1

(Q and/or W)

dni = 0

(Q and/or W)

2
First law for a closed system:

dnU dQ rev dWrev

In Thermodynamics I:

dWrev P dnV and dQ rev T dnS

Together these three equations give

dnU TdnS PdnV (1.1)

P, V, T, U, and S are primary thermodynamic

properties. 3
Additional thermodynamic properties arise
from definition in relation to these primary
properties :

Enthalpy

H U PV (1.2)

Helmholtz free energy:

A U TS (1.3)

Gibbs free energy:

G H TS (1.4)
4
Upon multiplication by n, eqs. (1.2) (1.4) may
be differentiated to yield:

dnH TdnS nVdP (1.5)

dnA nSdT PdnV (1.6)

dnG nVdP nSdT (1.7)

5
Application of these equations is to one mole
(or to a unit mass) of homogeneous fluid of
constant composition:

dU TdS PdV (1.8)

dH TdS VdP (1.9)

dA SdT PdV (1.10)

dG VdP SdT (1.11)

6
If F = F(x, y), the total differential of F is:

F F
dF dx dy
x y y x

dF Mdx Ndy (1.12)

with

F F
M and N
x y y x
7
Euler's reciprocity relation reads:

M 2F

y x y x
M N
(1.13)
2 y x x y
N
F

x y x y

When F is a function of x and y, the right side of

eq. (1.12) is an exact differential expression ;
because eq. (1.13) must be satisfied, it serves as
the criterion of exactness.
8
 M N
dF Mdx Ndy
y x x y

dU TdS PdV T P
(1.14)
V S S V

T V
dH TdS VdP (1.15)
P S S P

S P
dA SdT PdV (1.16)
V T T V

S V
dG VdP SdT (1.17)
P T T P
9
As a function of T and P, S can be expressed as

H HT,P

Total differential of the above equation is

H H
dH dT dP (1.18)
T P P T

10
(H/T)P is obtained from the definition of CP:

H
CP (1.19)
T P

(H/P)T is obtained by dividing eq. (1.9) with dP

for constant temperature:

H T S V
(1.20)
P T P T

11
Combining eq. (1.20) with Maxwell equation
(1.17):

H V T V
(1.21)
P T T P

Introducing eqs. (1.19) and (1.21) into eq. (1.18)

results in :

V
dH CPdT V T dP (1.22)
T P
12
 As a function of P and T, we may express:

S ST,P

Total differential of the above equation is

S S
dS dT dP (1.23)
T P P T

13
(S/P)T is obtained from the Maxwell eq. (1.17)

S V
(1.17)
P T T P

(S/T)P is obtained by dividing eq. (1.9) with dT

for constant pressure:

H T S
(1.24)
T P T P

14
Combining eq. (1.19) with (1.24):

S CP (1.25)

T P T

Introducing eqs. (1.17) and (1.25) into eq.

(1.23) results in :

dT V
dS CP dP (1.26)
T T P

15
 U H PV

U H P V V

P T P T P T

Then, by Eq. (1.21):

U T V P V (1.27)

P T T P P T
16
 RT Vig R
V
ig
(1.28)
P T P P

Substituting these equations into Eqs. (1.22)

and (1.26) reduces them to:

dH C dT
ig ig
P (1.29)

dT dP
dS C
ig ig
P R (1.30)
T P
17
f(P, V, T) = 0 V = V(T, P)

V V
dV dT dP
T P P T

18
 V V
dV dT dP
T P P T

Volume expansivity:
1 V

V T P

Isothermal compressibility:

1 V

V P T

19
 S V S V

P T T P P T
(1.17)

H V T V H 1 T V

P T T P P T
(1.21)

U T V P V U P T V

P T T P P T P T
(1.27)
20
When (V/T)P is replaced in Eqs. (1.22) and
(1.26) in favor of the volume expansivity,
they become:

dH CPdT 1 T V dP (1.31)

dT
dS CP V dP (1.32)
T

Since and V are weak functions of pressure

for liquids, they are usually assumed constant
at appropriate average values for integration
of the final terms of Eqs. (1.31) and (1.32). 21
Example 6.1
Determine the enthalpy and entropy changes of
liquid water for a change of state from 1 bar and
298.15 K to 1000 bar and 323.15 K. The
following data for water are available:

