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B49CE

Multiphase Thermodynamics

Heriot-Watt University

CONTENTS 2

a retrieval system or transmitted in any form or by any means without

express permission from the publisher.

and Petroleum Engineering.

Multiphase Thermodynamics

CONTENTS 3

Acknowledgements

Thanks are due to the members of Heriot-Watt, School of Engineering and Physical

Science who planned and generated this material.

We would like to acknowledge the assistance and contributions from colleagues across

the University and students in preparing this and support material.

CONTENTS 4

Contents

1.1 INTRODUCTION .................................................................................................................. 3

1.2 CRITERION FOR EQUILIBRIUM ............................................................................................. 4

1.2.1 Pure Species Phase Equilibrium ......................................................................... 4

1.2.2 Pure Species Chemical Potential ........................................................................ 8

1.2.3 Pure Species Gibbs Energy Relation................................................................... 9

1.2.4 Pressure Dependence of Pure Species Chemical Potential .............................. 10

1.3 PURE SPECIES FUGACITY ................................................................................................ 12

1.3.1 Fugacity as a Criterion for Pure Species Phase Equilibrium .............................. 14

1.3.2 Fugacity using Residual Volume ....................................................................... 15

1.3.3 Example 1.1 ...................................................................................................... 16

1.3.4 Fugacity using Compressibility Factors ............................................................. 17

1.3.5 Compressibility Factor Charts............................................................................ 17

1.3.6 Example 1.2 ...................................................................................................... 20

1.3.7 Fugacity using Charts ........................................................................................ 21

1.3.8 Example 1.3 ...................................................................................................... 22

1.3.9 Fugacity of Pure Saturated Liquids .................................................................... 23

1.3.10 Fugacity of Compressed Liquid States ........................................................... 25

1.3.11 Example 1.4 .................................................................................................... 27

1.3.12 Fugacity Coefficient using Cubic EOS ............................................................. 28

1.4 TUTORIAL 1..................................................................................................................... 29

1.5 BIBLIOGRAPHY ................................................................................................................ 31

APPENDIX A.......................................................................................................................... 32

Simple Gas Z-Factor Chart......................................................................................... 32

Non-Simple Gas Z-Factor Chart ................................................................................. 33

APPENDIX B.......................................................................................................................... 35

Simple Gas Fugacity Coefficient Chart High Pressure............................................. 35

Non-Simple Gas Fugacity Coefficient Chart High Pressure ..................................... 36

Simple Gas Fugacity Coefficient Chart Low Pressure ............................................. 37

Non-Simple Gas Fugacity Coefficient Chart Low Pressure ...................................... 38

APPENDIX C ......................................................................................................................... 39

Fugacity Coefficient using Cubic EOS ........................................................................ 39

CONTENTS 5

2.1 INTRODUCTION .................................................................................................................. 3

2.1.1 The Apportioning Rule, the Recombination Rule and Gibbs-Duhem.................... 3

2.2 CRITERIA FOR PHASE EQUILIBRIUM .................................................................................... 5

2.2.1 Gibbs Free Energy of a Mixture ........................................................................... 5

2.2.2 Daltons Law........................................................................................................ 7

2.2.3 Fugacity Coefficient of a Component in a Mixture................................................ 7

2.2.4 Ideal Solutions and Lewis-Randall Rule .............................................................. 8

2.2.5 Criterion for Multicomponent Phase Equilibrium ................................................ 10

2.2.6 Fugacity as a Criterion for Mixture Phase Equilibrium........................................ 12

2.2.7 Finding Fugacity Coefficient of a Component in a Mixture ................................. 13

2.3 VLE FOR NON-POLAR SYSTEMS ...................................................................................... 15

2.3.1 Rigorous Phi-Phi Approach to VLE .................................................................... 15

2.3.2 Liquid and Vapour as Ideal Solutions ................................................................ 17

2.3.3 Raoults Law: Liquid as an Ideal Solution and Vapour as an Ideal Gas ............. 18

2.3.4 Phi-Phi VLE Summary ....................................................................................... 19

2.3.5 Finding K-Values using Charts .......................................................................... 20

2.3.6 Example 2.1 ...................................................................................................... 22

