Fall 2014

1

Advanced Chemical Engineering Thermodynamics

CHEG522
Course Instructor: Distinguished and Chair Professor Cor J . Peters

Department of Chemical Engineering
Bu Hasa Building 2.219
The Petroleum Institute
P.O. Box 2533, Abu Dhabi
e-mail: cpeters@pi.ac.ae
August 26, 2014 Advanced Chemical Engineering
Thermodynamics
Basic Thermodynamics


Fall 2014
2

Refreshing Basic Thermodynamics
Contents:

Fundamentals
Properties of Pure Substances
Properties of Mixtures

August 26, 2014
Advanced Chemical Engineering
Thermodynamics


Fall 2014
3

Systems and their Properties (1)
System Material Heat Work
Isolated No No No
Adiabatic No No Yes
Closed No Yes Yes
Open Yes Yes Yes
Interaction System Surrounding
August 26, 2014
Advanced Chemical Engineering
Thermodynamics


Fall 2014
4

Systems and their Properties (2)
Equilibrium
A system is in thermodynamic equilibrium
if there exists no gradients inside the
system or between system and the
surrounding, i.e.,
But, partial equilibrium is possible!
, , , , ,... 0 T P c =
August 26, 2014
Advanced Chemical Engineering
Thermodynamics


Fall 2014
5

P,T-Diagram of Carbon
August 26, 2014
Advanced Chemical Engineering
Thermodynamics


Fall 2014
6

State Properties
State Properties: Depend only on the initial and
final state of a system, e.g.,
DU = U(V
2
,T
2
) - U(V
1
,T
1
)
Also: H, A, G, S, V,

Heat (Q) and work (W) are forms of energy that may
occur when a system undergoes a change of state, and
their amounts depend on the path followed by the
process.

Work = Force x path dW = Fdz dW = -PdV
August 26, 2014
Advanced Chemical Engineering
Thermodynamics


Fall 2014
7

First Law of Thermodynamics
DU = Q + W (macroscopic form)

dU = dQ + dW (differential form)

dU = dQ PdV (reversible process)
August 26, 2014
Advanced Chemical Engineering
Thermodynamics


Fall 2014
8

Second Law of Thermodynamics
Statements:
No apparatus can operate in such a way that its
only effect (in system and surroundings) is to
convert heat absorbed by a system completely
into work.

No process is possible which consists solely in
the transfer of heat from one temperature level to
a higher one.

August 26, 2014
Advanced Chemical Engineering
Thermodynamics


Fall 2014
9

Second Law of Thermodynamics
0
rev
dQ
T
=

State Function!
rev
dQ
dS
T

Entropy
( ) ( ) ( ) 0 S total S System S Surrounding = +
= reversible process > irreversible process
August 26, 2014
Advanced Chemical Engineering
Thermodynamics


Fall 2014
10

P,T-Diagram
August 26, 2014
Advanced Chemical Engineering
Thermodynamics


Fall 2014
11

P,V-Diagram
August 26, 2014
Advanced Chemical Engineering
Thermodynamics


Fall 2014
12

P,v-Diagram Changes of State
August 26, 2014
Advanced Chemical Engineering
Thermodynamics


Fall 2014
13

Fundamental Equations (1)
Reversible Process of a Closed System:
, ,
and
( , , ) constant!
rev
V n S n
n
dU dQ dW
dQ TdS dW PdV
dU TdS PdV U U S V n
U U
dU dS dV
S V
= +
= =
= = =

| | | |
= +
| |

\ . \ .
August 26, 2014
Advanced Chemical Engineering
Thermodynamics


Fall 2014
14

Fundamental Equations (2)
Reversible Process of an Open System:
1 1
1
, ,..., , ,...
, ,
1 2
1
, ,
, ,...,
Ch
( , , ) con
emical Potential
stant!
N N
i
i
N
i
i
V n n S n n i
S V n
N
i i
i
i
N
i
S V n
U U S V n
U U U
dU dS dV dn
S V n
dU TdS PdV
n n n
dn
U
n

=
=
= =
| |

| | | |
= + +
|
| |

\ . \ .
\ .
= +
| |

\ .

August 26, 2014

Advanced Chemical Engineering
Thermodynamics


Fall 2014
15

Fundamental Equations (3)
1
1
1
1
H U+PV, A U-TSand G H-TS
Thermodynamic Func
( , , )
( , , )
( , , )
( , , )
tions:
N
i i
i
N
i i
i
N
i i
i
N
i
i i
i
i
i
i
dU TdS PdV dn
dH TdS VdP dn
dA SdT Pd
U U S V n
H H S P n
A A T V n
G G T P n
V dn
dG SdT VdP dn

