PROBLEM 1

Consider a liquid-liquid mixture of acetone and chloroform. The vapor pressure above the
mixture was measured at 50 °C as a function of the mole fraction of acetone in the liquid
phase, x1, and as a function of the mole fraction of acetone in the vapor phase, y1. Part of
the experimental data is given in Table E1.1, and part of the pressure-composition diagram
is shown in Figure E1.1.

p (kPa) x1 y1 p (kPa) x1 y1 p (kPa) x1 y1

69.3 0.00 0.00 67.0 0.06 0.04 61.6 0.30 0.279

68.4 0.02 0.012 65.8 0.10 0.071 60.9 0.38 0.380

67.7 0.04 0.026 63.0 0.20 0.165 61.2 0.40 0.422

Table E1.1: Pressure-composition data for a mixture of acetone and chloroform at 50 °C.
The Table shows the composition of the liquid (x1) and vapor (y1), respectively at the
vapor pressure (p) above the liquid.

Figure E1.1: Pressure-composition diagram for a mixture of acetone and chloroform at 50

°C.

(a)
(i) Complete the pressure-composition diagram using the data given in Table E1.1.
(ii) Indicate in Figure E1.1 in which part(s) of the diagram, the mixture is all vapor, all liquid,
and when there is co-existence between liquid and vapor phases.

1
ANSWER:
(i) See diagram below.
(ii) Co-existence is found between the lines connecting the data points. Above the highest
line, all is liquid, below the lowest line, all is vapor.

(b)
(i) What is an azeotrope?
(ii) Does this mixture have an azeotrope, and if so, what is the composition of the
azeotrope?

ANSWER:
(i) An azeotrope is a mixture for which the composition of the liquid is the same as that of
the vapor with which the liquid is at equilibrium, or the vapor of the boiling liquid has the
same composition as the liquid.
(ii) This mixture does have an azeotrope. It can be seen from Table E1.1 that at a pressure
of 60.9 kPa, the compositions of liquid and vapor are identical, viz. a mole fraction of
acetone equal to 0.380. (This means that chloroform is present at mole fraction 0.720.)

(c) The liquid mixture at mole fraction x1 = 0.60 is placed in a piston, and the pressure is
slowly lowered by pulling the piston at a constant temperature of 50 °C.
(i) At which pressure will the liquid mixture start to boil and
(ii) what is the composition of the vapor at this pressure?

ANSWER:
(i) The boiling point can be found by drawing a vertical line in Figure E1.1 at x1 = 0.60, and
determining the intersection with the upper co-existence line. The pressure of this
intersection is 65 kPa.

2
(ii) The composition of the vapor at this pressure can be found by drawing a horizontal line
at 65 kPa and determining the intersection with the lower co-existence line. The
composition of the vapor can be seen to be y1 = 0.685.

(d) Calculate the amount (in mole) of chloroform in the vapor that is at equilibrium with the
liquid at 50 °C and a pressure of 68 kPa, if the total amount of material is 2.8 mol and the
overall mole fraction of chloroform is 0.27.

ANSWER: Use the lever rule correctly.

Draw a horizontal line at 68 kPa and determine the intersections with the upper and lower
co-existence curves around an overall mole fraction z1 = 0.73. These are found at x1 =
0.70 and y1 = 0.79, respectively.
The ratio between the total amounts of material in the vapor and liquid phases,
respectively, is given by the lever rule as:
ng ll z1 − x1 0.73 − 0.70 3 1
= = = = =
nl lg y1 − z1 0.79 − 0.73 6 2
The amount of chloroform in the vapor is the mole fraction of chloroform in the vapor
multiplied by the amount of material in the vapor phase:
−1
⎛ n ⎞
= y2 ng = (1− y1 )ng ; ntot = ng + nl ⇒ ng = ⎜ 1+ l ⎟ ntot = (1+ 2 ) ntot
Chl −1
n g
⎝ ng ⎠
2.8mol 2.8mol
ngChl = (1− 0.79 ) × = 0.21× = 0.196mol
3 3

(e) Describe what can be seen if acetone is gradually added to pure chloroform in a closed
vessel, while keeping the temperature constant at 50 °C and the pressure constant at 63
kPa. Describe the appearance and compositions of the phase(s).

