Gazi University Faculty of Engineering

Department of Chemical Engineering

ChE 244 Physical Chemistry, Problem Set #1-1

PROBLEM SET – 1-1

DEFINITIONS AND PROPERTIES OF GASES

1. Calculate the followings:

a) The molar volume of an ideal gas at 20 oC and 1.000 bar
b) The density of N2 at 20 oC and 0.967 bar
c) The volume of one mole of an ideal gas at i) 0oC & 1 atm; ii) 25oC & 1 atm; iii) 100oC & 1 atm.
d) For a certain hydrocarbon gas, 20.0 mg exerts a pressure of 24.7 torr in a 500 cm 3 vessel at 25 oC.
Find the molecular weight of the gas.
e) The density of gaseous HBr at 0 oC and 1 atm is 3.64-44 g/l. Find the volume that would be
occupied by one mole of HBr under these conditions.

2. The mole fraction of main components of dry air at sea level are 0.78 for nitrogen, 0.21 for oxygen,
0.0093 for argon and 0.0003 for carbon dioxide. Find the partial pressure of each of these gases in dry air at
1.00 atm and 20 oC.

3. Calculate the pressure in atmospheres exerted by 2.00 moles of chlorobenzene vapor confined to 10.0
liters at 25oC,

a) using the ideal gas law

b) using the van der Waals’ equation of state. (a = 25.43 L2.atm.mole-2 ; b = 0.1453 L.mole-1)

4. The following data for the density of a gas at 300 K are given:

P (atm) 0.4000 0.8000 1.000

Density (g/lt) 1.512 3.088 3.900

Find the molecular weight of the gas as accurate as possible.

5. For a gas described by the Berthelot equation,

RT a
P= - -
V–b TV2
Express a, b, and R in terms of critical constants and write the equation of state in terms of reduced
variables.

6. For 1.00 mole of N2 gas at 0 oC, the following volumes are observed as a function of pressure:

P, atm 1.0000 3.0000 5.0000

V, cm3 22405 7461.4 4473.1

Calculate and plot PV/nT vs P for these points and extrapolate to P=0 to evaluate R.

7. The virial equation that has been given for one mole of methane at 20 oC is,

PV/RT = 1- 2.0236 x 10-3P + 3.723 x 10-6 P2

Calculate the compressibility factor for methane at 20 oC and 150 atm.
 Gazi University Faculty of Engineering
Department of Chemical Engineering
ChE 244 Physical Chemistry, Problem Set #1-2

PROBLEM SET – 1-2

KINETIC THEORY OF GASES

1. What is the ratio of the probability that a gas molecules have two times the mean speed to the probability that
they have the mean speed?

2. For CH4(g) at 300 K and 1 bar, calculate the probability that a molecule picked at random has its speed in the
range 400.000 to 400.001 m/s. This interval is small enough to be considered infinitesimal.

3. For CO2 at 500 K and for N2 at 300 K calculate

(b)  (c)  mp
1
(a)  2 2

4. Find the molecular weight of hydrocarbon gas that effuses 0.872 times as fast as O 2 through a small hole the
temperatures and pressures being equal.

5. Use F(  )d  function for  to find 

3
for ideal gas molecule. Does 
3
equal to 
2
 .

6. Calculate the total molecular translational kinetic energy at 25 oC and 1 atm for 2 moles of N2.

7. The average translational kinetic energy for a molecule (є) is given by

1
є= m v2
2
3kT
where m is the mass of the molecule and v 2 is the average of the square of the velocity. Given v 2  ,
m
where k is Boltzmann’s constant, calculate the ratio of the kinetic energies at 200 0C and 100 0C.

8. For 1.00 mol of O2 at 300 K and 1.00 atm, calculate (a) the number of molecules whose speed lies in the range
500.00 to 500.001 m/s (b) the number of molecules with  z in the range 150.00 to 150.002 m/s

9. For molecular oxygen at 25 oC, a) Define collision frequency, b) Define collision density.
c) calculate the collision frequency Z1 and the collision density Z11 at a pressure of 1 bar. ( d O = 3.61x10-10 m)
2

10. What are the mean free paths in meters for O2 at (a) 1 bar pressure and (b) 0.1 Pa pressure?

11. For an equimolar mixture of H2 and I2 at 500 K and 1 atm, calculate the number of collisions per second per
cm3 between H2-H2 and H2-I2 molecules. ( d H 2 = 2.18x10-8 cm) ( d I 2 = 3.76x10-8 cm)

