314 ( 1473 ) ln
0.08
(
0.6 ∙ 0.4 )
J
∆ G=15893
mol

Since delta G is positive, the reaction will not proceed under these conditions.

[b]
Setting delta G = 0

o
0=∆ G + RTln ( wt % Pb∙a wt % O )
PbO

0=29347.5+8.314 ( 1473 ) ln ( 0.6 ∙0.08

wt % O )
wt % O=0.683
This is the wt% O required for the reaction to proceed.

Using the maximum wt% O obtained from the Cu-O phase diagram,
 wt % O=
0.1 mol % O ( 116molg )
0.1 mol % O ( 116molg )+0.9 mol % Cu ( 63.546
1 mol )
g

wt % O=3.02 %

Calculating for wt% Pb:

0=29347.5+8.314 ( 1473 ) ln ( wt % Pb∙

0.08
3.02 % )
wt % Pb=0. 29 % Pb

This is the minimum wt% Pb in copper that can be achieved.

[e]
Liquid = 83.83 %
Zincite = 12.5 %
Wustite = 3.68 %
The proportions are estimated from the lever rule in assumption of stoichiometris solid phases. Also, the
diagram used is for CaO/SiO2 = 0.71, which is slightly different from 0.6, and this difference has been
neglected.