ANSWER:
Draw a horizontal line at 63 kPa in the pressure-composition diagram, and follow this line
from z1 = 0 to z1 = 1; this reflects the increasing amount of acetone. 63 kPa is below the
vapor pressure of pure chloroform. (In the pressure-composition diagram we should look
at z1=x1=y1=0.) Therefore, the vessel is initially filled with pure chloroform vapor (and no
liquid). Adding acetone, the mixture remains in the vapor phase until an overall mole
fraction of acetone of 0.165 is reached (see Table E1.1), where the lower co-existence
curve is intersected. The vapor is now at equilibrium with the liquid: first droplets of
condensate form. The composition of the condensate is x1 = 0.200 (see Table E1.1).
Adding more acetone, more and more liquid forms; this will be present as a layer at the
bottom of the vessel. The relative volume of the liquid phase will increase as acetone is
added, but the compositions of liquid (x1 = 0.200) and vapor (y1 = 0.165) will not change.
At an overall mole fraction of 0.200 acetone, all material will be in the liquid phase and the
vessel will not contain any vapor. This situation remains until the overall mole fraction of
acetone is approximately 0.53, where the horizontal line at 63 kPa again intersects one of
the co-existence curves. Now, bubbles of vapor are formed in the liquid. The composition
of these bubbles is y1 = 0.59, which can be seen from the intersection with the other co-
existence line. Adding acetone until an overall mole fraction of 0.59 leads to a clear
separation of vapor and liquid, where the relative volume of the vapor keeps increasing. At
and above an overall mole fraction of 0.59 acetone, all material is once again in the vapor
phase.

3
(f)
(i) Calculate the Henry constant for solvation of acetone in chloroform at 50 °C from the
data given in Table E.1.1.
(ii) Is the interaction in the liquid between acetone and chloroform more or less favorable
than the interaction between acetone and acetone in the liquid? Briefly explain your
answer.

ANSWER:
(i) The Henry constant is the slope of the tangent to the partial vapor pressure at low
overall mole fraction of the solute. Using the data in Table E1.1, the slope is estimated by
taking finite differences between the first data points. To obtain the partial pressure of
acetone, the total pressure must be multiplied by the mole fraction of acetone in the vapor.
This is application of Dalton’s law: p1 = y1* p. Now:

p x1 p1 KH p x1 p1 KH
(kPa) (kPa) (kPa) (kPa) (kPa) (kPa)

69.3 0 0 67.7 0.04 1.76 44.0

68.4 0.02 0.82 41.0 67.0 0.06 2.68 44.7

A good estimate of the Henry constant is somewhere between 41 and 44 kPa.
(ii) Henry’s constant is considerably lower than the vapor pressure of pure acetone (well
over 80 kPa, as can be seen in Figure E1.1). This means that the vapor pressure in the
mixture is always lower than the vapor pressure of an ideal mixture, in which the
interactions between the different components are as favorable as the interactions
between the pure components. Thus, the interaction between acetone and chloroform is
more favorable (attractive) than between acetone and acetone.

4
(g) The total vapor pressure and the partial vapor pressures of acetone and chloroform at
50 °C as a function of x1 are shown in Figure E1.2. How does this Figure change when
the temperature is increased? Briefly explain your answer. You may use a sketch to clarify
your answer.

Figure E1.2: Total vapor pressure (black) and partial vapor pressures of an acetone-
chloroform mixture at 50 °C as a function of the mole fraction acetone in the liquid.

ANSWER: Usually, gasses behave more like ideal/perfect gasses at higher temperatures.
Similarly, liquid mixtures behave more like ideal mixtures at higher temperatures. Thus, the
lines will be straighter (closer to ideal behavior). Also, the vapor pressures of both pure
liquids will be higher, and the extremes move to higher pressures. It is not easy to say
which vapor pressure will increase more. 


5
PROBLEM 2

A space ship in orbit around Jupiter is hit by some debris, leaving a hole in the hull of the
vessel. The air in the vessel starts escaping through the hole. The crew inspects the
damage: the hole is circular with a radius of 10 cm. The crew intends to repair the hole by
covering it with the first object of the correct shape (the ashtray). The crew must now
decide how much time there is to complete the repair work. One of them paid close
attention during Biology lectures and remembers the oxygen (m(O2) = 32 u) pressure
should not fall below 0.10 bar. The manual of the space ship furthermore reveals that the
total volume of the vessel is 3.000 103 m3, the temperature is maintained at 300 K and the
partial pressure of oxygen should be 0.20 bar under normal circumstances. Apart from
oxygen, the air contains nitrogen (m(N2) = 28 u), at a partial pressure of 0.80 bar under
normal circumstances.