12. Find  for (a) H2 at 0 oC and 1 atm, (b) N2 at 25 oC and 1 atm.

13. For a gas with collision diameter of 3x10-8 cm, calculate the mean free path at 0 oC and 1 atm.

14. Calculate the thermal conductivity of Argon at 300 K and 15 Mbar. Gas is confined in a cubic vessel of side 15
cm, one wall being 305 K and one opposite at 295 K. What is the rate of flow of energy as heat from one wall to
the other?

15. For 1.00 mol of O2 at 300 K and 1.00 atm, calculate (a) the number of molecules whose speed lies in the range
500.00 to 500.001 m/s (b) the number of molecules with v z in the range 150.00 to 150.002 m/s (c) the number of
molecules that simultaneously have vz in the range 150.00 to 150.001 m/s and have v x in the range 150.00 to
150.001 m/s.
 Gazi University Faculty of Engineering
Department of Chemical Engineering
ChE 244 Physical Chemistry, Problem Set #2-1
PROBLEM SET 2-1
1) Discuss the following overall reactions with respect to order
(a) 2A 4B+C  r  kC A
1
(b) A+B C  r  kC A C B
1 / 2
(c) 2A+B 2C  r  kC A C C
2C  r  kC A C B
2
(d) 2A+B

2) The second order rate constant for the reaction A + B C + D is 0.11 L/mol.sec. What is the concentration of
C after 10 min. when the reactants are mixed with initial concentration of [A] o = 0.05 mol/L, [B]o = 0.1 mol/L

3) Hydrogen peroxide reacts with thiosulfate ion slightly acidic solution as follows:

H2O2 + 2S2O3-2 + 2H+2 2H2O + S4O6-2

This reaction rate is independent of hydrogen ion concentration in the pH range 4 to 6. The following data were
obtained at 25 oC and pH 5. Initial concentrations:
[H2O2] = 0.036 mol/L, [S2O3-2] = 0.0204 mol/L.

t/min 16 36 43 52
-2 -3
[S2O3 ]/10 mol/L 10.3 5.18 4.16 3.13

(a) What is the order? (b) What is the rate constant?

4) (a) Integrate the rate equation

dC
  kC 1 / 2
dt
(b) How could a group of data be checked graphically to see if they describe a half order
(c) Derive an expression for the half life t1/2 interms of k and Co
(d) What is the unit of k

5) A solution A is mixed with an equal volume of a solution of B containing the same number of moles and the reaction
A+B C occurs. At the end of 1 h, A is 75 % reacted. How much of A will be unreacted at the end of 2 h if
the reaction is (a) first order in A and zero order in B (b) first order in both A and B (c) zero order in both A and B.

6) Show that for a first order reaction R P the concentration of the product can be represented as a function of
time [P] = a+bt+ct2+………and express a, b, c, interms of [R]o and k.

7) The following table gives kinetic data for the following reaction at 25 oC.
OCl-1 + I- OI-1 + Cl-1

[OCl-] (mol/L) [I-] (mol/L) [OH-] (mol/L) d[OI-1]/dt(10-4mol/Ls)

0.0017 0.0017 1 1.75
0.0034 0.0017 1 3.5
0.0017 0.0034 1 3.5
0.0017 0.0017 0.5 3.5
What is the rate law for the reaction and what is the value of the rate constant.

8) Consider the gaseous reaction; cyclo-C5H8 H2 + cyclo-C5H6

If P is the total pressure
(a) How dP/dt related to –d[C5H8]/dt
(b) If the reaction is first order what are the units of k
(c) Derive the integrated rate equation interms of P and P o
 Gazi University Faculty of Engineering
Department of Chemical Engineering
ChE 244 Physical Chemistry, Problem Set #2-1

9) The composition of a liquid reaction 2A B was followed by spectrophotometric method

t(min) 0 10 20 30 40 ∞
[B] (mol/L) 0 0.089 0.153 0.2 0.23 0.312

Show the order is first order and find k.

