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# Chapter 1

FUNDAMENTA
L EQUATIONS

(Q and/or W)

(Q and/or W)

## A closed system is one that does not

exchange matter with its surroundings,
although it may exchange energy.
dni = 0(i = 1, 2, ..)

(1.1)

## No internal energy transported across

boundary.
All energy exchange between a closed
system and its surroundings appears as
heat and work.
The total energy change of the
surroundings equals the net energy
transferred to or from it as heat and

dU TdS PdV

(1.2)

dU TdS PdV

(1.3)

## th T dS = dQrev : heat absorbed by the system

- P dV = dWrev : work done by the system

dU TdS PdV

(1.4)

## The internal energy change can be

calculated by integrating eq. (1.2):
S2

V2

U U2 U1 TdS PdV
S1

V1

(1.5)

dUS,V 0

(1.6)

## At constant S and V, U tends toward a

minimum in an actual or irreversible
process in a closed system, and
remains constant in a reversible
process.

ENTHALPY
Definition:
H U PV

(1.
7)

dH dU PdV VdP

to

## dH TdS PdV PdV VdP

dH TdS VdP

(1.
r a closed system at constant S and P : 8)
(1.
dHS,P 0
9)

## ELMHOLTZ FREE ENERGY

the Helmholtz free energy (A) is a
thermodynamic potential that measures
the useful work obtainable from a
closed system at a constant temperature
and volume.
Definition:
A U TS

dA dU TdS SdT

(1.1
0)

TdS SdT
dA TdS PdV

dA SdT PdV

(1.1
1)

dAT,V 0

(1.1
2)

## A = the maximum amount of work

extractable from a thermodynamic
process in which temperature and
volume are held constant.
Under these conditions, it is minimized at

## GIBBS FREE ENERGY

Gibbs free energy (G) is a
thermodynamic potential that measures
the "useful" or process-initiating work
obtainable from a thermodynamic system
at a constant temperature and pressure
(isothermal, isobaric).
The Gibbs free energy is the maximum
amount of non-expansion work that can
be extracted from a closed system; this
maximum can be attained only in a

Definition:
G H TS

(1.1
3)

dG dH TdS SdT

## Combining the above equation with eq.

dG TdS VdP TdS SdT

dG VdP SdT

(1.1
a closed system at constant P and T : 4)
dGT,P 0

(1.1
5)

MAXWELL EQUATION
= F(x, y), the total differential of F is:
F
F

dF
dy
dx
x y
y x
dF Mdx Ndy

with
F

x
F
N

(1.1
6)

## urther differentiation yields

2F
M

y x xy

x y xy

x
x

dF Mdx Ndy
Hence from equation:

we obtain:
N
M

y x x

(1.1
7)

Resume:
(1.3) dU TdS PdV

(1.
8)

dH TdS VdP

1)
(1.1 dG VdP SdT
4)

T P

V S
S
T V

P S S
S

(1.19)

(1.20)

S V

P T
T

(1.18)

(1.21)

H H T,P

H
H

dH
dT
dP
T P
P T

(1.22)

H

CP

T P

(1.23)

## P)T is derived from fundamental equation:

dH TdS VdP

(1.
8)
rentiation with respect of P at constant T yield
H T S V

(1.24)

H V T V

P T
T

(1.25)

V

dH CPdT V T
dP
T P

(1.26)

## ntropy as a Function of T and P

function of P and T, we may express:
S S T,P

S
S

dS
dT
dP
T P
P T

(1.27)

S V

P T
T

(1.21)

## T)P is derived from fundamental equation:

dH TdS VdP

(1.
8)
rentiation with respect of T at constant P yield
H T S

(1.28)

S CP

T P T

(1.29)

dT V
dS CP
dP
T T P

(1.30)

## ernal Energy as a Function of P

The pressure dependence of the internal
energy is obtained by differentiation of
the equation
U H PV
U H P V V

P T P T P T
H V T V

P T
T

U T V P V

P T
T P P

(1.31)

IDEAL GAS
RT
V
P

Vig

ig

P
P

(1.32)

From eq. (1.26)

ig

V
ig
ig
ig
dP
dH CP dT V T
T P

P

ig
P

dHig CPigdT

ig

(1.33)

Penjelasan:
RT
V
P

R
1

dV dT RT 2 dP
P
P

ig

ig

R
RT
dV dT 2 dP
P
P
ig

## dVig RdT RTdP R RTdP

2
2
dT PdT P dT P P dT

dVig R

dT P

Vig

P
P

(P konstan)

