Introduction

SYLLABUS
1. GASES

Properties of gases
The Gas Laws: Ideal gas law, Boyles,
Avogadro's Hypothesis
Gas Mixtures, Partial Pressure, Mole
Fractions
van der Waals Equation and Others
Equations of State
SYLLABUS
2. KINETIC THEORY OF GASES
Elementary Kinetic Theory
Application to the gas law
Distribution of Molecular speeds
Types of Average Molecular Speeds,
V
rms
, V and V
mp

Transport Phenomena of Gases
Diffusion, thermal conductivity and
viscosity of gases

SYLLABUS
3. THE RATES OF REACTION
Definition of Rate
Rate Law and Rate Constant
Reaction Order
Determination of Rate Laws
Integrated Rate Laws
Reaction Mechanism
Half-life and Time Constant
Collisions Theory
The Arrhenius Parameters
Transition State Theory

SYLLABUS
4. CHEMICAL THERMODYNAMIC
The Nature of Energy and Types of Energy
Energy Changes in Chemical Reaction
Enthalpy
Standard Enthalpy of Formation and
Reaction
Calorimetry
Heat of Solution and Dilution
First Law of Thermodynamic
Work and heat
Enthalpy and the First Law of
Thermodynamic

SYLLABUS
5. ENTROPY, FREE ENERGY AND
EQUILIBRIUM
Entropy
The Second Law of Thermodynamic
Calculation of Entropy Change
The Gibbs Energy
Standard Free-Energy Changes
Free energy and Chemical Equilibrium
SYLLABUS
6. THE PROPERTIES OF MIXTURE
Ideal Solutions
Ideal-dilute Solutions
Colligative Properties

SYLLABUS
7. CHEMICAL EQUILIBRIUM
The Concept of Equilibrium and the
Equilibrium Constant
Writing Equilibrium Constant Expression
The Reaction Gibbs Energy
Reaction at Equilibrium
The Relationship between Chemical
Kinetics and Chemical Equilibrium
Factor that affect Chemical Equilibrium
SYLLABUS
8. SOLID SURFACE
Surface growth
Surface Composition and Structure
Physisorption and Chemisorption
Adsorption isotherms
The Rates of Surface Processes
Mechanism of Heterogeneous Catalysis
Examples of Catalysis

REFERENCES
1. Atkins, P and Julio de. P. Elements of Physical
Chemistry 5
th
ed., Freeman, Oxford, 2009.
2. Atkins, P and JulioD. P. Physical Chemistry 8
th
ed.,
Oxford, 2006.
3. Chang, R. Chemistry 8
th
ed., McGraw Hill, 2005.
4. Ira, N. Levine. Physical Chemistry 5
th
ed., McGraw
Hill, 2003.
5. Silbey, R. J., Alberty, A. A. and Bawendi, M. G.
Physical Chemistry. John Wiley & Sons. 2005.
6. Atkins, P. W. Physical Chemistry 6
th
ed., Oxford
University Press. 2000
7. Raymond, C. Chemistry 7
th
ed., Mc Graw Hill. 2002



ASSESSMENT

Item
Test 1
Test 2
Quizzes
Assignment
Final Exam
Total


Percentage (%)
15
15
10
20
40
100

CHAPTER 1
GASES
BSK1113
COURSE LECTURER:
Assoc. Prof. MOHD TAHIR ABD RAHMAN, PhD
tahir@ump.edu.my
Subtopics
1.1 Properties of gases
1.2 The gas laws
1.3 Gas mixtures
1.4 Van der Waals equation of
state

1.1 THE PROPERTIES OF GASES
The Perfect Gas
Gas is a collection of molecules or atoms in
continuous random motion, with speeds that
increase as temperature is raised

Except during collisions, the molecules of gas
are widely separated from one another and
move in paths unaffected by intermolecular
forces

The state of a pure gas is specified by its
volume (V), number of moles (n), pressure
(p), and temperature (T)
THE PROPERTIES OF GASES
The Perfect Gas
Experimentally established that by
specifying only three of the variables, the
fourth variable can be determined; i.e. it is
described by an equation of state,
p = f(T, V, n)