10) For the reaction A + B C + D [A]o=400 mmol/L, [B]o=0.4 mmol/L gave the following data

t(s) 0 120 240 360 ∞

104 [C] (mol/L) 0 2 3 3.5 4

And a run [A]o=0.4 mmol/L, [B]o=1000 mmol/L gave the following data

t(s) 0 69 208 485 ∞

104[C] (mol/L) 0 2 3 3.5 4

Find the rate law and constant if –r=k[A]2[B]

11) For the reaction OCl-1 + I-1 OI-1 + Cl-1 in aqueous solutions at 25 oC initial rates ro as a function of initial
concentrations

103 [OCl-1] (mol/L) 4 2 2 2

103 [I-1] (mol/L) 2 4 2 2
103 [OH-1] (mol/L) 1000 1000 1000 250
103 ro (mol/Ls) 0.48 0.5 0.24 0.94

Find the rate constant.

12) The decompositions of benzendiazonium chloride in water is given by

C6H5N2+ + H2O C6H5OH + N2 + H3O+
Since the concentration of water is nearly fixed we can determine the pseudo order with respect to benzendiazonium
chloride as with a reaction having a single reactant. Moelwyn-Hughes and Johnson followed the reaction at 40℃
by monitoring the pressure of nitrogen evolved by the reaction. The following data were taken with the pressure in
arbitrary units.

Time (s) 0 120 360 600 1200 2400 3600

P∞ - P 60 21.55 19.45 17.6 13.62 8.15 4.88

a) Determine the pseudo first order rate constant at this temperature.

b) Find the pressure of evolved nitrogen at 1500s.

13) At t=0 butadiene was introduced to an empty vessel at 326℃ and dimerization takes place 2C4H6 C8H12
followed by monitoring the total pressure. Show that reaction is second order. Find the rate constant.

Time (s) 0 0.731 1.751 2.55 3.652 5.403 7.14

P(torr) 632 584.2 535.4 509.3 482.8 453.3 432.8

14) The reaction between ethylene bromide (A) and potassium iodide (B) in 99% methanol (inert) has been found to be
first order with respect to each reactant (second order overall). The reaction can be presented by,

C2H4Br2 + KI C2H4 + 2KBr + KI3 or A + 3B Products

Derive an equations for calculating the second-order rate constant k.

Gazi University Faculty of Engineering
Department of Chemical Engineering
ChE 244 Physical Chemistry, Problem Set #2-2

PROBLEM SET – 2-2

(CHEMICAL KINETICS)
1) The reaction between ethylene bromide (A) and potassium iodide (B) in 99% methanol (inert) has
been found to be first order with respect to each reactant (second order overall). The reaction can be
presented by,

C 2 H 4 Br2  3KI  C 2 H 4  2 KBr  KI 3 or A  3B  Pr oducts

a) Derive an equation for calculating the second-order rate constant k.
b) At 60oC in one set of experiments, for which C Ao = 0.0266 and CBo = 0.2237 mol/L, the
bromide (A) was 59.1 % reacted at the end of 15h. Calculate the value of the rate constant, k,
and specify the units.

2) The first order reaction AB is carried out in a constant-volume batch reactor (k=0.23 min-1).

a) Derive the equation for time as a function of reactant concentration.

b) Calculate the time necessary to reduce the number of moles of A to 1 % of its initial value.

3) For a gas reaction at 400 K the rate is reported as;

1 dn A
 rA    kC A2 , mol / m 3 . s
V dt

What is the value of the rate constant for this reaction if the rate equation is expressed as;

4) The rate constants for two different reactions are given:

for rxn. 1 k=4.852x108 s-1 at 190oC and

k=2.203x104 s-1 at 103oC

for rxn. 2 k=4.852x108 s-1 at 190oC and

k=8.886x106 s-1 at 103oC

a) Calculate the activation energy for the two reactions.

b) Find out the temperature rises needed to double the reaction rate, at 103 oC for each
reaction.
c) Comment on the results of part a and b.

5) Liquid A decomposes in a batch reactor. Initially there is 1 mole/lt A. 50% of A is

converted in a 5 minute run. How much longer would it take to reach 75% conversion?

a) For first order kinetics. b) For second order kinetics.

