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1

N. Zabaras

INTRODUCTION TO THERMODYNAMICS OF MATERIALS


Thermodynamic systems, extensive and intensive variables
Energy, work and heat
Important state functions: H, F, G, etc.
Reversible and spontaneous processes, entropy
The first and second laws of thermodynamics
Conditions of equilibrium for single- or multi-component multi-phase alloys

Introduction to thermodynamics of materials

Materials Process Design and Control Laboratory

N. Zabaras

INTRODUCTION TO THERMODYNAMICS OF MATERIALS


Thermodynamics deals with energy and its transformations
Structure of materials determines properties. Thermodynamics is used to:
understand how the properties of materials are affected by thermodynamic processes (processes that involve changes in the material energy)
to control properties through its determination of structure
Thermodynamics includes two subjects:
Classical thermodynamics:
Phenomenological in nature focuses on the macroscopic properties
of materials and their relationships
Statistical thermodynamics:
Based on how the material behaves at the microscopic level allows
the description of the macroscopic properties
Introduction to thermodynamics of materials

Materials Process Design and Control Laboratory

N. Zabaras

THERMODYNAMIC VARIABLES
The state of a material system is described with the value of certain
variables of the system: T, P,V, S, c, etc.
A thermodynamic process is a real or virtual change in the system state
affected by varying the variables of the system such that the system is no
longer at equilibrium. A process is completed when the system reaches
its new equilibrium state.
State variables are independent of the system history and depend only on
the system state and not on the process by which the system was taken to
that state. For any state property,
R(A B) = RB RA
Process variables are defined only when a specific path is specified i.e.
by how the process was carried out. Examples include the heat q and work
w.
Introduction to thermodynamics of materials

Materials Process Design and Control Laboratory

N. Zabaras

EXTENSIVE AND INTENSIVE VARIABLES


Intensive variables do not depend on the system size and can be defined
at any point in the system: Examples include T , P, etc.
Not additive as they do not scale with the system size
Extensive variables depend on the system size and cannot be defined at
a point in the system, e.g. V , m, N (number of atoms), etc.
Additive as they scale with the system size, e.g. V + = V +V
Derived intensive quantities can be defined by scaling with another
extensive quantity
Densities can be introduced by scaling with total volume: Vm , VN , etc.
Nj
, also denoted as
The molar species number is defined as N j = Ntotal
X j ( j X j = 1). We will later introduce the partial molar value of any
E
extensive property E as Ei = N
|T,p,N j such that E = i NiEi
i
Partial quantities are used to associate chemical species with intensive
quantities, e.g. the partial pressure of species j: Pj = X j P ( j Pj = P)
Introduction to thermodynamics of materials

Materials Process Design and Control Laboratory

N. Zabaras

THERMODYNAMIC SYSTEM AND ITS BOUNDARY


Thermodynamic system separated from its surroundings from its system
boundary
System boundaries can be: rigid, impermeable, adiabatic or any combinations
System types include:
Isolated No energy or matter may be passed through its boundary
(e.g. the universe)
Closed or open allowing or not exhange of matter
Adiabatic No heat transfer can pass through its boundary
Single- or multi-component
Reacting or non-reacting
Homogeneous (single phase) or heterogeneous (multiple phases)

Introduction to thermodynamics of materials

Materials Process Design and Control Laboratory

N. Zabaras

ENERGY AND THE FIRST LAW OF THERMODYNAMICS


Energy is the potential to do work it can only be measured indirectly in
terms of other system variables such as m,v (e.g. E = 12 mv2), etc.
First law of thermodynamics
The energy of the universe is constant
Any change in the change of the energy of a system is balanced by an
opposite change in the energy of the surroundings. This change in the
energy of the surroundings is transferred to the system as heat or work
through the system boundary
When we talk on the energy of a system we usually mean the internal
energy U: The energy associated with the atomic motions in the material
(the kinetic and gravitational energy sources are typically ignored)
The internal energy U is intrinsic to the body

Introduction to thermodynamics of materials

Materials Process Design and Control Laboratory

N. Zabaras

THE FIRST LAW OF THERMODYNAMICS


We define the energy of the system as a state variable U, e.g.
U = U(P,V ) and U = U(P2 ,V2 ) U(P1,V1)
For all processes, the change of U for the system is balanced by an equal
and opposite change of U of the surroundings
The 1st law of thermodynamics is stated as: dU = q + w
q is the heat transfered to the system and w is the work done on the
system
w represents energy transfers due to forces other than temperature
gradients
w = i Fi dxi in terms of generalized forces and displacements, e.g.
the compression work for a pure fluid: w = PdV (note dV < 0 for
compression)
H
H
q and w are not exact differentials, e.g. dw = PdV = 0
Introduction to thermodynamics of materials

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N. Zabaras

FORMS OF WORK dw = V E dD +V H dB +V i j i j + . . .
POLARIZATION WORK: dw = V E dD
Let E be the applied electric field and D the electric displacement
P the polarization of the material due to local charge displacement
The following relations are applied:
D = 0E + P, 0 = the permittivity of free space
For isotropic materials: P = 0E, is the dielectric susceptibility and
thus D = E, = 0(1 + )=permittivity of the material
dw = V E dD w = 12V E 2
P = 0E
= dielectric susceptibility tensor
The response of the material depends on the orientation of E with
respect to the crystal orientation
Introduction to thermodynamics of materials

