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Thermodynamic Relations PDF

The document discusses key thermodynamic relations and formulas. It covers: 1) Mathematical relations for partial derivatives used in thermodynamics. 2) Definitions of important thermodynamic potentials and functions, including the Helmholtz and Gibbs functions. 3) Maxwell relations relating changes in variables like pressure, temperature, and volume. It provides this information to summarize important concepts in thermodynamics.

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Annshun Kiat
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© © All Rights Reserved
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60 views10 pages

Thermodynamic Relations PDF

The document discusses key thermodynamic relations and formulas. It covers: 1) Mathematical relations for partial derivatives used in thermodynamics. 2) Definitions of important thermodynamic potentials and functions, including the Helmholtz and Gibbs functions. 3) Maxwell relations relating changes in variables like pressure, temperature, and volume. It provides this information to summarize important concepts in thermodynamics.

Uploaded by

Annshun Kiat
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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Thermodynamic Relations: Summary Notes

A Few Useful Mathematical Formulas

z
y

y
x

x
z

=
x

y
=
z
=

1
!
y
z x

x
y

!
w

EME2146. Trimester 2, 2014-2015

z
x
y
z

!
y

!
w

-1-

Thermodynamic Relations: Summary Notes

Helmholtz and Gibbs Functions

Helmholtz function:
A = U TS
Gibbs function:
G = H TS

Internal energy U
Enthalpy H = U + pV
Entropy S =

Q
T

!
rev

First Law of Thermodynamics:


dU = Q W
Reversible process: heat transfer Q = T dS, work done W = pdV

dU = T dS p dV
dH = T dS + V dp
dA = S dT p dV
dG = S dT + V dp

EME2146. Trimester 2, 2014-2015

-2-

Thermodynamic Relations: Summary Notes

Maxwell Relations

p
S

V
S

S
V

S
p

=
p

=
T

T
=
V
T
p

p
T

V
=
T

EME2146. Trimester 2, 2014-2015

-3-

Thermodynamic Relations: Summary Notes

Other Relations

U
S

H
S

A
T

G
T

U
V

A
V

H
p

G
p

=
S

=
S

=T
p

= S
p

= p
T

=V
T

EME2146. Trimester 2, 2014-2015

-4-

Thermodynamic Relations: Summary Notes

First Order Phase Transformation:


Clausius-Clapeyron Equation

Defining relations:
g1 = g2
g1
T

g1
p

6=
p

6=
T

g2
T

g2
p

!
T

Examples: melting, evaporation, sublimation

Clausius-Clapeyron equation:
dp
dT

=
1,2

h2 h1
(v2 v1 ) T

EME2146. Trimester 2, 2014-2015

-5-

Thermodynamic Relations: Summary Notes

Specific Heats, Expansivity, Compressibilities

q
Cv lim
=
Tv 0 Tv
q
=
Tp 0 Tp

Cp lim
1

v
T

1
T
v
s

1
v

u
T

h
T

!
p

v
p
v
p

!
T

!
s

Cp
T
=
Cv
s

EME2146. Trimester 2, 2014-2015

-6-

Thermodynamic Relations: Summary Notes

Internal Energy, Enthalpy, Entropy:


Some Useful Relations

"

du = Cv dT + T

p
T

dh = Cp dT + v T
dT
p
ds = Cv
+
T
T

v
dT

ds = Cp
T
T

Cv
ds =
T

T
p

p dv
v

v
T

!
dp
p

dv
v

dp
p

Cp
dp +
T
v

EME2146. Trimester 2, 2014-2015

T
v

dv
p

-7-

Thermodynamic Relations: Summary Notes

Ideal Gases

pV = mRT,

pV = nRT

u = u (T )
h = h (T )
Cv = Cv (T )
Cp = Cp (T )
Cp Cv = R
u2 u1 =
h2 h1 =
s2 s1 =
s2 s1 =

Z T2
T1

Z T2
T1

Z T2
T1

Z T2
T1

Cv (T ) dT
Cp (T ) dT
Cv (T )
v2
dT + R ln
T
v1
Cp (T )
p2
dT R ln
T
p1

EME2146. Trimester 2, 2014-2015

-8-

Thermodynamic Relations: Summary Notes

Real Gases

conditions at the critical point:


p
v

2p
v 2

= 0,

T cr

=0

T cr

van der Waals equation of state:


p=

RT
a
2
vb v

pr =

3
8Tr
2
3vr 1 vr

pr =

p
,
pcr

Tr =

T
,
Tcr

vr =

v
vcr

to use the Generalized Charts:


pv
Z=
RT
h2 h1 = (h2 h2 ) + (h2 h1 ) + (h1 h1 )
s2 s1 = (s2 s2 ) + (s2 s1 ) + (s1 s1 )

EME2146. Trimester 2, 2014-2015

-9-

Thermodynamic Relations: Summary Notes

Third Law of Thermodynamics

Nernsts Heat Theorem. In the neighborhood of absolute zero, all reactions in a liquid
or solid in internal equilibrium take place with no change in entropy.
Plancks Statement. The entropy of every solid or liquid substance in internal equilibrium at absolute zero is itself zero.
Modern Statement. The entropy of a perfect crystal is zero at absolute zero temperature.

EME2146. Trimester 2, 2014-2015

-10-

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