2.3.7 Vapour Pressure Correlation ............................................................................. 25

2.3.8 Temperature-Composition Diagram for Binary System ...................................... 27

2.3.9 Significance of K-Values.................................................................................... 28

2.4 PHASE EQUILIBRIUM CALCULATIONS ................................................................................ 29

2.4.1 Bubble Point Calculations .................................................................................. 29

2.4.2 Dew Point Calculations...................................................................................... 31

2.4.3 Example 2.2 ...................................................................................................... 32

2.4.4 Example 2.3 ...................................................................................................... 34

2.4.5 Flash Calculations ............................................................................................. 36

2.4.6 Example 2.4 ...................................................................................................... 42

2.5 TUTORIAL 2..................................................................................................................... 44

2.6 BIBLIOGRAPHY ................................................................................................................ 51

APPENDIX A.......................................................................................................................... 52

De Priester Charts see next page............................................................................ 52

A1 High Temperature Chart: ...................................................................................... 53

A2 Low Temperature Chart: ....................................................................................... 54

A3 Antoine Coefficient Table ...................................................................................... 55

APPENDIX B.......................................................................................................................... 56

Rigorous Phi-Phi VLE Worksheet ............................................................................... 56

APPENDIX C ......................................................................................................................... 61

Review of Partial Molar Properties ............................................................................. 61

C-1 Partial Molar Property Overview .......................................................................... 62

C-2 Definition of Partial Molar Property ...................................................................... 64

C-3 Partial Molar Properties from Correlations ........................................................... 66

C-3 Partial Molar Properties from Diagrams ............................................................... 68

C-4 Recombination Rule ............................................................................................ 71

C-5 Gibbs-Duhem Equation....................................................................................... 72

C-6 Partial Molar Property Relations .......................................................................... 73

CONTENTS 6

3A.1 INTRODUCTION ............................................................................................................... 3

3A.2 MODELS OF IDEALITY AND STANDARD STATES .................................................................. 4

3.2.1 Lewis-Randall Model of Ideality ........................................................................... 4

3.2.2 Henrys Law Model of Ideality .............................................................................. 5

3A.3 REAL MIXTURES ............................................................................................................. 7

3.3.1 Excess Properties ............................................................................................... 7

3.3.2 Activity Coefficients ............................................................................................. 8

3A.4 THE GAMMA-PHI APPROACH TO VLE ............................................................................. 12

3.4.1 Rigorous Gamma-Phi Approach to VLE ............................................................ 13

3.4.2 Vapour Phase as an Ideal Solution.................................................................... 14

3.4.3 Vapour Phase as an Ideal Gas .......................................................................... 15

3.4.4 Both Phases as Ideal Solutions ......................................................................... 15

3.4.5 Raoults Law...................................................................................................... 16

3A.5 PHASE EQUILIBRIUM DIAGRAMS ..................................................................................... 17

3.5.1 P-x-y Diagrams.................................................................................................. 18

3.5.2 T-x-y Diagrams .................................................................................................. 19

3.5.3 Example 3A.1 .................................................................................................... 22

3.5.4 The x-y Diagram ................................................................................................ 24

3.5.5 Example 3A.2 .................................................................................................... 26

3A.6 MODELS OF SOLUTION BEHAVIOUR ................................................................................ 28

3.6.1 The One Parameter Model ................................................................................ 28

3.6.2 Margules Two Parameter Model ....................................................................... 31

3.6.3 Van Laars Two Parameter Model ..................................................................... 32

3.6.4 Wilsons Local Composition Model .................................................................... 35

3.6.5 Example 3A.3 .................................................................................................... 36

3A.7 TUTORIAL 3A ................................................................................................................ 37

3A.8 BIBLIOGRAPHY .............................................................................................................. 40

APPENDIX A.......................................................................................................................... 41

Real Mixtures ............................................................................................................. 41

A.1 Property Changes on Mixing ................................................................................ 42

A.2 Property Changes on Mixing for Ideal Solutions ................................................... 43

A.3 Activity of a Species in a Mixture.......................................................................... 45

A.4 Excess Properties ................................................................................................ 47

APPENDIX B.......................................................................................................................... 49

B.1 Positive & Negative Deviation from Ideality .......................................................... 49

B.2 Formation of Azeotropes ...................................................................................... 52