6) The gas phase reaction AB+C is to be carried out isothermally in a 20 dm3 constant-volume batch
reactor. Twenty moles of pure A is initially placed in the reactor. The reactor is well mixed.
Gazi University Faculty of Engineering
Department of Chemical Engineering
ChE 244 Physical Chemistry, Problem Set #2-2

a) If the reaction is first order : -rA = k CA with k= 0.865 min-1

Calculate the time necessary to reduce the number of moles of A in the reactor to 0.2 mole.

b) If the reaction is second order : -rA = k CA2 with k= 2 dm3 /mol.min-1.

Calculate the time necessary to consume 19.0 mol of A.

c) If the temperature is 127oC, what is the initial total pressure? What is the final total pressure
assuming the reaction goes to completion ?

7) The first order reversible liquid reaction. A R, CAo = 0.5 mol/liter, CRo =0
takes place in a batch reactor. After 8 minutes, conversion of a is 33.3 % while equilibrium conversion
is 66. 7 %. Find the rate equation for this reaction.

8) Aqueous A at a concentration of CA0= 1 mol/L is introduced into a batch reactor where it reacts
away to form product R according to stoichiometry AR. The concentration of A in the reactor is
monitored at various times, as shown below:
Table
t, min 0 100 200 300 400
CA, mol/m³ 1000 500 333 250 200

For CA0= 500 mol/m³, find the conversion of reactant after 5 hours in the batch reactor.

9) Find the overall order of the irreversible reaction

2 H2 + 2 NO  N2 + 2 H2O
From the following constant-volume data using equimolar amounts of hydrogen and nitric oxide :
Table
Total Pressure, mm Hg 200 240 280 320 360
Half-life, sec 265 186 115 104 67

10) Moelwn-Hughes has tabulated the following values of the rate constant for the reaction:
1
N 2 O5  N 2 O4  O2
2

T, oK 288.1 298.1 313.1 323.1 338.1

k, sec-1 1.04x10-5 3.38x10-5 2.47x10-4 7.59x10-4 4.87x10-3

If the rate constant obeys Arrhenius law, determine the pre-exponential factor and activation
energy.
Gazi University Faculty of Engineering
Department of Chemical Engineering
ChE 244 Physical Chemistry, Problem Set #3
PROBLEM SET 3

1. Consider the following mechanism:

k1
A B  C
k2

C  Dk3

(a) Derive the rate law using the steady-state approximation to eliminate the concentration of C.
(b) Assuming that k3<<k2, express the pre-exponential factor A and Ea for the apparent second order rate constant
in terms A1, A2 and A3 and Ea1, Ea2 and Ea3 for the three steps.

2. The reaction NO2Cl =NO2+ ½ Cl2 is first order and appears to follow the mechanism
NO 2 Cl 
k1
NO 2  Cl
NO 2 Cl  Cl 
k2
NO 2  Cl 2

(a) Assuming a steady state for the chlorine atom concentration, show that the emprical first order rate constant
can be identified with 2k1
(b) The following data were obtained at 180 0C. In a single experiment the reaction is first order, and the empirical
rate constant is represented by k. Show that the reaction is second order at these low gas pressures and calculate
the second order rate constant.
c/ 10-8mol cm-3 5 10 15 20
k/ 10-4 s-1 1,7 3,4 5,2 6,9

3. Isopropenyl allyl ether in the vapor state isomerizes to allyl acetone according to a first order rate equation.
The following equation gives the influence of temperature on the rate constant (in s -1):
k=5.4 X 1011e-123000/RT
where the activation energy is expressed in J mol-1. At 150 0C, how long will it take to build up a partial pressure
of 0.395 bar of allyl acetone, starting with 1 bar of isopropenyl allyl ether?

4. The following rate constants were obtained for the first order decomposition of acetone bicarboxylic acid in
aqueous solution:
t/ 0C 0 20 40 60
k/ 10-5 s-1 2.46 47.5 576 5480

(a) Calculate the energy of activation.

(b) Calculate the pre-exponential factor A.
(c) What ist he half life of this reaction at 80 0C?

5. A gas reaction A  2B is first order in A and goes to completion in a reaction vessel of constant volume and
temperature with the half-life of 10 min. If the initial pressure of A is 1 bar, what are the partial pressures of A
and B at 10 min.

