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# 1

## Centre for Energy

1
Thermodynamic Potentials & Equilibrium
Lecture 3, 26
th
February 2014
Centre for Energy
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Outline
1. The Thermodynamic Potentials
2. Equilibrium Criteria from the Potentials
3. Open Systems & The Chemical Potential
4. Phase Equilibrium Requirements
Text References:
Kyle, Chapters 4.6, 5.1-5.3, 7.1-7.3, 9.3-9.6
Prausnitz, Chapter 2.1-2.8
different sign convention for W
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The Thermodynamic Potentials
Four functions that each contain all the
Each contains same information, but in different
forms choose the one thats convenient
U Internal Energy
PV U H + Enthalpy
TS U A Helmholtz Energy
TS H G Gibbs Energy
Also known as
free energies or
work functions
(symbol F sometimes used)
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The Thermodynamic Potentials
Only changes in the potentials are knowable
unless you have a microscopic model
In practice, datum or reference states are defined
Fundamental EOS model the potentials directly
contain calorific and volumetric properties
U
H A
G
TS
TS
PV
PV
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Independent Variables
Consider the form of the Fundamental Equation
This implies that: (1) S & V are the independent variables
for U and (2) T & P are the first partial derivatives of U
We can consider U for a system at equilibrium
as a surface and its thermodynamic properties
as the slopes, curvatures, etc. of that surface
PdV TdS dU =
dV
V
U
dS
S
U
dU
S V
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
=
) , ( V S U U =
V
S
U
T
|
.
|

\
|
c
c
=
S
V
U
P
|
.
|

\
|
c
c
=
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Changing Potentials & Variables
Differentiate the defining equations for H, A, G:
VdP TdS dH + =
) , ( P S H H =
SdT PdV dA =
) , ( V T A A =
SdT VdP dG = ) , ( P T G G =
Potential choice based on convenient variables
T, P & V easiest to measure G, A used often
Thermodynamic network of partial derivatives
T
C
T
H
T T
S
T
G
P
P P
P
= |
.
|

\
|
c
c
= |
.
|

\
|
c
c
=
|
|
.
|

\
|
c
c 1
2
2
V T
T
P
V
S
|
.
|

\
|
c
c
= |
.
|

\
|
c
c
Maxwell relation
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Potentials & Equilibrium
For a process at constant S & V:
These equations characterise what equilibrium is!
They establish requirements for phase equilibria & stability
0
,
s
V S
dU 0
,
=
V S
dU
At Equilibrium
Similarly:
0
,
s
P S
dH 0
,
=
P S
dH
0
,
s
V T
dA 0
,
=
V T
dA
0
,
s
P T
dG 0
,
=
P T
dG
An equilibrium
state is a local
minimum of the
potential along
a specified path
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Equilibrium Requirements
Consider 2 parts, o & |, of an isolated system
|
o
isolated system
No heat
transfer
No work
done
const. S
const. V
0
,
=
V S
dU At equilibrium:
0
) ( ) ( ) ( ) ( ) ( ) ( ) ( ) (
= + =
| | | | o o o o
dV P dS T dV P dS T dU
0
) ( ) (
= +
| o
dS dS 0
) ( ) (
= +
| o
dV dV
Eliminating dS
(|)
& dV
(|)
:
0 ) (
) (
) ( ) ( ) (
) ( ) ( ) (
=
=
o | o
o | o
dV P P
dS T T dU
) ( ) (
) ( ) (
| o
| o
P P
T T
=
=
Eqbm
requires:
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Thermodynamic Potentials for Open System
Closed System
Internal Energy of a system depends on the number of
moles of each component in that system.
) , ( V S U U =
) , ( P S H H =
) , ( V T A A =
) , ( P T G G =
Open System
) ,.., , , (
1 N
n n V S U U =
) ,.., , , (
1 N
n n P S H H =
) ,.., , , (
1 N
n n V T A A =
) ,.., , , (
1 N
n n P T G G =
Vary moles
of i
th

component
Allow mass
to enter
Relations still hold for open system
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The Chemical Potential
From Calculus, the total differential becomes

=
|
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
=
N
i
i
n V S
i n S n V
dn
n
U
dV
V
U
dS
S
U
dU
j
i i
1
, ,
, ,
i
n V
S
U
T
,
|
.
|

\
|
c
c
=
i
n S
V
U
P
,
|
.
|

\
|
c
c
=

=
+ =
N
i
i i
dn PdV TdS dU
1

Fundamental Eqn
for Open Systems
j
n V S
i
i
n
U
, ,
|
|
.
|

\
|
c
c

Extensive properties
Intensive properties
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The Chemical Potential
Chemical potential can be defined in other ways
j j j j
n P T
i
n V T
i
n P S
i
n V S
i
i
n
G
n
A
n
H
n
U
, , , , , , , ,
|
|
.
|

\
|
c
c
=
|
|
.
|

\
|
c
c
=
|
|
.
|

\
|
c
c
=
|
|
.
|

\
|
c
c
=
Partial
molar
Gibbs
Energy

=
+ + =
N
i
i i
dn VdP TdS dH
1

=
+ =
N
i
i i
dn PdV SdT dA
1

=
+ + =
N
i
i i
dn VdP SdT dG
1

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Closed Heterogeneous System
Consider 2 phases, o & |, in an isolated, 1 component
system. Treat each phase as an open system
|
(open system)
o
(open system)
1 component
isolated system
0
,
=
V S
dU
At equilibrium:
) ( ) ( ) ( ) ( ) ( ) ( ) ( o o o o o o o
dn dV P dS T dU + =
) ( ) ( ) ( ) ( ) ( ) ( ) ( | | | | | | |
dn dV P dS T dU + =
0
) ( ) (
= +
| o
dS dS
0
) ( ) (
= +
| o
dV dV
Extensive quantities
conserved
0
) ( ) (
= +
| o
dn dn
Eliminating dS
(|)
, dV
(|)
& dn
(|)
0 ) ( ) (
) (
) ( ) ( ) ( ) ( ) ( ) (
) ( ) ( ) (
= +
=
o | o o | o
o | o
dn dV P P
dS T T dU
0
) ( ) (
= +
| o
dU dU
mass transfer
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Phase Equilibrium Requirements
1 component, 2 phase system:
vapour
(open system)
liquid
(open system)
N component
isolated system
mass transfer
) ( ) ( | o
T T =
Eqbm requires:
) ( ) ( | o
P P =
) ( ) ( | o
=
N component, vapour-liquid system:
The extra N
equations needed to
solve the standard
flash problem
Eqbm requires:
) ( ) ( V L
T T =
) ( ) ( V L
P P =
) (
1
) (
1
V L
=
) ( ) ( V
i
L
i
=
) ( ) ( V
N
L
N
=

## Eqns for an N component, H -phase system?

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Lecture 3: Core Ideas
1. The Thermodynamic Potentials: U, H, A, G
ALL the information about a system convenience
2. Equilibrium Criteria from the Potentials
0
,
=
P T
dG
0
,
=
V S
dU
0
,
=
V T
dA 0
,
=
P S
dH
4. Phase Equilibrium Requirements
N new equations:
) ( ) ( V
i
L
i
=
) ,.., , , (
1 N
n n P T G G =
j
n P T
i
i
n
G
, ,
|
|
.
|

\
|
c
c
=
3. Open Systems and the Chemical Potential