APPENDIX C ......................................................................................................................... 54

Gamma-Phi VLE Worksheet for Azeotrope ................................................................ 54

CONTENTS 7

AND MISCIBILITY

3B.1 INTRODUCTION ............................................................................................................... 3

3B.2 PURE SPECIES ............................................................................................................... 4

3.2.1 P-T Diagrams ...................................................................................................... 4

3.2.2 P-v Diagrams ...................................................................................................... 6

3B.3 BINARY SYSTEMS AND MISCIBLE VLE .............................................................................. 7

3.3.1 P-T Diagrams ...................................................................................................... 8

3.3.2 P-x-y Diagrams.................................................................................................. 13

3.3.3 T-x-y Diagrams .................................................................................................. 14

3.3.4 x-y Diagrams ..................................................................................................... 15

3.3.5 Azeotropes ........................................................................................................ 15

3B.4 PARTIALLY MISCIBLE SYSTEMS ...................................................................................... 20

3.4.1 Liquid-Liquid Solubility Diagrams ....................................................................... 20

3.4.2 VLLE and P-x-y Diagram ................................................................................... 22

3.4.3 VLLE and T-x-y Diagram ................................................................................... 24

3.4.4 VLLE at Higher Temperature ............................................................................. 26

3.4.5 Quantitative Treatment of VLLE ........................................................................ 28

3.4.6 Example 3B.1 .................................................................................................... 34

3B.5 IMMISCIBLE SYSTEMS .................................................................................................... 36

3.5.1 Quantitative Treatment ...................................................................................... 37

3.5.2 Example 3B.2 .................................................................................................... 39

3B.6 TUTORIAL 3B ................................................................................................................ 40

3B.7 BIBLIOGRAPHY .............................................................................................................. 41

APPENDIX A.......................................................................................................................... 42

Rigorous Approach to LLE ......................................................................................... 42

A.1 Liquid-Liquid Equilibrium ...................................................................................... 43

APPENDIX B.......................................................................................................................... 46

Heating or Cooling a VLLE System. ........................................................................... 46

B.1 Isobaric Cooling from A ..................................................................................... 47

B.2 Isobaric Cooling from B ..................................................................................... 48

B.3 Isobaric Cooling from C ..................................................................................... 49

B.4 Isobaric Vaporisation from X .............................................................................. 50

4.1 INTRODUCTION .................................................................................................................. 3

4.2 REACTION STOICHIOMETRY ............................................................................................... 5

4.2.1 Extent of Reaction ............................................................................................... 5

4.2.2 Example 4.1 ........................................................................................................ 7

4.3 EQUILIBRIUM CRITERION .................................................................................................... 9

4.3.1 Equilibrium Constant ......................................................................................... 11

4.3.2 Approximate Temperature Dependence of K ..................................................... 14

4.3.4 Accurate Temperature Dependence of K........................................................... 17

4.3.5 Example 4.2 ...................................................................................................... 20

4.4 GAS PHASE CHEMICAL EQUILIBRIUM ................................................................................ 22

CONTENTS 8

4.4.2 Ideal Solution Mixture ........................................................................................ 24

4.4.3 Ideal Gas Mixture .............................................................................................. 25

4.4.4 Effect of Pressure on Chemical Equilibrium ....................................................... 25

4.4.6 Calculation of Equilibrium Conversion ............................................................... 26

4.4.7 Example 4.3 ...................................................................................................... 29

4.5 LIQUID PHASE CHEMICAL EQUILIBRIUM ............................................................................. 31

4.5.1 Rigorous Non-Ideal Mixture ............................................................................... 32

4.5.2 Ideal Solution Mixture ........................................................................................ 33

4.6 HETEROGENEOUS REACTIONS ......................................................................................... 36

4.6.1 Heterogeneous Reactions with Solids ............................................................... 37

4.7 TUTORIAL 4..................................................................................................................... 38

4.8 BIBLIOGRAPHY ................................................................................................................ 44

5.1 INTRODUCTION .................................................................................................................. 4

5.1.1 P-T Diagram ........................................................................................................ 4

5.1.2 P-v Diagrams ...................................................................................................... 6

