Chap.

1: Thermodynamics
1.1: Physical Chemistry
1.2: Thermodynamics
1.3: Temperature
1.4: The Mole
1.5: Ideal Gases
1.7: Equations of States
1.1: Physical Chemistry
Physical Chemistry is the study of the
underlying physical principles that govern the
properties and behavior of chemical systems.
The structure of Physical Chemistry: Fig-1.1
Thermodynamics
1 - 13
Statistical
Mechanics
14, 15, 21, 23
Kinetics
15, 16, 22
Quantum
Chemistry
18, 19, 20
Quantum Chemistry
An applications of quantum mechanics (under
appropriate approximations) to molecular level.
Statistical Mechanics
A bridge between microscopic world and
macroscopic world.
Thermodynamics
A macroscopic study of the equilibrium states.
Kinetics
A study of the rate of change (dynamic process).
Theoretical Chemistry
Computational Chemistry
Experimental Physical Chemistry
Chemical Engineering
Instrumental Analysis
The Sub-branches of Physical Chemistry
1.2: Thermodynamics
Thermodynamics
The study of heat, work, and the changes they
produce in the states of systems.
Equilibrium Thermodynamics
The study of the fairly slow processes at equilibrium.
Irreversible Thermodynamics
Deals with non-equilibrium systems and rate
processes.
Thermodynamics Systems
Universe (Isolated System)
System:
The part of the universe under study
o Open System: Matter & energy transfer
o Closed System: Energy transfer
o Isolated System: No matter or energy transfer
Surroundings (Environment):
The parts of the universe that can interact with the
system.
Walls
o Rigid: hard
o Non-rigid: moveable
o Permeable: matter can pass
o Impermeable: no matter can pass
o Adiabatic: heat can not transfer
o Non-adiabatic: thermally conductive
Equilibrium
An isolated system is in equilibrium when its
macroscopic properties remain constant with time.
A non-isolated system is in equilibrium when the
following two conditions hold:
(a) The systems macroscopic properties remain
constant with time.
(b) Removal of the system from contact with its
surroundings causes no change in the properties
of the system.
Steady State: (a) holds but (b) does not.
Mechanical / Material / Thermal:
Thermodynamic Properties
Extensive: Size / quantity dependent
Intensive:
Homogeneous: each intensive properties is
constant throughout a system.
Phase: A homogeneous part of a system.
Heterogeneous: A system composed of two
or more phases.
Thermodynamic State is specified by the
values of its thermodynamic properties, e.g.,
Temperature, Volume, Pressure, and Density.
1.3: Temperature
Question: can we justify temperature?
Thermometer:
Temperature:
Two systems in thermal equilibrium with each other
have the same temperature; two systems not in
thermal equilibrium have different temperatures.
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.
If O
A
= O
C
, O
B
= O
C
, then O
A
= O
B
1.4: The Mole
Relative Atomic Mass: H
2
O molecular formula
Lavorsier Dalton / Avogadro Gay-Lussac
Avogadro Number: N
A
= 6.022 10
23
mol
-1
The number of C atoms in (exact) 12 g of
12
C.
The Amount of Substance: Mole
Molar Mass:
Mole Fraction:
i
i
i
n
m
M
tot
i
i
n
n
_
1.5: Ideal Gases
Gas Laws:
Boyles Law (1662): PV = k
T
Charless Law (1787): V/T = k
P
Gay-Lussacs Law (1802): P/T = k
V
Combined Gas Law(1802): PV/T = k
Avogardos Law (1811): V/n = k
T,P
Ideal Gas Law: PV = nRT
Universal Gas Constant: R = 8.31446 J/molK
The Units of pressure: atm, torr, mmHg, bar, psi
Example 1.1 on p. 16: Density of an ideal gas
1 atm 101325 Pa 760 torr (exact)
1 atm= 760 mmHg
1 atm 14.7 psi
1bar 100,000 pa = 100 kPa
The key idea of Example-1.1 on p. 16:
( )
RT
MP
RT
M
RT
M
V
m
P
RT
M
m
nRT PV
=
= =
= =

1.7: Equations of State

Equation of State:
Volumetric equation of state: V = f(P, T, n
1
, n
2
, )
Molar Volume: V
m
= V/n
For an ideal gas: V
m
= RT/P (see Fig-1.13, p. 23)
Van der Waals Equation:
Approximate Equation of State:
( ) ( ) or
2 2
2
RT b V
V
a
P nRT nb V
V
an
P
m
m
=
|
|
.
|

\
|
+ =
|
|
.
|

\
|
+
PT c P c T c T c c P T V
m 5 4
2
3 2 1
) , ( + + =
Thermodynamic Processes
Isothermal: fix T unchanged
Isobaric: fix P unchanged
Isochoric: fix V unchanged
See Fig-1.14 on p. 23 Changes for H
2
O
Six useful partial derivatives:
m m
V V
P
m P
m
T
m T
m
P
T
T
P
V
T
T
V
V
P
P
V
|
.
|

\
|
c
c
|
.
|

\
|
c
c
|
|
.
|

\
|
c
c
|
.
|

\
|
c
c
|
|
.
|

\
|
c
c
|
.
|

\
|
c
c



The Eulers Chain Rule Applied on V
m
(T,P)
The chain rule is very useful. For example, if
you want to get , you can use chain rule:
1 =
|
|
.
|

\
|
c
c

|
.
|

\
|
c
c

|
.
|

\
|
c
c
T
m V P
m
V
P
P
T
T
V
m
m
V
T
P
|
.
|

\
|
c
c
T
m
P
m
P
m
T
m V
P
V
T
V
T
V
V
P
T
P
m
|
.
|

\
|
c
c
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c

|
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
Thermal Expansivity (Cubic Expansion
Coefficient): Equ-1.43*
Isothermal Compressibility: Equ-1.44*
We can prove that:
P
m
m n P
T
V
V T
V
V
P T
|
.
|

\
|
c
c

|
.
|

\
|
c
c

1 1
) , (
,
o
T
m
m n T
P
V
V P
V
V
P T
|
.
|

\
|
c
c

|
.
|

\
|
c
c

1 1
) , (
,
k
k
o
=
|
.
|

\
|
c
c
m
V
T
P
Example 1.3 on p. 24:
For an ideal gas, find expressions for and
and verify that Equ-1.45 holds.
Example 1.4 on p. 25:
Estimate the percentage increase in volume
produced by a 10.0 C temperature increase
in a liquid with the typical value 0.001K
-1
,
approximately independent of temperature.