MSEG 803

Equilibria in Material Systems

4: Formal Structure of TD
Prof. Juejun (JJ) Hu
hujuejun@udel.edu

1st law and 2nd law in a simple system

1st law: dU Q PdV
2nd law:

dU TdS PdV
1
P
dS dU dV
T
T

Q TdS

The functions U(S, V, N) and S(U,V, N) are called

fundamental equations of a system. Each one of them
contains full information about a system.
Generally dU TdS

y dx
i

energy representation

yi
1
dS dU dxi
T
i T

entropy representation

Equations of state

The intensive variables in the fundamental

equations written as functions of the extensive
variables (for fixed mole numbers):

dU TdS PdV

T T ( S ,V )

1
P
1 1
dS dU dV
( S ,V )
T
T
T T

Generally yi yi ( x1 , x2 ,..., xi ,...)

P P( S ,V )
P P
( S ,V )
T T

Chemical potential and partial molar quantities

Chemical potential i for the component i

U
i

N i S ,V ,...

S
i

T
N i S ,V ,...

Quasi-static chemical work

Wc i dN i

dU TdS PdV i dN i

The partial molar quantity x (x is an extensive function)

associated with the component i (when T, P are constant)
x

N
i T , P , N

xi
j

( j i )

V
partial molar volume

N
i T , P , N

V i
j

( j i )

Euler relation

U and S are both homogeneous first order

functions of extensive parameters
U ( X 1 , X 2 ,..., X i ,...) U ( X 1 , X 2 ,..., X i ,...)

is a constant

U ( x1 , x2 ,..., xi ,...) U ( x1 , x2 ,..., xi ,...)

U
i

U ( x1 , x2 ,..., xi ,...) ( xi )
U ( x1 , x2 ,..., xi ,...)

xi
( xi )

( xi )
i

U ( x1 , x2 ,..., xi ,...)
xi yi xi
( xi )
i
i
i
1
P
U

TS

PV

N
S

Ni
Simple systems
i i i

T
T
i T

Let = 1 U

Gibbs-Duhem relation
U TS PV i N i dU d (TS ) d ( PV ) d ( i N i )
i

1st law of TD: dU TdS PdV i dN i

i

TdS PdV i dN i d (TS ) d ( PV ) d ( i N i )

i

SdT VdP N i d i 0
i

i
1
P
Ud ( ) Vd ( ) N i d ( ) 0
T
T
T
i

in simple systems

In a single component simple system: d sdT vdP

Summary of the formal structure of TD

The fundamental equation by itself contains full

information about the system
# of conjugate variables: N
# of generalized work terms: N - 1
# of variables: 2N
# of independent variables (thermodynamic degree of
freedom): N - 1
# of equations of state: N

An individual equation of state does not completely

characterize the system
All equations of state together contain full information about
the system (Euler relation)

Example: ideal gas

PV NRT

Not an eq. of state in the energy representation

U NcV T

Not a fundamental equation

P R

T v
1 cV

T u

1
P
d ( ) u d ( ) v d ( )
T
T
T
du
dv
cV ( ) R ( )
u
v

Gibbs-Duham eq. in the

entropy representation

1
T

P
T

Combine all 3 equations of state: S ( )U ( )V ( ) N

u
v
s cP ( )0 s0 cV ln( ) R ln( )
T
u0
v0

Energy minimum principle

Entropy maximum principle: in an isolated system,

equilibrium is reached if S is maximized

When dU = 0 (isolated system), S is maximized in equilibrium

S
0
x U

2 S
0

2
x U

Energy minimum principle: for a given value of total

entropy of a system, equilibrium is reached if U is
minimized

When dS = 0, U is minimized
in equilibrium
2

0
x S

U
0

2
x S

Energy minimum principle

At state A, S takes the maximum value if U is taken as a constant;

similarly, U takes the minimum value if S is taken as a constant.

