SIFAT VOLUMETRIK

FLUIDA MURNI
 Kaidah Fase Gibbs
Pada Kesetimbangan Fase dan tidak ada
reaksi kimia, berlaku :
F=2–π+N
Dengan :
F = derajat kebebasan
π = jumlah fase
N = jumlah komponen
 F=2–π+N
Contoh:
Air (cair) setimbang dengan uapnya
F=2–2+1=1

Pada kurva penguapan :

π = 2, N = 1  F = 2 – 2 + 1 = 1
Jadi pd kurva penguapan kita bisa memilih T
tertentu, atau P tertentu. Tapi ingat hanya 1
pilihan T saja atau P saja, yg lain mengikuti
saja.
Derajat kebebasan pada titik tripel:
π = 3, N = 1  F = 2 – 3 + 1 = 0
Jadi Titik Tripel sudah tertentu.
 Persamaan Keadaan
(Equation of State = EOS)
adalah :
Persamaan yang menunjukkan hubungan
antara P, V dan T suatu zat
atau
f(P, V, T) = 0
Khas untuk tiap zat
 Gas Ideal
 EOS berbentuk : PV = RT
atau Z = PV/RT dan Z = 1
dengan
Z = faktor kompresibilitas
P = pressure, Pa
V = volume molar, m3/mol
T = temperature absolut, K
R = konstanta gas umum,
= 8,314 m3 Pa mol-1 K-1 = 8,314 J mol-1 K-1
Untuk satuan lain, lihat appendix A SVNA

 U = f(T) Energi dalam hanya fungsi suhu

 Berlaku pada tekanan sangat rendah
Contoh :
Hitung densitas gas Nitrogen (g/cm3) pada
tekanan 1 atm dan suhu 30oC? (Asumsi:
Gas ideal)

Jawab: ??
 Hubungan antar Sifat pada
Gas Ideal
 U  dU
Cv      Cv(T )
 T V dT
H  U  PV  U (T )  RT  H (T )
 H  dH
Cp      Cp(T )
 T  P dT
dH dU d ( RT )
Cp     Cv  R  Cp  Cv  R
dT dT dT
dU  Cv dT U   Cv dT

dH  Cp dT H   Cp dT
 Perhitungan Proses dengan
Persamaan Gas Ideal
PROSES ?
Proses-proses yg akan dibahas (untuk
sistem tertutup), a.l. :
1. Proses Isotermal
2. Proses Isobarik
3. Proses Isokhorik
4. Proses Adiabatik
 Proses Isotermal (ΔT = 0)

 U 
   Cv
ΔU = Cv ΔT = 0 ingat  T V

 H 
ΔH = Cp ΔT = 0 ingat    Cp
 T  P
U  Q  W  0
V2
RT
Q  W   P dV (ingat P  )
V1
V
V2
RT V2
Q  W  V V dV  RT ln
V1
1

P1V1 P2V2 V P
(ingat  dan T2  T1 sehingga 2  1 )
T1 T2 V 1 P2

P1 P2 V2
Q  W  RT ln   RT ln  RT ln ( T tetap)
P2 P1 V1
 Proses Isobarik
ΔU = ∫ Cv dT dan ΔH = ∫ Cp dT
Q = ΔH = ∫ Cp dT (P tetap)

W = -∫ P dV = - P∫dV = -∫R dT = -R∫dT

= -R (T2 – T1) = -P (V2 – V1)

Cek dgn Hk I : ΔU = Q + W
Cv dT = Cp dT – R dT
Cv = Cp – R  Cp = Cv + R
 Proses Isokhorik (ΔV=0)
ΔU = ∫ Cv dT dan ΔH = ∫ Cp dT
Q = ΔU = ∫ Cv dT (V tetap)
=0

W = -∫ P dV = 0  W = 0

Cek dgn Hk I : ΔU = Q + W  ΔU = Q
 Proses Adiabatik (Q=0)
R
T2  P2  CP
dQ  dW  CV dT   
T1  P1 

dW   PdV PV   tetap
CP
dT R dV T2  V2 
R
CV 
    CV
T CV V T1  V1 

 1  1
T V  1  tetap  T1V1  T2V2
T P (1 ) /   tetap
P V   tetap

γ = 1,67 pada gas monoatomik ( He, Ne, Ar dsb)