5.1.3 Relation between P-T & P-v Diagrams ................................................................ 8

5.2 VOLUME EXPANSIVITY AND ISOTHERMAL COMPRESSIBILITY ................................................. 9

5.2.1 Liquids and Solids ............................................................................................. 10

5.2.2 Gases................................................................................................................ 11

5.2.3 Worked Example 5.1 ......................................................................................... 12

5.2.4 Worked Example 5.2 ......................................................................................... 13

5.2.5 Reversible Volume Work ................................................................................... 14

5.2.6 Worked Example 5.3 ......................................................................................... 15

5.3 COMPRESSIBILITY FACTOR .............................................................................................. 16

5.3.1 Two-Parameter Generalised Correlations.......................................................... 17

5.3.2 Three-Parameter Generalised Correlations ....................................................... 18

5.4 VIRIAL EOS .................................................................................................................... 21

5.4.1 Truncated Virial EOS ......................................................................................... 23

5.4.2 Worked Example 5.4 ......................................................................................... 24

5.4.3 Worked Example 5.5 ......................................................................................... 25

5.4.4 Worked Example 5.6 ......................................................................................... 26

5.4.5 Worked Example 5.7 ......................................................................................... 27

5.5 SECOND VIRIAL COEFFICIENT B ..................................................................................... 28

5.5.1 Experimental Determination .............................................................................. 29

5.5.2 Generalised Correlations ................................................................................... 30

5.5.3 Worked Example 5.8 ......................................................................................... 31

5.5.4 Worked Example 5.9 ......................................................................................... 32

5.5.5 Worked Example 5.10 ....................................................................................... 33

5.5.6 Worked Example 5.11 ....................................................................................... 34

5.6 CUBIC EOS .................................................................................................................... 35

5.6.1 Manual Iteration Schemes ................................................................................. 35

5.6.2 Generalised Correlations for Cubic Parameters................................................. 37

5.6.3 Worked Example 5.12 ....................................................................................... 38

CONTENTS 9

5.6.5 Worked Example 5.13 ....................................................................................... 41

5.7 BIBLIOGRAPHY ................................................................................................................ 43

CONTENTS 10

TOPIC 1. Pure Species Phase Equilibrium 1

Topic 1

Contents

TOPIC 1: PURE SPECIES PHASE EQUILIBRIUM

1.1 INTRODUCTION .................................................................................................................. 3

1.2 CRITERION FOR EQUILIBRIUM ............................................................................................. 4

1.2.1 Pure Species Phase Equilibrium ......................................................................... 4

1.2.2 Pure Species Chemical Potential ........................................................................ 8

1.2.3 Pure Species Gibbs Energy Relation................................................................... 9

1.2.4 Pressure Dependence of Pure Species Chemical Potential .............................. 10

1.3 PURE SPECIES FUGACITY ................................................................................................ 12

1.3.1 Fugacity as a Criterion for Pure Species Phase Equilibrium .............................. 14

1.3.2 Fugacity using Residual Volume ....................................................................... 15

1.3.3 Example 1.1 ...................................................................................................... 16

1.3.4 Fugacity using Compressibility Factors ............................................................. 17

1.3.5 Compressibility Factor Charts............................................................................ 17

1.3.6 Example 1.2 ...................................................................................................... 20

1.3.7 Fugacity using Charts ........................................................................................ 21

1.3.8 Example 1.3 ...................................................................................................... 22

1.3.9 Fugacity of Pure Saturated Liquids .................................................................... 23

1.3.10 Fugacity of Compressed Liquid States ........................................................... 25

1.3.11 Example 1.4 .................................................................................................... 28

1.3.12 Fugacity Coefficient using Cubic EOS ............................................................. 29

1.4 TUTORIAL 1..................................................................................................................... 30

1.5 BIBLIOGRAPHY ................................................................................................................ 32

APPENDIX A.......................................................................................................................... 33

Simple Gas Z-Factor Chart......................................................................................... 33

Non-Simple Gas Z-Factor Chart ................................................................................. 34

APPENDIX B.......................................................................................................................... 36

Simple Gas Fugacity Coefficient Chart High Pressure............................................. 36

Non-Simple Gas Fugacity Coefficient Chart High Pressure ..................................... 37

Simple Gas Fugacity Coefficient Chart Low Pressure ............................................. 38

Non-Simple Gas Fugacity Coefficient Chart Low Pressure ...................................... 39

APPENDIX C ......................................................................................................................... 40

Fugacity Coefficient using Cubic EOS ........................................................................ 40

TOPIC 1. Pure Species Phase Equilibrium 2

Prerequisite knowledge

Process Industries C.

