What is Physical Chemistry?

The subject of physical chemistry

• Physical chemistry is the science about laws of
chemical processes and chemical phenomena.

• Its concepts are used to explain and interpret

observation on the physical and chemical
properties of matter.

• It explains the phenomena based on physical

foundations and tends to quantitative
description of chemical processes.
The structure of physical chemistry
Thermodynamics

Electrochemistry
Physical chemistry Kinetics

Quantum mechanics

Theoretical base

Chemical Chemical
research engineering
 What is thermodynamics?
• Thermodynamics is the science of the
utilization and conversion of energy.

Postulates about thermodynamic

equilibrium:
• 1. System passes into equilibrium state at
constant external properties on boundary with
time (in process of time) (exactly t → ∞).
• 2. All properties of thermodynamic system
(including all value of the internal parameters)
are unambiguous (unique) function of external
parameters and composition of system.
Structure of thermodynamics
 Basics of thermodynamics
• Thermodynamic system is a body (a complex of
bodies) that can exchange energy with other bodies
(itself) and/or substances separated from surroundings
by a real or imaginary boundary.

Open
Homogeneous

Thermodynamic
Closed system

Heterogeneous
Isolated
 What is thermodynamic process?
• A thermodynamic
process is a change
of thermodynamic
system state
accompanied by
changing at least
one of its
parameters.
Thermodynamics processes
 What is thermodynamic parameter?

• A thermodynamic parameter is one of

thermodynamic values describing the state
of thermodynamic system.

Thermodynamic parameter

Intensive Extensive
 Temperature
• The temperature, T,
is the property that
tells us the direction
of the flow of
energy.
• The temperature is
a property that tells
us whether two
objects would be in
thermal equilibrium
The Zeroth Law of thermodynamic

If object A is in
thermal equilibrium
with B, and B is in
thermal equilibrium
with C, then C is
also in thermal
equilibrium with A.
 Pressure
• The pressure, P, is
the property that
tells us the direction
of the flow of
matter.
• The pressure is a
property that tells
us whether two
objects would be in
mechanical
equilibrium
 The Perfect Gas Laws
Boyle’s law:
at constant
temperature the
volume of a gas is
inversely proportional
to the pressure
V ∝ 1/p, or
pV = constant
 The Perfect Gas Laws

I. Charles's law: the

volume increased linearly
with the temperature,
whatever the identity of
gas, provided it was at
low pressure

V = constant x (θ + 273 °C)

At T = constant
 The Perfect Gas Laws
II. Charles's law:
the pressure of a
sample of gas is
monitored under
conditions of
constant volume is
p = constant x T
(at V = constant)
 The Perfect Gas Laws
Avogadro's principle
The volume of a sample of gas is proportional to
the amount of molecules (in moles), present,
and that the constant of proportionality is
independent of the identity of gas

V = constant x n
(at constant pressure and temperature)
 The Combined Gas Law
Perfect gas equation:
• pV = constant x nT
• pV = nRT
• R – gas constant
 Using the perfect gas equation
• In an industrial process, nitrogen is heated to
500K in a vessel of constant volume. If it enters
the vessel at a pressure at 100 atm and a
temperature of 300K, what pressure would it
exert at the working temperature if it behaved as
a perfect gas?
• Data:
n P V T
initial Same 100 Same 300
final Same ? Same 500
 Solution
PV PV
Initial state
1 1
= nR Final state 2 2
= nR
T1 T2

PV PV
1 1
= 2 2

T1 T2
P1 P2 T2
V1 = V2 = P2 = P1
T1 T2 T1

500
Result P2 = 100 = 167 atm
300
 Using the perfect gas equation
• What temperature would result in the same
sample exerting a pressure of 300 atm?

n P V T
initial Same 100 Same 300
final Same 300 Same ?
 Solution
PV PV
Initial state
1 1
= nR Final state 2 2
= nR
T1 T2

PV PV
1 1
= 2 2

T1 T2
P1 P2 P2
V1 = V2 = T2 = T1
T1 T2 P1

300
Result T2 = 300 = 900 K
100
 Mixtures of gases
Dalton’s law: Partial pressure
the pressure exerted by of a perfect gas is
a mixture of perfect gas the pressure that
is the sum of the partial it would exert if it
pressures of the gases. occupied the
container alone.
P = pA + pB + …

For each substance J:

nJ RT
pJ =
V
 Using Dalton’s law
• A container of volume 10L holds 1 mol N2
and 3 mol H2 at 298K. What is the total
pressure (in atm) if each component
behaves as a perfect gas?
 Solution
RT
P = p A + pB = ( nA + nB )
V

8.2 ⋅10−2 ⋅ 298

Result P = (1 + 3) = 9.78atm
10
 Mixtures of gases
Mole fractions and partial pressures
• Mole fraction, xJ is the amount
of J expressed as a total
amount of molecules, n, in the
sample:
nJ
xJ = n = nA + nB + ...
n
x A + xB + ... = 1
• Partial pressure, pJ :
p J = xJ P
p A + pB + ... = ( xA + xB + ...) P = P
Calculating partial pressures
• The mass percentage composition of
dry air at sea level is approximately
N2 : 75,5; O2 : 23,2; Ar: 1,3.
What is the partial pressure of each
component when the total pressure is
2 atm?
 Solution
m = 100 g 100 ⋅ 0.755
n ( N2 ) = = 2.69mol
28
mJ 100 ⋅ 0.232
nJ = n ( O2 ) = = 0.725mol
MJ 32
100 ⋅ 0.013
n ( Ar ) = = 0.033mol
40
n = 3.45mol
N2 O2 Ar
nJ
xJ = Mole 0.780 0.210 0.0096
n fraction
Partial 1.560 0.420 0.019
p J = xJ P pressure
 The Real Gas Laws
Van der Waals equation:
2
nRT ⎛n⎞
P= − a⎜ ⎟
V − nb ⎝V ⎠
V
Vm = Molar volume
n
RT a
P= − 2
Vm − b Vm
 Home work
Two separate bulbs contain ideal gases A
and B, respectively. The density of gas A
is twice that of gas B, and the molecular
weight of gas A is half that of gas B. The
two gases are at the same temperature.
Calculate the ratio of pressure of gas A to
that of gas B.