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Advanced Thermodynamics: Outline

1) The document discusses four thermodynamic potentials - internal energy (U), enthalpy (H), Helmholtz energy (A), and Gibbs energy (G) - which each contain full thermodynamic information about a system and can be used interchangeably depending on convenience. 2) Equilibrium criteria are derived from the potentials, requiring the potentials to be at a minimum or unchanging along specified paths at equilibrium. 3) The chemical potential is introduced to describe open systems and is defined in terms of partial derivatives of the extensive properties with respect to mole amounts of components.

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85 views

Advanced Thermodynamics: Outline

1) The document discusses four thermodynamic potentials - internal energy (U), enthalpy (H), Helmholtz energy (A), and Gibbs energy (G) - which each contain full thermodynamic information about a system and can be used interchangeably depending on convenience. 2) Equilibrium criteria are derived from the potentials, requiring the potentials to be at a minimum or unchanging along specified paths at equilibrium. 3) The chemical potential is introduced to describe open systems and is defined in terms of partial derivatives of the extensive properties with respect to mole amounts of components.

Uploaded by

xx_aleksa_hrvatska_xx
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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1

Centre for Energy


1
Advanced Thermodynamics
Thermodynamic Potentials & Equilibrium
Lecture 3, 26
th
February 2014
Advanced Thermodynamics
Centre for Energy
2
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
2
Advanced Thermodynamics
Centre for Energy
3
The Thermodynamic Potentials
Four functions that each contain all the
thermodynamic information about a system:
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)
Advanced Thermodynamics
Centre for Energy
4
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
3
Advanced Thermodynamics
Centre for Energy
5
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
=
Advanced Thermodynamics
Centre for Energy
6
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
4
Advanced Thermodynamics
Centre for Energy
7
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
Advanced Thermodynamics
Centre for Energy
8
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:
5
Advanced Thermodynamics
Centre for Energy
9
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
Advanced Thermodynamics
Centre for Energy
10
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
6
Advanced Thermodynamics
Centre for Energy
11
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

Advanced Thermodynamics
Centre for Energy
12
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
7
Advanced Thermodynamics
Centre for Energy
13
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?


Advanced Thermodynamics
Centre for Energy
14
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

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