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N. Zabaras

FORMS OF WORK dw = V E dD +V H dB +V i j i j + . . .
MAGNETIC WORK: dw = V H dB
Let H be the applied magnetic field and B the magnetic induction of the
local net field
I the magnetization of the material (magnetic moment per unit volume)
The following relations are applied:
B = 0H + I, 0 = the permeability of vacuum
For isotropic materials: I = 0H, is the magnetic susceptibility
> 0 the induced magnetic moments align with H paramagnetic
material
< 0 the induced magnetic moments aligns antiparallel with H diamagnetic material
Thus B = H, = 0(1 + )=magnetic permeability of the material
dw = V H dB w = 12V H 2
Introduction to thermodynamics of materials

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N. Zabaras

HEAT AND WORK


Heat transfer occurs when there is a temperature gradient
Heat flows from regions of high T to regions of low T
Heat is the transfer of energy accomplished through random and chaotic
atomic motions
Heat transfer is thus a disordered process
Work is an ordered process of organized atomic motions

Introduction to thermodynamics of materials

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N. Zabaras

HEAT CAPACITIES
q
Constant volume heat capacity CV : CV = T
|V = U
T |V
q
Constant pressure heat capacity CP: CP = T
|P

One can show that generally CP > CV


Consider two ideal (fluid) systems that receive the same q under constant V and P conditions, respectivelly:
R TV
R Tp
TV T0
<CP >
=
q = T0 CV dT = T0 CPdT (using mean value theorem) <C
TP T0
V>
After the end of the constant V process, with a subsequent process
one should be able to expand the fluid and bring it to the same conditions as those at the end of the constant P pressure. At this additional
process, work is done on the surroundings. We can store this work
and pass it back as heat to the system (under constant V ) thus leading
<CP>
>1
to an increase in T : Thus TV > TP <C
V>
larger difference between CP and CV for gases rather then liquids
for solids the difference between CP and CV is negligible
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THE FIRST LAW FOR IDEAL PROCESSES


General form with compression work: dU = q PdV
Adiabatic processes q = 0: dU = PdV
Isothermal processes dT = 0: dUT = qT PT dVT
Isobaric processes dP = 0: dUP = qP PPdVP
Isometric processes dV = 0: dUV = qV
For all processes, to computer dU, one needs to know
an equation of state P(T,V )
comes from the specific properties of a material (material property)
and the heat flow dq

Introduction to thermodynamics of materials

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THE FIRST LAW FOR IDEAL GAS PROCESSES: U = U(T ) and


PV = nRT (or PV = RT ), R = gas constant = 8.3144 joules/(degree mole)
For an ideal gas, the particles do not interact and have no volume: U = U(T )
dU
CV = U
|
=
V
T
dT
q
V
CP = T
|P = U
|
+
P
| = CV + nR CP = CV + nR, or CP = CV + R
P
T
T P

Isothermal processes dT = 0: dUT = 0 = qT PT dVT = qT nRT


dVT
VT
qT = wT = nRT lnVV21 = nRT ln PP21
dT
Adiabatic processes q = 0: dU CV dT = PdV = nRT
dV

C
=
V
V
T
T2
V2
nR dV

C
ln
=
nRln
V
V
T1
V1
T2
V1 nR/CV
P2 nR/CP

=
(
)
=
(
)
or
PV
= constant, = CP/CV
T1
V2
P1

van der Waals extension to the ideal gas law:


(P + Va2 )(V b) = RT , a, b constants
Introduction to thermodynamics of materials

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N. Zabaras

A NEW STATE FUNCTION: ENTHALPY H = U + PV


Defined by subtracting from the internal energy the compression energy
H is the heat associated with constant pressure processes:
dH = dU + PdV + dPV (using the 1st law) dH = q +V dP
dH|P = q|P
Thus H can be interpreted as the available thermal energy at constant P
For constant P and small PdV (small dV and small P):
dH = U + PdV U
This approximation is applicable to condensed phases
Can now redefine CP as follows:
q
|P = H
|
CP = T
T P

Introduction to thermodynamics of materials

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N. Zabaras

NATURAL DIRECTION OF PROCESSES


REVERSIBLE PROCESSES
The natural direction of processes is one which increases the entropy
(randomness) of the universe
transform organized motion (e.g. work) to disorganized motion (e.g.
heat)
A process is reversible when it can reverse itself with an infinitesimal
driving force: they involve no production of entropy and occur infinitely
slowly
e.g. solidification of a pure material at the melting temperature

Introduction to thermodynamics of materials

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N. Zabaras

SPONTANEOUS PROCESSES
A process is spontaneous if it proceeds without an external driving force
and produces entropy
equalization of T when two bodies of initially unequal T are brought in
contact
conversion of work into heat
e.g. heat flows down a temperature gradient without an external force
spontaneous processes are irreversible: cannot create order from disorder
As a spontaneous process continues, the system is brought near equilibrium and the ability of the system for a spontaneous change is decreased

