Lecture 1

Thermodynamics

Energetics/1ST Law of

1.Quantisation

(Chapter 2, pp 74-83)

Planck suggested that energy was not continuous but

made up of several packets of energy called quantum.
Planck showed that the energy of quantisation
E h

Where h = 6.626 x 10-34 J s

Properties of wave /particle

wave number

Or
E h h

E hc

Experimental Proof of this effect (Photoelectric

effect)

e-

When light is shone at the surface of a metal, electrons

are emitted from the surface.
Classical Physics suggested
(a)
When electron leaves surface of metal they
leave with an energy which is proportional to the
intensity of incident radiation.
Energy leaving electrons proportional to
intensity of incident radiation
(b)
Electrons should be released at all frequencies
(c)
Induction period may be required before
electrons leave surface (energy may not be enough
to get electron immediately out), the energy can be
accumulated.

Facts
(a) There is a threshold frequency below which
no electrons are emitted.
(b) Electrons are emitted instantaneously at
threshold

(c)
Energy of the electrons is proportional to
and not to
intensity.

Can be modelled by potential well

e-

For electron to get out of Box, a large enough

quantum is required.
Plot of kinetic energy versus frequency

k.e.

slope = h

vo
quantum gap

frequency

At minimum frequency ( ), electron just able to

leave atom.

k .e. E W

Where E is incident energy and W is work function

k .e. h h o
k .e. h o

This can be used to experimentally determine

Plancks constant (h).
This introduces the concept of quantisation of
microparticles, the behaviour of the individual
small particles like electrons, atom or molecules.

2.INTRODUCTION TO THERMODYNAMICS (Chapter

14)
In thermodynamics, we are interested in the
behaviour of the macroscopic system not the
individual atoms or molecules.
(a) Conservation of Energy
The Universe can be described as being made up
of System and Surroundings.
SYSTEM + SURROUNDINGS = UNIVERSE
SYSTEM = Part of the world of interest; e.g. reaction
vessel
SURROUNDINGS = Rest of World (Universe)

system

surroundings

System

A system consisting of a gas enclosed in a vessel (or

cylinder) with a moveable piston, which moves on
expansion or contraction.
(i)

Heat (q) can be supplied to the system, e.g.

chemical reaction which releases a gas.

(ii) External work (w) may be done by moving

the piston out against an external pressure,
Pext.
(iii) The (whole) system can be described in
terms of the following variables: Pressure,
temperature, volume and chemical
composition.

(b) Internal Energy (U)

(i)

The energy contained in substance(s), especially

gases, in system is called the internal energy (U)
U = sum of all kinetic and potential energies of
all atoms, ions or molecules in system.
Written mathematically
U E k .e or translation. E rotational E vibrational Eelectronic E nucleus

For practical purposes in thermodynamics we

deal only with U and not with U itself.
One or more of these are changed when heat is
supplied to a system.

(ii) Any change in P, T, V and composition of a

system changes the internal energy from some
state A to some state B

UB

UA

U is called a state function; i.e. process

depends on its initial and final state and not on
the pathway (or route).

3.Relationship between different kinds of energy

For any process q and w can be in principle
measured
The summation of q + w of system is equal to
internal energy change (U)
Mathematically described by
U U B U A q w

This is called the First Law of Thermodynamics

When a chemical system changes from one state to

another state, the net transfer of energy to its
surroundings must be balanced by a corresponding
change in the internal energy of the chemical system
(U).
- Also called the Conservation of energy principle
For a small change
dU dq dw

For a large change occurring in small steps:

UB

UA

U dU dq dw
U q w

U is state property
q and w are not state properties; i.e. values of q and
w depend on the pathway.

4. Work
Chemist recognise PV work only
For the work component of the 1st law of
thermodynamics
When the only type of work is that done against the
external pressure (Pext), there are two special cases:
(i) Definition of work

From physics: Work done = force opposing x

distance moved
Work done = F x h
Pext
h

From physics

F
A

Rearrangement
Therefore

F PxA
w ( P x A) x h
w P x ( A x h)

Change in volume in system

Therefore
Dimension check:
Nm (or J)

(V) = A x h

w = -PV
Work done = N m-2 x m3 =

(ii) Processes at Constant Volume

Pext

If P is always equal to Pext through change, process is

called reversible.
w PV Pext V

Therefore
Since at constant volume

V = 0, therefore

w PV 0

Re:

U q w

Therefore
This normally written as

U q at cons tan t volume

U U B U A qV

I.e. all the heat supplied is converted into internal

energy

Physical Description: The increase in internal

energy U of the system in the change A B is equal
to the heat absorbed from the surroundings.

(iii) Processes at Constant Pressure

Pext (external pressure)
B

height (h)

A
Area (A)
P (internal P)

Re:

w PV Pext V

If the volume changes

for a reversible process

V V B V A
w PVB V A Pext VB V A

Assuming the only work done is against

external pressure
From 1st law of Thermodynamics
U U B U A q w

Therefore

U B U A q p PV B V A

Where heat at constant pressure is denoted

Rearrange

the equation ( )
q P U B U A PVB V A

Therefore

q P U B PVB U A PV A

qP

Therefore

q P U B PVB U A PV A

The quantity (U +PV) is called heat content of

e.g. B or A (also called enthalpy)
Then

q P H B H A H

H is a state property

Physical description:
For constant pressure
process heat absorbed in the system from the
surroundings is equal to the increase in heat
content of the system.

24th February 2015