From eq. (1.31)
ig
dT

ig
ig
dS CP
dP
T T P

dT dP
dS C
R
T
P
ig

ig
P

(1.34)

## Kalau sistem mengalami proses dari keadaan

(T1, P1) ke (T2, P2), maka perubahan entropynya
Sig
2

T2

P2
dT
dP
ig
ig
igdS CP T R P
T1
P1
S1

T2
P2

S S S C ln
Rln
T1
P1
ig

ig
2

ig
1

ig
P

## al Energy and Entropy as Functions of T

Temperature and volume often serve as
more convenient independent variables
than do temperature and pressure.
The most useful property relations are
then for internal energy and entropy.
Required here are the derivatives (U/T)V,
(U/V)T, (S/T)V, and (S/V)T.

dU TdS PdV

At constant V:
U T S

T V T

U

CV

S CV

T V T

(1.35)

At constant V:
U T S P

V T V T
Equation (1.20):
S

U T P P

V T T V
(1.36)

U U T,V

U
U

dU
dT
dV
T V
V T

S S T,V

S
S

dS
dT
dV
T V
V T

## The partial derivatives in these two

equations are given by Eqs. (1.20), (1.35),
(1.36), and the definition of CV.
P

(1.37)
dU CVdT T
P dV
T V
P

dS CVdT
dV
T V

(1.38)

## The fundamental property relations for

homogeneous fluids of constant composition
given by Eqs. (1.3), (1.8), (1.11), and (1.14)
show that each of the thermodynamic properties
U, H, A, and G is functionally related to a special
pairdG
ofvariables.
VdP SdT In particular
(1.14
)
presses the functional relation:

G G P,T
Thus the special, or canonical variables for the
Gibbs energy are temperature and pressure.
Since these variables can be directly measured
and controlled, the Gibbs energy is a
thermodynamic property of great potential

## An alternative form of Eq. (1.14), a

fundamental property relation, follows
from the mathematical identity:
d G 1 dG G dT

RT2
RT RT

dG VdP SdT

## Substitution for dG by Eq. (1.14) and for

G by Eq. (1.13) gives:
d G 1 VdP SdT H TS dT

RT
RT2

RT

G
V
H

d
dP 2 dT
RT
RT RT

(1.39)

Penjelasan:
d G 1 d G 1

RT R T

1 1
1
dG

G
d

R T
T

1 1
G
dG 2 dT
R T
T

1
G
dG 2 dT
RT
RT

1
1
1
d T 2 dT
T
T

V G RT

RT
P

(1.40)

H
G RT

T
RT
T

(1.41)
P

## When G/RT is known as a function of T

and P, V/RT and H/RT follow by simple
differentiation. The remaining properties
are given by defining equations. In
S H G
U H PV
particular,

and
R RT RT

RT RT RT

Penjelasan:
d G V dP H dT

RT2
RT RT
d G RT V dP H dT V H dT

2
2
dP
RTdP RT dP RT RT dP
Untuk T konstan, dT = 0
d G RT V

dP
RT

(T konstan)

V d G RT

RT
dP

V G RT

RT
P

(T konstan)

## Thus, when we know how G/RT (or G) is

related to its canonical variables, T and P,
i.e., when we are given G/RT = g(T, P), we
can evaluate all other thermodynamic
properties by simple mathematical
operations.
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.

RESIDUAL PROPERTY
No experimental method for the direct
measurement of numerical values of G or
G/RT is known.
However, the concept of the Gibbs energy
as a generating function for other
thermodynamic properties carries over to
a closely related property for which

## definition for the generic residual property is:

MR M Mig

(1.42)

where M and Mig are the actual and idealgas 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.

