CY1001

BASIC CONCEPTS

T. Pradeep
22574208
pradeep@iitm.ac.in
9/19/2013
1
Lecture 1
Atomists and ionists
1. Chemical thermodynamics
2. Statistical thermodynamics
3. Kinetics
4. Surface science

Books:
1. Kuhn Hans, Frsterling Horst-Dieter and Waldeck David H, Priniples
of Physical Chemistry, 2
nd
Ed., Wiley(2009).
2. Atkins P W and de Paula Julio, Physical Chemistry, Oxford University
Press, 8
th
Ed., (Indian Student Edition) (2009).
3. Silbey Robert J, Alberty Robert A, Bawendi Moungi G., Physical
Chemistry, (4
th
Ed.), Wiley (2006).

Lecture schedule
Tutorials
Evaluation

Property
Variable Time
Quantum mechanics

Statistical mechanics

Thermodynamics

Variation of heat with process
UNIVERSE
4
SYSTEM SURROUNDING
OPEN CLOSED
ISOLATED

Pressure, Volume, Temperature, Heat,
Mass
Intensive and Extensive
Variables

What is unique about Thermodynamics?

Independent of atomic and molecular theory.

In chemical systems, thermodynamics helps to keep a record of energy flow.

Equilibrium state of a chemical system can be understood from
thermodynamics.

It is a logical science, three statements describe thermodynamics; deductions
from these laws constitute the equations.

Validity of thermodynamic laws depends only on the basic laws and the logical
deductions which follow from them.

Since thermodynamics is itself a science, not dependent upon the foundations of
other branches, it has an existence of its own.
A theory is the more impressive the greater the simplicity of its
premises, the more different kinds of things it relates, and the
more extended its area of applicability. Hence the deep
impression that classical thermodynamics made upon me. It is
the only physical theory of universal content concerning which I
am convinced that, within the framework of the applicability of
its basic concepts, it will never be overthrown.

Albert Einstein
System

Surroundings

Characterization of a system
Based on properties
(1) intensive properties and (2) extensive properties

Types of systems
(1) open, (2) closed, and (3) isolated systems.
(1) homogeneous or (2) heterogeneous

Chemical system
Phase, Component

Process, Path
State function, Path function
Exact and inexact differentials
Zeroth Law
A B and B C, then A C { = thermal
equilibrium}
First Law
Law of conservation of energy
Work, heat
Exothermic, endothermic
First Law

dU = dq dw
Internal energy of an isolated system is constant

Work = -P
ex
dV
Free expansion = 0
Isothermal work = -(nRT/V) dV = - nRT ln V
f
/V
i
(reversible)
P
ex
dV
P
ex
V
i
V
f
P
Indicator diagram
J ames Watt
9/19/2013
10
q and w are positive, when energy is transferred to the system
q and w are negative, when energy is lost from the system



Exact and Inexact differentials

=
b
a
a b
w w w w ) (
Exact differential
Inexact
differential
U U U dU
b
a
a b
= =

9/19/2013
11
Sum of two inexact differentials can be
an exact differential (first law)
Test for exactness-Euler's theorem
) , ( y x f z =
dy
y
z
dx
x
z
dz
x
y
|
|
.
|

\
|

+
|
.
|

\
|

=
if then,
When
y
x
x
y
y
z
x x
z
y
(
(

|
|
.
|

\
|

=
(
(

|
.
|

\
|

Then z is an
exact differential
Inexact differentials can be converted to exact differentials by
multiplying with integrating factors
The General Expression for Work
9/19/2013
12
From Physics, Work, w =Fd cos
When =180
0
, Work, w =-Fd

dw = -F.dz

But, F =Pressure x Area =P.A
Therefore, dw =-P.A.dz
Now, A.dz = dV
dw =-P.dV
F
w

=
2
1
V
V
PdV w
9/19/2013
13
Concept of reversibility

P
1
, V
1
, T


m
m
h
P
1
P
2
V
2
V
1 P
1,
V
1
P
2,
V
2
SINGLE STEP COMPRESSION
) (
1 2 2
V V P mgh w = =
Two, three and infinite number of steps
Same compression can be
Done with less work !