22
Solution

P
b

1 a

T
(Selasa, 16-8-2017)
23
 U U
U UT, V dU dT dV
T V V T

(1.33)

S S
S ST, V dS dT dV
T V V T

(1.34)

24
We begin with Eq. (1.8): dU TdS PdV

At constant V:

U T S

T V T V

S C V
From the definition of CV:
T V T
U
CV (1.35) (1.36)
T V

25
At constant T:

U T S P

V T V T

U T P P
Equation (1.20):
V T T V

S P (1.37)

V T T V

26
Combining eqs. (1.33), (1.35), and (1.37) gives:

P
dU CVdT T P dV (1.38)
T V

Combining eqs. (1.20), (1.34), and (1.36) gives:

P
dS CV dT dV (1.39)
T V

27
Another fundamental property relation:

G 1 G (1.40)
d dG 2
dT
RT RT RT
(1.4)
(1.11)

G 1
V dP S dT H TS
d 2
dT
RT RT RT

G V H
d dP 2
dT (1.41)
RT RT RT
28
From eq. (1.41)

V G RT
(1.42)
RT P T

H G RT
T (1.43)
RT T P

Other properties are given by :

S H G U H PV
and
R RT RT RT RT RT
29
The Gibbs energy when given as a function
of T and P therefore serves as a generating
function for the other thermodynamic
properties, and implicitly represents
complete property information.

30
The definition for the generic residual property is:

MR M Mig (1.44)

where M and Mig are the actual and ideal-gas

properties are at the same temperature and
pressure.
M is the molar value of any extensive
thermodynamic property, e.g., V, U, H, S, or G.
31
Residual Gibbs energy

GR G Gig (1.45)

The residual volume:

ZRT RT
V VV
R

ig

P P

RT
V
R
Z 1 (1.46)
P
32
Equation (1.41):
G V H
d dP 2
dT
RT RT RT

for the special case of an ideal gas:

Gig Vig Hig

d dP 2
dT
RT RT RT

Subtracting this equation from Eq. (1.41) gives:

GR VR HR
d dP 2
dT (1.47)
RT RT RT
33
This fundamental property relation for residual
properties applies to fluids of constant
composition. Useful restricted forms are:

VR GR RT
(1.48)
RT P T

HR GR RT
T (1.49)
RT T P

34
Gibbs energy: G H TS

For ideal gas: G H TS

ig ig ig

by difference: GR HR TSR

The residual entropy is therefore:

SR HR GR
(1.50)
R RT RT
35
The GR serves as a generating function for the
other residual properties, and here a direct link
with experiment does exist.

It is provided by Eq. (1.48), written:

VR GR RT
(1.48)
RT P T

VR
dG RT
R
(constant T)

RT dP

GR VR
d dP (constant T)
RT RT
36
Integrating from P = 0 to arbitrary P

GR P VR
dP (constant T) (1.51)
RT 0 RT

At the lower limit GR/RT is equal to zero

because the zero-pressure state is an ideal-
gas state.

37
Introducing eq. (1.46) to equation (1.51) yields:

GR P 1 RT
Z 1dP (constant T)
RT 0 RT P

GR P dP
Z 1 (constant T) (1.52)
RT 0 P

38
According to eq. (1.49), HR/RT can be obtained
by differentiating Eq. (1.52) with respect to
temperature.

HR GR RT
T (1.49)
RT T P

HR P
Z dP (1.53)
T (constant T)
RT 0 T P P

39
The residual entropy is found by combination
of Eqs. (1.50), (1.52), and (1.53):

SR P
Z dP P
T Z 1dP (const T)
RT 0 T P P 0

(1.54)

40
RESIDUAL PROPERTY FROM VIRIAL EOS

For two-term virial EOS:

BP BP
Z 1 Z 1
RT RT

R
G P
B
From eq. (1.47): dP (constant T)
RT 0 RT

We get:
R
G BP (1.55)

RT RT
41
Eqs. (1.49) and (1.55):

HR GR RT BP
T T
RT T P T RT P

BP P B
T
RT RT T P
2

HR P B dB
(1.56)
RT R T dT

42
 R R R
S H G (1.50)

R RT RT

H R
P B dB GR BP

RT RT
RT R T dT
(1.56) (1.55)

SR P dB
(1.57)
R R dT
Senin, 14-8-2017
43
RESIDUAL PROPERTY FROM CUBIC EOS

Eqs. (1.52) - (1.54) are not compatible with

pressure-explicit eos, and must be transformed
so that V is the variable of integration:

ZRT (1.58)
P
V

RT ZRT
dP dZ 2 dV (constant T)
V V

dP dZ dV
(constant T) (1.59)
P Z V
44
Residual Gibbs energy

Introducing eq. (1.59) to eq. (1.52):

GR P dZ dV
Z 1 (constant T)
RT 0 Z V

GR Z dZ V dV
Z 1 Z 1 (constant T)
RT 1 Z V

GR V
Z 1 (constant T)
Z 1 ln Z dV
RT V V
(1.60)
45
Residual Enthalpy

GR VR HR
d dP 2
dT (1.47)
RT RT RT

HR VR GR
2
dT dP d
RT RT RT

Division by dT and restriction to constant V gives

HR VR P GR RT

RT 2
RT T V T V
46
Differentiation of eq. (1.58) gives

P ZR RT Z

T V V V T V

Differentiation of eq. (1.60) gives

GR RT Z 1 Z
V
1 Z
dV
T V T V Z T V V T V

47
Substitution leads to

HR V
1 Z
Z 1 T dV (1.61)
RT V T V

The residual entropy is found from eq. (1.50):

SR V
1 Z V
dV
ln Z T dV Z 1
R V T V V

(1.62)

48
Generalized eos

RT a
P
V b V b V b

R2 Tc2
a a
Pc

R Tc
b b
Pc

49
 PARAMETERS FOR CUBIC EOS

EOS a b
vdW 1 0 0 27/64 1/8
RK RK 1 0 0.42748 0.08664
SRK SRK 1 0 0.42748 0.08664
PR PR 1 + 2 1 - 2 0.45724 0.07779

1 2
RK T r

SRK = [1 + (0.48508 + 1.5517 - 0.15612) (1 - TR0.5]2

PR= [1 + (0.37464 + 1.54226 - 0.26992) (1 - TR0.5]2

50
GR V b a V b
Z 1 ln Z ln
RT V bRT V b
(1.63)

HR a V b
Z 1 T ln
RT bRT T V V b
(1.64)

SR V b a V b
ln Z ln ln
R V bR T V V b
(1.65)
51
Van der Waals EOS

GR V b a
Z 1 ln Z ln (1.66)
RT V RTV

HR a
Z 1 (1.67)
RT RTV

SR V b
ln Z ln (1.68)
R V
52
RK and SRK EOS

GR V b a V
Z 1 ln Z ln ln (1.69)
RT V bRT V b

H R
a V
Z 1 T ln (1.70)
RT bRT T P V b

SR V b a V
ln Z ln ln (1.71)
R V bR T P V b
53
 PR EOS

GR V b a V 0.4142b
Z 1 ln Z ln ln
RT V 2.8284bRT V 2.4142b
(1.72)

HR a V 0.4142b
Z 1 T ln
RT 2.8284bRT T P V 2.4142b
(1.73)

S R
V b a V 0.4142b
ln Z ln ln
R V 2.8284bR T P V 2.4142b
(1.74)
54
 12

RK T 1 2 Tc

RK EOS
T
r

0.5 c
T 0.5

1.5
T P T

SRK and PR EOS

SRK 1 0,48508 1,55171 0,15613
2
2
1 Tr0 ,5

1 f 1 T
0 ,5 2
r

21 f 1 T 0 ,5 0.5f 1
0.5

T P
r
Tc T
55
EXAMPLE 2

Find GR, HR, and SR for n-butane gas at 500 K and

50 bar as given by RK eos.

