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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.
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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
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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
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HEAT CAPACITIES
q
Constant volume heat capacity CV : CV = T
|V = U
T |V
q
Constant pressure heat capacity CP: CP = T
|P
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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
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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
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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
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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!)
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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)
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H (enthalpy)
warm water
freezing water
hot ice
c
P (ice)
cold ice
P=1 atm
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)
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= 7.997 joules/degree
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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
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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Maxwell relations
S
V = P
|T
= V1 V
P |T
HEAT CAPACITIES CV AND CP
CV = U
|
T V
CP =
q
T |P
qV,rev = CV dTV
qP,rev = CPdTP
S
CV = T T
|V
S
CP = T T
|P
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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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P,n
T,n
i=1 ni |T,P,n j dni
i
i
T
P
=
j
i
ni |S,V, n j
i
i=1
i=1
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dU = T dS PdV + idni
i=1
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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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|
+ 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
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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U = T S PV + ini ()
i=1
U = T S PV + ini
i=1
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dU = T dS PdV + idni
i=1
Using U = T S PV
+ ki=1 ini
i=1
i=1
SdT +V dP nidi = 0
i=1
i=1
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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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E = Eini
i=1
p,n
T,n
i=1 Ei dni
i
i
T
P
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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
= TH2i
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P,n
T,n
i=1 Ei dni ()
i
i
T
P
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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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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+
V
U = T S PV S = U
T
T
Similarly, S = U
+
V
T
T
P
U
P
T
T
T
T
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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
Similarly, dS =
dU
T
+ T dV T dn
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:
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is defined as:
U
|S ,V ,n j
n
k
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dU
P
dS = + dV k dnk
T
T
k=1 T
dU P C k
dS = { + dV dnk }
T
=1 T
k=1 T
For an isolated system the following holds:
=2
=2
=2
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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
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 }
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i=1
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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