Physical Chemistry

CEB1023

Semester
Sep 2022
Prof. Dr. Masaharu Komiyama Dr. Bhajan Lal
Chemical Engineering Department Chemical Engineering Department
Universiti Teknologi PETRONAS Universiti Teknologi PETRONAS
 Lecturer and CR contact details

Pchem class representative

Name:
Phone number:
Email address:

Lecturer: Prof. Dr. Masaharu Komiyama

Office: 05-00-02
Phone: 014-243-4085
Email: [email protected]
GA:
Discussion: Office hours (anytime), Please
email before schedule a time slot

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3
 Assessment
• Course work
1. Tests 20 % (Two Tests)
2. Labs 20 %
3. Quizzes 10 % (Two Quizzes)
• Final Exam 50 %

Passing marks : 40 % for Course Work

40 % for Final Exam
• Attendance (Lectures & Tutorials) Compulsory
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 Lab experiment
EXPT 1: REACTION RATE AND ACTIVATION ENERGY OF ACID
HYDROLYSIS OF ETHYL ACETATE (Chemical kinetics)

EXPT 2: PARTIAL MOLAR VOLUMES (Phase/Sol)

EXPT 3: ADSORPTION OF ACETIC ACID ON ACTIVATED

CHARCOAL (Catalysis)

EXPT 4: LIQUID-VAPOR EQUILIBRIUM IN BINARY SYSTEM

(Phase/Sol)
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 GRADING SYSTEM

Letter Grades:
1. 85-100 A
2. 80-84.9 A-
3. 75-79.9 B+
4. 65-74.9 B
5. 55-64.9 C+
6. 50-54.9 C
7. 45-49.9 D+
8. 40-44.9 D
9. 0-39.9 F

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 Announcement
Tutorial : Start from 2nd or 3rd week (watch for announcement)
Lab : Start from 3rd week (watch for announcement)

Quiz 1 : 23rd September, 8:00-8:20 pm  Chapter 1 & 2, Venue: ULearn

Test 1 : 7th October  Venue & Time: TBA

Quiz 2 : 3rd November, 8:00-8:20 pm  Chapter 4 & 5, Venue: ULearn

Test 2 : 18th November  Venue & Time: TBA

Final Exam : 1st – 11th December  Venue: TBA

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 COURSE OUTLINE

1. Introduction
2. The 1st and 2nd Laws of Thermodynamics
3. Phase and Solutions
4. Chemical Kinetics
5. Catalysis
6. Electrochemical Systems
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 COURSE OUTCOME
At the end of this course, students should be able to:
 Understand the principles and theoretical aspect of ideal
1 gas, 1st and 2nd laws of thermodynamics, phase behavior,
reaction kinetics, catalysis, and electrochemical systems.
 Analyze the complex problems of 1st and 2nd laws of
2 thermodynamic, phase behavior, reaction kinetics,
catalysis, and electrochemical systems to solve
complex chemical engineeering problem.
3  Analyze problems related to thermodynamics, phase
behavior, reaction kinetics, catalysis, and electrochemical
systems.

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 LEARNING OUTCOME
At the end of this course, students should be able to apply:
 The theoretical aspect of ideal gas and 1st and 2nd laws of
1 thermodynamics.
 The principles of phase transformation and equilibrium.
2
 The principles of reaction kinetics, order of reaction
3 and elementary reaction.
 The Fundamentals of catalysis and catalytic reactions.
4
 The principles of electrochemical systems, their
5 applications and thermodynamics.

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Active Learning 1

Brainstorming

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 Physical Chemistry
Physical Chemistry is a branch of chemistry concerned with interactions and
transformations of materials. It deals with the principles of physics underlying all
chemical interactions, seeking to measure, correlate, and explain the quantitative
aspects of reactions. The field includes quantum mechanics, chemical thermodynamics,
reaction kinetics and catalysis, electrochemistry, photochemistry and surface chemistry
(Britannica). It is the study of how matter behaves on a molecular and atomic level and
how chemical reactions occur (American Chemical Society).

Prerequisites:
Foundation Chemistry

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 Scale-up

benzene, B.P.=80.1°C acetone, B.P.=56.2°C 13

Measurements

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 Chapter 1

Introduction
Types of system
Thermodynamic Properties
Ideal Gas Equation

https://create.kahoot.it/details/a8631796-3e3b-46b4-a3a9-4c263ad03dfd

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 Learning Outcomes

Able to differentiate intensive and extensive properties.

Able to perform calculations using ideal gas equations

for partial pressures, mole fractions, amounts of gases and
gas density.

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Active Learning 2

Opening Question

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Extra Material
 Introduction to Thermodynamics
• Thermodynamics is a branch of physics concerned with heat and temperature,
and their relation to energy and work.
• The behavior of these quantities is governed by the four laws of thermodynamics
(Zeroth, First, Second and Third) irrespective of the composition or specific
properties of the material or system in question.
• Thermodynamics applies to a wide variety of topics in science and engineering,
especially physical chemistry, chemical engineering and mechanical engineering.

