09/19/2001 Notes from R.T.

DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)

4-1
Chapter 4
Thermodynamic Variables
and Relations
Notes on
Thermodynamics in Materials Science
by
Robert T. DeHoff
(McGraw-Hill, 1993).
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-2
Thermal Expansion Coefficient
Volumetric Thermal Expansion Coefficient
P
V
T
V
V

'
+

'

'
+

'

=
1
E
... , , X P T f
V
= E
P
L
T
L
L

'
+

'

'
+

'

=
1
E
L V
E E 3 =
3 2 1 L L L
E E E = =
Isotropic Material
Linear Thermal Expansion Coefficient
(SI Units = K
-1
)
(SI Units = K
-1
)
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-3
Thermal Expansion Coefficient
Isotropic Material

P
V
T
L L L
L L L

'
+

'

'
+

'

=
3 2 1
3 2 1
1
E
L V
E E 3 =
3 2 1 L L L
E E E = =

'
+

'

'
+

'

'
+

'

'
+

'

=
P P P
V
T
L
L L
T
L
L L
T
L
L L
L L L
3
2 1
2
3 1
1
3 2
3 2 1
1
E

'
+

'

'
+

'

'
+

'

=
P P P
V
T
L
L T
L
L T
L
L
3
3
2
2
1
1
1 1 1
E
? A
3 2 1 L L L V
E E E E + + =
&
If isotropic:
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-4
Coefficient of Compressibility
Volumetric Coefficient of Compressibility
T
V
P
V
V

'
+

'

'
+

'

=
1
F
... , , X P T f
V
= F
Approximately:
Note negative sign in definition.
E = Elastic Modulus E
V
/ 3 = F
j i Vi Vj
E E / / = F F
(SI Units = atm
-1
)
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-5
Heat Capacity
At Constant Pressure:
HQ
rev,P
= C
P
dT
P
(SI Units = J/mole-K)
C
P
= f(T,P,X,)
Empirical Fit: C
P
(T) = a + bT + c/T
2
At Constant Volume:
HQ
rev,V
= C
V
dT
V
(SI Units = J/mole-K)
C
V
= f(T,P,X,)
In General: C
P
" C
V
& C
P
C
V
= TVE
2
/F
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-6
Internal Energy
dU = HQ + HW +HW
/
HQ
rev
= TdS
HW
rev
= PdV
1st & 2nd Laws: dU = TdS - PdV +HW
/
Coefficient relations:
T
S
U
V
=

'
+

'

P
V
U
S
=

'
+

'

s V
V
T
S
P

'
+

'

'
+

'

Maxwell relation:
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-7
Enthalpy
Defining an energy & state function: H = U + PV
Differentiating: dH = dU + PdV + VdP
Substituting for dU: dH = TdS-PdV+dW
/
+PdV+VdP
1
st
& 2
nd
Laws: dH = TdS + VdP +HW
/
Good for isobaric processes: dP = 0
Coefficient relations:
T
S
H
P
=

'
+

'

V
P
H
S
=

'
+

'

P S
S
V
P
T

'
+

'

'
+

'

Maxwell relation:
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-8
Helmholtz Free Energy
F (DeHoff) or A (Arbeiten)
Defining an energy & state function: F = U TS
Differentiating: dF = dU TdS SdT
Substituting for dU: dF = TdS-PdV+dW
/
-TdS-SdT
1
st
& 2
nd
Laws: dF = - SdT PdV +HW
/
Good for isothermal processes: dT = 0
Coefficient relations:
S
T
F
V
=

'
+

'

P
V
F
T
=

'
+

'

V T
T
P
V
S

'
+

'

'
+

'

Maxwell relation:
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-9
Gibbs Free Energy
G (DeHoff) or F (Others)
Defining an energy & state function: G = H - TS
Differentiating: dG = dU+PdV+VdPTdS-SdT
Substituting for dU: dG = TdS-PdV+dW
/
+PdV+VdP-TdS-SdT
1
st
& 2
nd
Laws: dG = SdT + VdP +HW
/
Good for isothermal/isobaric processes: dT=0, dP=0
Coefficient relations:
S
T
G
P
=

'
+

'

V
P
G
T
=

'
+

'

P T
T
V
P
S

'
+

'

'
+

'

Maxwell relation:
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-10
State Functions (Table 4.4)
State Variables
Temperature T
Pressure P
Volume V
Energy Functions
Internal Energy U
Enthalpy H
Helmholtz Free Energy F
Gibbs Free Energy G
Entropy S
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-11
Energy Functions
Internal Energy U
Enthalpy H = U + PV
Helmholtz Free Energy F = U TS
Gibbs Free Energy G = H TS
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-12
Combined 1
st
& 2
nd
Laws
dU = TdS PdV + HW
/
dH = TdS + VdP + HW
/
dF = SdT PdV + HW
/
dG = SdT + VdP + HW
/
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-13
Coefficient Relations
S
T
G
P
=