Process Engineering B.

Kinetics and Thermodynamics

Learning objectives

After studying this Pure Species Phase Equilibrium topic you should be able

to:

Write down phase equilibrium criterion for a pure species.

Identify and differentiate between the potentials for heat transfer, work

transfer and interphase mass transfer.

Define (for a pure species) the chemical potential, the fugacity and the

fugacity coefficient and write down relationships between them.

Show how fugacity may be determined from measurable P v T

data.

Explain the background to Corresponding States Principle and

compressibility factor. Outline and distinguish between the two-

parameter and the three-parameter Law of Corresponding States.

Review and solve problems using generalised compressibility factor

charts.

Demonstrate how generalised compressibility charts may be used to

determine the fugacity coefficient and fugacity knowing only reduced

temperature, reduced pressure and acentric factor.

Show how the fugacity coefficient and the fugacity may be calculated

for both a saturated and a subcooled liquid.

TOPIC 1. Pure Species Phase Equilibrium 3

1.1 Introduction

written as follows:

aA + bB cC + dD

taking part in the reaction was related to the equilibrium constant K through

the expression

K=

[C ]c [D]d

[A]a [B]b

This provides a criterion for chemical equilibrium but it only applies (in this

form) to an ideal system. Later it will be shown how this may be adapted and

applied to non-ideal systems.

What is also important is the degree to which a given species will transfer from

one phase to another. This type of problem is known as phase equilibrium.

Important operations, such as distillation, absorption and extraction, are

concerned with the transfer of species between different phases.

The rate at which a species is transferred from one phase to another depends

on how far the system is from equilibrium. This degree of departure from

equilibrium is usually referred to as the driving force or simply the potential.

Far from equilibrium the driving force (potential) is high and the rate of

transfer of species between phases is high.

Close to equilibrium the driving force (potential) is low and the rate of

transfer of species between phases is correspondingly low.

As equilibrium is approached, the rate of transfer of species between

phases becomes slower as the potential is reduced.

Phase equilibrium implies zero driving force (zero potential), zero

transfer of a species between phases and no change in composition of

the different phases.

Thus, equilibrium is approached asymptotically since it is a theoretical

entity that requires the potential to be zero.

engineering phase equilibrium is assumed when no further changes in phase

composition are measurable.

Liquid-vapour equilibrium systems are the most common, but other phase

equilibrium situations are possible, such as liquid-solid, solid-solid, vapour-

solid and even vapour-liquid-solid and vapour-liquid-liquid systems.

TOPIC 1. Pure Species Phase Equilibrium 4

potential for work transfer). For thermal equilibrium there can be no

temperature gradient (this is the potential for heat transfer). But, for phase

equilibrium:

What is the potential that drives interphase mass transfer?

What is the criterion for phase equilibrium?

How can this criterion be used to solve phase equilibrium problems,

especially for non-ideal systems?

obvious. However, it is only when this potential approaches zero that phase

equilibrium can be assumed.

There are two distinct problems that need to be solved in order to understand

phase behaviour:

1. Why do different phases exist?

2. How do we deal with mixtures and changes in composition?

Although this subject deals principally with mixtures, it is better to start with a

discussion of phase equilibrium involving a single species. A common example

would be a steam-water system (but equally an ice-water, or an ice-steam

system are also possible, as indeed is an ice-steam-water system).

Consider a closed system with two phases but only one component (this

could be a steam-water system).

Take it that both phases within this closed system are at constant temperature

and pressure, T & P , and that any heat or work, Q or W , that is transferred

between the system/surroundings takes place reversibly.

Initially, the system is not in phase equilibrium and net mass transfer of the

component is free to take place in either direction. The total entropy change of

the surroundings dS SURR , units of (kJ/K), is given by

dQ SURR

dS SURR =

TSURR

But since heat transfer (either to or from the surroundings) can only come from

the system, it follows that the heat exchanged between the system dQSYS and

surroundings dQSURR must be equal and opposite.