(a) Show that the rate at which the partial pressure of a component in the air mixture in the
space ship changes, is given by Eq. (E2.1), where A0 is the area of the hole in the hull.

1/2
dp ⎛ kBT ⎞ pA0
− =
dt ⎜⎝ 2π m ⎟⎠ V (E2.1)

ANSWER:
Use the formula for the collision flux (Formula Sheet), and set the rate of the
disappearance of particles from the space ship equal to the collision flux multiplied b the
area of the hole. Then, rewrite to pressure using the ideal gas law.

d ( pV ) 1 N
1/2 1/2 1/2
dN pV =NkBT
1 ⎛ 8k T ⎞ pV dp ⎛ k BT ⎞ p ⎛ kT ⎞ pA0
− = ZW A0 ⇒ − = c A0 = ⎜ B ⎟ A0 ⇒ − = A0 = ⎜ B ⎟ QED
dt k BTdt 4 V 4 ⎝ πm ⎠ k BTV dt ⎜⎝ 2π m ⎟⎠ V ⎝ 2π m ⎠ V

(b *) Calculate the rate of change of the partial pressure of oxygen immediately after the
impact of the debris.

ANSWER: Use the data given and apply to Eq. (E2.1):

0.20 × 10 5 N ⋅ m -2π (10.0 × 10 −2 m )

1/2 1/2 2
dp ⎛ kBT ⎞ pA0 ⎛ 1.380658 × 10 −23 J ⋅ K -1 × 300K ⎞
− = =⎜ = 23.3N ⋅ m -2 ⋅s-1
dt ⎜⎝ 2π m ⎟⎠ V ⎝ 2π × 32u × 1.66054 × 10 −27 kg ⋅ u -1 ⎟⎠ 3.000 × 10 3 m 3

6
(c)
(i) Show that Eq. (E2.1) leads to Eq. (E2.2) for the partial pressure as a function of time.
(ii) Show by calculation that the crew has 594 s to repair the hole.
⎛ −t ⎞ 1/2
⎛ 2π m ⎞ V
p ( t ) = p ( 0 ) exp ⎜ ⎟ , with τ = ⎜
⎝τ ⎠ ⎝ kBT ⎟⎠ A0
(E2.2)

ANSWER: Integrate Eq (E2.1) by separating variables, and introduce the constant tau.
1/2 1/2 1/2
dp ⎛ k BT ⎞ pA0 dp ⎛ kT ⎞ A0 dt ⎛ 2π m ⎞ V
− = ⇒ = −⎜ B ⎟ dt = − ; τ = ⎜
dt ⎜⎝ 2π m ⎟⎠ V p ⎝ 2π m ⎠ V τ ⎝ k BT ⎟⎠ A0
p( t )
dt ′ p (t ) p (t )
t
dp 1 t
∫p 0 p = − ∫0 τ ⇒ ln p ( 0 ) = − τ (t − 0 ) = − τ ⇒ p ( 0 ) = e ⇒ p (t ) = p ( 0 ) e QED
−t τ −t τ
⇒
( )

1/2
⎛ 2π × 32u × 1.66054 × 10 −27 kg ⋅ u -1 ⎞ 3.000 × 10 3 m 3
τO =⎜ = 857s
⎝ 1.380658 × 10 −23 J ⋅ K -1 × 300K ⎟⎠ π (10.0 × 10 −2 m )0
2
2

p (0) 0.20bar
p ( t ) = p ( 0 ) e−t τ ⇒ t = τ ln = 857s × ln = 594s
p (t ) 0.10bar

(d) Every gram counts in rocket science and therefore all items on board are extremely
light-weight. This means that the ashtray cannot deal with pressures larger than 0.55 bar.
Will the crew be able to repair the hole by placing the ashtray in front of it? Briefly explain
your answer.

ANSWER: The total pressure must be below 0.55 bar, while the partial pressure of oxygen
must be at least 0.10 bar. While oxygen was leaving the vessel, nitrogen also escapes.
The rate of escape of nitrogen is a bit larger than that of oxygen (lower mass). The partial
pressure of nitrogen after 594 s is:
τN ⎛ 28u ⎞
1/2

=⎜ ⇒ τ N = 857s × 0.9354 = 802s

⎝ 32u ⎟⎠
2

τO 2
2

p ( N 2 ,594s ) = 0.80bar × e−594 802 = 0.38bar; ptot = 0.10 + 0.38 = 0.48bar < 0.55bar

Thus, the repair can be successful, but the crew must live at lower pressure. It may be a
good idea to find a better long-term solution and to reach that, the partial pressure of
oxygen can be raised a bit. 