Introduction to thermodynamics of materials

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N. Zabaras

THE SECOND LAW OF THERMODYNAMICS


Entropy is a state function that can be expressed in terms of measurable
coordinates of the system and is an intrinsic property of the system related to
the degree of disorder in the system
The change of the entropy of the universe (system and surroundings) is positive and zero only for reversible processes:
dStotal 0, dStotal = 0 only for reversible processes
As one of the many alternative statements of the 2nd law, we can also state
that heat is not observed to spontaneously pass from a cold to a hot body
The entropy of a system can be computed by a reversible path from an arbitrary chosen reference state by integrating the heat absorbed by the system
divided by the system temperature

Introduction to thermodynamics of materials

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N. Zabaras

REVERSIBLE PROCESSES: dSrev = dqTrev


dV
For an ideal gas undergoing a reversible process: dqTrev = CV dT
+
nR
,
T
V
which implies that dqTrev is integrable over segments of dT and dV and
thus at least for ideal gases a state function

We call this perfect differential dS, the new state function S called
entropy
Any process can be considered as a
number of segments of constant T
and V
For a reversible process, the only heat involved is the transfer of energy
between the system and the surroundings via heat
No additional random motion is generated in the system or in the surroundings
Introduction to thermodynamics of materials

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N. Zabaras

ORDER AND DISORDER


The disorder (randomness) of the system is measured in terms of quanta
of energy, atom arrangements and motion, etc.
A material is more ordered as a crystalline solid than liquid
The system disorder is related to the detail required to specify the microscopic state of the system
Example: Isothermal expansion (dU = 0) of an ideal gas
V2
dU = 0 = dqrev pdV dqrev = pdV = nRT dV

q
=
nRT
ln
rev
V
V1

S = nRlnVV21

For V2 > V1 , S > 0: the expanded gas has higher entropy as its randomness has increased (more places for an atom to be!)
Introduction to thermodynamics of materials

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EQUIVALENT FORMS OF THE SECOND LAW


No process is possible in which heat (disordered motion) is absorbed from
a resorvoir and is completely converted to work (ordered motion)
The entropy change dS of a system is associated with a transfer of entropy
from the surrondings dStrans (which can be > 0 or < 0) and from entropy
dSprod produced within the system (always dSprod > 0):
dS = dStrans + dSprod, dSprod > 0

Introduction to thermodynamics of materials

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N. Zabaras

COMBINED FIRST AND SECOND LAWS


U
U is a state function, i.e. U = U(S,V ): dU = U
|
dS
+
| dV
V
S
V S

For reversible processes


dqrev = T dS and considering only mechanical work, dw = pdV . The combined first and second laws take the form:
dU = T dS pdV

U
|
and
P
=

T = U
V
S
V |S
For irreversible processes
Since U is a state function, one can find a reversible process that connects the
states (S + dS,V + dV ) and (S,V ). This will result in the same dU as for the
irreversible process and all equations given above for reversible processes are
still applicable!
R any state dqrev
T = 0 taken as the reference state:
S(any state) = T =0
T
(3nd Law of thermodynamics)

Introduction to thermodynamics of materials

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22

N. Zabaras

THE WORK DONE BY THE SYSTEM IS MAXIMUM FOR


REVERSIBLE OR QUASISTATIC PROCESSES
Consider a change of the material state from A to B. Using the 1st law:
UB UA = q + w
The entropy change of the system that absorbs heat dq from a resorvoir at
temperature Tr is: dSs = dq
Tr + d, d 0 from the 2nd law
+ d
From the first law: dq = dUs dw dSs = dUsTdw
r
dw = Tr dSs dUs Tr d dw Tr dSs dUs
For a constant Tr (large reservoir) by integration of the equation above:
w Tr (SB SA) (UB UA) wmax
Conversely the work which must be done on a system to bring it to a given
state is minimum for reversible processes. For irreversible processes a
greater amount of work is needed & energy is dissipated as heat

Introduction to thermodynamics of materials

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N. Zabaras

HEAT STORED DURING PHASE CHANGES OF PURE MATERIALS


H(Tm 0o) H(Tm + 0o) = Hsolidification = Hmelting
cP (water)

Variation of enthalpy with temperature at constant pressure for a pure


material (here water)

H (enthalpy)

warm water
freezing water
hot ice
c

P (ice)
cold ice

P=1 atm

For P=constant, H = q = CPT

T=0 C

The change H at the transforma Hot ice (T > 0) melts, undertion temperature Tm is the heat abcooled water (T < 0) solidifies
sorbed during the transformation:
and Suniverse > 0
H(Tm 0o) H(Tm + 0o) =
Cold ice (T < 0) does not melt,
Hsolidification = Hmelting
warm water (T > 0) does not solidify if they did Suniverse < 0 Phase transformations can be
exothermic (heat released, e.g.
Suniv = 0 for phase transformasolidification) or endothermic (heat
tion only at Tm = 0 for H2O at 1
absorbed, e.g. melting)
l
l
s
s
atm H T S = H T S at Tm
T (temperature)

