Chemistry 311 Physical Chemistry (Fall 2000)

Examination 3

1. One mole of benzene is mixed with two moles of toluene to form an ideal solution. (a) As the pressure
is reduced, holding the temperature constant at 60◦ C, at what pressure will boiling begin? (b) What will
be the composition of the first bubble of vapor formed? [At 60◦ C, the vapor pressures of pure benzene
and toluene are 51.3 and 18.5 kPa, respectively.]
Equations given: Equations applicable to liquid-vapor equilibria involving ideal solutions:
Raoult’s Law :pA =xA PA∗
Dalton’s Law :pA = yA P

Bubble-point line :P = PB∗ + (PA∗ − PB∗ )xA

PA∗ PB∗
Dew-point line :P
PA∗ + (PB∗ − PA∗ )yA
=

Answer:

Let us denote benzene by B and toluene by T .

(a) From the bubble-point line, we get the pressure at which the first bubble is formed.
P =PT∗ + (PB∗ − PT∗ )xB
=18.5 + (51.3 − 18.5) × (1/3) kPa

=29.4 kPa

(b) From Dalton’s Law, we get

x P∗
yB = B B
P
(1/3) × 51.3
=
29.4
=0.581

2. Construct the phase diagram for the Mg-Cu system from the following data:
• Cu (MW=63.54 g/mol) melts at 1085◦C, and Mg (MW=24.312 g/mol) melts at 648◦C.
• Two compounds, MgCu2 (M.P=800◦C), and CuMg2 (M.P=580◦C) are formed.
• Three eutectics, at 680◦C, 560◦C, and 380◦C are formed at compositions 9.4%, 34% and 65% by weight
of Mg, respectively.
In each two-phase region, indicate the solid that separates out from the liquid phase. [Atomic masses:
Mg: 24.31 g mol−1 , Cu: 63.55 g mol−1 .]

Equations given: None

Answer:

The weight % of Mg in the two compounds are found as follows:

151.41 g of MgCu2 contains 24.31 g of Mg. Therefore, the weight percent of Mg in this comound is
24.31 g
151.41 g × 100 = 16.06.
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 Similarly, 112.17 g of Mg2 Cu contains 48.62 g Mg. Therefore, the weight percent is

48.62 g × 100 = 43.35.

112.17 g
The phase diagram is shown below with the labes for each region.

Phase Diagram of Magnesium-Copper

1100

1000

MgCu 2(s)
900 +
Temperature/°C

Liquid
Cu(s)
800 +
Liquid Mg2Cu(s)
700 +
Liquid

600
Cu(s)
500 +
MgCu 2(s) MgCu 2(s)
+ Mg(s) + Liquid
400 Mg2Cu(s)
Mg2Cu(s) + Mg(s)
300
0 20 40 60 80 100

Wt % Mg

3. When the liquid C is added to two partially miscible liquids A and B, it dissolves in both layers to give
rise to a layer rich in A, in equilibrium with a layer rich in B. The equilibrium compositions of the two
layers corresponding to various amounts of added C are given below.

Layer rich in A Layer rich in B

Wt % A Wt % C Wt % B Wt % C
95.0 0.0 92.5 0.0
85.0 10.5 82.0 12.0
73.0 20.0 64.0 25.0
57.5 30.0 50.0 35.0
45.0 35.0 35.0 40.0

(a) Construct the phase diagram and draw the tie-lines. (b) If 20.0 g of C is added to a mixture of 50.0 g
of A and 30.0 g B, state the number of phases formed and their compositions. (c) If we wish to reduce
the number of phases by adding C to the mixture in (b), at what weight percentages of A, B and C will
this happen?
Equations given: None

Answer:

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(a) The phase diagram is given below:

Plot Title
C

20 80

40 60

60 40

80 20

A 20 40 60 80 B

(b) The total weight of the solution: 20.0 + 30.0 + 50.0 = 100.0 g. Therefore, the composition corresponds
to 20 % by weight in C and 50 % by weight in A. This corresponds to the point marked by the solid
square shown above, in the two phase region. The two layers will have the compositions indicated by
the tie-line passing through the point. From the tie-line the layer rich in A will have the composition 19
% by weight in C and 75% by weight in A while the layer rich in B will have the composition 22% by
weight in C and 68% by weight in B.
(c) When C is added to the mixture in part (b), the total composition moves along the line drawn from the
point marked by the solid square along the solid line towards the apex of the triangle where pure C is
located. When the total composition reaches the point marked by the empty circle, the two phases merge
to form a single phase. This point has the composition of 39% by weight in A, 24% by weight in B and
37% by weight in C.
4. After the passage of a constant current for 1 h, 40 mg of copper (atomic weight = 63.5 g mol-1) was
deposited from a solution of CuSO4. Calculate the current.

Equations given: The “electrolysis equation:”

wnF = It.
M
Answer

The current:

I = wnF
Mt
0.040 g × 2 mol e−/mol Cu × 96500 C (mol e− )−1
63.5 g (mol Cu)−1 × 3600 s
= 0.0338 C s−1 = 0.0338 A.
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5. The conductivity κ of a 0.0312 M solution of weak base B is 1.53 × 10−4 Ω−1 cm−1 . If the sum of the
ionic conductances for BH+ and OH− is 237.0 Ω−1cm2 mol−1 , what is the value of the base dissociation
constant, Kb ?
Equations given: Λ = κc Ω−1 cm2 mol−1,α = Λ/Λ◦;Λ◦ = Λ+ + Λ−, Kc = α2c/(1 − α).
Answer:

From the conductivity κ and the given value of concentration, we get

Λ= κc = 01.0312
.53 × 10−4 Ω−1cm−1
× 10−3 mol cm−3
=4.904 Ω cm2 mol−1
−1

Therefore, the degree of dissociation α is given by

.904 Ω−1cm2 mol−1
α= ΛΛ◦ = 4237 .0 Ω−1cm2 mol−1
=0.02069
Now, the base dissociation constant can be calculated as [the concentration units should be mol L−1 (
mol kg−1 for dilute aqueous solutions) because of the standard state commonly adopted for c ] K
K = 1α−cα
2
b

= 0.02069
2 × 0.0312

1 − 0.02069
=1.3638 × 10−5
6. The Ag(s)|AgBr(s)| Br− (aq) and the Ag(s)| Ag+ (aq) half-cells undergo the following reduction reactions
to give rise to the indicated standard reduction potentials:

AgBr(s) + e− → Ag(s) + Br− (aq); E◦ .

= 0 0713 V
Ag+ (aq) + e− → Ag(s); E◦ .
= 0 7996 V

(a) Construct a cell (i.e., write the cell abbreviation) in which the total cell reaction can be used to
measure the solubility product of AgBr(s). (b) What is the standard cell potential for this cell? (c) Find
the solubility product of AgBr at 25◦ C. (d) Find the solubility of AgBr at 25◦C.
Equations given: Nernst equation for the cell reaction αA βB → γC δD
+ + :


aγC aδD
E E◦ − RT
nF .
aαA aβB
= ln

Answer:
(a) The cell is Ag(s)|Ag+ (aq)||Br− (aq)|AgBr(s)|Ag(s). The following reactions take place in this cell:

Ag(s)→Ag+ (aq) + e−
AgBr(s) + e− →Ag(s) + Br− (aq)

Therefore the total cell reaction is AgBr(s) → Ag+(aq) + Br−(aq).

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(b) The standard cell potential is (−0.7996 + 0.0713) V = −0.7283 V.
(c) From the cell reaction, the Nernst equation for this cell at equilibrium (when E ) is
= 0

.
0 7283 V= − RT
F
aAg+ × aBr−
ln( eq
)

−. ×
8 3145
K298
=
96500
ln sp
from which we get

ln Ksp − .
= 28 3652

Ksp . ×
=4 80 10
−13

(d) Since Ksp = (aAg+ × aBr− )eq  [Ag+] [Br−], and [Ag+] = [Br−], the solubility is

Ag+ =Br−  = Ksp


=6.93 × 10−7 mol L−1 .