Hence, we have the well known equation of
state for a PERFECT GAS, p = nRT/V ,
where R is a constant

or, pV = nRT

Pressure
Defined as force (F) divided by the area (A) the force
is applied

Force exerted by gas is due to continuous (non-stop)
collision of gas molecules on walls of its container


The collision is so numerous that they exert an
effectively steady force experienced as a steady
pressure


The SI unit of pressure is pascal (Pa), defined as 1
newton per metre squared,

1 Pa = 1 N m
-2

Pressure Units
Name Symbol Value
pascal 1 Pa 1 Nm
-2
, 1 kg m
-1
s
-2
bar 1 bar 105 Pa
atmosphere 1 atm 101,325 Pa
Torr 1 Torr (101325/760) Pa
mm mercury 1 mmHg 133.322 Pa
lb per sq inch 1 psi 6,894,757 kPa



Temperature
Concept of temperature came from
observation that a change in physical state
(e.g. volume) can occur when two objects
are in contact with one another e.g. red
hot metal plunged into water


The change in physical state results from
flow of energy (as heat) from one object to
another. Temperature (T) is the property that
tells the direction of flow energy.
Temperature
If A and B are in contact, separated by a
diathermic boundary, and energy flows
from A to B, then A has higher
temperature (without knowing the actual
value)


Temperature is a property which tells
whether two objects are in thermal
equilibrium when in contact. Thermal
equilibrium is established if no change of
state occurs.
GAS LAW
The gas laws
The equation of state of low-pressure gas is a
combination of a series of empirical laws
described below:


1.Boyles law

The pressure and volume of a fixed amount
of gas at constant temperature are related by

pV = constant
2. Charless law

The volume of a gas at contant pressure
increased linearly with absolute temperature

V/T = constant
3. Avogadros Principle

Equal volumes of gases at same pressure
and temperature, contain the same
number of molecules

V/n = constant
The single expression that combines the
above observations is called the perfect
gas equation

pV= nRT where R is the gas
constant

The combined gas law
nRT PV =
Ideal Gas
BOYLES LAW P-V relationship




when T is constant, the V of gas decreases as P increases. i.e.

(1.a)



where k
1
is a constant called the proportional constant
equation (1.a) is an expression of Boyles law : the pressure of a
fixed amount of gas maintained at constant temperature is
inversely proportional the volume of the gas
V
P
1
o
V
k P
1
1
=
Rearrange equation 1:

(1.b)

For a given sample of gas under 2 dif. set of conditions
at constant T, we have

or (2)

Where V
1
and V
2
are the volumes at pressure P
1
and
P
2
, respectively

From equation (1), k
1
= nRT



1
k PV =
2 2 1 1
V P k V P = =
2 2 1 1
V P V P =
BOYLES LAW P-V relationship
Increasing or decreasing the V of gas at a constant
temperature,

P = (nRT) 1 nRT is constant
V




EXAMPLE
An inflated balloon has V of 0.55 L at sea (1.0 atm)
and is allowed to rise to a height at 6.5 km, where
the P is about 0.40 atm. Assuming that the T remains
constant, what is the final volume of the balloons?
Reasoning and solutions
Note that the number of moles and T of the gas are
kept constant: we need Boyles law. From equ. (2)
P
1
V
1
= P
2
V
2

P
1
= 1.0 atm P
2
= 0.40 atm
V
1
= 0.55 L V
2
= ?

Therefore

V
2
= V
1
x P
1
= 0.55 L x 1.0 atm
P
2
0.40 atm
= 1.4 L
CHARLESS LAW and GAY LUSSACs
LAW: the T-V relationship
The dependence of V
gas
on T is given by
V o T
V = k
2
T
V = k
2
T (3)

where k
2
is proportional constant
Equation (3) is known as Charless and Gay-Lussacs
Law or simply Charless Law : V of a fixed amount of
gas maintained at constant pressure is directly
proportional to the absolute T
gas

From equ. (3) k
2
=nR/P



Another form of CHARLESs law show

P o T
P = k
3
T
P = k3 (4)
T
k
3
= nR/V
Just we did for P-V relationship at T
constant
,

we can
compare 2 set of V-T conditions at P
constant
.