Introduction to thermodynamics of materials

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EXAMPLE OF ENTROPY CREATION IN THE SOLIDIFICATION OF


AN UNDERCOOLED MELT AT CONSTANT P
Consider 1 mole of undercooled lead at 590
K (Tm = 600 K)
cP(l) = 32.4 3.1 103T joules/degree,
cP(s) = 23.6 + 9.75 103T joules/degree and
latent heat of lead qrev = 4810 joules/mole
To find Ssys we follow the reversible path
R b cP(l)dT qrev
a b c d: Ssys = a T + Tm +
R d cP(s)dT
c

= 7.997 joules/degree

The heat entering the constant-T reservoir at 590 K is given as: H =


R
R
Hab +Hbc +Hcd = ab cP(l) dT qrev cd cP(s)dT = 4799 joules
H
= 8.134 joules/degree
Thus the change of the entropy Sreservoir = 590
and the entropy created is: S = Ssys + Sreservoir = 7.994 + 8.134 =
0.137 joules/degree
Introduction to thermodynamics of materials

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N. Zabaras

TWO NEW STATE FUNCTIONS: THE HELMHOLTZ FREE


ENERGY F AND GIBBS FREE ENERGY G
F = U TS
F is defined by subtracting from the internal energy the thermal energy
dF = dU T dS SdT dF = SdT pdV dF|T = pdV |T
F represents the compression work that can be done by the system for
constant T
G = U + PV T S = H T S
Represents the available internal energy after the thermal energy and the
compressive energy are removed
Represents the available energy that can be extracted from the system at
constant T and P
Related to the energy associated with the internal degrees of freedom of
the system at constant T and P
Introduction to thermodynamics of materials

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PHASE TRANSFORMATIONS AT FIXED V and T or FIXED P and T


Transformation with fixed V in a reservoir of fixed T
Fsys = Usys T Ssys SsysT Fsys = q pV T Ssys SsysT
From the 2nd law: Ssys = q
+ Suniv
T
Finally: Fsys = T Ssys T Suniv pV T Ssys SsysT
Fsys = T Suniv pV SsysT
Fsys|V,T = T Suniv
Transformation with fixed P in a reservoir of fixed T
Gsys = Usys + PV +V P T Ssys T Ssys
Gsys = q +V P T Ssys T Ssys
From the 2nd law: Ssys = q
T + Suniv
Finally: Gsys = T Ssys T Suniv +V P T Ssys T Ssys
Gsys = T Suniv +V P T Ssys
Gsys|T,P = T Suniv
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SUMMARY OF EQUILIBRIUM CONDITIONS FOR PHASE


TRANSITIONS
Suniv = 0
Applicable to all cases
All subsystems affected by the process need to be included
Fsystem = 0
Applicable for isothermal constant volume phase transitions
You need to consider only the system under phase change
Gsystem = 0
Applicable for isothermal phase transitions with constant P
You need to consider only the system under phase change
Introduction to thermodynamics of materials

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THE PHASE WITH THE LOWEST VALUE OF G INDICATES


WHICH PHASE IS MOST STABLE
Molar free energies of solid and liquid
Liquid
phases versus temperature
P = constant
The phase with the smallest G at a
G
given T is the most stable phase at that
Solid
particular T
At equilibrium Teq Tm: G solid =
G liquid
T
T (temperature)
m

Plot of phase fractions f s, f l versus H


during a phase transformation
Plot of the molar Gibbs free energy
versus H [2] note that during the
transformation, the molar Gibbs free
energy of each phase is equal regardless of how much material is present
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VARIOUS COEFFICIENT RELATIONS USING LEGENDRE


TRANSFORMATIONS
Legendre transformations are used to replace the differential CidXi with the
differential XidCi in the combined 1st and 2nd laws: dU = T dS PdV
Legendre transformations
H = U (PV ) = U + PV, F = U T S & G = U + PV T S
U(S,V ) :
H(S, P) :
F(T,V ) :
G(T, P) :

dU = T dS PdV
dH = T dS +V dP
dF = SdT PdV
dG = SdT +V dP

dH|P = qrev
dF|T = wrev

Coefficient relations
H
|
=
T = U
V
S
S |P
F
P = U
|
=

S
V
V |T
G
S = F
T |V = T |P
G
V = H
|
=
S
P
P |T
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MAXWELL RELATIONS
These four relations are derived using the property relations given earlier
and applying the 2nd derivative property of continuous functions Y (X1, X2, . . . , Xn)
(here for U, H, F and G):
dY = C1dX1 + +CndXn
Coefficient relations
H
|
=
T = U
V
S
S |P
F
P = U
|
=

S
V
V |T
G
S = F
T |V = T |P
G
V = H
|
=
S
P
P |T

Introduction to thermodynamics of materials

2Y
Xi X j

2Y
X j Xi

Ci
X
=
j

C j
Xi

Maxwell relations
T
P
|
=

S
V
S |V
T
V
|
=
S
P
S |P
S
P
V |T = T |V
V
S
|
=

T
P
T |P

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COEFFICIENTS OF THERMAL EXPANSION AND


COMPRESSIBILITY
V
= V1 T
|P

Maxwell relations

S
V = P
|T

= V1 V
P |T
HEAT CAPACITIES CV AND CP
CV = U
|
T V
CP =

q
T |P

Introduction to thermodynamics of materials

qV,rev = CV dTV
qP,rev = CPdTP

S
CV = T T
|V
S
CP = T T
|P

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THE STATE FUNCTIONS S,V,U, H, F, G