SOLUTION

For n-butane:
Tc = 425.1 K T/Tc = 1.1759
Pc = 37.96 bar

R = 0.083145 L bar mol-1 K-1

= 8.314 J mol-1 K-1 56
a
0.42748 0.08314 425.2
2 2

14.068
37.96

b
0.08664 0.08314 425.2
0.0807
37.96

1.1759 0.5 0.9222

T 0.5

0.5 c 0.5 425 .1 0.5
4
1.5 1.5
9.22 10
T P T 500

RT 0.08314 500
V0 0.8314
P 50
57
Vi
RT
b
a Vi1 b
P P Vi1 b Vi1 b

i Vi (L/mol) error
0 0.8314
1 0.6552 2.69E-01
2 0.6030 8.67E-02

8 0.5698 4.48E-04
9 0.5697 1.91E-04
10 0.5697 8.17E-05

Z
PV

50 0.5697
0.6852
RT 0.08314 500
58
GR V b a V
Z 1 ln Z ln ln 0.8067
RT V bRT V b

H R
a V
Z 1 T ln 1.0832
RT bRT T P V b

SR V b a V
ln Z ln ln 0.7869
R V bR T P V b

G (0.8067)(8.314)(500) 3353.5 J mol

R

HR (1.0832)(8.314)(500) 4503.03 J mol

SR (0.7869)(8.314) 6.54 J / mol / K 59

TWO-PHASE SYSTEMS

60
61
62
During - phase transition:
T = T dT = 0
P = P dP = 0
V < V dV 0

dnU TdnS PdnV 0

dnH TdnS nVdP 0

dnA nSdT PdnV 0

dnG nVdP nSdT 0

63
 For vapor-liquid equilibrium:
d(nG) = 0
For a closed system, n is
constant:
dG = 0

G = G (1.75)

64
If T of the system is changed, then P must also
change if the two phases continue to coexist in
equilibrium.
Because eq. (1.75) applies throughout the
change,
dG = dG

V dPsat S dT V dPsat S dT

dPsat S S S


dT V V V
65
Integration of eq. (1.9) for this change yields the
latent heat of phase transition:

H TS (1.76)

Substituting this eq. to the previous eq.:

dPsat H
(1.77)
dT TV

This is the Clapeyron equation

66
For phase transition from liquid (L) to vapor (V):

dPsat HLV
(1.78)
dT TVLV

But VLV RT Z LV

Psat
Combination of the last two equations:

d lnPsat HLV
(1.79)
dT RT 2 Z LV
d ln Psat HLV
(1.80)
d1 T R Z LV

67
Over a small range of T, the right hand side of
eq. (1.80) can be assumed constant, and eq.
(1.80) is integrated to yield:

HLV 1
lnPsat constant
RZ T
LV

or B (1.81)
lnP sat
A
T
where A and B are constants for given species.

68
The previous equation gives a rough
approximation of the vapor pressure relation
for the entire temperature range from the
triple point to the critical point.
A more satisfactory equation for general use is
the Antoine equation:

B
lnP sat
A (1.82)
T C

The values of constants A, B, and C are

available for large number of species.

69
Two-Phase Liquid/Vapor Systems

nV nL VL nV V V

V x L VL x V V V

V 1 x V VL x V VV
V

M 1 x V ML x VMV (1.83a)
L

M ML x VMLV (1.83b)
70
THERMODYNAMIC DIAGRAMS

The most common diagrams are:

Temperature/entropy,
Pressure/enthalpy (usually In P vs. H), and
Enthalpy/entropy (called a Mollier
diagram).

71
72
73
74
75
76
TEMPERATURE (F)

77
ENTROPY

78
SPECIFIC VOLUME

79
 MOLLIER DIAGRAM

80
81
Soal nomor
6.14(e)
6.16(e)
6.17

82