γ = 1,4 pada gas diatomik ( H2, N2, O2)
γ = 1,3 pada gas poli atomik sederhana ( CO2, SO2, NH3, CH4)
Proses Adiabatik (lanjutan)
dari Hk I : U  Q  W  W  U
R
W   Cv dT  Cv T (Cv  )
 1
R RT2  RT1 P2V2  P1V1
 T  
 1  1  1
 1  1
   
P1V1  P2   RT  P  
W    1  1 
 2   1
  1  P1     1  P1  
   
 Proses Politropik
"turning many ways”   = konstan
 1  1
T V  1  tetap  T1V1  T2V2   1
   1

P1V1  P2  
 RT1  P2  

T P (1 ) /   tetap W    1     1
  1  P1     1  P1  
   
P V   tetap

isobarik

isotermal

adiabatik

isokhorik
 Gas Non Ideal
Z = PV/RT Z≠1 (Z = faktor kompresibilitas)
EOS untuk gas non ideal:
1. Bentuk Virial
a. Z  1  B ' P  C ' P 2  D ' P 3  ...

B C D
b. Z  1   2  3  ...
V V V
B’, C’, D’ dst dan B, C, D dst : koefisien virial
2. Bentuk Kubik (Cubic EOS) (Pangkat Tiga)
a.l.
 Persamaan Van der Waals : RT a
P  2
Dalam bentuk polinomial : V b V

 RT  2 a ab
V  b 
3
V  V  0
 P  P P
2 2
27 R Tc 1 RTc
a b
Tc = suhu kritik

64 Pc 8 Pc Pc = tekanan kritik
Persamaan Redlich-Kwong
RT a
P 
V  b V (V  b) T
R 2Tc2,5 RTc
a  0,42748 b  0,08664
Pc Pc

(Pada buku SVNA mrpk parameter  dan )

Persamaan Soave-Redlich-Kwong

RT a (T )
P 
V  b V (V  b)
( RTc ) 2 RT
a (Tc )  ac  0,42748 b  0,08664
Pc Pc
a (T )  ac   (T ) T
Tr 
m  0,480  1,574  0,176 2 Tc

 
 (T )  1  m 1  Tr 
2

 = acentric factor (lihat tabel)  faktor bentuk molekul

seberapa dekat dengan bentuk bola
 Pers. bentuk kubik lain masih banyak lagi, tetapi cukup 3 pers.
di atas sebagai contoh.
 Persamaan bentuk kubik membentuk kurva sbb:
 Application of the virial equations
• Differentiation:
 Z   Z 
 B
  B  2C P  3DP  ...  
2

 P T  P T ; P 0
• the virial equation truncated to two terms satisfactorily represent the PVT
behavior up to about 5 bar
BP B
Z  1  BP Z  1
RT
 1
V
At low
pressure
• the virial equation truncated to three terms provides good results for
pressure range above 5 bar but below the critical pressure
B C
Z  1  BP  C P 2 Z  1  2
V V
Reported values for the virial coefficients of isopropanol vapor at 200°C are:
B = -388 cm3/mol and C = -26000 cm6/mol2. Calculate V and Z for isopropanol
vapor at 200 °C and 10 bar by (1) the ideal gas equation; (2) two-term virial
equation; (3) three-term virial equation.

(1) For an ideal gas, Z = 1:

RT 83.14  473.15 3
V   3934 cm
P 10 mol

(2) two-term virial equation:

RT 3 PV
V  B  3934  388  3546 cm Z  0.9014
P mol RT
(3) three-term virial equation:
RT  B C    388  26000  cm 3
Vi 1  1   2   39341   
2 
 3539 1st iteration
P  Vi Vi   3934 (3934)  mol

Ideal gas value

...

3 PV
After 5 iterations V4 ~ V5  3488 cm Z  0.8866
mol RT
 Generalized correlations for gases
(Korelasi Umum)
• Pitzer correlations for the compressibility factor:

– Z = F (Tr, Pr)
0 0 Z  Z 0  Z 1
– Simple linear relation between Z and ω for given values of
Tr and Pr.
– Of the Pitzer-type correlations available, the Lee/Kesler
correlation provides reliable results for gases which are
nonpolar or only slightly polar (App. E, table E.1 – E.4)).
– Only tabular nature (disadvantage)
• Selain tersedia dalam bentuk tabel, metode Lee Kesler
juga menyediakan bentuk grafik
 Pitzer correlations for the 2nd virial
coefficient
• Correlation:
BP 0 Pr 1 Pr
Z  1  1 B  B Z  Z 0  Z 1
RT Tr Tr
Pr 1 P
Z 0  1 B 0 Z  B1 r
– Validity at low to moderate pressures Tr Tr
– For reduced temperatures greater than Tr ~ 3, there appears
to be no limitation on the pressure.
– Simple and recommended. 0.422
B 0  0.083  1.6
Tr
– Most accurate for nonpolar species.
0.172
B1  0.139 
Tr4.2
 Determine the molar volume of n-butane at 510K and 25 bar by, (1) the ideal-gas
equation; (2) the generalized compressibility-factor correlation; (3) the generalized
virial-coefficient correlation.
(1) The ideal-gas equation
RT cm3
V  1696.1
P mol
(2) The generalized compressibility-factor correlation
510 25 the acentric factor
Tr   1.200 Pr   0.659   0.200
425.1 37.96

the Lee/Kesler correlation

ZRT cm3
Z  0.865
0
Z  0.038
1
Z  Z  Z  0.873 V 
0 1
 1480.7
P mol
(3) The generalized virial-coefficient correlation
510 0.422 1 0.172
Tr   1.200 B  0.083  1.6
0
B  0.139 
425.1 Tr Tr4.2

Pr P 3
Z  1  B0  B1 r  0.879 V  ZRT  1489.1 cm
Tr Tr P mol
What pressure is generated when 1 (lb mol) of methane is stored in a volume of 2
(ft)3 at 122°F using (1) the ideal-gas equation; (2) the Redlish/Kwong equation; (3)
a generalized correlation .
(1) The ideal-gas equation
RT 0.7302(122  459.67)
P   212.4 atm
V 2
(2) The RK equation
581.67  (Tr ) R 2Tc2 atm RTc
Tr   1.695 a (T )    453 .94 b    0.4781 ft 3

343.1 Pc ft 6 Pc
RT a (T )
P   187.49 atm
V  b V (V  b)
(3) The generalized compressibility-factor correlation is chosen (high pressure)
ZRT Z (0.7302)(122  459.67)
P   212.4 Z atm
V 2
P Z 581.67 Z starts at Z = 1 and
Pr   Tr   1.695
45.4 0.2138 343.1 converges on Z = 0.890
P  189.0 atm
A mass of 500 g of gases ammonia is contained in a 30000 cm 3 vessel immersed in
a constant-temperature bath at 65°C. Calculate the pressure of the gas by (1) the
ideal-gas equation; (2) a generalized correlation .
Vt cm3
V  1021.2
n mol
(1) The ideal-gas equation
RT
P  27.53 bar
V

(2) The generalized virial-coefficient correlation is chosen (low pressure, P r ~ 3 )

338.15 0.422 0.172
Tr   0.834 B 0
 0 .083  B 1
 0.139 
405.7 Tr1.6 Tr4.2
27.53
Pr ~  0.244 the acentric factor
112.8   0.253

Z  1  B 0  B1 
Pr P
 1  0.541 r
Tr Tr
ZRT
P  23.76 bar
V
 Generalized correlations for liquids
• The generalized cubic equation of state (low accuracy)
• The Lee/Kesler correlation includes data for subcooled liquids
– Suitable for nonpolar and slightly polar fluids
• Estimation of molar volumes of saturated liquids
– Rackett, 1970: (1Tr ) 0.2857
V sat
 Vc Z c
• Generalized density correlation for liquid (Lydersen,
Greenkorn, and Hougen, 1955):

 Vc
r  
c V
 Fig 3.17

 r1
V2  V1
r 2
For ammonia at 310 K, estimate the density of (1) the saturated liquid; (2) the
liquid at 100 bar
(1) Apply the Rackett equation at the reduced temperature

Tr 
310 V  72.47 Z c  0.242
 0.7641 c
405.7

0.2857 cm 3
V sat  Vc Z c(1Tr )  28.33
mol
(2) At 100 bar
100
Pr   0.887
112 .8 Fig 3.17
 r  2.38 Vc cm3
310 V  30.45
Tr   0.7641 r mol
405.7

 r1  r1,310 K , saturated liquid 2.34 cm3

V2  V1 V 310 K
 29.14  28.65
r 2  r 2,100bar 2.38 mol