IN TERMS OF T AND P
dS = CTP dT V dP
dV = V dT V dP
dU = T dS pdV = (CP PV )dT +V (P T )dP
dH = T dS +V dP = CPdT +V (1 T )dP
dF = SdT PdV = (S + PV )dT + PV dP
dG = SdT +V dP

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OPEN AND CLOSED SYSTEMS


All earlier developments were for closed systems, e.g. dU = dq + dw,
, etc.
dS dq
T
These developments are not applicable to open systems or closed systems that undergo irreversible changes in composition
All earlier developments are of course still applicable for the universe
Let us see why dU = T dS pdV becomes ambiguous
For an isolated system dU = dV = 0 dS = 0
However dS can increase because of a chemical reaction of because of
mixing of various substances that were initially separated
Let us similarly see why dG = SdT +V dP becomes ambiguous
Consider dT = dP = 0 dG = 0
However dG can increase just by doubling the amount of the system
at constant T and P (G is extensive)
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OPEN AND CLOSED SYSTEMS


Two state variables (e.g. T and P) are not sufficient to define the state
of an open system
We need to introduce additional state variables related to the composition
and size of the system

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THE CHEMICAL POTENTIAL


Let ni be the number of moles of substance i.
For variable ni, U = U(S,V, n1 , n2, . . . , nk ) and:
k
U
U
U
|V,ni dS +
|S,ni dV +
|S,V,n j dni
dU =
S
V
i=1 ni
For constant n1, n2, . . . , nk , dU = T dS pdV T = U
| and
S V,ni
P = U
V |S,ni . We can thus write:

k
U
dU = T dS PdV +
|S,V,n j dni = T dS PdV + idni
i=1 ni
i=1
where the chemical potential i is defined as follows:
U
i =
|S,V,n j (an intensive property)
ni
i represents the tendency of a substance to diffuse from one phase to
another
k

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INTRODUCING THE CHEMICAL POTENTIAL THROUGH G


k G
G
G = G(T, P, n1, . . . , nk ) dG = G
|
dT
+
|
dP
+

P,n
T,n
i=1 ni |T,P,n j dni
i
i
T
P

For constant n1, n2, . . . , nk (closed system), dG = SdT +V dP


G
|
and
V
=
S = G
P,n
i
T
P |T,ni . We can thus write:
k
k
G
dG = SdT +V dP + |T,P,n j dni = SdT +V dP + idni
i=1 ni
i=1
G
U
The definition of i = n
|T,
P,
n
is
the
same
as

=
j
i
ni |S,V, n j
i

Indeed, recall that: dU = T dS PdV + ki=1 idni


Add on both sides: d(PV T S) to derive:
k

i=1

i=1

dG = T dSPdV + idni +d(PV T S) = SdT +V dP+ idni


i is thus the amount by which the capacity of the phase for doing work
other than work of expansion is increased per unit amount of substance
i added for an infinitesimal addition at constant T and P
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COMBINED FIRST AND SECOND LAWS FOR AN OPEN SYSTEM


U = U(S,V, n1 , n2, . . . , nk ): dU = T dS PdV + ki=1 idni
G = G(T, P, n1, n2, . . . , nk ): dG = SdT +V dP + ki=1 idni
H = H(S, P, n1, n2, . . . , nk ): dH = T dS +V dP + ki=1 idni
F = F(T,V, n1, n2, . . . , nk ): dF = SdT PdV + ki=1 idni
U
G
H
F
i =
|S,V, n j =
|T, P, n j =
|S, P, n j =
|T,V, n j
ni
ni
ni
ni

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ki=1 idni AS A WORK TERM


k

dU = T dS PdV + idni
i=1

For a reversible change in composition of a closed system,


ki=1 idni can be interpreted as the chemical work (work
other than compression work)
For open systems, we cannot interpret ki=1 idni as work:
When there is simultaneous transfer of energy and
mass as in open systems, the term heat is ambiguous
and we cannot interpret T dS as heat so the remaining terms in the equation above cannot be interpreted
as work! (see Denbigh, section 2.7)

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VARIOUS COEFFICIENT RELATIONS FOR OPEN SYSTEMS


USING LEGENDRE TRANSFORMATIONS:
H = U + PV, F = U T S & G = U + PV T S
U(S,V, n1 , n2, . . . , nk ) : dU = T dS PdV + ki=1 idni
H(S, P, n1, n2, . . . , nk ) : dH = T dS +V dP + ki=1 idni
F(T,V, n1 , n2, . . . , nk ) : dF = SdT PdV + ki=1 idni
G(T, P, n1, n2, . . . , nk ) : dG = SdT +V dP + ki=1 idni
Coefficient relations

Maxwell relations

H
|
=
|
T = U
V,n
i
S
S P,ni

T
P
|
=

|
S,n
i
V
S V,ni
T
V
|
=
|
S,n
i
P
S P,ni
S
P
| = T
|V,ni
V T,ni
S
V
|
=

|
T,n
i
P
T P,ni

F
P = U
|
=

|
S,n
i
V
V T,ni

S = F
| = G
|
T V,ni
T P,ni
G
V = H
|
=
|
S,n
i
P
P T,ni

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Equations resulting from the coefficient relations


