BATAA EL

GAFAARY

PHYSICAL CHEMISTRY I
CHEM 3310
1444 H

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PHYSICAL CHEMISTRY I

◾ Chem. 3310
◾ First Semester 1444H
◾ Credit Hours : 5

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LECTURES TABLE

◾ Monday / 8.00:9.40 AM
◾ Wednesday / 10.0:11.40 AM

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Gases and Kinetic molecular theory
Physical Characteristics of Gases Boyle’s
Law
Avogadro’s Law
Real Gas Equation
Dalton’s Law of Partial Pressures
Kinetic Molecular Theory of Gases

 Work, heat and energy

Isobaric, Isothermal and Adiabatic processes Exothermic
process and ENDOTHERMIC PROCESS Internal energy
Heat Capacities

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 laws of Thermodynamics

The zeroth Law

The firtst Law
The secondnd
Law
The thirdrd Law

 Chemica
l
equilibri
um

Homogenous equilibrium
Equilibrium Constant Expressions
Calculating Equilibrium
Concentrations
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Le Chatelier’s Principle
Chemical Kinetics and Chemical Equilibrium
 Solutions and Phases
Solution, solvent and solute
Mass percent, weight percent, Mole fraction, Molarity and
Molality COLLIGATIVE PROPERTIES
Types of Solutions
Gibb,s Phase Rule , Miscibility, Solubility, Component and Phase
Equilibria
Phase Equilibria
Gibb,s Phase Rule , Miscibility, Solubility, Component and Phase
Equilibria.

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 Electrochemical cells.

 Redox reaction and Thermodynamics of redox

reaction.
 Galvanic cells.
 Spontaneous and Non Spontaneous processes.

 Revision

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◾ Suggested Textbook:

◾ Physical Chemistry, Kieth Laidler, Meisser and Sanctury, Oxford university

press, 4 th edition,2003.

◾ Physical Chemistry, Peter Athins and Julio de Paula, Oxford

university press, 9 th edition,2010.

BATAA EL GAFAARY

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 KINETIC-MOLECULAR THEORY

•Remember that matter exists

on

Earth in the forms of solids, liquids,

and gases.

9
•In the late nineteenth century, scientists
developed the kinetic-molecular theory to
account for the behavior of atoms and
molecules that make up matter.
•The kinetic-molecular theory is based on
the idea that particles of matter are always in
motion.

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THE KINETIC-MOLECULAR THEORY OF GASES
•The theory provides a model of what is called an ideal gas.

•An ideal gas is an imaginary gas that perfectly fits all the
assumptions of the kinetic-molecular theory.
•The kinetic-molecular theory of gases is based on the
following five assumptions.

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 ASSUMPTION ONE

1. Gases consist of large numbers of

tiny particles that are far apart
relative to their size.
• Most of the volume occupied by a
gas is empty space.

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ASSUMPTION TWO

2. Collisions between gas particles and between particles and

container walls are elastic collisions.
• An elastic collision is one in which there is no net loss of total
kinetic energy.
• In other words, in an elastic collision the
total energy of the colliding bodies after
collision is the same as
their total kinetic energy before 8/29/2022 13

collision.
ASSUMPTION THREE

3. Gas particles are in continuous,

rapid, and random motion.
• They therefore possess kinetic

energy, which is energy of motion.

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 ASSUMPTION FOUR

4. There are no forces of attraction or

repulsion between gas particles.

“Attraction”

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 ASSUMPTION FIVE

5. The temperature of a gas depends on the average kinetic

energy of the particles of the gas.
• The average speeds and kinetic energies of gas particles
increase with an increase in temperature and decrease
with a decrease in temperature.

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THE KINETIC-MOLECULAR THEORY AND THE NATURE OF GASES

•Expansion – Gases do not have a

definite shape or a definite volume.
•Gas particles move rapidly in
all directions (assumption 3)
without
significant attraction between them
(assumption 4).
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• Compressibility – During compression, the
gas particles which are initially very far
apart (assumption 1), are crowded closer
together.

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DEVIATIONS OF REAL GAS FROM IDEAL BEHAVIOR

•A real gas is a gas that does not behave

completely according to the
assumptions of the kinetic- molecular
theory.