from equ. (3)
V = k
1
= V
2
T
1
T
2
(5)

Where V
1
and V
2
are the volume of the gases at T
1

and T
2
(both in Kelvin), respectively
Heating or cooling a gas at constant
pressure
V = nR T nR is constant
P P

Heating or cooling a gas at constant volume
P = nR T nR is constant
V V
CHARLESS Law and GAY LUSSACs
Law: the T-V relationship
A 452mL sample of fluorine gas is heated from
22
o
C to 187
o
C at constant pressure. What is
its final V?
EXAMPLE
Reasoning and Solution
This change occur at constant pressure and number of moles of
the gas, so we apply Charless law [equ.(5)]
V
1
= V
2
T
1
T
2
Where,
V
1
= 452 mL V
2
=?
T
1
= (22 + 273) K = 295 K T
2
= (187 + 273) K =460K

Hence, V
2
= V
1
x T
2
T
1
= 452 mL x 460 K
295 K
= 705 mL
* As you see, when the gas is heated at constant pressure, it
expands
AVOGADROS LAW the V-n
Relationship
V o n
V = k
4
n (6)
where n represent the number of moles and k
4
is the
proportionality constant

Equ. (6) is the mathematical expression of Avogadros
law: at constant number of moles of the gas
present

k
4
= RT/P
Dependence of V on amount of gas at constant T
and P is,

V = RT n RT is constant
P P
AVOGADROS LAW the V-n
Relationship
Boyles law : V o 1 (at constant n and T)
P

Charless law : V o T (at constant n and P)

Avogadros law : V o n (at constant P and T)
IDEAL GAS EQUATION
Combine all 3 expression will form a single master equ.
for the behavior of gas,

V o nT
P
= R nT
P
so, PV = nRT (7)
where R, the proportional constant is called the gas
constant

Equa. (7) is called the IDEAL GAS EQUATION: describes
the relationship among the 4 variables P, V, n and T

An IDEAL GAS is a hypothetical gas whose P-V-T
behavior can be completely accounted for by the
IDEAL GAS EQUATION

At 0
o
C (273.15K) and 1 atm pressure, many real gases
behave like and ideal gas
The conditions 0
o
C and 1 atm are called standard T
and P, often abbreviated STP. From equa. (7) we
can write

R = PV
nT
= (1 atm) (22.414 L)
(1 atm) (273.15 K)
= 0.082057 L . atm
K . Mol
= 0.082057 L . atm/K . Mol

* 22.414 is the molar volume of gas at STP
Ideal Gas
Perfect gas
equation
At low pressure and
high temperature,
the density of the
gases decrease
and the gas
behave as an ideal
gas.
Some values of the
gas constant, R
M mRT PV
nRT PV
/ =
=
P = Pressure
V = volume
T = Temperature
R = gas constant
8.314 kJ/(kmolK)
8.314 kPam
3
/(kmolK)
1.986 Btu/(lbmolR)
1545 ftlbf/(lbmolR)
10.73 psiaft
3
/(lbmolR)
0.082 L atm/K.mol

RT Pm =
Sulfur hexafluoride (SF
6
) is a colorless, odorless,
very unreactive gas. Calculate the P (in
atm) exerted by 1.82 moles of the gas in a
steel vessel of V 5.43 L at 69.5
o
C
EXAMPLE
This problem provides information about the number
of moles, V, and T of a gas, but no change in any
quantities occurs. Therefore, to calculate the P we
can use the ideal gas equation. Which can be
rearranged to give

P = nRT
V
= (1.82 mol) ( 0.0821 L . atm/K . mol) (69.5 + 273) K
5.43 L
= 9.42 atm
Reasoning and Solution
The IDEAL GAS EQUATION is useful for problems that
do not involve changes in P, V, T, and n for a gas
sample

At time, however we need to deal with changes in P,
V, and T, or even in amount of a gas.