Gibbs-Helmholtz equations
G = H TS = H

|
+ T G
T P,ni

F = U TS = U

+ T F
|
T V,ni

G
T
|
T P,ni

= TH2

F
T
|
T P,ni

= TU2

The thermodynamic equation of state


Relation between U, T, V and P
k

dU = T dS PdV + idni
i=1

S
U
|T,n = T |T,ni P (using Maxwell relations)
V i
V
P
U
|T,ni = T |V,ni P
V
T

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INTEGRATION OF THE BASIC EQUATIONS


Let us consider dU = T dS PdV + ki=1 idni
Let the phase under examination be enlarged from V to kV
T , P & i remain unchanged (intensive variables). Thus we can write:
k

U = T S PV + ini ()
i=1

Because U, S and ni are extensive variables, U = (k 1)U, S =


(k 1)S and ni = (k 1)ni and Equation () becomes:
(k 1)U = T (k 1)S P(k 1)V + ki=1 i(k 1)ni. Finally:
k

U = T S PV + ini
i=1

dH = T dS +V dP + ki=1 idni H = T S + ki=1 ini U (PV )


dF = SdT PdV + ki=1 idni F = PV + ki=1 ini U T S
dG = SdT +V dP + ki=1 idni G = ki=1 ini U (PV ) T S
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DERIVING G = ki=1 ini USING THE CONCEPT OF


HOMOGENEOUS FUNCTIONS
With T and P being intensive variables, we note that:
G(T, P, n1, . . . , nk) = G(T, P, n1, . . . , nk )
e.g. G is homogeneous in ni of degree 1
Differentiation with respect to leads to the following:
dG(T, P, n1, . . . , nk )
= G(T, P, n1, . . . , nk )
d
or
G(T, P, ni) (ni)
(ni) = G(T, P, ni)
i=1
k

Finally, we obtain: ki=1 ini = G(T, P, n1, . . . , nk )

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THE GIBBS-DUHEM EQUATION


Consider our initial fundamental equation:

dU = T dS PdV + idni
i=1

Using U = T S PV

+ ki=1 ini

i=1

i=1

dU = SdT + T dS V dP pdV + nidi + idni


Subtracting the two equations leads to the Gibbs-Duhem equation:
k

SdT +V dP nidi = 0
i=1

If there are k substances in the phase, the number of independent


intensive variables is: k + 1
For a multiphase alloy, there are Gibbs-Duhem equations:
k

S dT +V dP ni di = 0, for each phase = 1, . . . ,

i=1

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MOLAR QUANTITIES FOR A ONE COMPONENT ALLOY


Consider a phase with one component: dU = T dS PdV + dn ()
We have already defined the molar variables: V = Vn , S = Sn , etc. From
these equations, we can write:

dU = ndU + Udn,
dS = nd S + Sdn,
dV = ndV + V dn
Equation () can thus be written as:

= T (nd S + Sdn)
ndU + Udn
P(ndV + V dn) + dn
or as follows:
ndU = T nd S PndV + ( U + T S PV )dn ()
We have shown that G = ki=1 ini (for k = 1 here)
= Gn = U+PVn T S = U + PV T S
Equation () is then simplified as follows: dU = T d S PdV
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FOR BOTH OPEN AND CLOSED SYSTEMS


WITH ONE COMPONENT
dU = T d S PdV
d H = T d S + V dP
PdV
d F = SdT
+ V dP
d G d = SdT
P), etc.
Note that e.g. G = G(T,

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PARTIAL MOLAR QUANTITIES FOR A MULTI-COMPONENT


ALLOY
We will like to define a quantity Ei of a property E obeying an equation
that the molar quantity E of one-component alloys
similar to E = En
satisfies, such as:
k

E = Eini
i=1

Define the partial molar value of E as:


E
Ei =
|T,P,n j
ni
k
E
From E(T, P, n1, . . . , nk ) dE = E
|
dT
+
|
dP
+

p,n
T,n
i=1 Ei dni
i
i
T
P

Integration of the above equation leads to: E = ki=1 Eini

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PARTIAL MOLAR QUANTITIES FOR A MULTI-COMPONENT


ALLOY
In summary:

U = ki=1 Uini, S = ki=1 Sini


H = ki=1 Hini, F = ki=1 Fini
V = ki=1 Vi ni, G = ki=1 Gini

Absolute values of Ei are never known they must be computed wrt a


reference state (same as that of E)
Note that i Gi

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PARTIAL MOLAR QUANTITIES FOR A MULTI-COMPONENT ALLOY


Ei are intensive variables (independent of the size of the system) but in
addition to T and P depend on the relative proportions of the various
components, e.g.
k

Ei = Ei(T, P, x1, x2, . . . , xk1), xi = ni/ ni


i=1

The relations between partial molar quantities are similar to those between the parent quantities:
H = U + PV Hi = Ui + PVi
G = H T S i = Hi T Si
Using dG = SdT +V dP + ki=1 idni, we can derive the following:
i
i
V
S
|
=
|
=
V
,
and
|
=

|
= Si
T,n
,n
T,P,n
i
P,n
,n
i j
j
i j
P
ni
T
ni T,P,n j
i
Combining the eqs. above gives: i = Hi T Si = Hi + T
|
,
P P,ni,n j