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 Thermodynamic Systems

System: Part of the universe under study.

Surroundings: Part of the universe that can interact with the system.
A boundary/wall separates the system from the surroundings and
the characteristics of that boundary determine whether the system
is open, closed or isolated.
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 Matter Thermodynamic Systems

⇋
Heat ⇋
Heat ⇋

Open system Closed system Isolated system

(wall is diathermic) (wall is diathermic) (wall is adiabatic) 21
 Thermodynamic Properties
Extensive property
• Depends on amount of matter in the substance/system.
• Eg: mass, m = m1 + m2 + m3 + …………
volume, V = V1 + V2 + V3 + ………..
Intensive property
• Does not depend on amount of matter
in the substance/system.
• Eg: density, ρ
temperature, T
molar volume, Vm = V/n
Homogeneous system: intensive property
is constant throughout.
Heterogeneous system: two or more
phases with different intensive properties. 22
Homogeneous and Heterogeneous system

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Three basic states of matter

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 Ideal or perfect gases
A hypothetical ideal or perfect gas is composed of
molecules which follow a few rules:
1. Ideal gas molecules do not attract or repel each other
(unaffected by intermolecular forces).
The only interaction between ideal gas molecules would
be an elastic collision upon impact with each other or with
the walls of the container.
2. Ideal gas molecules themselves take up no volume.
Ideal gas molecules are approximated as point particles
that have no volume in and of themselves.
In general,
- The speeds of the molecules increase as the temperature
is increased.

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 States of Gases (PVT relations)
The physical state of a substance is defined by an equation of state,
which correlates the variables describing that state.
• V = f ( p, T, n1, n2, ………..)
f: a function that depends on the nature of the system
V: volume of the system
n1, n2, ……… no of mols
p: pressure
T: temperature (absolute)
• For one-phase system composed of n mols of a single pure substance:
V = f ( p, T, n )
•For a perfect gas:

•Equation of state must be determined experimentally. 26

 Ideal Gas laws

Boyle`s Law

Charles`s Law

Avogadro`s Law

https://www.youtube.com/watch?v=kOp-3CMb6nY
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Exercise

escaped?

Please pay
attention to
Significant Figures:

← 3 digits

← 2 digits

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Gas constant, R, and Ideal Gas Equation of State

R= Universal gas constant

= 82.06 cm3atm/mol K
= 0.0821 L atm/mol K
= 8.314 J/mol K
= 1.987 cal/mol K
R/NA = kB (Boltzmann const.)
= 1.380649 × 10─23 J/K

Correlate densities of gases and liquids to temperatures and pressures.

Accurate for weakly polar gases at low pressures and moderate temperatures.
No single EoS that accurately predicts the properties of all substances under all conditions.

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 Active Learning 3

Question and Answer pair

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Exercise

A container holds 500 mL of CO2 at 20 °C and 742 Torr. What will be the
volume of the CO2 if the pressure is increased to 795 Torr?

A container holds 50.0 mL of nitrogen at 25 °C and a pressure of 736 mmHg.

What will its volume be if the temperature is increases by 35 °C?

5.00 L of a gas is known to contain 0.965 mol. If the amount of gas is

increased to 1.80 mol, what is the new volume that will result?

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Exercise If we have 1.00 mol of gas at 1.00 atm of pressure at 0 °C
(273.15 K), what would be the volume?
pV = nRT
V = nRT/p
V = (1.00 mol)(0.0821 L atm/mol K)(273.15 K) / (1.00 atm)
Therefore: V = 22.4 L
Nitrate salts (NO3─) when heated can produce nitrites (NO2─) plus
oxygen (O2). A sample of potassium nitrate is heated and the O2
gas produced is collected in a 750 mL flask. The pressure of the
gas in the flask is 2.8 atm and the temperature is recorded to be
53.6 °C. How many mols of O2 gas were produced?
pV = nRT
n = pV/RT
n = (2.8 atm × 0.75 L) / (0.0821 L atm/mol K × (53.6 + 273)K)
n = (2.1 atm L) / (26.81 L atm/mol)
Therefore: n = 0.078 mol of O2 were produced
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Exercise
Exercise

A student decomposes KClO3 and collects 36.5 cm3 of O2 over H2O

at 23 ºC. Barometer = 751 Torr, vapour pressure of H2O = 21.1 Torr.
Find the volume occupied by dry O2 at 0 ºC and 1.000 atm.

PO2 = 751 Torr - 21.1 Torr = 730 Torr

P1V1 P2V2 V1 P1T2

= ; ∴V2 =
T1 T2 P2T1

V2 =
(36.5 cm )(730 Torr )(273 K )
3

(760 Torr )(296 K )

= 32.3 cm3
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Exercise Ideal gas equation related problem

Problem 1: How many molecules are there in 985 mL of nitrogen at 0.0 °C and
1.00 × 10−6 mmHg?

Problem 2: Calculate the mass of 15.0 L of NH3 at 27 °C and 900 mmHg.