6. The equations for [A2] and [A3] in section 18.4 give an indeterminate result if k1=k2. Rederive the equations,
giving [A2] and [A3] as functions of time fort he special case that

A1 
k1
A2 
k1
A3
7. A dimerization 2A   A2 is found to be first order with a half life of 666 s. This somewhat surprising result
is explained by postulating the following mechanism
A 
k1
A* A *  A 
k2
A2
Where k2 >>k1 (a) What is the value for the rate constant k1? (b) if the initial concentration of A is 0.05 M, how
much time is required to reach [A] =0.0125 M?

8. Consider two consecutive first order nuclear decay reactions with the rate constants k 1 and k2
A 
k3
B and B 
k2
C
If k1=k2=0.1340 year-1 , draw [B]/[A]0 plot.
9. For the reaction OCl-1+I-1 
 OI-1+Cl-1 in aqueous solutions at 25 0C initial rates r0 as a function of initial
concentrations
103 [OCl-1] mol/L 4 4 2 2
3 -1
10 [I ] mol/L 2 4 2 2
103 [OH-1] mol/L 1000 1000 1000 250
103 r0 mol/L 0.48 0.5 0.24 0.94
Find the rate law.

10. For the reaction

2 NO  2 H 2 
 N 2  2 H 2 O

The overall rate expression is third order.

RN2=k[NO]2[H2]
Show that two mechanism below consistent with rate equation

2 NO  H 2 
k1
N 2  2 H 2O2 ( slow)
a)
H 2O2  H 2 
k2
2 H 2O ( fast)

k1
b) 2NO  N2O2 (fast)
k2

N 2 O2  H 2 
k3
N 2  2 H 2 O slow
H 2 O2  H 2 
k4
2H 2O ( fast)

11. a) Find the activation energy of the reaction whose rate constant is multiplied by 6.5 when T is increased
from 300 to 310 °C.

b) For the reaction with Ea= 19 KJ/mol (4.5 Kcal/mol) by What factor k multiplied when T increases from 300
to 310 °C.
CI
12. The hydrolysis of (CH2)6C
CH3

In 80% ethanol follows the first order rate equation. The values of the specific reaction rate constants are as
follows

t, ℃ 0 25 35 45
k, s-1 1.06x10-5 3.19x10-4 9.86x10-4 2.92x10-3
a) Calculate the activation energy.
b) Calculate the pre-exponential factor.

13. The mechanism of the pyrolysis of acetaldehyde at 520 ℃ and 0.2 bar is
CH3CHO  
k1 CH3 + CHO
CH3 + CH3CHO  
k2
CH4 + CH3CO
CH3CO   CO + CH3
k3
k4
CH3 + CH3   C2H6

What is the rate law for the reaction of acetaldehyde, using the usual assumptions? (As a simplification further
reactions of the radical CHO have been omitted and is the rate equation may be ignored.)

14. The composition of a liquid reaction 2A 

 B was followed by spectrophotometric method

t (min) 0 10 20 30 40 ∞
[B] mol/L 0 0.089 0.153 0.2 0.23 0.312

Show the order is first order and find k.

Gazi University Faculty of Engineering
Department of Chemical Engineering
ChE 244 Physical Chemistry, Problem Set #4

PROBLEM SET 4

1) a) Find the equilibrium constant at298 K for the reaction

PCI5  PCI3 + CI2(g)

b) Find the total pressure if 0.001 mol of PCI5 is placed in a vessel with a volume of 20 L at 298 K and allowed
to equilibrate. Assume ideal gas behavior.

2) a) Find Ho, Go and Kp at 298 K for I2(g)  2I(g)

b) Assume Ho constant find temperature at which Kp=1
c) Assume Ho constant find Kp at 1000 K.
d) Assume Cp constant find Kp at 1000 K.

3) A certain gas mixture held at 395 K has the following initial pressures. P(Cl 2) = 351.4 torr, P(COCl2) = 0. At
equilibrium total pressure is 439.5 torr is held constant. Find K at 395 K for
CO + Cl2  COCl2

4) For the ideal gas reaction PCI5  PCI3 + CI2(g)

State wheather equilibrium shifts to the right or left when each of the following changes is made in an
equilibrium mixture at 25 oC
a) T is decreased at constant P
b) V is decreased at constant T
c) Some PCl5 is removed at constant T and V
d) He(g) is added at constant T and V
e) He(g) is added at constant T and P

5) For 2 CO (g) + O2(g)  2 CO2(g) assume ideal gas behavior and Go298 = -514.382 kj/mol and HoT (kj/mol)
= -565.968 + 0.0015(T-298) + 2.85*10-6(T2-2982)+1448((1/T)-(1/298))
Find an expression for lnKp(T) and calculate Kp at 1000 K for this reaction.