Ti
T |P,ni,n j

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PARTIAL MOLAR QUANTITIES IN TERMS OF MOLE FRACTIONS


Let us start with E = ki=1 Eini, dE = ki=1 Eidni + ki=1 dEini ()
k
E
But dE = E
|
dT
+
|
dP
+

P,n
T,n
i=1 Ei dni ()
i
i
T
P

Subtracting Equs. (*) and (**) leads to:


k
E
E
|
dT
+
|
dP

P,n
T,n
i=1 dEi ni = 0 (for E = G, the Gibbs-Duhem Equ.)
i
i
T
P
For constant T and P, the above equations lead to the following:
ki=1 nidEi = 0 or ki=1 xidEi = 0 (with xi = ni/ ki=1 ni)
As a result Ei = Ei(T, P, x1, . . . , xk1) k 1 independent mole fractions
i
di = SidT +VidP + k1
i=1 xi |T,P,x j dxi where we used the results shown

earlier:

i
|
P T,ni ,n j

= Vi , and

i
|
T P,ni,n j

= Si

i
Similarly using Hi = T Si + i, dHi = T dSi +VidP + k1
i=1 xi |T,P,x j dxi
i
Finally, dUi = T dSi PdVi + k1
i=1 xi |T,P,x j dxi

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REVISITING THE EQUILIBRIUM CONDITIONS


From the 2nd law: Suniv 0
For an isolated system, we also can write: Ssys 0
For an isolated system there are no interactions with the surroundings
For a given process that changes the system state, all changes in the
entropy of the universe are localized within the system
Since there is no heat transfer between the system and its surroundings,
all changes in Suniv represent entropy generated within the system
For an isolated
system:

Suniv 0
Suniv = Ssurr + Ssys 0
Ssys 0

Since Ssys can only increase, is there a maximum in the system entropy?
In an isolated system at equilibrium Ssys is maximum
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EQUILIBRIUM CONDITIONS
Spontaneous processes increase the entropy of the system
The driving forces in a spontaneous process are the potential for entropy
increases
When the driving forces for spontaneous change in the system become
exhausted, the system reaches equilibrium
In an isolated system at equilibrium Ssys is maximum
For any possible variation S with U = V = 0, the following is
true: S|U=0,V =0 0 S is maximum at constant U and V
Equivalently: For any possible variation U with S = V = 0:
U|S=0,V =0 0 U is minimum at constant S and V
U
U
|V S +
|SV U = T S 0
U =
S
V
At equilibrium the state is maintained without external driving forces
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HOW DO YOU CHECK IF A SYSTEM IS AT EQUILIBRIUM


We maximize the entropy of an isolated system
The state conditions are the same regardless if the system is isolated
or not
To check if the system is in equilibrium, we perform a virtual experiment: We isolate the system and check if its state remains
unchanged.
Note that systems that appear to be in steady-state conditions are not
necessarily at equilibrium
The internal conditions of the system need to be responsible for the
steady-state conditions and not an external driving force
For example, a system corresponding to steady-state temperature
conditions within an applied temperature gradient is not at equilibrium (isolating the system will lead to temperature changes!)
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THERMODYNAMIC EQUILIBRIUM OF TWO SEPARATED


REGIONS (T , P) AND (T , P) [2]
Consider the state of the two regions. The following
holds: V = V +V , U = U +U , S = S + S
Consider an arbitrary virtual change with U = V = 0

+
V
U = T S PV S = U

T
T

Similarly, S = U
+
V

T
T

P
U
P

For the whole system: S = U


+
V
+
+
V

T
T
T
T

For an isolated system: V = V , U = U

Finally, we can write: S = ( T1 T1 )U + ( TP TP )V


For an isolated heterogeneous system, the entropy is maximum (system at equilibrium) when S = 0, i.e.:
T = T (thermal equilibrium) no heat flow between and
P = P (mechanical equilibrium) no volume changes of or
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THERMODYNAMIC EQUILIBRIUM OF A
ONE-COMPONENT TWO-PHASE SYSTEM
Consider the state of the two phases:
(T , P,V , S, n, . . .) and (T , P,V , S, n, . . .)
The following holds for extensive variables:
V = V +V
U = U +U
S = S + S
n = n + n
Consider an arbitrary process:

+
dV

dn
dU = T dS PdV + dn dS = dU

T
T
T

where the chemical potential is defined as: = U


|
n S ,V

Similarly, dS =

dU
T

+ T dV T dn

Finally, for the whole system:

dU
P
dU
P

dS = T + T dV T dn + T + T dV T dn
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THERMODYNAMIC EQUILIBRIUM OF A
ONE-COMPONENT TWO-PHASE SYSTEM
For the whole system:

dU
P
dU
P

dS = T + T dV T dn + T + T dV T dn
For an isolated system the following hold:
dV = dV
dU = dU
dn = dn
Finally we can write:

dS = ( T1 T1 )dU + ( TP TP )dV ( T T )dn


For an isolated unary two phase system, the entropy is maximum
(system at equilibrium) when dS = 0, i.e.:
T = T (thermal equilibrium) no heat flow between and
P = P (mechanical equilibrium) no volume changes of or
= (chemical equilibrium) no changes in n and n
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EQUILIBRIUM MINIMUM INTERNAL ENERGY


