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# Termodinamika Lanjut (PTK 213 ) (Advance Thermodynamics)

LITERATURES

## Credit : 3 credits/SKS Evaluations:

References/Textbook:

Smith, J.M., Van Ness, H.C., and Abbott, M.M. (2001). Introduction to Chemical Engineering Thermodynamics. 6th Edition. New York: McGraw Book Co. Elliot, J. R. and Lira, C.T., (1999), Introductory Chemical Engineering Thermodynamics, Prentice Hall PTR. etc

## Outlines for 2nd Stage Course

1. 2. 3.

Introduction to Multicomponents VLE Systems VLE Calculation in Mixtures by an Equation of State Activity Models
Modified Raoult's laws Margules Equation Van Laar Equation Regular-Solution Theory Wilson's Equation UNIQUAC UNIFAC

4.

## Introduction to Multicomponents VLE Systems

Click to add text

## Click to add an outline

Mass Balance

F = L + V (over all)

## F (initial mole number), L (moles of liquid), V (moles of vapor)

==> 1 = L/F + V/F zAF = yAV + xAL (zA = overall mole fraction) ==> zA = yA.V/F + xA.L/F de Percentage of liquid: L/F = (zA-yA) / (xA-yA) ==> ce cd Percentage of vapor: V/F = (xA-zA) / (xA-yA) ==> ce Remember that: L/F + V/F = 1

## Fugacity for Gas Mixtures

The simplest type of mixture bevavior is IDEAL GAS BEHAVIOR A component fugacity coefficient is to quantify the deviations from component behavior in ideal-gas mixtures. Fugacity of a vapor-phase component in real solutions: IDEAL SOLUTIONS are intermediate between ideal gases and real mixtures.

=y P fi i

i =

fi yi P

=y P f i i i

## Fugacity of Non-Ideal Liquid Mixtures

For ideal gases ==> i = 1 and fio =P For LIQUID: Activity: ==> Activity Coefficient ==>

=y P fi i
ai= i/ f f

i = i /x i f f

o i

GAMMA APPROACH V L Pi P sat i i Remember: Fugacity of component i in LIQUID: f io = i sat P isat exp RT

i i i i

P P
i i sat

RT

L =i x i P sat i

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Ideal Solutions

Ideal Solutions:

No synergistic effect of the components in mixture each component operates independently no energy change for mixing no volume change

LEWIS/RANDALL Rule:

is fi fi

is =xi i =xi f i f

## VLE in Ideal Solutions

Bagaimana menghitung Ki yi /xi Equilibrium constraint: In ideal solutions: Fugacity of the liquid: Combining the equations:

V= f L f i i
f L = sat P
i i V sat exp

y i f i =x i f i
L

P P
i i sat i

i

Ki=

yi xi

P =

sat

sat

isat exp V

[ P P / RT ]
i L i i sat

RT V L P i P

sat

RT
i
V

=1, dan

exp V

[ P P / RT ]
i L i i sat

Ki=

Pi

sat

atau
Pi

y i P= xi Pisat

7 1 1 1 3 T r,i

Ki=

sat Pi

Pc,i 10

VLE CALCULATIONS

## Jenis-jenis Perhitungan VLE:

Bubble-point Pressure (BP) Dew-point Pressure (DP) Bubble-point Temperature (BT) Dew-point Temperature (DT) Isothermal Flash (FL)

## Jenis-jenis Perhitungan Kesetimbangan Fase

Tipe Diketahui Dihitung Kriteria Konvergensi

BP DP BT DT FL

y i = K i xi =1
i i

y i = K i xi =1
i i

x i = Ki =1
i i i

x i = Ki =1
i

z i 1K i
i

K i L /F 1K i

## Perhitungan Kesetimbangan Fasa untuk Hukum Raoult Biner

Bubble Pressure Calculation:
y i =1, or
i

K i x i=1 ,
i i

Pi

sat

xi =1
sat sat

P1

sat

x1

P2

sat

x 2 =1

P=x1 P 1 x 2 P2

Tidak diperlukan iterasi, karena temperature dan tekanan uap diketahui. Hk Raoult linear bubble pressure line (P-x,y) x 2 =1 x1
P=x1 P sat 1x 1 P sat =x 1 P sat P sat P sat 1 2 1 2 2