6) Suppose 1.0 mol of CO2 and 1.0 mol of COF2 are placed in a very big vessel at 25 oC and a catalyst for the
gas phase reaction 2 COF2  CO2 + CF4 is added. Find the equilibrium amounts. Go298 = -35 kj/mol

7) For the ideal gas reaction N2 + 3H2  2 NH3 suppose 1 mol of N2 and 3 mol of H2 react at constant T and P,
no other gases are present initially. Let x be the number of moles of N2 that have reacted when equilibrium is
reached. (x = eq)
Show that,
X=1-[1-s/(s+4)]1/2, s= (27 Kp)1/2 P/P*

8) Nitrogen trioxide dissociates according to the reaction

N2O3(g)  NO2(g) + NO(g)
When one mole of N2O3(g) is held at 25 oC and 1 bar total pressure until equilibrium is reached, the extent of
reaction is 0.30. What is rGo for this reaction at 25 oC

9) Calculate the molar Gibbs energy of butane isomers for extents of reaction of 0.2, 0.4, 0.6 and 0.8 for the
reaction n-butane = isobutene at 1000 K and 1 bar.
At 1000 K rGo(n-butane)=270 kJ/mol, rGo(n-butane)=276.6 kJ/mol
Make a plot and show that the minimum corresponds to the equilibrium extent of reaction.

10) At 250 oC, PCl5 is 80 % dissociated at a pressure of 1.013 bar, and so K=1.80. What is the extent of reaction
at equilibrium after sufficient nitrogen has been added at constant pressure to produce a nitrogen partial pressure
of 0.9 bar? The total pressure is maintained at 1 bar.
Gazi University Faculty of Engineering
Department of Chemical Engineering
ChE 244 Physical Chemistry, Problem Set #5-1

PROBLEM SET 5-1

1) Find F for the following systems

a) a gaseous mixture of N2, H2 and NH3 with no catalyst present (so the rate of reaction is zero); b)
A gaseous mixture of N2, H2 and NH3 with a catalyst present to establish reaction equilibrium; c) the
system of (b) with the added condition that all the N2 and H2 must come from the dissociation of the
NH3; d) a system formed by heating pure CaCO3(s) to give CaCO3(s), CaO(s), CO2(g), CaCO3(g)
and CaO(g).

2) The following table gives mole percent acetic acid in aqueous solutions and in the equilibrium vapor
at the boiling point of the solution at 1.013 bar.

b.p., oC 118.1 113.8 107.5 104.4 102.1 100

Mole% of acetic acid
In liquid 100 90 70 50 30 0
In vapor 100 83.3 57.5 37.4 18.5 0

Calculate the minimum number of the theoretical plates for the column required to produce an initial
distillate of 28 mole acetic acid from a solution 80 mol % acetic acid.

3) From the data given in the following table, construct a complete temperature-composition
diagram for the system ethanol-ethyl acetate for 1.013 bar. A solution containing 0.80 mole
fraction ethanol is distilled completely at 1.013 bar.

a) What is the composition of the first vapor to come off?

b) What is the composition of the last drop of liquid to evaporate?
c) What would be the values of these quantities if the distillation were carried out in a cylinder
provided with a piston so that none of the vapor escapes?

XEtOH YEtOH b.p., oC XEtOH YEtOH b.p., oC

0 0 77.15 0.563 0.507 72
0.025 0.07 76.7 0.71 0.6 72.8
0.1 0.164 75 0.833 0.735 74.2
0.24 0.295 72.6 0.942 0.88 76.4
0.36 0.398 71.8 0.982 0.965 77.7
0.462 0.462 71.6 1.00 1.00 78.3

4) Plot the following boiling point data for benzene-ethanol solutions.

a) Estimate the azeotropic composition.
b) State the range of mole fraction of benzene for which pure benzene could be obtained by
fractional distillation at 1 atm.

b.p., oC 78 75 70 70 75 80
Mole% of acetic acid
In liquid 0 0.04 0.21 0.86 0.96 1.00
In vapor 0 0.18 0.42 0.66 0.83 1.00

5) One mole of benzene (component 1) is mixed with 2 moles of toluene (component 2) at 60 oC

the vapor pressures of benzene and toluene are 51.3 and 18.5 kPa respectively.
a) As the pressure reduced at what pressure will boiling begin?
b) What is composition of the first bubble of vapor?
 Gazi University Faculty of Engineering
Department of Chemical Engineering
ChE 244 Physical Chemistry, Problem Set 5-2

PHASE EQUILIBRIUM
1) The boiling point of benzene is 80.1 oC at 1 atm. Estimate the vapor pressure of benzene at 25 oC.