'
+

'

V
P
G
T
=

'
+

'

S
T
F
V
=

'
+

'

P
V
F
T
=

'
+

'

T
S
H
P
=

'
+

'

V
P
H
S
=

'
+

'

T
S
U
V
=

'
+

'

P
V
U
S
=

'
+

'

09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-14
Maxwell Relations
s V
V
T
S
P

'
+

'

'
+

'

P S
S
V
P
T

'
+

'

'
+

'

V T
T
P
V
S

'
+

'

'
+

'

P T
T
V
P
S

'
+

'

'
+

'

09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-15
State Functions=f(T,P)
(Table 4.5)
VdP SdT dG + =
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-16
Volume Relations
to Temperature & Pressure
P T V V , =
VdP VdT dV F E =
dP
P
V
dT
T
V
dV
T P

'
+

'

'
+

'

=
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-17
State Functions=f(T,P)
(Table 4.5)
dP V dT V dV F E =
VdP SdT dG + =
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-18
Entropy Relations
to Temperature & Pressure
P T S S , =
VdP dT T C dS
P
E =
dP
P
S
dT
T
S
dS
T P

'
+

'

'
+

'

=
TdS dT C Q
P rev
= = H
P T
T
V
P
S

'
+

'

'
+

'

09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-19
State Functions=f(T,P)
(Table 4.5)
dP V dT V dV F E =
dP V dT
T
C
dS
P
E =
dP T P V dT PV C dU
P
E F E + =
dP T V dT C dH
P
) 1 ( E + =
dP PV dT PV S dF F E + =
VdP SdT dG + =
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-20
Relations Between State Variables
Identify the variables. Z=Z(X,Y)
Write the differential form. dZ=MdX+NdY
Convert dX & dY in terms of dT & dP.
dZ=M[X
T
dT+X
P
dP]+N[Y
T
dT+Y
P
dP]
where dX=X
T
dT+X
P
dP; dY=Y
T
dT+Y
P
dP
Collect terms. dZ=[MX
T
+NY
T
]dT+[MX
P
+NY
P
]dP
Obtain: Z=Z(T,P) & dZ=Z
T
dT+Z
P
dP
Set: MX
T
+NY
T
=Z
T
MX
P
+NY
P
=Z
P
Solve for M & N, integrate dZ=MdX+NdY
between end points.
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-21
Example: Find T=T(S,V)
Identify the variables. T = T(S,V)
Rearrange. S = S(T,V)
Write the differential form. dS = MdT+NdV
Convert dT & dV in terms of dT & dP by substituting
dT = dT & dV = VEdT-VFdP
dS = MdT+N[VEdT-VFdP]
Collect terms.
dS = [M+NVE]dT-NVFdP
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-22
Example: Find T=T(S,V)
dS = [M+NVE]dT-NVFdP
Obtain: S=S(T,P) & dS=(C
P
/T)dT-VEdP
Set: [M+NVE]=(C
P
/T) & -NVF= -VE
Solve for M & N:
M = 1/T(C
P
-TVE
2
/F) & N = EF
Insert M & N in differential form: dS=MdT+NdV
dS = 1/T(C
P
-TVE
2
/F)dT+EFdV
Note the relation: C
P
C
V
= TVE
2
/F
dS = (C
V
/T)dT+(EFdV
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-23
Example: Find T=T(S,V)
dS= (C
V
/T)dT+(EFdV
Solve for dT:
dT= (T/C
V
)dS-(ETFC
V
dV
For isentropic process:
dT
S
= (ETFC
V
dV
S
Integrating:

1 2
1
2
ln V V
C T
T
V
=

'
+

'

F
E

=
1 2 1 2
exp V V
C
T T
V
F
E
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-24
Ideal Gas
PV = nRT
E = 1/T F = 1/P
Monatomic: C
P
= 5/2 R C
V
= 3/2 R
Diatomic: C
P
= 7/2 R C
V
= 5/2 R
U & H depend only on temperature:
(U = C
V
dT (H = C
P
dT
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-25
Ideal Gas

'
+

'

'
+

'

'
+

'

'
+

'

=
P
nR
nRT
P
T
V
V
P
V
1
E
T
V
1
= E

'
+

'

'
+

'

'
+

'

'
+

'

=
2
1
P
nRT
nRT
P
P
V
V
T
V
F

-1
P nRT V =
T
P
nR
V

'
+

'

'
+

'

'
+

'

P
nR
T
V
P

2
=

'
+

'

P nRT
P
V
T
P
V
1
= F
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-26
4.4 Compare the (S for the following processes.
(a.) One gr-at of Ni is heated at 1 atm from 300 K to 1300K.
Need S = S(T,P) evaluated for P = constant.
VdP dT T C dS
P
E =
For constant P, dP=0.
dT T C dS
P
=
For this state function, integrate between limits.