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SUMMERY

◾ Physical Characteristics of Gases:

A. Particles in an ideal gas…
1. have no volume.
2. have elastic collisions.
3. are in constant, random, straight-line motion.
4. don’t attract or repel each other.
5. have an avg. KE directly related to Kelvin temperature.
B. Particles in a REAL gas…
1. have their own volume
2. attract each other

◾ Gas behavior is most ideal…

◾ at low pressures
◾ at high temperatures 8/29/2022 20
CHARACTERISTICS OF GASES
1. Gases expand to fill any container.
random motion, no attraction
2. Gases are fluids (like liquids).
no attraction
3. Gases have very low densities. no
volume = lots of empty space
4. Gases can be compressed.
no volume = lots of empty space
5. Gases undergo diffusion & effusion. 8/29/2022 21

random motion
Boyle’s Law states that

• the pressure of a gas is inversely

related to its volume when T and n
are constant.

• if volume decreases, the pressure

increases.

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PV CONSTANT IN BOYLE’S LAW
In Boyle’s Law, the product P x V is constant as long as T
and n do not change.
P1V1 = 8.0 atm x 2.0 L = 16 atm L
P2V2 = 4.0 atm x 4.0 L = 16 atm L
P3V3 = 2.0 atm x 8.0 L = 16 atm L

Boyle’s Law can be stated as

P1V1 = P2V2 (T, n
constant) 8/29/2022 23
CALCULATION WITH BOYLE’S LAW

Freon-12, CCl2F2, is used in refrigeration systems. What is

the new volume (L) of a 8.0 L sample of Freon gas initially at
550 mm Hg after its pressure is changed to 2200 mm Hg at
constant T?

1. Set up a data table:

Conditions 1 Conditions 2
P1 = 550 mm Hg P2 = 2200 mm
Hg V1 = 8.0 L V2 = 8/29/2022 24
2. When pressure increases, volume decreases.

Solve Boyle’s Law for V2:

P 1V 1 = P 2V 2

V2 = V 1 x P1
P2
V2 = 8.0 L x 550 mm Hg = 2.0 L
2200 mm Hg
pressure ratio
decreases
volume

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The relationship between temperature and volume

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 HOW VOLUME VARIES WITH TEMPERATURE

If we place a balloon in liquid

nitrogen it shrinks:

So, gases shrink if cooled.

Conversely, if we heat a gas it expands (as in a
hot air balloon).

Let’s take a closer look at temperature

before we try to find
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the exact relationship of V vs. T.

 30

25

20

Volume (mL)
15

10

0 100
– 273 8/29/2022 28

Temperature (C)
 CHARLES’S LAW

◾ Looking back at the temperature vs. volume graph, notice that there
is a direct relationship.

◾ It can be shown that V/T = constant

Charles’s Law: as the temperature of a gas increases, the volume

increases proportionally, provided that the pressure and amount
of gas remain constant,

V1/T1 = V2/T2
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 2. A sample of gas occupies 3.5 L at 300 K. What volume
will it occupy at 200 K?

V1 = 3.5 L, T1 = 300K, V2 = ?, T2 = 200K

Using Charles’ law: V1/T1 =
V2/T2 3.5 L / 300 K = V2 / 200 K
V2 = (3.5 L/300 K) x (200 K) = 2.3 L

3. If a 1 L balloon is heated from

22°Cnew volumewhat
to 100°C, be? will its V = 1 L, T = 22°C = 295 K
1 1

V2 = ?, T2 = 100 °C = 373 K
V1/T1 = V2/T2, 1 L / 295 K = V2 / 373 K 8/29/2022 30

V = (1 L/295 K) x (373 K) = 1.26 L

In Avogadro’s Law
• the volume of a gas is directly related to
the number of moles (n) of gas.

• T and P are constant.

V1 = V2

n1 n2

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If 0.75 mole helium gas occupies a
volume of 1.5 L, what volume will
1.2 moles helium occupy at the same
temperature and pressure?