Problem 3: Calculate the density in g/L of 478 mL of krypton at 47 °C and 671

mmHg.

Problem 4:: 6.3 mg of boron hydride is contained in a flask of 385 mL at 25.0 °C

and a pressure of 11 Torr.
(a) Determine the molar mass of the hydride.
(b) Which of the following hydrides is contained in the flask, BH3,
B2H6 or B4H10?
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 Mixtures of Gases
• When we have a mixture of two or more gases,
what contribution do each of the member gases
make to the overall pressure of the system?
• Dalton’s Law: The total pressure exerted by a
homogeneous mixture of gases is equal to the sum
of the partial pressures of the individual gases.
The partial pressure of a gas is the pressure it
would exert if all the other gases in the mixture
were absent.
» Law of Additivity

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Exercise
The mole fractions of all the gases in a closed system are given:
xN2 = 0.78, xO2 = 0.21, xAr = 0.0093, xCO2 = 0.0003.
(a) Find Pi at 1.00 atm and 20 ºC.
(b) Find mi in a 15 ft × 20 ft × 10 ft room at 20 ºC and 740 Torr.
Calculate ρ.

(a) Pi = xi P
PN2 = (0.78)(1.00 atm) = 0.78 atm
PO2 = 0.21 atm
PAr = 0.0093 atm
PCO2 = 0.0003 atm
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 (b)

3 3
 12inch   2.54cm 
V = (15 ft × 20 ft ×10 ft )    = 8.5 × 107 cm3
 1 ft   1inch 

 740Torr 
 ( 7
 8.5 × 10 cm
PV  760Torr / atm 
3
)
ntot = = = 3.44 × 103 mol
RT  82.06cm3 atm 
 (293K )
 mol.K 

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 ( ) (
nN 2 = x N 2 (ntot ) = (0.78) 3.44 ×103 mol )
(
mN 2 = (28.0 g / mol ) 2.68 × 10 mol = 75kg
3
)
𝑚𝑚𝑂𝑂2 = 23 𝑘𝑘𝑘𝑘, 𝑚𝑚𝐴𝐴𝐴𝐴 = 1.3 𝑘𝑘𝑘𝑘, 𝑚𝑚𝐶𝐶𝑂𝑂2 = 45 𝑔𝑔

mtot mN 2 + mO2 + m Ar + mCO2

⇒ ρ= =
V V
99.3 𝑘𝑘𝑘𝑘 3
𝜌𝜌 = = 0.00117 𝑔𝑔/𝑐𝑐𝑚𝑚
8.5 × 107 𝑐𝑐𝑚𝑚3

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Exercise
What is the density of nitrogen gas ( N2 ) at 248.0 Torr and 18º C?
D (density) = PM/RT

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Exercise
A mixture of N2 and O2 has a density of 1.185 g/L at 25 °C and
101.3 kPa. Find the mole fraction of O2 in the mixture.
Hint: the given data and the unknown are all intensive properties, so the
problem can be solved by considering any convenient fixed amount of
mixture.

Take 1 litter of gas. This volume has m = 1.185 g = mN2 + mO2.

From PV = ntotRT
P = 101.3 kPa = 1.01 × 105 Pa = 1 atm
V = 1 L = 1000 cm3, R = 82.06 cm3 atm/ mol K
T = 298 K
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 (1atm )(1000cm3 )
ntot = = 0.0409mol
(82.06cm3atm / mol.K )(298K )
mN 2 mO2
ntot = nN 2 + nO2 = +
M N2 M O2

0.0409mol =
mN 2
+
(
1.185 − m )
N2

(28.0 g / mol ) (32.0 g / mol )

solving ⇒ 𝑚𝑚𝑁𝑁2 = 0.862 𝑔𝑔

∴ 𝑚𝑚𝑂𝑂2 = 1.185 𝑔𝑔 − 0.862 𝑔𝑔 = 0.323 𝑔𝑔

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 0.862 𝑔𝑔
Then 𝑛𝑛𝑁𝑁2 = = 0.0308 𝑚𝑚𝑚𝑚𝑚𝑚
28.0 𝑔𝑔/𝑚𝑚𝑚𝑚𝑚𝑚

0.323 𝑔𝑔
𝑛𝑛𝑂𝑂2 = = 0.0101 𝑚𝑚𝑚𝑚𝑚𝑚
32.0 𝑔𝑔/𝑚𝑚𝑚𝑚𝑚𝑚

0.0101
xO2 = = 0.247
0.0101 + 0.0308

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 Summary
1. The importance and application of Physical Chemistry in
chemical industries.
2. Important concepts in thermodynamics, e.g, system,
surroundings, walls (boundaries), intensive and extensive
properties, equation of state.
3. Ideal gases obey the ideal gas equation of state PV = nRT.
4. The partial pressure of gas i in any mixture is Pi = xi P.
5. Mol fraction of i is xi = ni / ntot.

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Active Learning 4

Reflection

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Active Learning 5

One Final Question

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Extra Material