7
PROBLEM 3

Consider the reaction Cl2(g) + Br2(g) → 2 BrCl (g) at 500 K and at a total pressure of 1.00
bar. The initial mixture contains exactly 1 mol Cl2 and exactly 1 mol Br2 and no BrCl. A
number of thermodynamic data are collected in Table E3.1.

Compound ΔfH0 (500 K) (kJmol-1) ΔfG0 (500 K) (kJmol-1)

Cl2 (g) +6.84 -1.92

Br2 (g) +38.18 +1.07

BrCl (g) +21.64 -3.69

Table E3.1 Enthalpies and Gibbs free energies of formation at 500 K.

Assuming that all gases behave according to the perfect gas law, it can be shown that the
total Gibbs free energy of the reaction mixture can be written as a function of the extent of
reaction, x (that’s a bit more convenient than using ξ), is given by Eq. (E3.1):

1− x
G ( x ) = (1− x ) GCl0 + (1− x ) GBr
0
+ 2xGBrCl
0
+ 2 (1− x ) RT ln + 2xRT ln x (E3.1)
2 2
2
Here, GJ0 is the Gibbs free energy of exactly 1 mol of pure J at standard pressure.

(a) Using Eq. (E3.1), show that the equilbrium of the reaction is given by Eq. (E3.2).

⎡ 2xeq ⎤
3.27kJ ⋅ mol-1 = RT ⎢ ln ⎥ (E3.2)
⎢⎣ 1− xeq ⎥⎦

ANSWER: Equilibrium is reached when the total Gibbs free energy is a minimum. The
minimum can be found by differentiating Eq. (E3.1) to x and setting it zero:
dG ( x ) 1− x d 1− x d
= 0 ⇒ −GCl0 − GBr 0
+ 2GBrCl
0
− 2RT ln + 2 (1− x ) RT ln + 2RT ln x + 2xRT ln x =
dx 2 2
2 dx 2 dx
1− x 1 d
−GCl0 − GBr0
+ 2GBrCl
0
− 2RT ln + 2 (1− x ) RT × (1− x ) + 2RT =
2 2
2x 1− x dx
2x −2 × (−3.69) − 1.92 + 1.07 2x
−GCl0 − GBr0
+ 2GBrCl
0
+ 2RT ln ⇒ = RT ln = 3.265kJ ⋅ mol-1
2 2
1− x 2 1− x

8
(b)
(i) Show by calculation that the composition of the equilibrium mixture is given by xeq =
0.523, and
(ii) that the equilibrium constant Kp for this reaction is equal to 4.8.

Solving Eq. (E3.2) for xeq yields:

2x 2x 3.265 × 10 3 J ⋅ mol-1 2x 2.193
RT ln = 3.265kJ ⋅ mol-1 ⇒ ln = = 0.7854 ⇒ = exp[0.7854] = 2.193 ⇒ x = = 0.523
1− x 1− x 8.314J ⋅ K -1 ⋅ mol-1 × 500K 1− x 2 + 2.193
The equilibrium constant is then:
2
⎛ PBrCl ⎞
⎜⎝ P 0 ⎟⎠ ( x )2 4x 2 4 × 0.5232
K= = = 2 = 2 = 4.81
⎛ PCl ⎞ ⎛ PBr ⎞ ⎛ 1− x ⎞ ⎛ 1− x ⎞ (1− x ) (1− 0.523 )
⎜ 0 ⎟ ⎜ 0 ⎟ ⎜⎝ 2 ⎟⎠ ⎜⎝ 2 ⎟⎠
2 2

⎝ P ⎠⎝ P ⎠

(c) Calculate the equilibrium constant for the reaction at 564.30 K, under the assumption
that the enthalpy of reaction does not depend on temperature.

ANSWER: Integrate the van ‘t Hoff equation (see Formulat Sheet), under the condition that
the enthalpy of reaction does not depend on temperature.