When conditions change, we must employ a modified
form of the ideal gas equation that takes into
account the initial and finals conditions
We derive the modified equa. as follows. From equa.
(7)

R = P
1
V
1
(before change)
n
1
T
1
and
R = P
2
V
2
(after change)
n
2
T
2

so that,
P
1
V
1
= P
2
V
2

n
1
T
1
n
2
T
2



If n
1
= n
2
, as is usually the case; the amount of gas
normally does not changes, the equation then
becomes

P
1
V
1
= P
2
V
2
(8)


T
1
T
2



A small bubbles rises from the bottom of
a lake, where the T and P are 8
o
C and
6.4 atm, to the waters surface, where
the T is 25
o
C and P is 1.0 atm.
Calculate the final V (in mL) of the
bubbles if its initial V was 2.1 mL
EXAMPLE
The problem involves the changes of T, P, and V, but
not the number of n of gas. Thus we can use
Equation (8) to calculate the final V

P
1
= 6.4 atm P
2
= 1.0 atm
V
1
= 2.1 mL V
2
= ?
T
1
= (8 = 273) K = 281 K T
2
= (25 + 273) K = 298 K

The amount of gas in the bubbles remains constant, so
that n
1
= n
2
. To calculate the final volume, V
2
, we
arrange Equa. (8) as follows:
Reasoning and Solution
V
2
= V
1
x P
1
x T
2
P
2
T
2
= 2.1 mL x 6.4 atm x 298 K
1.0 atm 281 K
= 14 mL

thus, the bubbles V increases from 2.1L to 14 mL
because the decrease of water P and the increase
in T
DALTONs LAW of Partial Pressure
e.g for a study of air pollution, we may be interested in
the P-V-T relationship of a sample air, which may
contains several gases

Daltons Law: total P of a mixture gas is just the sum of
the P that each gas would exert if it were present
alone.
Consider a case in which 2 gases, A and B, are in a
container of V. The pressure exerted by gas A,
according to the ideal gas equation, is
P
A
= n
A
RT
V
Where n
A
is the number of moles of A present. Similarly,
the pressure exerted by gas B is
P
B
= n
B
RT
V
In the mixture of gases A and B, the total pressure, P
T
is
the result of the collisions of both types of molecules.
A and B, with the walls of the container. Thus
according to Daltons law

P
T
= P
A

+
P
B

= n
A
RT + n
B
RT
V V
= RT (n
A
+ n
B
)
V
= nRT
V
Where n, the total number of moles gases present, is given by n =
n
A
+ n
B
, and P
A
and P
B
are the partial of gases A and B,
respectively

In general, the total pressure of mixture of gases is given by

P
T
= P
1
+ P
2
+ P
3
+..
Where P
1
, P
2
, P
3
,are the partial pressure of components 1, 2, 3,...


To see how each partial P is related to the total P,
consider the case of a mixture of 2 gases A and B,
dividing P
A
by P
T
, we obtain

P
A
= n
A
RT/V
P
T
(n
A
+ n
B
) RT/V
= n
A
n
A
+ n
B
= X
A

Where X
A
is called the mole fraction of gas A
Mole fraction = dimensionless quantity that express the
ratio of the number of moles of one component to
the number of moles of all component present (<1
except when A is the only component present)
in the case, n
B
= 0 and X
A
= n
A
/n
A
= 1
we can express the partial P
A
of as
P
A
= X
A
P
T

similarly,
P
B
= X
B
P
T

the sum, of the mole fraction for the mixture of gases
must unity. If only 2 component are presents, then

X
A
+ X
B
= n
A
+ n
B
= 1
n
A
+ n
B
n
A
+ n
B

If a system contains more than 2 gases, then the
partial pressure of the its component is related to
the total pressure by

P
i
= X
i
P
T
(9)



Where X
i
is the mole fraction of substance i
A mixture of gases contains 4.46 moles of neon (Ne),
0.74 mole of argon (Ar), and 2.15 moles of xenon
(Xe). Calculate the partial pressure of the gases if
the total pressure is 2.00 atm at a certain
temperature.
EXAMPLE
To calculate the partial pressure, we apply Dalton law.
First, we determine the mole fraction of Ne as follows