2) Liquid mercury has a density of 13.690 g/cm3, and solid mercury has a density of 14.193 g/cm3, both being
measured at the melting point, -38.87 °C, at 1 bar pressure. The heat of fusion is 9.75 J/g. Calculate the
melting points of mercury under a pressure of (a) 10 bar and (b) 3540 bar. The observed melting point under
3540 bar is -19.9 °C.

3) For the decomposition reaction of CaCO3 at equilibrium:

CaCO3(s)  CaO(s) + CO2(g)
How many degrees of freedom are there when all three phases are present at equilibrium?

4) For each of the following systems, find the number of degrees of freedom F:
(a) Aqueous solution of sucrose (b) An aqueous solution of sucrose and ribose (c) Solid sucrose and an
aqueous solution of sucrose and ribose (d) Solid sucrose, solid ribose and an aqueous solution of sucrose and
ribose (e) Liquid water and water vapor (f) An aqueous sucrose solution and water vapor (g) Solid sucrose,
an aqueous sucrose solution and water vapor.

5) n-Propyl alcohol has the following vapor pressure at different temperatures:

T, oC 40 60 80 100
P, kPa 6.69 19.6 50.1 112.3
Plot these data so as to obtain nearly straight line, and calculate
a) The enthalpy of vaporization b) The boiling point at 1 atm.

6) The vapor pressures of benzene and toluene have the following values in the temperature range between
their boiling points at 1 bar;
T, oC 79.4 88 94 100 110
P*(C6H6), bar 1.00 1.285 1.526 1.801
P*(C7H8), bar 0.508 0.616 0.742 1.00

a) Calculate the composition of the vapor and liquid phases at each temperature and plot the boiling point
diagram.
b) If a solution containing 0.5 mole fraction benzene and 0.5 mole fraction toluene is heated at what
temperature will the first bubble of vapor appears and what will be its composition?

7) The following data were given for the vapor pressures of liquid and solid SnBr 4 at various temperatures:
Solid Liquid
T, oC 9.8 21.0 30.7 41.4
P, torr 0.116 0.321 0.764 1.493
Calculate (a) the triple point,
(b) the molar enthalpy of sublimation,
(c) the molar enthalpy of fusion, of SnBr4. Solve (b) and (c) both by an algebraic method and by
a graphical method.
8) For uranium hexafluoride the vapor pressures for the solid and liquid are given by
In Ps = 29.411 -5893.5/T
In PI = 22.254 -3479.9/T Calculate the temperature and pressure of the triple point.

9) The heats of vaporization and of fusion of water are 2490 J g-l and 33.5 J g-l at 0 °C.
The vapor pressure of water at 0 °C is 611 Pa. Calculate the sublimation pressure of ice at -15 °C, assuming
that the enthalpy changes are independent of temperature.

11) A compound containing only boron, nitrogen, and hydrogen was found to be 40.3% B, 52.2% N, and
7.5% H by mass. When 3.301 g of this compound is dissolved in 50.00 g of benzene, the solution produced
freezes at 1.30 °C. The freezing point of pure benzene is 5.48 °C; Kb for benzene is 5.12 °C m-1. What is the
molecular weight of this compound?
a) Determine the molecular weight of the solid.
b) Determine the molecular formula of the solid
c) Determine the mole fraction of the solid in the solution
d) If the density of this solution is 0.8989 g/mL , calculate the molarity of the solution?

12) For the system of figure suppose that a liquid solution with B mole fraction 0.4 is placed in a closed
container.
a) Find out P*A ve P*B
b) Give the composition of the first vapor formed and the total pressure at that point
c) Give the composition of the last drop of liquid vaporized and the pressure at that point
d) Give the composition of the each phase present when half of the moles of liquid have been vaporized