## Hukum Raoult Biner ..(2)

Dew-Pressure Calculation: y y1 P y 2 P sat =1 x i =1, or Ki =1 sat
i i i

P1

P2

Diselesaikan tanpa iterasi, sebab tekanan uap adalah tertentu pada temperatur yang ditentukan, sehingga:

P=

1 y1 P1 sat y2 P sat 2

## Hukum Raoult Biner ..(3)

Bubble-Temperature Calculation: sat sat yi =1, or K i xi=1 P=x1 P 1 x 2 P2
i i

Diselesaikan dengan iterasi Temperatur (yang mengubah Pisat), hingga tekanan sama dengan tekanan yang diketahui.

## Hukum Raoult Biner ..(4)

Dew-Temperature Calculation:
x i =1, or Ki =1
i i i

P=

1 y1
sat P1

y2 P sat 2

Diselesaikan dengan iterasi Temperatur (yang mengubah Pisat), hingga tekanan sama dengan tekanan yang diketahui.

## Hukum Raoult Biner ..(5)

Flash-drum Calculation:
Feed: liquid/cairan (vaporized after entering flash drum) Feed composition = zi dan L/F = liquid-to-feed ratio L V V/F = 1-L/F, Component balance:

z i =x i

==>

xi=

zi K i L 1K i F yi=

yi

## ==> yi=Kixi ==>

zi K i L K i 1K i F

## Binary Flash Calculation ....(6)

Dalam perhitungan flash, L/F harus diiterasi hingga xi=1, Tetapi dalam flash, kita juga harus menyelesaikan yi=1 Untuk penyelesaian uap dan cairan, maka secara simultan: (xi-yi)=0 ==> fungsi objective Note that: 0<L/F<1 Kasus-kasus flash: zi, feed flow rate, P, T ==> diketahui

## Multicomponent VLE Calculations

Bubble Calculation:

y i=1,
i

atau

xi K i =
i

xi Psat i
i

=1

Dew Calculation:

x i=1,
i

atau

Ki
i

= P
i

yi Pisat

=1

Rules:

bubble- & dew-pressure calculation ==> no iteration required bubble- & dew-temperature calculation ==> iteration required

## Tebakan awal Temperatur ==> scr. kasar

T = xi T i
i

sat

atau T =

y i T r ,i T sat i
i

y i T c, i
i

## General formula for ISOTHERMAL FLASH Calculation:

i i x i yi = K L / F 1K = Di = 0 i i i i i

z 1K

## Contoh Perhitungan VLE dgn MS Excel

Produk atas suatu kolom distilasi (seperti pada gambar) mempunyai komposisi (zi) sebagai berikut: 23% propane, 67% isobutane, dan 10% n-butane. Jika dianggap kolom ideal, uap yang meninggalkan tray dalam keadaan keseimbangan fasa dengan cairan yang meninggalkan tray tersebut. Dalam kasus partial condenser maka uap dan cairan meninggalkan condensor dalam keadaan kesetimbangan fasa. a) Hitung temperatur kondensor agar uap dari kolom distilasi bisa terkondensasi semua pada tekanan 8 bar. b) Jika diasumsikan bahwa produk atas kolom distilasi berkeseimbangan dengan cairan di tray paling atas, hitunglah temperatur produk uap dan komposisi cairan di tray tersebut jika dioperasikan pada tekanan 8 bar. c) Berapakah fraksi cairan hasil kondensasi, jika uap terkondensasi dlm sebuah kondensor parsial pada 8 bar dan 320 K

Penyelesaian
(a) Temperatur dimana semua uap terkondensasi ==>
bubble point temperatur Dengan MS Excel:
zi Pci (bar) Tci (K) 0,23 42,48 369,8 0,67 36,48 408,1 0,1 37,96 425,1 1 Tekanan (bar) = Tebak T (K) = Ki 0,152 1,609 0,181 0,612 0,200 0,433 8 310 Tebak T (K) = yi Ki 0,370 2,027 0,410 0,795 0,043 0,571 0,82 320 yi 0,47 0,53 0,06 1,06