Energy minimum principle

2 S
0

2
x U

S
Start with
0
x U

S

U
S
x U
T

x S
x

x
2U
2 S
T

2
2
x S
x

0
U

0
U

See Callen section 5-1

Example 1: equilibrium in an isolated

system after removal of an adiabatic
partition (i.e. only allows heat flow
between sub-systems)
Constraint:

dStot

T1

T2

U tot U1 U 2 is a constant Q2 Q1

S1

S 2
1
dS1 dS 2
dU1
dU 2 Q1 (
T1
U1
U 2

T1 T2

1
)
T2

thermal equilibrium

Now, instead of the enclosure condition (dU = 0), lets start from
the new constraint that dStot = dS1 + dS2 = 0

dU tot

U1
U
2
dU1 dU 2
dS1
dS 2 dS1 (T1 T2 )
S 2
S1

T1 T2

thermal equilibrium: the same equilibrium state results!

Simple mechanical systems

Entropy remains constant in a

purely mechanical system
U mgx F x dx where F kx
k is the spring constant

dU mgdx Fdx 0
mg F kx

Legendre transformations

Both S and U are functions of extensive variables; however, in

practical experiments typically the controlled variables
(constraints) are the intensive ones!
Legendre transformations: fundamental relations expressed
as functions of intensive variables

Legendre transformations preserve the informational content

Legendre transform of a fundamental equation is also a
fundamental equation

Enthalpy H(S, P, N) = U + PV = TS + N

Partial Legendre transform of U: replaces the extensive parameter V

with the intensive parameter P
For a composite system in mechanical contact with a pressure
reservoir the equilibrium state minimizes the enthalpy over the manifold of states of constant pressure (equal to that of the reservoir).
Enthalpy change in an isobaric process is equal to heat taken in or
given out from the simple system
Differential: dH d (U PV ) TdS VdP
dN

Enthalpy minimization principle

Consider a composite system where all sub-systems

are in contact with a common pressure reservoir
through walls non-restrictive with respect to volume
Apply U minimum principle to reservoir + system:

dU tot dU sys dU r dU sys P r dV r dU sys P r dVsys 0

The system is in mechanical equilibrium with the
r
reservoir: P P

dU tot dU sys Psys dVsys d (U sys PsysVsys ) dH sys 0

d 2U sys ( S sys , Vsys ) d 2 (U sys P rVsys ) d 2 H sys 0

Helmholtz potential F(T, V, N) = U - TS = - PV + N

Partial Legendre transform of U: replaces the extensive

parameter S with the intensive parameter T
For a composite system in thermal contact with a
thermal reservoir the equilibrium state minimizes the
Helmholtz potential over the manifold of states of
constant temperature (equal to that of the reservoir).
Differential: dF d (U TS ) SdT PdV dN

Helmholtz free energy

System in thermal contact with a

heat reservoir
W dU Q dU T r dS r
d (U TS ) dF
The work delivered in a reversible
process, by a system in contact with
a thermal reservoir, is equal to the
decrease in the Helmholtz potential
of the system
Helmholtz free energy: available
work at constant temperature

Heat
reservoir at T

Q
System

State A B: dF

Work performed by a system in contact with

heat reservoir

A cylinder contains an internal piston on each side of

which is one mole of a monatomic ideal gas. The cylinder
walls are diathermal, and the system is immersed in a
heat reservoir at temperature 0C. The initial volumes of
the two gaseous subsystems (on either side of the
piston) are 10 L and 1 L, respectively. The piston is now
moved reversibly, so that the final volumes are 6 L and 5
L, respectively. How much work is delivered?
Solution 1: direct integration of PdV (isothermal process)
Solution 2: W = F

Helmholtz potential minimization principle

Consider a composite system where all sub-systems

are in thermal contact with a common heat reservoir
through walls non-restrictive with respect to heat flow
Apply U minimum principle to reservoir + system:

dU tot dU sys dU r dU sys T r dS r dU sys T r dS sys 0

The system is in thermal equilibrium with the reservoir:

T r T dU tot d (U sys Tsys S sys ) dFsys 0

d 2 Fsys d 2 (U sys Tsys S sys ) d 2U sys ( S sys ,Vsys ) 0

Gibbs potential G(T, P, N) = U - TS + PV = N

Legendre transform of U: replaces both S and V with the

intensive parameters T and P
For a composite system in contact with a thermal
reservoir and a pressure reservoir the equilibrium state
minimizes the Gibbs potential over the manifold of states
of constant temperature and pressure.
Differential: dG d (U TS PV ) SdT VdP dN

Gibbs free energy and chemical potential

Simple systems: G U TS PV i N i
Single component systems:

G
N

molar Gibbs potential

G
xi i
Multi-component systems:
N
i

Consider a chemical reaction:

v A
i

partial molar
Gibbs potential
0

dN i
dG SdT VdP dN v d N
0
const d N
i i i i i i
dvi

v
i

0 chemical equilibrium condition

First order phase transition

At Tm = 0 C and 1 atm, liquid water and ice can

coexist

dGwater-ice = d(H - TS) = 0 at Tm = 0 C, 1 atm

Swater-ice = Hwater-ice/Tm ~ Uwater-ice/Tm at Tm = 0 C, 1

atm
The discontinuity of H and U are characteristic of
first order phase transition

At T > 0 C and 1 atm, ice spontaneously melts

dGwater-ice = d(H - TS) > 0 at T > 0 C, 1 atm

Swater-ice > Hwater-ice/T = Qwater-ice/T: irreversible

process

Constraints

Thermodynamic
potential

Extremum
principle

Example

U, V constant
dU = 0, dV = 0

S(U, V, N) = U/T + PV/T N/T

dS = 1/T*dU + P/T*dV /T*dN

S max
dS = 0, d2S < 0

Isolated systems

S, V constant
dS = 0, dV = 0

U(S, V, N) = TS - PV + N
dU = TdS - PdV + dN

U min
dU = 0, d2U > 0

Simple mechanical
systems consisting of
rigid bodies

S, P constant
dS = 0, dP = 0

H(S, P, N) = TS + N
dH = TdS + VdP + dN

H min
dH = 0, d2H > 0

Systems in contact with

a pressure reservoir
during a reversible
adiabatic process

T, V constant
dT = 0, dV = 0

F(S, V, N) = - PV + N
dF = - SdT - PdV + dN

F min
dF = 0, d2F > 0

Reactions in a rigid,
diathermal container at
room temperature

T, P constant
dT = 0, dP = 0

G(T, P, N) = N
dG = - SdT + VdP + dN

G min
dG = 0, d2G > 0

Experiments performed
at room temperature and
atmospheric pressure

Generalized Massieu functions

Legendre transforms of entropy S

Maximum principles of Massieu functions apply

General case

Legendre transform replaces a variable with its conjugate

For a thermodynamic system, its TD function will be the
Legendre transform where the variables are constrained

dU TdS dN

i x, y,z

V0 ii d ii

wall

Controlled variables: zz, xx, yy

wall
Beam

d d (U TS V0 xx xx V0 yy yy )

SdT dN V0 zz d zz V0 xx d xx V0 yy d yy

(T , N , xx , yy , zz ) is the TD potential that

is minimized in equilibrium

z
x

Deriving equilibrium conditions

Equilibrium in a system surrounded
by diathermal, impermeable walls in
contact with a pressure reservoir after Pr
removal of an impermeable partition
(i.e. allows mass flow between subsystems).
Constraints:

T, N1

T ,N2

T , P are constants
N tot N1 N 2 is a constant dN 2 dN1

G1
G
2
Gibbs potential minimization: dGtot
dN1
dN 2
N1
N
2
dN1 ( 1 2 ) 0

1 2 chemical equilibrium

Pr

Coupled equilibrium

+ +
+

+
+
+
+ +

A box of an electrically conductive solution

containing a positively charged ion (+Ze)
species is separated into two parts by an
+
impermeable, electrically insulating internal
Ve
partition. A voltageV is applied across
the two parts. If the partition becomes permeable to the ion but still remains
insulating, what is the equilibrium condition with respect to the ion (assuming
constant temperature and pressure)?
Fundamental equation: dG SdT VdP dN Vdq

G1
G
1

G1
G1
dGtot
1 dq2
dN1
dN 2 dq
N1
N
2

q1
q2
dN1 ( 1 2 ) dq1 (Ve ,1
Ve ,2 ) dN1 (1 2 ) dq
1
Ve
Constraints: dN1 dN 2

dq1 dq2

dq1 Ze dN1

dGtot dN1 ( ZeVe ) 0 1 ZeVe ,1 2 ZeVe ,2

Electrochemical potential
Describes the equilibrium condition of charged
chemical species (ions, electrons)
Chemical potential:
Electrochemical potential: ZeVe
where Z is the valence number
of the ion (dimensionless), e is
the elementary charge, and V
is the local electrical potential

Example: ion diffusion across

cell membrane