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Statistical Thermodynamics

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Thermodynamics

Basic principles and

applications

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

on the system, e.g:

dw pdV

Reversible pV-work

Mechanical work

Thermodynamics (2)

Types of mechanical work

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

The universe seeks higher entropy

Thermodynamics (7)

Concentrate on the system:

dq

dS

0

T

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

Gibbs free energy

H

T

G

T

For a natural or

spontaneous change.

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.

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).

{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

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

(E, p, fluctuating)

kT

k: Boltzmanns constant

T: Temperature

Partition function plays central in equilibrium

statistical thermodynamics

A kT ln Q

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

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

Pi

S, A and G are

very difficult to

compute.

S k Pi ln Pi

i

States i

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

from thermodynamics (2)

Solute in a solvent

m

kT ln kT ln

m

m

kT ln

m

kT ln

standard molality (molarity).

Interactions between solute molecules.

1 if m0 At very low concentration

(dilute).

thermodynamics (1)

A B AB

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

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

thermodynamics (2)

Gas

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

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.

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