X
Ne
= n
Ne
= 4.46 mol
n
Ne
+ n
Ar
+ n
Xe
4.46 mol + 0.74 mol + 2.15 mol

From equa. (9)
P
Ne
= X
Ne
P
T
= 0.607 x 2.00 atm
= 1.21 atm

Reasoning and Solution
Similarly,
P
Ar
= 0.10 x 2.00 atm
= 0.20 atm
and P
xe
= 0.293 x 2.00 atm
= 0.586 atm

* To check the correctness of the answer, make sure
that the sum of the partial pressure is equal to the
given pressure; that is, (1.21 + 0.20 + 0.586) atm = 2.00
atm
1
k PV =
2 2 1 1
V P V P =
KEY EQUATIOS
(1. b) Boyles Law. Costant T and n


(2) Boyles Law ; for calculating
changes in pressure or volume

V = k
2
(3) Charless Law. Constant P and n
T
P = k3 (4) Charless Law. Constant V and n
T
V
1
= V
2
(5) Charless Law. For calculating T or
T
1
T
2
V changes










V = k
4
n (6) Avogadro Law. Constant P and T

PV = nRT (7) Ideal gas equation

P
1
V
1
= P
2
V

(8) For calculating changes in pressure
T
1
T
2

P + an
2
(V nb) = nRT(9) van der Waals equation. For
V
2
calcukating the P of nonideal gas






Temperature Scale
Ice point
Temperature equilibrium between pure ice and
liquid water with air saturated with vapor
0
o
C at 1 atm
Steam point
Temperature equilibrium between pure liquid
water and water vapor
100
o
C at 1 atm
Celcius scale (SI) and Fahrenheit scale
(English)
Conversion Unit
T K T = C+ 273.15

= F+ 459.67 T R T

T R T K = 1.8
T F T C + =
9
5
32
Pressure



P
Force
Area
F
A
= =
1 10
1 10 10
3
2
6
2
3
kPa
N
m
MPa
N
m
kPa
=
= =
Ideal Gas
Perfect gas
equation
At low pressure and
high temperature,
the density of the
gases decrease
and the gas
behave as an ideal
gas.
Some values of the
gas constant, R
M mRT PV
nRT PV
/ =
=
P = Pressure
V = volume
T = Temperature
R = gas constant
8.314 kJ/(kmolK)
8.314 kPam
3
/(kmolK)
1.986 Btu/(lbmolR)
1545 ftlbf/(lbmolR)
10.73 psiaft
3
/(lbmolR)
0.082 L atm/K.mol

RT Pm =
Ideal gas mixtures and
Daltons Law
Total pressure of an ideal gas mixture is
equal to the sum of the partial pressure
of the individual gases ~ Daltons Law

+ + =
B A
P P P
V
RT
n n
V
RT n
V
RT n
P
B A
B A
) ( + + = + + =
P y P
n
n
P i
i
i
= =
Partial pressure P
i
of gas i in a
gas mixture
REAL GASES
Real Gases
High pressure and low temperature ~
deviate from ideal gas behavior.
As the pressure is reduced to zero, the
compressibility factor approaches unity.
As the pressure increase, the compressibility
factor greater than unity.
At very high pressure the molecules of the
gas are pushed closer together.
Compressibility factor, Z=PV/RT ~ to measure
the deviation from ideal gas behavior.
REAL GASES
Real gases show deviations
from perfect gas law
because molecules DO
interact with each other.
Repulsive forces
assists expansion; are
significant only when
molecules are almost in
contact and at high
pressure

Attractive forces
assists compression; have
relatively long range and
effective over several
molecular diameters when
they are fairly close
together but not touching.
The forces become
ineffective when
molecules are far apart.
Molecular interactions give rise to two
types of intermolecular forces:
Compression Factor, Z
Departure of real gases from ideal
gases can be demonstrated by its
compression factor Z




For a perfect gas, Z = 1 under all
conditions; deviations of Z from 1 is a
measure of departure from perfect
behaviour

RT
PV
Z
m
=
Variation of Z with pressure at 0C
For perfect gases, Z is
always 1 at all
pressures

At very low pressures
all gases show Z ~ 1;
behaving nearly like
perfect gas

At high pressures all
gases have Z > 1

All gases approach Z
= 1 with its own
character

At large molar volumes and high
temperatures the gas behaves
almost like a perfect gas