1) 0.94 L
2) 1.8 L
3) 2.4 L

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 SOLUTION
3) 2.4 L

STEP 1 Conditions 1 Conditions 2

V1 = 1.5 V2 = ???
L
n1 = 0.75 mole He n2 = 1.2 moles He

STEP 2 Solve for unknown V2

V2 = V1 x n2
n1
STEP 3 Substitute values and
solve for V2.
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V2 = 1.5 L x 1.2 moles He
= 2.4 L
At standard temperature and pressure (STP), 1 mole of a
gas occupies a volume of 22.4 L, which is called its
molar volume.

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What is the volume occupied by 2.75 moles N2 gas
at STP?

The molar volume is used to convert moles to

liters.

2.75 moles N2 x 22.4 L = 61.6 L

1 mole

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COMBINING ALL 3 LAWS…

◾ V  (1/p)(T)(n)
◾ V  nT/p
◾ Rearranging, pV = (constant)nT

◾ Thus we get the ideal gas equation:

pV = nRT
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FAILURES OF IDEAL GAS EQUATION

◾ Failure of Charles’ Law

◾ At very low temperatures

◾ Volume do not decrease to zero

◾ Gas liquefies instead

◾ Remember the extrapolated lines?

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FAILURES OF IDEAL GAS EQUATION

◾ From pV = nRT, let Vm be molar volume

◾ pVm = RT

◾ pVm / RT = 1

◾ pVm / RT is also known as Z, the compressibility factor

◾ Z should be 1 at all conditions for an ideal gas

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JOHANNES DIDERIK VAN DER WAALS

◾ November 23, 1837 – March 8,

1923

◾ Dutch

◾ 1910 Nobel Prize in Physics

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VAN DER WAALS EQUATION

◾ Combining both derivations…

◾ We get the Van der Waals Equation


n 
2

p + a    [V-nb] = nRT

 V  
 OR
 a2 
p+ V [Vm -b] = RT
 m
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REMEMBER Boyle’s Law

P  1/V
P x V = constant Constant temperature
P1 x V1 = P2 x V2 Constant amount of gas
5
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Variation of Gas Volume with Temperature at Constant Pressure

Charles’ Law

VT Temperature must be in Kelvin

V = constant x T T (K) = t (0C) + 273.15

V1/T1 = V2 /T2 8/29/2022 42
The conditions 0 0C and 1 atm are called standard
temperature and pressure (STP).

Experiments show that at STP, 1 mole of an ideal gas

occupies 22.414 L.

PV = nRT

PV (1 atm)(22.414L)
R = nT = (1 mol)(273.15 K)

R = 0.082057 L • atm / (mol • K)

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 Molar Volume Vm

m PM
d = V = RT
m is the mass of the gas in g
M is the molar mass of the gas
◾ Vm = V/n

◾ Vm = RT/P Molar Mass ( M ) of a Gaseous Substance

dRT d is the density of the gas in g/L

M= P

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 Kinetic Molecular Theory of Gases
1. A gas is composed of molecules that are separated from each other by
distances far greater than their own dimensions.
2. The molecules can be considered to be points; that is, they possess
mass but have negligible volume.
3. Gas molecules are in constant motion in random directions, and they
frequently collide with one another. Collisions among molecules
are elastic.
4. Gas molecules exert neither attractive nor repulsive forces on one
another.
5. The average kinetic energy of the molecules is proportional to the
temperature of the gas in kelvins. Any two gases at the same
temperature will have the same average kinetic energy

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 Dalton’s Law of Partial Pressures
V and T are constant

P1 P2
Ptotal = P1 + P2
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Consider a case in which two gases, A and B, are in a
container of volume V.

PA = nART nA is the number of moles of A

V

PB = nBRT nB is the number of moles of B

V
nA nB
PT = PA + PB XA XB =
n A + nB nA + nB
=
PA = XA PT PB = XB PT

47
A sample of natural gas contains 8.24 moles of CH4, 0.421 moles of C2H6, and
0.116 moles of C3H8. If the total pressure of the gases is 1.37 atm, what is the
partial pressure of propane (C3H8)?
Pi = Xi PT PT = 1.37 atm

0.116
Xpropane = 8.24 + 0.421 + 0.116 = 0.0132

Ppropane = 0.0132 x 1.37 atm = 0.0181 atm

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