Statistical

Thermodynamics
Basic principles and
applications

From microscopic interactions to

macroscopic quantities.

http://www.biochem.oulu.fi/Biocomputing/juffer/Teaching/Biocomputing/

Thermodynamics (1)
First Law of Thermodynamics: The energy U of
an isolated system is constant.

dU dq dw U w q
Amount of heat
supplied to the system.

dq CV dT

dq C p dT

At constant V
At constant p

Amount of work done

on the system, e.g:

dw pdV
Reversible pV-work
Mechanical work

Thermodynamics (2)
Types of mechanical work

pdV : Change of volume (dV )

d : Change of surface area (d )
fdl : Change of length (dl )
dq : Change of charge (dq)
: Surface tension
l : Length
: Electrostatic potential

Thermodynamics (3)
The temperature T of a system of N particles
is a quantity related to the averaged kinetic
energy of the disordered motion of the
particle in the C-frame of reference.

T Ek ,ave

1 2
i 2mi vi

Mass of particle i

Velocity of
particle i

Thermal equilibrium:
Average kinetic energy is the same in all regions of the system

Thermodynamics (4)
Second Law of Thermodynamics: The
entropy S of an isolated system increases
during any spontaneous change.
Spontaneous

Low
entropy
gas

S 0

Not observed

High
entropy

Thermodynamics (5)
Only irreversible processes
generate entropy.
The entropy change of reversible
process is exactly zero.
Most basic irreversible process is
the generation of heat:
dq
dS
T

Thermodynamics (6)
dS surroundings

dSuniverse dS dS surroundings
dSuniverse 0

dS
System

Surroundings

Heat:

dSuniverse 0

dqsurroundings
T

For an equilibrium
process

System + Surroundings = Universe

The universe seeks higher entropy

Overall entropy production

Thermodynamics (7)
Concentrate on the system:

dq
dS
0
T

dq : heat supplied to the system

dS : Change of entropy of system due to internal processes.
At Constant V
no pV-work
dw=0

At constant pressure
No non-pV work
dp=0

dU dq
dU
dS
0
T
dU TdS 0
dA 0

dq dH
dH
dS
0
T
dH TdS 0
dG 0

H U pV
dH dU pdV Vdp
dq pdV pdV Vdp
dq Vdp

dU dq dw

Thermodynamics (8)
A U TS
G H TS

G H TS
G
H

S
T
T

G
G 0
0
T

Helmholtz free energy

Gibbs free energy

S : Entropy of the system

H

: Entropy of the surroundings

T
G

: Total entropy of the universe

T
For a natural or
spontaneous change.

Microscopic world versus

macroscopic world
Classical
mechanics
Quantum
mechanics

Microscopic
Interactions
Phase space
Wave function

Statistical Averaging

Statistical
mechanics

Macroscopic
quantities

Observables:
Dynamic and
Thermodynamic
quantities

Concept of an ensemble
1

M Pi M i
i

Pi is probability of state i.

Members of the ensemble

represents a state of a system in
accordance with external
macroscopic parameters (e.g. N, V,
T).
A state is either defined classically
(a point in phase space) or quantum
mechanically (quantum numbers).
Mechanical quantities M are
averages over the ensemble:
Pressure, volume, energy, ..
But not entropy S and free energies
(A, G).

A point in phase space

{p}
momenta

N particles

6N dimensional
space

{q}
Coordinates
Trajectory

Up

One-dimensional
harmonic oscillator
2N dimensional
phase space

Quantum numbers
The state of the system is fully described by the
wave function.
The state of the system is fully described by a
set of quantum numbers (n, m, l, ..).
The total energy of the system is given from
Schrdinger equation. An observable such as
the energy E corresponds to an operator such
as H.
r1 , r2 ,..., t

H E

Probability of state i
(quantum version)

M Pi M i
i

Average of quantum (discrete) states:

Probability Pi depends on the type of
ensemble.

1
Pi ( N , V , T )
e Ei Boltzmann factor
Q N ,V , T

Q e

Ei

Partition function

M e

Ei

Ei

Canonical ensemble (N,V,T)

(E, p, fluctuating)

kT

k: Boltzmanns constant
T: Temperature

Free energy and entropy (1)

Partition function plays central in equilibrium
statistical thermodynamics

A kT ln Q

Helmholtz free energy.

ln Q
S k Pi ln Pi kT

T
i
ln Q
p kT

N ,T

pi e
i

N ,V

Ei
e

k ln Q

Entropy

TS U A

Pressure
Q e Ei
i

Free energy and entropy (2)

Both entropy and free energy
depend on the full phase
space, or:
One must sample all possible
states.
Reason: Entropy:

A U TS kT ln Q
Internal energy
Ensemble average

Free energy and entropy (3)

Pi

S, A and G are
very difficult to
compute.

S k Pi ln Pi
i

States i

The solute chemical potential

from thermodynamics (1)
Solute in a solvent

kT ln a

Standard
chemical potential
(reference state)

m
a
m
Activity

: Activity coefficient
m : Molality (molarity)
mol/kg (mol/m3)
m=1 mol/kg

The solute chemical potential

from thermodynamics (2)
Solute in a solvent

m
kT ln kT ln
m

m
kT ln
m
kT ln

Measures the deviation from

standard molality (molarity).

Measures the deviation from ideality:

Interactions between solute molecules.
1 if m0 At very low concentration
(dilute).

Equilibrium constant from

thermodynamics (1)
A B AB

Chemical equilibrium condition

G 0

A B AB

G AB
A B kT ln K

a AB
m AB AB m m

a AaB m A mB A B m

AB m m
m AB

G kT ln
kT ln

m A mB
A B m

K is dimensionless

Experimentally: Measurement of concentrations provides K

only if it is assumed that =1 for all reactants.

Equilibrium constant from

thermodynamics (2)
Gas

Transfer of solute from one phase

to another phase:

Asol Agas

pm

Gt kT ln kT ln f kT ln
p m

Solution
Real gas

p
g kT ln kT ln f
p

Equilibrium constant from

thermodynamics (3)
Previous formulation for G (or K) is not
suitable for computational purposes.
Instead what is required are expressions for:
Standard chemical potential or some related
quantity.
Activity coefficients, for low or moderate to high
concentrated solutions.