1 2 Vapor

## Click to add an outline

1 Flash Feed 3 Liquid

Stream No. Name - - Overall - Molar flow kmol/h Mass flow kg/h Temp K Pres bar Vapor mole fraction Vapor mass fraction Enth MJ/h Heating values (60 F) Gross J/kmol Net J/kmol Actual vol m3/h Std liq m3/h Std vap 0 C m3/h Component mole fractions Propane I-Butane N-Butane

1 Feed 1.0000 54.8968 100.0000 8.0000 0.0000 0.0000 -166.77 2.722E+009 2.511E+009 0.0743 0.0991 22.4136 0.230000 0.670000 0.100000

## 2 Vapor Produc 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.00000

3 Liquid Produ 1.0000 54.8968 319.7421 8.0000 0.0000 0.0000 -142.68 2.722E+009 2.511E+009 0.1072 0.0991 22.4136 0.230000 0.670000 0.100000

## (b). Dew point Temperature

(b) uap kesetimbangan dgn cairan ==> Uap jenuh ==>
point temperatur Dengan MS Excel:
Tekanan (bar) = Tebak T (K) = Ki 0,152 2,262 0,181 0,900 0,200 0,651 8 325 Tebak T (K) = xi Ki 0,102 2,027 0,744 0,795 0,154 0,571 0,999

dew

zi

Pci (bar) Tci (K) 0,23 42,48 369,8 0,67 36,48 408,1 0,1 37,96 425,1 1,000

## Dengan interpolasi: T = 325 + ((1,00-0,994)/(1,123-0,994))*(320-325) = 324,8 K

(b). ChemCAD 2
1 2 Vapor 1 Flash

## Click to add an outline

Feed 3 Liquid

Stream No. Name - - Overall - Molar flow kmol/h Mass flow kg/h Temp K Pres bar Vapor mole fraction Enth MJ/h Heating values (60 F) Gross J/kmol Net J/kmol Actual vol m3/h Std liq m3/h Std vap 0 C m3/h Component mole fractions Propane I-Butane N-Butane

1 Feed 1.0000 54.8968 100.0000 8.0000 0.0000 -166.77 2.722E+009 2.511E+009 0.0743 0.0991 22.4136 0.230000 0.670000 0.100000

2 Vapor Produc 1.0000 54.8968 324.9329 8.0000 1.000 -125.26 2.722E+009 2.511E+009 2.8142 0.0991 22.4136 0.230000 0.670000 0.100000

## (c). Isothermal Flash Calculation

(c) Partial condenser ==>
Dengan MS Excel:
zi Tekanan (bar) 8 Temperature (K)= 320 Tebak L/F 0,5 Tebak L/F = Pci (bar) Tci (K) Ki Di 0,23 42,48 369,8 0,152 2,027 -0,1560 0,67 36,48 408,1 0,181 0,795 0,1531 0,1 37,96 425,1 0,200 0,571 0,0546 1,000 0,0517 Tebak L/F = Ki
i i x i yi = K L /F 1K = Di = 0 i i i i i

## Flash to Liquid and Vapor

0,6 Di -0,1674 0,1497 0,0518 0,0341

z 1K

## 0,77 Di -0,1910 0,1442 0,0476 0,0008

xi=

zi K i L 1K i F

yi =

zi K i L K i 1K i F

2 Vapor

1 Flash Feed

## Click to add an outline

3 Liquid Stream No. Name - - Overall - Molar flow kmol/h Mass flow kg/h Temp K Pres bar Vapor mole fraction Enth MJ/h Heating values (60 F) Gross J/kmol Net J/kmol Average mol wt Actual vol m3/h Std liq m3/h Std vap 0 C m3/h Component mole fractions Propane I-Butane N-Butane 1 Feed 1.0000 54.8968 100.0000 8.0000 0.0000 -166.77 2.722E+009 2.511E+009 54.8968 0.0743 0.0991 22.4136 0.230000 0.670000 0.100000 2 Vapor Produc 0.0356 1.8823 320.0000 8.0000 1.000 -4.3367 2.626E+009 2.421E+009 52.8252 0.0992 0.0034 0.7987 0.377689 0.557528 0.064784 3 Liquid Produ 0.9644 53.0145 320.0000 8.0000 0.0000 -137.72 2.726E+009 2.514E+009 54.9733 0.1035 0.0956 21.6150 0.224543 0.674156 0.101301