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Termodinamika Lanjut (PTK 213 ) (Advance Thermodynamics)

Dr. Istadi, ST, MT Ir. Danny Soetrisnanto, MEng Year 2010-2011

Master Program in Chemical Engineering, Diponegoro University

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.

Fitting Activity Models to Experimental Data

Solving Problem with: EXCEL, MATLAB, CHEMCAD, and/or HYSYS

Introduction to Multicomponents VLE Systems


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Phase Diagrams (T-xy & P-xy)

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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

Activity, Activity Coefficient, Fugacity Coefficient

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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

For non-ideal Liquid ===?

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

= x f = x P exp f L i i o i i sat sat


i i i i

For low to moderate pressure, fio Pisat

P P
i i sat

RT

L =i x i P sat i

Summary for Component Fugacities

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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

y i i P=xi sat P sat exp


i

Dinyatakan dalam rasio Ki :


Ki=

yi xi

P =

sat

Pada tekanan rendah: Hukum Raoult

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

System of Raoults Law binary system

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Shortcut Estimation of VLE K-ratios


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

T, xi=zi T, yi=zi P, xi=zi P, yi=zi P, T, zi

P, yi P, xi T, yi T, xi xi, yi, L/F

y i = K i xi =1
i i

y i = K i xi =1
i i

x i = Ki =1
i i i

Paling mudah Mudah Sulit Sulit Paling sulit

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

flashing liquid partial condensation

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

Multicomponent VLE Calculations.....(2)

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

Dengan Interpolasi: T = 310 + ((1,000-0,827)/(1,061-0,827))*(320-310)=317 K

(a) with ChemCAD


1 2 Vapor

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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

0.0000 0.0000 0.0000 0.000000 0.000000 0.000000

(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

320 xi 0,11 0,84 0,18 1,13

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

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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

3 Liquid Produ 0.0000 0.0000 0.0000 0.0000 0.0000 0.00000

0.0000 0.0000 0.0000 0.000000 0.000000 0.000000

(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

2,027 0,795 0,571

Dengan interpolasi: L/F = 0,7684 K

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

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1 Flash Feed

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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