GR G Gig

(1.43)

## where G and Gig are the actual and the

ideal-gas values of the Gibbs energy at
the same temperature and pressure.
Other residual properties are defined in
an analogous way. The residual volume,
for example, is:
RT ZRT RT
R
ig
V V V V

P
P
P
RT
V Z 1
P
R

(1.44)

Equation (1.39):
G
V
H

d
dP 2 dT
RT
RT RT
Can be written for the special case of an
ideal gas:
Hig
Gig Vig
d
dP 2 dT

RT
RT RT

HR
GR VR
d
dP 2 dT
RT
RT RT

(1.45)

Penjelasan:
G
V
H

d
dP 2 dT
RT
RT RT
Hig
Gig Vig
d
dP 2 dT

RT
RT RT

()

H Hig
G Gig V Vig
d
dP
dT

2
RT
RT
RT
GR VR
HR
d
dP 2 dT
RT
RT RT

## This fundamental property relation for

residual properties applies to fluids of
constant composition. Useful restricted
forms are:
VR GR RT

RT
P
R

(1.46)
T

G
T

H
RT

RT
T

(1.47)

## The defining equation for the Gibbs

energy:
G H TS
For the special case of an ideal gas:
Gig Hig TSig
by difference:
GR HR TSR

R

S H G

R RT RT

(1.48)

## Thus the residual Gibbs energy serves as a

generating function for the other residual
properties, and here a direct link with
experiment does exist.
It is provided by Eq. (1.46), written:
R

d G

V
RT

RT
dP
R

GR VR
d
dP
RT RT

(constant T)

(constant T)

## Integration from zero pressure to

arbitrary pressure P yields:
GR P VR
dP
RT 0 RT

(constant T)

(1.49)

## where at the lower limit GR/RT is equal to

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

Penjelasan:
R
R
G
V

d
dP
RT RT
GR

(constant T)

V
G
R d RT RTdP(constant T)
0
Gig
R

igR

P R
G G
V

dP (constant T)
RT RT 0 RT

GR P VR
dP
RT 0 RT

(constant T)

GR G Gig

ig R

Gig Gig 0

RT
V Z 1
P
R

## o equation (1.49) yields:

GR P 1 RT

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

(constant T)

(1.50)

## According to eq. (1.47), HR/RT can be

obtained by differentiating Eq. (1.50)
with respect to temperature.
HR
GR RT
T
(1.47)

RT
T P

P
HR
Z dP

RT
0 T P P

(const T)

(1.51)

## The residual entropy is found by

combination of Eqs. (1.48), (1.50), and
(1.51):
P
P
SR

Z
dP

T
Z 1 dP (const T)
(1.52)

RT
0 T P P
0

BP
Z 1
RT

BP
Z 1
RT

## From Eq. (1.45):

GR P B
dP
RT 0 RT
We get:

GR BP

RT RT

(constant T)

(1.53)

(1.53)

(1.54)
(1.54
)

(1.51)

(1.55)
(1.53)

(1.55)

(1.52)

(1.56)

(1.53) (1.55)

(1.56)

(1.57)

(1.58)

(1.58)

(1.50)
(1.59)

(1.59)

(1.60)

(1.60)

(1.61)

(1.56)

(1.62)

Residual enthalpy:

Residual entropy:

(1.63)

(1.64)

## PARAMETERS FOR CUBIS EOS

EOS

vdW
RK

1
RK

0
1

0
0

SRK

SRK

PR
PR
1 2
RK Tr

1+
2

27/64
1/8
0,42748 0,0866
4
0
0,42748 0,0866
4
1 - 2 0,45724 0,0777
9

SRK 1 0,48508
1,55171
0,15613

2
0,5 2
PR 1 0,37464
1,54226
0,2699
1 Tr
2

1 Tr0,5

GR
V b
a

Z 1 lnZ ln

RT
V RTV

(1.65)

HR
a
Z 1
RT
RTV

(1.66)

SR
V b

lnZ ln

R
V

(1.67)

## RK and SRK EOS

GR
V b
a V

Z 1 lnZ ln
ln

RT
V bRT V b

(1.68)

H
a
V

Z 1
T
ln

RT
bRT
T P V b

(1.69)

SR
V b
a
V

lnZ ln

ln

R
V bR T P V b

(1.70)

PR EOS
GR
V b
a
V 0.4142
b

Z 1 lnZ ln
ln

RT
bRT V 2.4142
b
V 2.8284
(1.71)
HR
a
V 0.4142
b

Z 1
T
ln

RT
2,8284
bRT
b
T P V 2.4142
(1.72)
S
V b
a

V 0.4142
b

lnZ ln

ln

R
bR T P V 2.4142
b
V 2.8284
(1.73)
R

RK EOS

1 2
r

RK T

Tc

12

0.5

0.5 c
1.5

T P
T

SRK EOS
1 f 1 T

0,5
r

1 f 1 T0,5 0.5 f 1

r
T P

TcT

0.5

TUGAS 1
Soal nomor
6.14(a)
6.15(a)
6.16(a)