PHYSICAL CHEMISTRY

Mr. Mohammed Faraj Elmenfy

B.Eng., M.Sc.,

Petroleum Engineering Department

[email protected]
094-5342671

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Introduction
CHAPTER 1

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Subtopics

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 Introduction to Physical
Chemistry
Physical chemistry is the study of macroscopic, and particulate
phenomena in chemical systems in terms of the principles,
practices, and concepts of physics such as motion, energy, force,
time, thermodynamics, quantum chemistry, statistical mechanics,
analytical dynamics and chemical equilibrium.
Physical chemistry can be divided into;
- Thermodynamics
- Quantum chemistry
- Statistical mechanics
- kinetics
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Introduction to Thermodynamics
Thermodynamics is:
Science of energy
Ways energy is stored within a body
How energy transforms
Involve heat and work (may take place)

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Thermodynamics System
System:
is a part of the physical universe
with a specified boundary which
is used direct observation in a
thermodynamics study.
Surrounding:
Mass or region outside the
system
Boundary:
Surface separate system from
surrounding

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Types of Thermodynamics System
Opened System:

Open systems have mass & energy flow across

their boundaries.

Mass Flow
mass
Open YES
System

energy
YES

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 Types of Thermodynamics System
Closed system:

Closed system does not have mass flow across the

boundary.
Only energy

Closed
System

dm 0
dt

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Types of Thermodynamics
System
Isolated system
◦ No interaction between system and surrounding
◦ Neither matter nor energy can be transferred between system and
surrounding.

NO

NO

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Interactions Between System
& Surroundings...
Surroundings
Heat
• Closed system (control
mass) – no mass can enter
System
or leave a system

Work Surroundings
Mass Flow
Heat
•Open system (control
volume) – usually encloses
a device that involves mass System
flow such as compressor, Mass
Power
turbine or nozzle. Flow
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Thermodynamic Boundary
Definition:

- the obvious separation between system and

surroundings
Types of boundaries:
◦ Rigid or non-rigid (moveable)
◦ Permeable (allow matter to pass through) or Impermeable
◦ Adiabatic (thermal conducting) or non-adiabatic

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Thermodynamics
Equilibrium
Definition:

- no changes, macroscopic properties remain

constant with time.
Types of equilibrium:
◦ Thermal
◦ Mechanical
◦ Phase
◦ Chemical/ material

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Thermodynamics Equilibrium
Thermal equilibrium:
The temperature is the same throughout the
entire system

IRON IRON
150oC 60oC

COPPER COPPER
20oC 60oC

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 Thermodynamics
Equilibrium
Mechanical equilibrium:
Related to pressure
There is no change in pressure at any point of the
system with time.

High Low Low High

Pressure Pressure Equal Pressure
Pressure Pressure
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Thermodynamics
Equilibrium
Phase equilibrium:
If a system involves two phases, it is in phase
equilibrium when the mass of each phase
reaches an equilibrium level and stays there.

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Thermodynamics
Equilibrium
Chemical equilibrium:
Chemical composition does not change with
time
No chemical reactions occur

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 Thermodynamics
Properties
Intensive variable
◦ Independent of the size of the
system
◦ Pressure (P), Temperature (T)

Extensive variable
◦ Depend on the size of the system
◦ E.g: Volume (V), mass (m), Density
(ρ)

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 Zeroth Law of
Thermodynamics
Two systems that are each found to be in thermal
equilibrium with a third system will be found to be
in thermal equilibrium with each other

Eq
m

A
riu

ui l
lib

ibr
ui

ium
Eq

B C
Equilibrium
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Zeroth Law justifies the concept of temperature & the use of
thermometer.
Suppose that B is a glass capillary containing mercury. Then,
when A is in contact with B, the mercury column in the latter
has a certain length. According to Zeroth Law, if the mercury
column in B has the same length when it is placed in contact
with another object C, then we can predict that no change of
state of A and C will occur when they are in contact.
Zeroth Law tell us that the temperature scale will fulfill its
function of telling whether or not the two systems are in
thermal equilibrium.

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 Temperature Scale
Ice point
◦ Temperature equilibrium between pure ice and liquid water
with air saturated with vapor
◦ 0oC at 1 atm

Steam point
◦ Temperature equilibrium between pure liquid water and
water vapor
◦ 100oC at 1 atm

Celcius scale (SI) and Fahrenheit scale

(English)
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Conversion Unit

T K = T C + 273.15

T R = T F+ 459.67
T R = 1.8 T K
9
T  F = T  C  32
5
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Pressure
Force F
P 
Area A

N
1 kPa  10 23

m
6 N
1 MPa  10 2  103 kPa
m

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Ideal Gas
Perfect gas equation PV  nRT
At low pressure and high PV  mRT / M
temperature, the density PmP =  RT
Pressure
of the gases decrease and V = volume
the gas behave as an T =
ideal gas. Temperature
R = gas
Some values of the gas constant
8.314 kJ/(kmolK)
constant, R 8.314 kPam3/(kmolK)
1.986 Btu/(lbmolR)
1545 ftlbf/(lbmolR)
10.73 psiaft
‫طبرق‬/(lbmolR)
3
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 Ideal Gas Mixtures &
Dalton’s Law
Total pressure of an ideal gas mixture is equal to
the sum of the partial pressure of the individual
gases ~ Dalton’s Law

P  PA  PB  
nA RT nB RT RT
P     (nA  nB  )
V V V

Partial pressure Pi of gas i in a ni

Pi  P  yiP
n
gas mixture
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Believe in yourself! Have faith in your
abilities! Without a humble but reasonable
confidence in your own powers you cannot be
successful or happy.

