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FUNDAMENTA
L EQUATIONS
(Q and/or W)
(1.1)
(1.2)
(1.3)
(1.4)
V2
U U2 U1 TdS PdV
S1
V1
(1.5)
(1.6)
ENTHALPY
Definition:
H U PV
(1.
7)
dH dU PdV VdP
dH TdS VdP
(1.
r a closed system at constant S and P : 8)
(1.
dHS,P 0
9)
(1.1
0)
TdS SdT
dA TdS PdV
dA SdT PdV
(1.1
1)
dAT,V 0
(1.1
2)
Definition:
G H TS
(1.1
3)
dG dH 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)
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
T P
V S
S
T V
P S S
S
(1.19)
(1.20)
S V
P T
T
(1.18)
(1.21)
dH
dT
dP
T P
P T
(1.22)
CP
T P
(1.23)
(1.
8)
rentiation with respect of P at constant T yield
H T S V
(1.24)
P T
T
(1.25)
dH CPdT V T
dP
T P
(1.26)
dS
dT
dP
T P
P T
(1.27)
P T
T
(1.21)
(1.
8)
rentiation with respect of T at constant P yield
H T S
(1.28)
T P T
(1.29)
(1.30)
P T P T P T
H V T V
P T
T
P T
T P P
(1.31)
IDEAL GAS
RT
V
P
Vig
ig
P
P
(1.32)
ig
V
ig
ig
ig
dP
dH CP dT V T
T 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
2
2
dT PdT P dT P P dT
dT P
Vig
P
P
(P konstan)
ig
ig
dS CP
dP
T T P
dT dP
dS C
R
T
P
ig
ig
P
(1.34)
T2
P2
dT
dP
ig
ig
igdS CP T R P
T1
P1
S1
S S S C ln
Rln
T1
P1
ig
ig
2
ig
1
ig
P
At constant V:
U T S
T V T
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
dU
dT
dV
T V
V T
S S T,V
S
S
dS
dT
dV
T V
V T
(1.37)
dU CVdT T
P dV
T V
P
dS CVdT
dV
T V
(1.38)
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
RT2
RT RT
dG VdP SdT
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
RT
P
(1.40)
H
G RT
T
RT
T
(1.41)
P
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)
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.
(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.
(1.43)
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
(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
RT
P
R
(1.46)
T
G
T
H
RT
RT
T
(1.47)
S H G
R RT RT
(1.48)
d G
V
RT
RT
dP
R
GR VR
d
dP
RT RT
(constant T)
(constant T)
(constant T)
(1.49)
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
(constant T)
(1.50)
RT
T P
P
HR
Z dP
RT
0 T P P
(const T)
(1.51)
Z
dP
T
Z 1 dP (const T)
(1.52)
RT
0 T P P
0
BP
Z 1
RT
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)
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
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)
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)