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Chapter 1

FUNDAMENTA
L EQUATIONS

HOMOGENEOUS CLOSED SYSTEM


(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

st and second laws of Thermodynamics:


dU TdS PdV

(1.2)

For reversible process:


dU TdS PdV

(1.3)

th T dS = dQrev : heat absorbed by the system


- P dV = dWrev : work done by the system

he interaction occurs irreversibly:


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)

process occurring at constant S and V:


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

Differentiating eq. (1.7) yields:

(1.
7)

dH dU PdV VdP

Combining the above equation with eq.


(1.3) leads
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

Differentiating eq. (1.10) yields:


dA dU TdS SdT

(1.1
0)

Combining the above equation with eq.


(1.3) leads to

TdS SdT
dA TdS PdV

dA SdT PdV

a closed system at constant T and V :

(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

Differentiating eq. (1.13) yields:

(1.1
3)

dG dH TdS SdT

Combining the above equation with eq.


(1.8) leads to
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 dA SdT PdV


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)

thalpy as a Function of T and P

a function of P and T, we may express:


H H T,P

al differential of the above equation is


H
H

dH
dT
dP
T P
P T

(1.22)

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


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)

bining eq. (1.24) with Maxwell equation (1.21)


H V T V

P T
T

(1.25)

ucing eqs. (1.23) and (1.25) into eq. (1.22) res


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

l differential of the above equation is


S
S

dS
dT
dP
T P
P T

(1.27)

P)T is obtained from the Maxwell equation (1.2


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)

mbining eq. (1.23) with (1.28):


S CP

T P T

(1.29)

ucing eqs. (1.21) and (1.29) into eq. (1.27) res


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

Then, by Eq. (1.25):


U T V P V

P T
T P P

(1.31)

IDEAL GAS
RT
V
P

Vig

ig

P
P

(1.32)

Enthalpy of ideal gas


From eq. (1.26)

ig

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

C dT V T dP CPigdT Vig VigdP


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

ika P konstan maka dP = 0


dVig R

dT P

Vig

P
P

(P konstan)

Entropy of ideal gas


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
adalah:
Sig
2

T2

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

Jika CP konstan maka


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.

We begin with Eq. (1.3):


dU TdS PdV

At constant V:
U T S

T V T

rom the definition of CV:


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)

e chosen functional relations here are:


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)

Gibbs Energy as a Generating Function

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

From eq. (1.39)


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
numerical values are readily obtained.

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.

Residual Gibbs energy


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

acting this equation from Eq. (1.39) itself give


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

e residual entropy is therefore:


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

ntroducing equation (1.44):


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

IDUAL PROPERTY FROM VIRIAL EOS

or two-term virial EOS:


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

Van der Waals EOS


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)