Norman Vincent Peale

‘The Power of Positive Thinking’
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Ideal Gas Laws
 Boyle’s Law
- First description of ideal gas
(The pressure of a fixed amount of gas at
constant temperature is inversely
proportional to the volume)
- An approximation that for a constant n and
T; 1 1
p or V
V p
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 Charles’ Law
- States that the volume of a fixed n and P is
proportional to its T.
(The volume of a fixed amount of gas in a
container at constant pressure is directly
proportional to the absolutely temperature.
The pressure of a fixed amount of gas in a
container at constant volume is proportional to
the absolute temperature)
V T ( Kelvin) or P T ( Kelvin)
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Avogadro’s Principle
-Volume of any gas is directly proportional to the
particles number at constant T and P;

(The volume occupied by a sample of a gas at constant

pressure and temperature is proportional to the number of
moles of molecules present)

V n

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Perfect Gas Equation
 Combining
- Boyle’s Law
- Charles’ Law
- Avogadro’s Principle
 The equation is

pV = constant × nT = nRT
where R = gas constant
= k × NA
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 Dalton’s Law
Total pressure of an ideal gas mixture is equal
to the sum of the partial pressure of the
individual gases

P  PA  PB  
nA RT nB RT RT
P     (nA  nB  )
V V V
Partial pressure Pi of gas i in a ni
Pi  P  yiP
gas mixture n
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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.
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 Real gases
 Due to intermolecular forces;
- Attractive: dipole-dipole forces, H-bonds,
dispersion forces
- Repulsive: repulsion of electrons
 Measure;

- Compressibility factor, Z
- Virial equations
- Van Der Waals equation
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 Compressibility factor, Z

The compression factor of a gas can be defined as

pv
Z
RT

v is the molar volume of the gas, V /n

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 Ideal gas: Z = 1
- Departure from Z = 1 means that a gas is not
behaving as an ideal gas
 Intermediate Pressure: Z < 1

- Compression is favoured, due to dominance of

attractive forces
 High Pressure: Z > 1

- Expansion is favoured, as repulsive forces

come into play
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Equation of State for Real Gases
Van Der Waals a
( P  2 )(v  b)  R T
Table A-1: Critical Props v
(Thermodynamics) a
27 R 2 Tcr2
and b
RTcr
64 Pcr 8 Pcr
Virial Equation

Pv B C
• a: attractive effects Z  1  2
• b: repulsive effects RT v v
v  specific volume (m3 /mol)
B  virial coefficient (m 3 /mol)
C  virial coefficient (m 6 /mol 2 )
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Virial Equation of State
Virial: comes from that Latin word vis, viris, meaning force – the
coefficients in the virial equation depend on the forces of interaction
between molecules of the gas.

Pv B C
Z  1  2 v  specific volume (m 3 /mol)
RT v v
B  virial coefficient (m 3 /mol)
C  virial coefficient (m 6 /mol 2 )

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p = 0 : Close to ideal gas law, but not exact
p increases : B contributes, linear relation between Z and P
p higher : C and higher order terms contribute, deviation from linearity

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Second and Third
Virial Coefficients at 298.15K (25°c)
Gas B/10-6 m3/mol C/10-12 m6/mol-2
H2 14.1 350
He 11.8 121
N2 -4.5 1100
O2 -16.1 1200
Ar -15.8 1160
CO -8.6 1550
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Van Der Waals Equation
A semi empirical theory, which means it is based upon experimental
observations, combined with a rigorous thermodynamic treatment

a
( P  2 )(v  b)  R T
v

27 R 2 Tcr2 RTcr
a and b
64 Pcr 8 Pcr

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Exercise
A gas mixture being used to simulate the atmosphere of another planet
consists of 320 mg of methane, 175 mg of argon, and 225 mg of
nitrogen. The partial pressure of nitrogen at 300 K is 15.2 kPa. Calculate
(a) the total pressure and (b) the volume of the mixture.

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Calculate the pressure of 0.01 kg of oxygen confined to a
container of volume 100 cm3 at 25°C between treating it as a
perfect gas, van Der Waals and virial equations. Describe the
conditions that deviate O2 from the ideal gas and real gas
behaviour.
Given the Virial coefficients;
B = -16.1 x 10-6 m3 / mol C = 1200 x 10-12 m6 / mol2
MW O2 = 32 g/mol
R = 8.314 Pa. m3/ K mol
Tcr = 154.59 K Pcr = 5.043 MPa
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‫‪Thank you for your listening‬‬

‫قسم الهندسة النفطية‪ -‬جامعة طبرق‬