Δr H 0 ⎛ 1 1⎞
T
Δr H 0 Δr H 0
( ) ( )
2
d
dT
ln K =
RT 2
⇒ ln K T2 − ln K T1 = ∫ RT 2 dT = − +
R ⎜⎝ T2 T1 ⎟⎠
T1

ln K ( 564.30 ) = ln 4.8 +
( 2 × 21.64 − 38.18 − 6.84 ) × 10 3 J ⋅ mol-1 ⎛
−
1
+
1 ⎞
⎜⎝ ⎟
8.314J ⋅ K -1 ⋅ mol-1 564.30K 500K ⎠
= 1.569 − 0.0477 = 1.521 ⇒ K ( 564.30 ) = exp[1.521] = 4.58

9
PROBLEM 4

Solving the Schrödinger equation for the rotational motion of linear molecules delivers the
rotational energy levels as given in Eq. (E4.1):

J ( J + 1) h 2
EJ = ; J = 0,1,2,...
8π 2 I (E4.1)

Here, J is the rotational quantum number, and I is the moment of inertia. Each energy level
has 2J + 1 states.

(a)
(i) Show that the canonical rotational partition function for a linear molecule can be
approximated by Eq. (E4.2).
8π 2 Ik BT
q lin
rot = (E4.2)
h2
(ii) In your answer, clearly indicate which approximation(s) are used.
d
Hint: 2J + 1 = J ( J + 1) ⇒ ( 2J + 1) dJ = d ⎡⎣ J ( J + 1) ⎤⎦
dJ

ANSWER:

The canonische partition function is given by:

J ( J + 1) h 2 ∞
h2
Q = ∑ e− β EJ ; E J = ⇒ Q = ∑ ( 2J + 1) e − J ( J +1)C
; C =
J 8π 2 I J =0 8π 2 IkBT
∞ ∞ ∞ ∞

Q = ∑ ( 2J + 1) e− J ( J +1)C ≈ ∫ ( 2J + 1) e− J ( J +1)C dJ = ∫ e− J ( J +1)C d ( J ( J + 1)) = ∫ e− xC dx =

J =0 0 0 0
∞
⎡ 1 − xC ⎤ 1 1 8π 2 IkBT
−
⎢⎣ C e ⎥⎦ = 0 + = = QED
0 C C h2

The approximation used here is that the sum can be replaced by an integral. This is
warranted or justified if the subsequent Boltzmann factors differ only slightly, which is the
case if the energy differences between states J and J+1 is small compared to kBT . In that
case, the integrand will be almost a horizontal line between J and J+1, and taking the sum
is close to taking the integral.

10
(b) Show that in general, the internal (mean) energy U is given by Eq. (E4.3).

d ln q
U=−
dβ (E4.3)

ANSWER: 


Use the expression for U on the Formula Sheet.

de− β En d
∑ nE e − β En
∑ dβ − dβ ∑ e− β En −1 dq d ln q
−
U = E = ∑ pn En = n − β E = n = n
= =−
n ∑e n q q q dβ dβ
n

(c) Show that the rotational energy of a linear molecule in the approximation used in (a) is
equal to kBT .

ANSWER: Apply Eq. (E4.3) to Eq. (E4.2):

d ln q d ⎡ ⎛ 8π 2 I ⎞ ⎤ d ⎡ ⎛ 8π 2 I ⎞ ⎤ 1
− =− ⎢ ⎜ 2 ⎟⎥
ln = − ⎢ ln ⎜ 2 ⎟ − ln β ⎥ = = kBT
dβ dβ ⎣ ⎝ h β ⎠ ⎦ dβ ⎣ ⎝ h ⎠ ⎦ β

11
(d) The approximation used in deriving Eq. (E4.2) is justified at high enough temperatures.
The temperature that can be considered high enough depends on the molecule studied. A
quick estimate of the temperature above which Eq. (E4.2) can be used follows from the so-
called rotational temperature, Eq. (E4.4).
h2
θ rot =
8π 2 IkB (E4.4)

Using Figure E4.1, calculate estimates for the minimum temperatures at which Eq. (E4.2)
is a justifiable approximation for the molecules CO2 and O2, respectively. The rotational
moments of inertia of CO2 and O2 are 7.179 10-46 and 1.946 10-46 kg.m2, respectively.

Figure E4.1: Rotational energy per molecule (in units of Rθ rot ), calculated by using the
exact expression (direct summation) and calculated by using the approximated
expression, both as a function of the reduced temperature T / θ rot .

ANSWER: The rotational temperatures of CO2 and O2 are 0.561 and 2.07 K, respectively.
It can be seen from Figure E4.1, that the rotational energy using the approximate formula
is bigger than the exact expression, but that they are very close at reduced temperatures
of about 2, which means that the temperature is roughly twice the rotational temperature.
Thus, the use of Eq. (E4.2) is justified at temperatures above 1.2 and 4.2 K for CO2 and
O2, respectively.

12