Basic Thermodynamics

Thermodynamics is a funny subject.

The first time you go through the
subject, you dont understand it at all.
The second time you go through it,
you think you understand it, except for
one or two small points. The third time
you go through it, you know you dont
understand it, but by that time you are
so used to the subject that it doesnt
bother you any more.
- Arnold Sommerfeld (1868-1951)

Basic Concepts of Thermodynamics

Thermodynamics is the study of transformations of energy

System and surroundings

the system is the part of the world in which we have a special interest. A system
has definite boundaries
the surroundings is everything outside the boundaries

Classification of systems:

An open system can exchange matter as well as energy with its surroundings
a closed system (rigid or adiabatic) can exchange energy with its surroundings.
No transfer of matter across the boundaries is possible
an isolated system can exchange neither energy nor matter with its
surroundings

Surface free
to do work

Ball:
mass exchange
Arrow:
energy exchange
Completely isolated

Isolated system

Thermally isolated, not

Adiabatic system mechanically isolated
(eg well-lagged piston)
Mechanically isolated,
not thermally isolated
(eg rigid box)

Closed system

Open system

Open = can exchange

matter, energy and
work with surroundings

Energy States
Changes in a system are associated
with the transfer of energy
Natural systems tend toward states
of minimum energy

Unstable:

Stable:

Metastable:
in low-energy perch

Work, Heat, and Energy

The energy of a system is a measure of its capacity to do work

The energy of a system is the sum of the kinetic and potential energies of all particles in
the system
The energy of a closed system can be changed by:

work done on or by the system

heat transfer across its boundaries

Work is transfer of energy using organised motion (expansion work, electrical work,
etc.)
Heat is transfer of energy using thermal motion (chaotic, random motion of molecules)

Heat Transfer

A process that releases energy as heat is called

exothermic
A process that absorbs energy as heat is called
endothermic

Zeroth Law of Thermodynamics

If two systems are each in thermal equilibrium with a third

system, then they are in thermal equilibrium with each other
This introduces temperature: hotness and coldness and
thermodynamic equilibrium

Internal Energy

The internal energy, U, is the total energy of a system (KE+PE)

We cannot give an absolute value of U but we can calculate U for a process

U = U f - U i

Uf = final value of U
Ui = initial value of U

U is a state function (the value of U depends only on the current state of the
system)
U is an extensive property (changes depending on amount of stuff)

The first law of thermodynamics

If the state of an otherwise isolated system is change

by the performance of work, the amount of work
needed depends solely on the change accomplished
and not on the means by which the work is performed
(i.e., mechanical work or heating), nor on the
intermediate stages through which the system passes
between initial and final stages

The First Law of Thermodynamics

Heat and work are equivalent (fire and whisk)
Energy is conserved in any transformation
The change of energy of a system is independent of the path taken

Energy can be neither created nor detroyed

For a closed system
U = q + w or dU = dq + dw
U=
q=
w=

internal energy
heat supplied to or removed from the system (q <0 if heat removed from system)
work done on or by the system (w <0 if work done by the system)

U = 0 for an isolated system

the internal energy of an isolated system is constant

dU = dq - P dV
P = pressure
V = volume

First Law of Thermodynamics = Conservation of Energy

energy cannot be created or destroyed, only converted between different forms
Example: CH4(g) + 2O2(g)
CO2(g) + 2H2O + energy
a) Reaction gives off energy as heat
b) Potential energy stored in chemical bonds is lowered
c) Total energy is unchanged
Exothermic

Endothermic
N2(g) + O2(g)

2NO(g) - energy

Work 1

dw = - pexdv

dw is the expansion work (pressure-volume work) when a

system undergoes a change
pex is the external pressure
dV is the change in volume
dw <0 (work is done by the system) when system expands
(dV>0)

w = - pexdV

integration from Vi to Vf when volume changes from Vi to Vf

Work 2

Free Expansion - no opposing force

Expansion against Constant Pressure

pex = 0 (expansion into a vacuum)

w=0

pex is constant
w = - pexV
(V is the volume change)

Isothermal Reversible Expansion of Perfect Gas

pex = p (reversible expansion)

p = nRT/V (ideal gas)
w = - nRT dV/V
w = - nRT ln(Vf/Vi)

Reversible Process

A process is regarded as thermodynamically reversible if it can

be caused to go in either direction by an infinitesimal change in
an external variable such as pressure or temperature
Reversible changes occur when a system is in equilibrium with its
surroundings
For a reversible expansion:

dp 0
p = pex
w = - p dV

p = pex + dp

PV-diagram

Work, w, can be obtained from p versus V

The amount of work done is given by area under curve

The maximum work available for a system operating

between specified initial and final states is obtained when the
change takes place reversibly

Whats wrong
with this figure?

