Thermodehoff 04

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
)
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:
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
)
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
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:
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
T
S
H
P
=
'
+
'
V
P
H
S
=
'
+
'
P S
S
V
P
T
'
+
'
'
+
'
Maxwell relation:
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
S
T
F
V
=
'
+
'
P
V
F
T
=
'
+
'
V T
T
P
V
S
'
+
'
'
+
'
Maxwell relation:
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
S
T
G
P
=
'
+
'
V
P
G
T
=
'
+
'
P T
T
V
P
S
'
+
'
'
+
'
Maxwell relation:
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
4-11
Energy Functions
Internal Energy U
Enthalpy H = U + PV
Helmholtz Free Energy F = U TS
Gibbs Free Energy G = H TS
4-12
Combined 1
st
& 2
nd
Laws
dU = TdS PdV + HW
/
dH = TdS + VdP + HW
/
dF = SdT PdV + HW
/
dG = SdT + VdP + HW
/
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
=
'
+
'
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
'
+
'
'
+
'
4-15
State Functions=f(T,P)
(Table 4.5)
VdP SdT dG + =
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
'
+
'
'
+
'
=
4-17
(Table 4.5)
dP V dT V dV F E =
VdP SdT dG + =
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
'
+
'
'
+
'
4-19
(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 + =
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.
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
4-22
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
4-23
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
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
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
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
4-27
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
4-28
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
4-29
(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
4-30
(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
4-31
(c.) One mole of ZrO
2
from 300 K to 1300 K at 1 atm.
VdP dT T C dS
P
E =
dT T C dS
P
=

= (
2
1
T
T
P
dT T C S
4-32
2
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
4-33
2
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
4-34
(d.) One mole of ZrO
2
at 300 K is isothermally compressed
from 1 atm to 100 kbars.
VdP dT T C dS
P
E =
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
4-35
(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
4-36
(e.) One mole of O
2
VdP dT T C dS
P
E =
dT T C dS
P
=

= (
2
1
T
T
P
dT T C S
4-37
(e.) One mole of O
2
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
4-38
(e.) One mole of O
2
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
= (
4-39
(f.) One mole of O
2
at 300 K is isothermally compressed from
1 atm to 100 kbars.
VdP dT T C dS
P
E =
dP
p
RT
T
dS
1
=
For 1 mole of an ideal gas.
P
RT
V =
T
1
= E
VdP dS E =
4-40
(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
=
'
+
'
= (
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
=
4-42
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
=
4-43

+ = (
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
4-44
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
= = (
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 = ( ) , (

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09/19/2001 Notes from R.T.

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

+ = ( 300 1300 0295 . 0

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