Small differences suggest that
perfect gas law (pV = nRT) is
actually the first term of an
expanded virial equation of state,








( ) ........ ' ' + + + =
2
1 p C p B RT pV
m


or in terms of volume,






B, C are second, third . virial
coefficients introduced to fit the
behaviour of real gas, normally
determined experimentally.
|
|
.
|

\
|
+ + + = ........
2
1
m m
m
V
C
V
B
RT pV
Second and Third
Virial Coefficients at 298.15K
Gas B/10
-6
m
3
/mol C/10
-12
m
6
/mol
-2

H
2
14.1 350
He 11.8 121
N
2
-4.5 1100
O
2
-16.1 1200
Ar -15.8 1160
CO -8.6 1550
Virial equation is very general; the
coefficients are not related to any
physical properties of gas

van der Waals suggested a model for
real gas
van der Waals model
of Real Gas
Repulsive interactions between
molecules cause the molecules to behave
like small but impenetrable spheres
The non-zero volume of the molecules
implies that the molecules are restricted
to move in a smaller volume V-nb
instead of V
The perfect gas law should therefore be
replaced by,

nb V
nRT
p

=
Van der Waals model of Real Gas
Attractive interactions reduce the
frequency and force of collisions of
molecules with the walls of container
The frequency and force of collisions
depends on molar concentration n/V
Hence the pressure is reduced in
proportion to the square of its molar
concentration n/V
The reduction is written as
2
|
.
|

\
|

V
n
a
Van der Waals model of Real Gas
2
|
.
|

\
|

=
V
n
a
nb V
nRT
p
Van der Waals model of Real Gas
Van der Waals equation for real gas:
( ) nRT nb V
V
an
p =
|
|
.
|

\
|
+
2
2
Van der Waals model of Real Gas
The resemblance to the ideal gas
equation pV= nRT when rearranged:
Van de Waals constant for a few gases
Gas a/(L
2
bar mol
-2
) b/(Lmol
-1
)
H
2
0.2476 0.02661
He 0.03457 0.02370
A 1.363 0.03219
Ne 0.232 0.01709
N
2
1.408 0.03913
O
2
1.378 0.03183
Cl
2
6.576 0.05622
NO 1.358 0.02789
NO
2
5.354 0.04424
H
2
O 5.538 0.03049
Van de Waals constant for a few gases
Gas a/(L
2
bar mol
-2
) b/(Lmol
-1
)
CH
4
2.283 0.04278
CCl
4
20.66 0.1383
C
2
H
6
5.562 0.06380
C
3
H
8
8.779 0.08445
C
4
H
10(n)
14.66 0.1226
C
4
H
10(iso)
13.04 0.1142
C
5
H
12(n)
19.26 0.1460
C
5
H
12(iso)
18.28 0.1417
CO 1.505 0.03985
CO
2
3.640 0.04267
Equation of state for real gases
Van Der Waals

Table A-1: Critical
Props
(Thermodynamics)

Virial Equation



( )( ) P
a
v
v b RT + =
2
a
R T
P
b
RT
P
cr
cr
cr
cr
= =
27
64 8
2 2
and
2
1
v
C
v
B
RT
Pv
Z + + = =
) /mol (m t coefficien virial C
/mol) (m t coefficien virial B
/mol) (m volume specific
2 6
3
3
=
=
= v
EXAMPLE
Estimate the volume of
0.117 mol of a gas at 27.0
o
C
and 4.00 bars from the ideal
gas law
1.
Calculate the number of
molecules inside a soap
bubbles 1.0 cm in diameter
at atmosphere pressure and
25
o
C
EXAMPLE
2.
EXAMPLE
3.0 L of gas at 500 mm Hg pressure
and 21.0
o
C weight 1.53g. What is it
molar mass?
3.
EXAMPLE
The vapor pressure of solid I
2
at 25
o
C
is 0.35 mmHg. Calculate the
concentration of I
2
in the vapor
phase
4.
EXAMPLE
The molar volume for methane is
0.528 L at 273 K and 40 bars. How does
the calculate pressure from
(a) the ideal gas law
(b) the Van de Waals equation
compare with the measure
pressure?
5.