U for Process at Constant Volume

dU = dq + dw

dwexp = 0

for a process taking place at constant volume

dU = dq

(if no electrical work)

dU = dqv (subscript v indicates process at constant volume)

U = q v

for process at constant volume

Heat Capacity at Constant Volume

CV = (U/T)V

U = CV T

CV is the heat capacity at constant volume

(U/T)V is a partial derivative which shows how U varies
with T when the volume is kept constant

i.e. the heat needed to change temperature by T

CV,m = CV/n

CV,m is the molar heat capacity at constant volume

Enthalpy H at constant P
H = U + PV
dH = dU + PdV + VdP
dU = dq - PdV (1st law)
dH = dq (dP=0)
The change in the enthalpy of a system (dH) during a reversible
change in state at constant pressure (dP=0) is equal to the heat absorbed
by the system during that change in state.
When dH is positive, the reaction is endothermic (heat flows from the
surroundings to the system);
When dH is negative, the reaction is exothermic (heat flows from the
system to the surroundings

Heats of Reaction
H = nH (products) - nH (reactants)
For example, evaporation: H2O(l)

H2O(g)

H = H(H2O(g)) - H(H2O(l))
H = (-57.80) - (-68.32) = 10.52 kcal
H is positive so the reaction is endothermic
(i.e., sweating is a mechanism for cooling the body)

Heat Capacity at Constant Pressure

When heat is added to a solid, liquid, or gas, the temperature of the substance
increases
Cp = (H/T)p

Cp is the heat capacity at constant pressure

Cp shows the variation of H with T at constant pressure

Cp,m = Cp/n

Cp,m is the molar heat capacity at constant pressure

dH = Cp dT

at constant pressure

H = C p T

at constant pressure (assuming Cp is independent of T)

Adiabatic Changes

q = 0 for adiabatic changes

no heat transfer

The following is true for adiabatic

compression (reduction of volume
of system in an adiabatic change:

work is done on the system

the internal energy of the system
increases
the temperature of the system
increases

The Second Law of Thermodynamics

It is impossible to construct a machine that is able to convey
heat by a cyclical process from one reservoir at a lower
temperature to another at a higher temperature unless
outside work is done (i.e, air conditioning is never free)
Heat cannot be entirely extracted from a body and turned into
work (i.e., an engine can never run 100% efficiently) a
certain fraction of the enthalpy of a system is consumed by
an
increase
in
entropy
Every system left to itself will, on average, change toward a
condition of maximum randomness entropy of a system
increases spontaneously and energy must be spent to
reverse this tendency

Entropy
The Heat Tax
Conversion of energy between forms is inefficient:
energy is lost as heat

The entropy of the universe always increases

or
You cant shovel manure into the rear end of a horse and
expect to get hay out of its mouth

Entropy
S = nS (products) - nS (reactants)
For example: H2O(l)

H2O(g)

S = S(H2O(l)) - S(H2O(g))
S = 45.10 - 16.71 = 28.39 cal/deg
When S is positive, entropy of the system increases with
the change of state;
When S is negative, entropy decreases

Direction of Processes and Reactions

Examples:
Ball at the top of a hill
Steel + H2O + O2

Ball at the bottom of a hill

Rust

Gas in one part of a container

Ice at 5 oC
Water at 5 oC

Gas filling a container

What is in common?
Increased Disorder = Increased Entropy = + S

Entropy = S = drives spontaneous reactions = disorder

Probability: there are many more ways for things to be disordered
Nature proceeds towards the most likely state
= state with greatest number of energetically equivalent arrangements

Configurational Entropy: depends on configuration in space

Changes in state depend on positional entropy
Ssolid < Sliquid << Sgas

Larger volume allows many more available positions for particles

Dissolving a solid provides more volume for particles to occupy
Example: What has highest configurational entropy?
1 mole solid CO2 or 1 mole of gaseous CO2?
1 mole N2 at 1 atm or 1 mole of N2 at 0.01 atm?

The fundamental equation of thermodynamics

The ratio of heat gained or lost to temperature will always be the same,
regardless of path, for a reversible reaction

dq = TdS
dU = TdS - P dV
(dq + dw)

2nd Law
1st Law

When dU = 0, T dS = P dV

dP S

dT V
dS = dq/T reversible process
dS > dq/T irreversible process

Latent Heat
The amount of energy released or absorbed during a change in state

Example 1: Getting out of a swimming pool

In the summer, upon exiting a swimming pool
you feel cool. Why?

Drops of liquid water are still on your skin after

getting out.
These drops evaporate into water vapor. This
liquid to gas phase change causes energy to
be absorbed from your skin.

Example 2: Citrus farmers

An orange crop is destroyed if

temperatures drop below freezing for a
few hours.

To prevent this, farmers spray water

on the orange trees. Why?

When the temperature drops below

0oC, liquid water freezes into ice.
This liquid to solid phase change
causes energy to be released to the
fruit.
Thus, the temperature of the orange
remains warm enough to prevent ruin.

Third Law of Thermodynamics

The entropy of a substance approaches zero

as the temperature approaches absolute zero

Thermodynamic potential energies