= =
2
1
V
V
PdV w w
A
mg
P =
2
Different situations
Free expansion
Expansion against constant pressure

If P is constant,


Isothermal reversible expansion

9/19/2013
14
F
w
w = - P (V
2
V
1
)

=
2
1
V
V
V
dV
nRT w
1
2
ln
V
V
nRT w =
9/19/2013
15
dV
V
U
dT
T
U
dU
T V
|
.
|

\
|

+
|
.
|

\
|

=
HEAT CAPACITY
U as a function of T and V
dV
V
U
P dT
T
U
q
T
ext
V
(

|
.
|

\
|

+ +
|
.
|

\
|

=
dV P q dU
ext
=
Since,
At constant volume,

d
T
U
q
V
V
|
.
|

\
|

=
V
V
V
C
T
U
dT
q
=
|
.
|

\
|

Heat capacity at constant volume

C
dT
q
=

Path dependant
(constant V or T)
HEAT CAPACITY
9/19/2013
16

=
2
1
T
T
V V
dT C U
V
V
T
U
C
|
.
|

\
|

=
If C
V
is constant over a small range of temperature, T C U
V V
=
gas
vacuum
We have seen that,
dV
V
U
dT
T
U
dU
T V
|
.
|

\
|

+
|
.
|

\
|

=
0 =
|
.
|

\
|

= dV
V
U
dU
T
Since J oule Found that

q = 0;
and
w
=0
0 =
|
.
|

\
|

T
V
U
Since dV0,
This is not correct for real gases.
Internal Pressure
9/19/2013
17
H = U + PV
Change of state at constant pressure
Enthalpy
) 1 2 (
1 2
V V P qp V P q U U U
P
= = =
( ) ( )
1 1 2 2
PV U PV U q
P
+ + =
1 2
H H q
P
=
dH q
P
=
9/19/2013
18
dP
P
H
dT
T
H
dH
T P
|
.
|

\
|

+
|
.
|

\
|

=
H as a function of T and P
and at constant P,
dH q
P
=
Since
Heat capacity at constant pressure
If C
P
is independent of temperature,
T C H
P
=
dT
T
H
q
P
P
|
.
|

\
|

=
P
P
P
C
T
H
dT
q
=
|
.
|

\
|

9/19/2013
19
C
P
- C
V
=nR
dV
V
U
P dT
T
U
q
T
ext
V
P
(

|
.
|

\
|

+ +
|
.
|

\
|

=
divide by dT and setting
P
P
C
dT
dq
=
P T
V P
T
V
V
U
P C C
|
.
|

\
|

|
.
|

\
|

+ =
For an ideal gas, and
P
nR
T
V
P
=
|
.
|

\
|

0 =
(

|
.
|

\
|

T
V
U
nR C C
V P
=
Enthalpy, H = U + PV
Calorimetry
Isotherm and adiabat

Thermochemistry
Heat of formation,
f
H
o

Hesss Law

Born-Haber Cycle

Kirchhoffs equation

r
H
o

(T
2
) =
r
H
o
(T
1
) +
r
C
p
o


Equipartition principle
Ad
Isotherm
P 1/V
Adiabat
P 1/V

P
V
dT
J oule experiment
T
= (U/ V)
T

J oule-Thomson Experiment
= (T/ P)
H

J ust to know
Galileo Galilei 1564-1642
It is all about heat.
T
h
e
r
m
o
d
y
n
a
m
i
c
s
,

H
i
s
t
o
r
y

Joseph Black, 1728 - 1799 Francis Bacon 1561-1626
James Prescott Joule 1818-1889

James Watt 1736 - 1819

Sadi Carnot 1796-1832
Rudolf Clausius 1822 - 1888


Lord Kelvin (William Thomson) 1824-1907

Ludwig Boltzmann 1844-1906

Josiah Willard Gibbs 1839-1903

Jacobus Henricus van 't Hoff 1852-1911
Walther Hermann Nernst 1864 - 1941
Gilbert Newton Lewis 1875-1946