= (
2
1
T
T
P
dT T C S
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-27
4.4 Compare the (S for the following processes.
(a.) One gr-at of Ni is heated at 1 atm from 300 K to 1300K.
From the Appendix.
K mol
J
bT a C
Ni
P

+ =
Where a = 17.0 & b = 0.0295.

= (
2
1
T
T
P
dT T C S
? A

+ =

'
+

'

+ = (
2
1
2
1
ln
T
T
T
T
bT T a dT b
T
a
S
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-28
4.4 Compare the (S for the following processes.
(a.) One gr-at of Ni is heated at 1 atm from 300 K to 1300K.
Substituting values for Ni and limits.
Where a = 17.0 & b = 0.0295.
? A
2
1
ln
T
T
bT T a S + = (

+ = ( 300 1300 0295 . 0

300
1300
ln 17 S
K at gr
J
S

= ( 4 . 54
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-29
4.4 Compare the (S for the following processes.
(b.) One gr-at of Ni is heated at 300 K is isothermally
compressed from 1 atm to 100 kbars.
Need S = S(T,P) evaluated for T = constant.
VdP dT T C dS
P
E =
For constant T, dT=0.
VdP dS E =
Assume E and V are independent of pressure.

2 1
2
1
P P V dP V S
P
P
= = (

E E
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-30
4.4 Compare the (S for the following processes.
(b.) One gr-at of Ni at 300 K is isothermally compressed from
1 atm to 100 kbars.
From Appendices:
mole cc V
Ni
O
/ 60 . 6 =
Substituting numerical values for E and V.

2 1
P P V S = ( E
1 6
10 40

= K x
Ni
V
E

K mol
atm cc
S

= = (

41 . 26 10 1 10 40 60 . 6
5 6
K mole
J
S

= = ( 65 . 2
06 . 82
314 . 8
41 . 26
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-31
4.4 Compare the (S for the following processes.
(c.) One mole of ZrO
2
from 300 K to 1300 K at 1 atm.
Need S = S(T,P) evaluated for P = constant.
VdP dT T C dS
P
E =
For constant P, dP=0.
dT T C dS
P
=
For this state function, integrate between limits.

= (
2
1
T
T
P
dT T C S
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-32
4.4 Compare the (S for the following processes.
(c.) One mole of ZrO
2
from 300 K to 1300 K at 1 atm.
From the Appendix.
K mol
J
cT bT a C
ZrO
P

+ + =
2
2
Where a = 69.6, b = 0.0075, c = -14.1x10
5
.

= (
2
1
T
T
P
dT T C S

|

+ =

'
+

'

+ + = (
2
1
2
1
2 3
2
ln
T
T
T
T
T
c
bT T a dT
T
c
b
T
a
S
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-33
4.4 Compare the (S for the following processes.
(c.) One mole of ZrO
2
from 300 K to 1300 K at 1 atm.
Substituting values for ZrO
2
and limits.
Where a = 69.6, b = 0.0075, & c = -14.1x10
5
.
? A
2
1
2
2
ln
T
T
T
c
bT T a S

+ + = (


|

'
+

'

+ + = (
2 2
5
300
1
1300
1
10 1 . 14 300 1300 0075 . 0
300
1300
ln 6 . 69 S
K at gr
J
S

= ( 177
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-34
4.4 Compare the (S for the following processes.
(d.) One mole of ZrO
2
at 300 K is isothermally compressed
from 1 atm to 100 kbars.
Need S = S(T,P) evaluated for T = constant.
VdP dT T C dS
P
E =
For constant T, dT=0.
VdP dS E =
Assume E and V are independent of pressure.

2 1
2
1
P P V dP V S
P
P
= = (

E E
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-35
4.4 Compare the (S for the following processes.
(d.) One mole of ZrO
2
at 300 K is isothermally compressed
from 1 atm to 100 kbars.
From Appendices:
mole cc V
ZrO
O
/ 02 . 27
2
=
Substituting numerical values for E and V.

2 1
P P V S = ( E
1 6
10 7
2

= K x
ZrO
V
E

K mol
atm cc
S

= = (

9 . 18 10 1 10 7 02 . 27
5 6
K mole
J
S

= = ( 92 . 1
06 . 82
314 . 8
9 . 18
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-36
4.4 Compare the (S for the following processes.
(e.) One mole of O
2
from 300 K to 1300 K at 1 atm.
Need S = S(T,P) evaluated for P = constant.
VdP dT T C dS
P
E =
For constant P, dP=0.
dT T C dS
P
=
For this state function, integrate between limits.