=
=
=
=

= +
= + +
=
=
=
=

= +
= + +

August 26, 2014

Advanced Chemical Engineering
Thermodynamics


Fall 2014
16

Example
1 1
1 1
1
1
, ,..., , ,...
, ,
, ,..., , ,...
, ,
( , , )
N N
i
N N
i
N
i i
i
N
i
i
P n n T n n i
P T n
i
P n n T n n i
i
P T n
dG SdT VdP dn
G G G
dG dT dP dn
G G
T P n
G G G
S V
T P
T n
n
P

=
=
= + +
| |

| | | |
= + +
|
| |

\ . \ .
\ .
| |

| | | |
= = =
|
| |

\
.
=
. \ .
\

August 26, 2014

Advanced Chemical Engineering
Thermodynamics


Fall 2014
17

Thermodynamic calculations
P T
dH dT
H H
d
T P
P

| | | |
| |

\ \ .
= +
.
System (p
1
,T
1
) System (p
2
,T
2
) Calculate DH?
Consider closed system H = H(p,T)
System (p
1
,T
1
) System (p
2
,T
2
) Calculate DS?
Consider closed system S = S(p,T)
P T
dS dT
S S
d
T P
P

| | | |
| |

\ \ .
= +
.
August 26, 2014
Advanced Chemical Engineering
Thermodynamics


Fall 2014
18

Maxwell relations
P T
S
dS dT
S
dP
T P

| |
|

| |
= +
|
.

. \ \
and
and
and also
T P T V
P T
P T
T P P T
p T
G G
dG SdT VdP dG dT dP
T P
G G
S V
T P
S V S P
P T V T
G V G S
T P T P T P

| | | |
= + = +
| |

\ . \ .

| | | |
= =
| |

\ . \ .
( (

| | |

| | | | | | | |
= =
| | | |

\ . \
| | | | |
= =
| |
. \ .
| | ( (

\ . \ . \ . \ .

.

August 26, 2014
Advanced Chemical Engineering
Thermodynamics


Fall 2014
19

Helmholtz relations
and
T
T T
P
T
U
dU dT dV dU TdS Pd
U
V
U P
T P
V
V
T
T
S
T P
V

| |
= + =
|

\ .

| |
= =
|

| |
|

\ .

| | | |

| |

\ . \ .

\ .
and
T
T P
V
T
H
dH dT dP dH TdS Vd
H
P
H V
V T
P
P
T
T
S
T V
P

| |
= + = +
|

\ .

| |
= + =
|

| |
|

\ .

| | | |

\
| |

\ . \ . .
August 26, 2014
Advanced Chemical Engineering
Thermodynamics


Fall 2014
20

Gibbs-Helmholtz relations
2 2
2
0
2
2
1
Similarly:
/
Application:
( ) ln ( )
Als
/
/
o:
P
P
V
P
G G TS G
T
G T H
T T T
G T H
T T
G T RT K T
A
T T
T U
T T

| |
= = =
|

\ .

| |
=
|

\ .
=

| |
=
|

\ .

| |

|

\ .
August 26, 2014
Advanced Chemical Engineering
Thermodynamics


Fall 2014
21

Phase Rule
Number of degrees freedom =
number of variables number of equations
Heterogeneous system with N components and phases:
...
...
... 1,...,
2 ( 1) ( 1 2 )
i i i
T T T
P P P
i N
N N F N




= = =
= = =
= = = =
= + = +
August 26, 2014
Advanced Chemical Engineering
Thermodynamics


Fall 2014
22

Ideal gas and Heat capacities
Ideal gas: or
T
PV n RT Pv RT = =
V Total volume and v Molar volume
and


v
V
V
P
P
P
P
p
V
V
u h
c c
T T
du Tds Pdv
dh Td
u s
T c
T T
h s
T s c
T
dP
T
v

| | | |
= =
| |

\ . \ .

| | | |
= =
| |

| | | |

| |

\ . \ .

\ . \ .
=
= +
August 26, 2014
Advanced Chemical Engineering
Thermodynamics


Fall 2014
23

Putting the pieces together (1)
2 2
1 1
and
P
P P
T
T
p T
P
P
P
P
h h s v
T c v T
T T
v
h c dT v T dP
T
T P

| | | |
= = =
| |

\ . \ .
(

| |
= +
| (

\ .

| | | |
| |

\ . \

.

System (p
1
,T
1
) System (p
2
,T
2
) Calculate Dh?
P T
dh dT
h h
d
T P
P

| | | |
| |

\ \ .
= +
.
August 26, 2014
Advanced Chemical Engineering
Thermodynamics


Fall 2014
24

Putting the pieces together (2)
2 2
1 1
and
P
P
P
T P
P
P
T P
T
v
T c
T
c v
s dT dP
T T
s s
T P

| |
= =
|

\

| | | |
|
.

| |
=
|
|

\ . \ .

\ .

System (p
1
,T
1
) System (p
2
,T
2
) Calculate Ds?
P T
ds dT
s s
d
T P
P

| | | |
| |

\ \ .
= +
.
August 26, 2014
Advanced Chemical Engineering
Thermodynamics