We showed earlier that:
dU = T dS PdV + dn
dU = T dS PdV + dn
Since the system is isolated:
dV = dV
dS = dS
dn = dn
Finally we can write for the whole system:
dU = (T T )dS (P P)dV + ( )dn
Minimization of the internal energy for an isolated system leads to:
T = T (thermal equilibrium)
P = P (mechanical equilibrium)
= (chemical equilibrium)
e.g. the same conditions as for equilibrium in an isolated system
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EQUILIBRIUM MINIMUM ENTHALPY


FOR P=CONSTANT
dH = T dS +V dP + dn
dH = T dS +V dP + dn
If we isolate the system, we obtain:
dS = dS
dn = dn
For the whole system:
dH = (T T )dS +V dP +V dP + ( )dn
Let us minimize H with constant P: dP = dP = dP = 0:
T = T (thermal equilibrium)
dP = dP = dP = 0 (constant pressure constraint)
= (chemical equilibrium)
Equilibrium is thus obtained when H is minimized under constant
pressure for an isolated system (constant material and entropy)
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EQUILIBRIUM MINIMUM F FOR T =CONST


dF = SdT PdV + dn
dF = SdT PdV + dn
For a rigid and impermeable boundary:
dV = dV
dn = dn
For the whole system:
dF = SdT SdT (P P)dV + ( )dn
Let us minimize F with constant T : dT = dT = dT = 0
dT = dT = dT = 0 (constant temperature constraint)
P = P (mechanical equilibrium)
= (chemical equilibrium)
Equilibrium is thus obtained when F is minimized under constant
temperature and the boundary is rigid and impermeable

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EQUILIBRIUM MINIMUM G FOR T & P CONSTANT


dG = SdT +V dP + dn
dG = SdT +V dP + dn
For a system with impermeable boundary:
dn = dn
For the whole system:
dG = SdT SdT +V dP +V dP + ( )dn
Let us minimize G with constant T and P:
dT = dT = dT = 0 (constant temperature constraint)
dP = dP = dP = 0 (constant pressure constraint)
= (chemical equilibrium)
Equilibrium is thus obtained when G is minimized under constant
temperature and pressure for a system with impermeable walls

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THE CHEMICAL POTENTIAL k FOR A


MULTI-COMPONENT MULTI-PHASE ALLOY
For each phase: dU = T dS PdV + Ck=1 k dnk
The chemical potential

is defined as:

U
|S ,V ,n j
n
k

A chemical potential gradient means that there is a driving force


for diffusion
As species move from regions of high potential to regions of
low potential, the potential is lowered in the regions from where
species came and increases in the regions where they arrived
Equilibrium conditions imply elimination of all driving forces for
diffusion, i.e. of all chemical potential gradients

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EQUILIBRIUM OF MULTI-COMPONENT MULTI-PHASE ALLOYS


For each phase: dU = T dS PdV + Ck=1 k dnk
Rearranging gives the follows:
C

dU
P
dS = + dV k dnk
T
T
k=1 T

Finally for the entire system: dS =


=1 dS

dU P C k
dS = { + dV dnk }
T
=1 T
k=1 T
For an isolated system the following holds:

=2

=2

=2

dV = dV 1, dU = dU 1, dnk = dn1k , for each k

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EQUILIBRIUM OF MULTI-COMPONENT MULTI-PHASE ALLOYS


Can easily write:

1
1
dU
dU dU 1
dU
=2 dU

=
+
=

=
(

)dU
T T T1 T

T1
T1
=1
=2
=2
=2 T

P P1
PdV
T = . . . = ( T T 1 )dV
=1
=2

Similarly using =2 nk = dn1k , we can write:

C
k
k
1k
T dnk = ( T T 1 )dnk
=1 k=1
=2 k=1

dS =

1
{(

=2 T

T11 )dU + ( TP

C
P1

T 1 )dV k=1( Tk

1k
T 1 )dnk }

At the maximum entropy dS = 0 (equilibrium), we conclude that for all


phases : T = T 1, P = P1 and k = 1k for all k
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THE GIBBS PHASE RULE


Consider phases with C components in equilibrium
The following number of equations is available (the T and P eqs not accounted here but are explictitly introduced in the number of variables):
k

(Gibbs Duhem Equations) S dT +V dP ni di = 0, and

i=1

C( 1) ( chemical potential conditions) k = 1k


TOTAL : (C C + )
The number of unknowns is: 2 (temperature and pressure) + C (concentrations); a total of C + 2
The number of degress of freedom f (the number of variables that I can
change and still remain in equilibrium) is then equal to:
f =C+2
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REFERENCES
Material presented in this lecture has been compiled from the following references
1. Thermodynamics, C. B. Musgrave
http://chemeng.stanford.edu/ charles/mse202/
2. Thermodynamics of materials, W. Craig Carter
http://pruffle.mit.edu/3.00/
3. Introduction to Metallurgical Thermodynamics, D. R. Gaskell
4. The Principles of Chemical Equilibrium, K. Denbigh

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