= (
2
1
T
T
P
dT T C S
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-37
4.4 Compare the (S for the following processes.
(e.) One mole of O
2
from 300 K to 1300 K at 1 atm.
From the Appendix.
K mol
J
cT bT a C
O
P

+ + =
2
2
Where a = 30.0, b = 0.0042, c = -1.7x10
5
.

= (
2
1
T
T
P
dT T C S

|

+ =

'
+

'

+ + = (
2
1
2
1
2 3
2
ln
T
T
T
T
T
c
bT T a dT
T
c
b
T
a
S
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-38
4.4 Compare the (S for the following processes.
(e.) One mole of O
2
from 300 K to 1300 K at 1 atm.
Substituting values for ZrO
2
and limits.
Where a = 30.0, b = 0.0042, & c = -1.7x10
5
.
? A
2
1
2
2
ln
T
T
T
c
bT T a S

+ + = (


|

'
+

'

+ + = (
2 2
5
300
1
1300
1
10 7 . 1 300 1300 0042 . 0
300
1300
ln 0 . 30 S
K at gr
J
S

= (
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-39
4.4 Compare the (S for the following processes.
(f.) One mole of O
2
at 300 K is isothermally compressed from
1 atm to 100 kbars.
Need S = S(T,P) evaluated for T = constant.
VdP dT T C dS
P
E =
For constant T, dT=0.
dP
p
RT
T
dS
1
=
For 1 mole of an ideal gas.
P
RT
V =
T
1
= E
VdP dS E =
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-40
4.4 Compare the (S for the following processes.
(f.) One mole of O
2
at 300 K is isothermally compressed from
1 atm to 100 kbars.

=
2
1
2
1
P
P
S
S
dP
P
R
dS

'
+

'

= (
2
1
ln
P
P
R S
Substituting numerical values.
K mole
J
S 72 . 95
10
1
ln 314 . 8
5
=

'
+

'

= (
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-41
4.6 Compute the (U when 12 liters of Ar at 273 K
and 1 atm are compressed to 6 liters with final
pressure = 10 atm. (a.) Find U=U(P,V) & integrate.
) , ( V P U U =
Compare to.
NdV MdP dU + =
dP V dT V N MdP dU F E + =
dP NV M dT NV dU F E + =
dP T P V dT PV C dU
P
E F E + =
E E PV C NV
P
=
E F F T P V NV M =
P
V
C
N
P
=
E
E
E
F
TV C M
P
=
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-42
4.6 Compute the (U when 12 liters of Ar at 273 K
and 1 atm are compressed to 6 liters with final
pressure = 10 atm. (a.) Find U=U(P,V) & integrate.
P
V
C
N
P
=
E
Using:
T
1
= E
P
1
= F
Using:
R C C
V P
+ =
PdV
R
C
VdP
R
C
dU
V V
+ =
RT PV 1 =
E
E
F
TV C M
P
=
R C
R
V
M
P
= R C
R
P
N
P
=
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-43
4.6 Compute the (U when 12 liters of Ar at 273 K
and 1 atm are compressed to 6 liters with final
pressure = 10 atm. (a.) Find U=U(P,V) & integrate.

+ = (
2
1
2
1
2 1
V
V
V
P
P
V
dV P
R
C
dP V
R
C
U
Simulate 2 step
process, constant
pressure + constant
volume.

+ = (
2
1
2
1
1 2
V
V
V
P
P
V
dV P
R
C
dP V
R
C
U
P
V
(P
1
V
1
)
(P
2
V
2
)

+ = (
2 2
1 1
2 2
1 1
V P
V P
V
V P
V P
V
PdV
R
C
VdP
R
C
U
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-44
4.6 Compute the (U when 12 liters of Ar at 273 K
and 1 atm are compressed to 6 liters with final
pressure = 10 atm. (b.) Use the temperature change.
2
2 2
1
1 1
nRT
V P
nRT
V P
=
1
1 1
2 2
2
T
V P
V P
T =
K T 365 , 1 273
12 1
6 10
2
=

=
T C U
V
( = (
R R U 638 , 1 273 1365
2
3
= = (
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
4-45
4.8 For one mole of nitrogen gas compute and plot
the surfaces that represent the variation with pressure
and volume over the range (1 atm, 22.4 l) to (10 atm,
8.2 l)of (a) the internal energy.
Use the result from 4.6b:
PdV
R
C
VdP
R
C
dU
V V
+ =
? A ) ( ) ( ) , ( ) , ( ) , (
1 1 1 R R
V
V V P P P V
R
C
V P U V P U V P U + = = (
? A
R R
V
V P PV
R
C
V P U = ( ) , (
By analogy
? A
R R
P
V P PV
R
C
V P H = ( ) , (