PHASE EQUILIBRIUM

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INTRODUCTION
A phase is a portion of a system that is physically homogeneous and bounded by a surface. Solid and liquid phases are called condensed phases The main subjects we are going to study in this chapter are phase law and phase diagrams.

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The Gibbs phase rule then can be written as

F CP2
C is called the number of components
P is the number of phase, and F is called degree of freedom

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The one component system

For one component system

C=1

F = 1P + 2 = 3 - P
F=2

Single phase P=1 ex : Ice , vapor , water

Two phases P=2 F=1 ex : mixture of ice and water , mixture of water and vapor

Three phases P=3 F=0 ex : mixture of ice, water and vapor

the maximum number of freedom is 2the phase diagram can be drawn in two dimensions
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typical one-component phase diagram

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The Clausius-Clapeyron equation

The Clausius-Clapeyron Equation expresses the relationship between vapor pressure and temperature. It is the equation for the vapor-pressure line

The relationship dpv/dT is the rate of change of vapor pressure with temperature. it represents the slope of the vapor-pressure line. Lv is the heat of vaporization of one mole of liquid, T is the absolute temperature VMg - VML represents the change in volume of one mole as it goes from liquid to gas
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Phase diagram for a pure substance

Normally, the molar volume of a liquid is somewhat smaller than the molar volume of the gas,

This is known as the Clausius-Clapeyron equation

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The vapor pressure line

This eq. indicates that a straight line results when the logarithm of vapor pressure is plotted against the reciprocal of absolute temperature. The slope of this line is Lv/R, and the intercept is C.

If C is the constant of integration,

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Example 1:
454.6 435

Plot the vapor pressure of n-hexane in a way that will result in a straight line.
Temperature , oF
155.7 199.4 269.1 331.9 408.9

Vapor Pressure of n-hexane, Psia

14.7 29.4 73.5 147 293.9

The intercept is C and the slope of the line is Lv/R. Calculate Lv !

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Liquid-vapor phase diagrams for ideal liquid mixtures of twocomponent systems For two-component systems, the phase rule takes the form of

F C P 2 4 P
When P=1, F=3, it is a trivariant system To make a two-dimensional phase diagram, we specify a fixed value for one variable. There are two principal types of two-dimensional phase diagrams for a two-component liquid mixture. One is the pressure-composition phase diagram, p-x diagram The other is temperature-composition phase diagram, T-x diagram

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Pressure-composition diagrams

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* pA pA xA yA p p

* * pB p pA

* pA 1 p

yA xA

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a
f b e c d h

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Example 2
Tekanan uap benzena dan toluena pada 60C adalah 51,3 dan 18,5 kPa
Hitung tekanan uap parsial benzena dan toluena, tekanan total, dan fraksimol benzena dan toluena di dalam fasa uap, dimana fraksi mol toluena 0,6

Solution :
Pbenzena = (0.4)(51,3 kPa) = 20,5 kPa Ptoluena = (0.6)(18,5 kPa) = 11,1 kPa Ptot = 31,6 kPa Ytoluena = 11,1/31,6 = 0.351
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Example 3
Pada 25oC tekanan uap karbon tetraklorida CCl4 adalah 19.1 kPa dan dari kloroform CHCl3 adalah 26.5 kPa. Cairan-cairan ini membentuk larutan yang sangat mendekati keadaan ideal yang satu terhadap yang lain. Bila 1 mol CCl4 dan 3 mol CHCl3 dicampurkan, berapa banyak fraksi mol CCl4 terdapat dalam fasa uap dan berapa tekanan uap dari larutan?

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Homework
Benzena dan toluena membentuk larutan yang sangat mendekati keadaan ideal. Pada 80oC, tekanan uap benzena dan toluena berturut2 adalah 100.4kPa dan 38.7kPa.
a. Untuk larutan yang mengandung 0.5 fraksi mol benzena dan 0.5 fraksi mol toluena, bagaimana komposisi uap dan tekanan uap total pada 80oC? (yA, yB, dan p total) b. Bagaimana komposisi fasa cair yang ada dalam kesetimbangan pada 80oC dengan uap benzena toluena yang mempunyai fraksi mol benzena 0.75 mol? (xA)

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T-x figure
Boiling-point -composing figure. For certain composing solution, the higher vapor pressure is, the lower the boiling point is. T-x figure can be drawed by the experiment data directly and also worked out from the p-x figure.

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From T-x to p-x figure

Benzene-toluene p-x figure at four different temp. Draw a horizontal line at the pressure P$ location. Mark the relationship of composing and boiling point. the bigger P* is, the lower Tb is.
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Temperature-composition diagrams

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The lever rule

DE: isothermal tie line. All of the material system points in DE are denoted by the composing of point D (Liquid) and E(Gas) Material system point is thought as pivot. . nl (CD) = ng (CE)

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Liquid-vapor phase diagrams for nonideal liquid mixtures

Deviations from ideality

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Liquid-vapor phase diagrams for nonideal liquid mixtures

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The positive warp is so large, the highest point in the p-x figure is formed. The one has highest point in the p-x figure, also has lowest point in the T-x figure. The lowest point: minimum azeotropic point.

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Azeotropes

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H2O-C2H5OH azeotrope
Combination of two simple T-x(y) figure. H2O-C2H5OH is 351.28K, it contains ethanol 95.57. If the ethanol content < 95.57, absolute alcohol can not be get. The absorber CaCl2 , molecule siever can make the ethanol content excess 95.57.

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Lowest point in p-x diagram

The one has lowest point in the p-x figure, also has highest point in the T-x figure, the highest point is called maximum azeotropic point.

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High-boiling azeotrope
In the T-x(y) figure, the mixture lies in the highest-boiling azeotrope is called maximum azeotropic mixture. The highest-boiling azeotrope temperature of H2O-HCl is 381.65K, it contains HCl 20.24. Usually, it is used to be the standard solution in chemical analysis.

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