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Thermodynamics: (developed in 19

th

century)

phenomenological theory to describe equilibrium properties of macro-

scopic systems based on few macroscopically measurable quantities

thermodynamic limit (boundaries unimportant)

state variables / state functions:

describe equilibrium state of TD system uniquely

intensive: homogeneous of degree 0, independent of system size

extensive: homogeneous of degree 1, proportional to system size

intensive state variables serve as equilibrium parameters

Laws of Thermodynamics

state variables / state functions:

intensive extensive

T temperature

p pressure

H magnetic field

E electric field

chemical potential

S entropy

V volume

M magnetization

P dielectric polarization

N particle number

conjugate state variable: combine together to an energy

T S, pV, HM, EP, N

unit [energy]

Laws of Thermodynamics

state variable: Z(X,Y)

Z: exact differential

Laws of Thermodynamics

Equilibrium parameters:

intensive state variables can serve as equilibrium parameters

Temperature (existence: 0

th

law of thermodynamics )

T

1

T

2

colder

characterizes state of TD systems

warmer

bridge

heat

flow

Ficks law

heat

current

temperature

gradient

T

1

< T

2

Laws of Thermodynamics

Equilibrium parameters:

intensive state variables can serve as equilibrium parameters

Temperature (existence: 0

th

law of thermodynamics )

T

1

T

2

colder

characterizes state of TD systems

warmer

bridge

heat

flow

T T

bridge

equilibrium

T

1

< T < T

2 Ficks law

heat

current

temperature

gradient

no heat

flow

Laws of Thermodynamics

Equilibrium parameters:

intensive state variables can serve as equilibrium parameters

Temperature (existence: 0

th

law of thermodynamics )

T

1

T

2

colder

characterizes state of TD systems

warmer

bridge

heat

flow

T T

bridge

equilibrium

other equilibrium parameters:

pressure p

chemical potential

no heat

flow

equilibrium parameter

constant everywhere

in TD system

Laws of Thermodynamics

Equations of state:

consider TD system described by state variables

subspace of equilibrium states:

equation of state (EOS)

Ideal gas:

Boltzmann constant

thermodynamic EOS

Laws of Thermodynamics

Equations of state:

consider TD system described by state variables

subspace of equilibrium states:

equation of state (EOS)

Ideal gas:

Boltzmann constant

thermodynamic EOS

response functions

isobar thermal

expansion coefficient

isothermal

compressibility

reaction of TD system to change

of state variables

Laws of Thermodynamics

1

st

law of thermodynamics

heat is like work a form of energy

heat

work

specific heat

C

V

: constant V

C

p

: constant p

gas

paramagnet

force displacement

internal energy U

isolated TD system

J.R. Mayer, J.P. Joule & H. von Helmhotz

~1850

Laws of Thermodynamics

1

st

law

internal energy

ideal gas (single atomic):

(equipartition)

Specific heat:

constant V

caloric EOS

Laws of Thermodynamics

1

st

law

internal energy

ideal gas (single atomic):

Specific heat:

constant p

(equipartition)

caloric EOS

Laws of Thermodynamics

1

st

law

internal energy

ideal gas (single atomic):

Specific heat:

ideal gas:

and

(equipartition)

caloric EOS

Laws of Thermodynamics

2

nd

law of thermodynamics

two equivalent formulations

R. Clausius: there is no cyclic process whose only effect is to transfer heat

from a reservoir of lower temperature to one with higher temperature

T

1

~

T

2

heat

flow

heat

flow

T

1

< T

2

W. Thomson (Lord Kelvin): there is no cyclic process whose effect is to take heat

from a reservoir and transform it completely into work;

there is no perpetuum mobile of the 2

nd

kind

Q Q

T

1

~

heat

flow

work

Q

W

Laws of Thermodynamics

2

nd

law

Carnot engine

T

2

T

1

~

Q

1

Q

2

W=Q

1

-Q

2

reversible Carnot process

definition of absolute temperature T

irreversible process

entropy as new state variable

Clausius

theorem

cyclic process

reversible

cyclic process

irreversible

Laws of Thermodynamics

2

nd

law

entropy

ideal gas:

V

1

V

2

V

1

V

2

reversible isothermal process dU=0

p

A

B

coupled to work reservoir

irreversible process

increase of entropy

waste of potential energy

A

B

Laws of Thermodynamics

2

nd

law

application to gas:

dS exact differential S(U,V)

caloric EOS

thermodynamic EOS

Laws of Thermodynamics

Thermodynamic potentials

natural state variables convenient simple relations

and

response functions:

specific heat

adiabatic compressibility

dS=0

internal energy (gas)

U(S,V)

Laws of Thermodynamics

Thermodynamic potentials

internal energy (gas)

U(S,V)

natural state variables convenient simple relations

and

Maxwell relations:

dU exact differential

Laws of Thermodynamics

Thermodynamic potentials

natural state variables convenient simple relations

other variables: (S,V) (T,V)

Helmholtz free energy (gas)

F(T,V)

Legendre transformation

response

functions

specific heat

isothermal

compressibility

Laws of Thermodynamics

Thermodynamic potentials

natural state variables convenient simple relations

other variables: (S,V) (T,V)

Helmholtz free energy (gas)

F(T,V)

Legendre transformation

Maxwell

relation

Laws of Thermodynamics

Thermodynamic potentials

natural state variables convenient simple relations

Enthalpy (gas)

H(S,p)

Maxwell

relation

Gibbs free energy (gas)

G(T,p)

Maxwell

relation

Laws of Thermodynamics

Equilibrium condition

entropy:

general

in equilibrium

S maximal

closed system: dU=dV=0

U,V fixed variables

fixed variables

T,V F minimal

T,p G minimal

S,V U minimal

S,p H minimal

potential

Laws of Thermodynamics

3

rd

law of thermodynamics

Nernst 1905

S = S(T,q,) entropy

e.g.:

independent of T, q,

Planck:

S

0

= 0

only within quantum statistical physics

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