Gazi University Faculty of Engineering March, 2021

Department of Chemical Engineering

ChE 244 Physical Chemistry, Problem Set #2
Prof. Dr. Nurdan SARAÇOĞLU, Prof. Dr. Nursel DİLSİZ,
Doç. Dr. Filiz DEREKAYA, Doç. Dr. Funda TURGUT BAŞOĞLU

PROBLEM SET - 1
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 O2 = 3.61x10-10 m)

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 vz 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 vx in the range 150.00 to
150.001 m/s.
 Gazi University Faculty of Engineering March, 2021
Department of Chemical Engineering
ChE 244 Physical Chemistry, Problem Set #2
Prof. Dr. Nurdan SARAÇOĞLU, Prof. Dr. Nursel DİLSİZ,
Doç. Dr. Filiz DEREKAYA, Doç. Dr. Funda TURGUT BAŞOĞLU

16.The vapor pressure of naphthalene (M=128.16 g/mol) is 17.7 Pa at 30°C. Calculate the weight loss in period of
2 h of a Knudsen cell fill with naphthalene and having a round hole 0.50 mm in diameter.

17) Calculate the number of total collision per unit volume per unit time in a sample of air at 25°C and 1 bar.
Assume the mole fraction N2 and O2 in air are 0.79 and 0.21 respectively and d(N2)=0.373 nm and d(O2)=0.353 nm.

18) a) Calculate the diffusion constant of N2 at 25°C and P=100 Pa, =0.36x10-18m2.
b) If a pressure gradient of 0.2 bar/m is established in a pipe. What is the flow of gas due to diffusion?

19) Calculate the probability density for νx for O2 molecules at 300 K at 0, 300 and 600 ms-1.
Gazi University Faculty of Engineering March,2021
Department of Chemical Engineering
ChE 244 Physical Chemistry, Problem Set #3
Prof. Dr. Nurdan SARAÇOĞLU, Prof. Dr. Nursel DİLSİZ,
Doç. Dr. Filiz DEREKAYA, Doç. Dr. Funda TURGUT BAŞOĞLU

PROBLEM SET - 3
(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 dnA
 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.

Gazi University Faculty of Engineering March,2021
Department of Chemical Engineering
ChE 244 Physical Chemistry, Problem Set #3
Prof. Dr. Nurdan SARAÇOĞLU, Prof. Dr. Nursel DİLSİZ,
Doç. Dr. Filiz DEREKAYA, Doç. Dr. Funda TURGUT BAŞOĞLU

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.

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
Department of Chemical Engineering
ChE 244 Physical Chemistry
2020-2021 Spring Semester
Prof. Dr. Nurdan Saraçoğlu
PROBLEM SET 3

1. Consider the following mechanism:

k1
A B  C
k2

C 
k3
D
(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
NO2 Cl 
k1
NO2  Cl
NO2 Cl  Cl 
k2
NO2  Cl2
(a) Assuming a steady state for the chlorine atom concentration, show that the
emprical first order rate constant can be identified with 2k 1.

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. The mechanism of the pyrolysis of acetaldehyde at 520 0C and 0.2 bar is
CH 3 CHO 
k 1
CH 3  CHO
CH 3  CH 3 CHO 
k2
CH 4  CH 3 CO
CH 3 CO 
k3
CO  CH 3
CH 3  CH 3 k4
C2 H 6
What is the rate law for the reaction of acetaldehyde CH3COH, using steady state
assumptions for the radicals CH3CO and CH3 .

6. A gas reaction A= 2B is first order in A in a reaction vessel of constant

volume 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 .

7. 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

8. 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?

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] 4 4 2 2
mol/L
103 [I-1] mol/L 2 4 2 2
 103 [OH-1] 1000 1000 1000 250
mol/L
103 r0 mol/L 0.48 0.5 0.24 0.94
Find the rate law.
10. Consider two consecutive first order nuclear decay reactions with the rate
constants k1 and k2

A 
k3
B and B 
k2
C
If k1=k2=0.1340 year-1 , draw [B]/[A]0 plot.

11. 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 2 O2 ( slow)
A.
H 2 O2  H 2 
k2
2H 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 )

14. a) Find the activation energy of reaction whose rate constant is multipled 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
multipled when T increases from 300 to 310 °C.
Gazi University Faculty of Engineering March,2021
Department of Chemical Engineering
ChE 244 Physical Chemistry, Problem Set
Prof. Dr. Nurdan SARAÇOĞLU, Prof. Dr. Nursel DİLSİZ,
Doç. Dr. Filiz DEREKAYA, Doç. Dr. Funda TURGUT BAŞOĞLU

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. 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?

3. Liquid mercury has a density of 13.690 cm-3, and solid mercury has a density of 4.193
9 cm-3 both being measured at the melting point, -38.87 °C, at 1 bar pressure. The heat of
fusion is 9.75 J g-l. 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.

4. 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?

5. 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.

6. 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.
Gazi University Faculty of Engineering March,2021
Department of Chemical Engineering
ChE 244 Physical Chemistry, Problem Set
Prof. Dr. Nurdan SARAÇOĞLU, Prof. Dr. Nursel DİLSİZ,
Doç. Dr. Filiz DEREKAYA, Doç. Dr. Funda TURGUT BAŞOĞLU

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. 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*(C-H8), 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?

9. 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.

10. 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.
Gazi University Faculty of Engineering March,2021
Department of Chemical Engineering
ChE 244 Physical Chemistry, Problem Set
Prof. Dr. Nurdan SARAÇOĞLU, Prof. Dr. Nursel DİLSİZ,
Doç. Dr. Filiz DEREKAYA, Doç. Dr. Funda TURGUT BAŞOĞLU

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