TOPIC 1. Pure Species Phase Equilibrium 5

dQSURR = dQSYS

Also, since the heat transfer is reversible, it follows that heat can only be

transferred through an infinitesimal temperature difference. Thus, the system

temperature T must be equal to surroundings temperature TSURR .

dQSYS

dS SURR =

T

dS SYS + dS SURR 0

Substitute the entropy change of the surroundings into the second law to get

dQSYS

dS SYS 0

T

or

dQSYS TdS

Notice that the surroundings have now been eliminated. The non-flow energy

equation (Process Engineering B) is given by

dQSYS = dU + PdV

In which U is the total system internal energy (kJ) and V is the total system

volume (m3). Here, internal energy and volume are both extensive properties.

Substitute the last equation into the previous one and re-arrange

dU + PdV TdS 0

dU T , P + d (PV )T , P d (TS )T , P 0

Which is identical to

d (U + PV TS )T , P 0 ..(1.1)

TOPIC 1. Pure Species Phase Equilibrium 6

G = H TS

In which H is the total system enthalpy (kJ) and G is the total system Gibbs

free energy (kJ). Enthalpy (Process Engineering B) is defined as

H = U + PV , so that the above may also be written as

G = U + PV TS

dGT , P 0 ....(1.2)

Equation (1.2) is used here to describe the situation where there are two

phases of a pure substance, together forming a closed system, but initially not

in phase equilibrium:

It shows that (for a spontaneous process) the total Gibbs energy of a

system at constant temperature and pressure always gets smaller, or

stays the same. It can never get larger.

The inequality dG < 0 applies to irreversible processes when the

system is not in equilibrium. This is the direction for spontaneous

change.

The equality dG = 0 applies to reversible processes and only occurs

when the system is at equilibrium.

Thus, the system always moves in a direction which minimises its Gibbs

energy and the point of equilibrium must, therefore, occur at the minimum

Gibbs energy. Mathematically equilibrium occurs whenever equation (1.3)

below is satisfied

dG = 0 ...(1.3)

For the case of a pure species distributed between two phases, call them the

-phase and the -phase (for instance, this could be a steam ( ) water ( )

system), the total Gibbs energy G of both phases together is given by

G = n g + n g (1.4)

In which g and g are the molar Gibbs energies (kJ/mol) of each phase

separately (intensive properties) and n & n are the number of moles of

each phase. Substitute this into equation (1.2) gives

d (n g + n g ) 0

TOPIC 1. Pure Species Phase Equilibrium 7

g dn + n dg + g dn + n dg 0

At this stage it is worth remembering that the temperature and pressure are

both constant. Under these conditions, what will happen to dg and dg ?

relation was derived

In which the volume v is the molar volume (m3/mol) and the entropy s is the

molar entropy (kJ/(mol K)) both intensive properties.

If T & P are constant, then equation (1.5) shows that there can be no change

in molar Gibbs energy of either phase and the phase equilibrium expression

reduces to

g dn + g dn 0

But, since there are only two phases present dn = dn and this becomes

g dn g dn 0

between two phases, this becomes

(g g )dn 0 ..(1.6)

If the system consists of two phases & and if g > g (while not in

equilibrium initially), then it follows that:

The first term g dn must be larger than the second term g dn .

In order to satisfy the inequality, the change in the number of moles in

the - phase must be less than zero, i.e. dn < 0 .

This means that the pure species must be transferred from the -

phase to the -phase.

Equation (1.4) shows that the total Gibbs energy of the system must

decrease as the system approaches equilibrium.

The transfer will continue until equation (1.6) is satisfied. This

corresponds to the point of equilibrium and minimum total Gibbs

energy.

TOPIC 1. Pure Species Phase Equilibrium 8

The opposite will happen if g > g . However, if the molar Gibbs energies of

both phases are equal g = g , then equation (1.6) shows that the equality is

satisfied. This is the reversible case and the system must be in equilibrium.

Thus, the potential for interphase mass transfer is the molar Gibbs free

energy and when the condition below is satisfied, according to equation (1.6),

net interphase mass transfer must cease

g = g ....(1.7)

Only when this potential (driving force) is zero g g = 0 , will net mass

transfer stop and only then can the two phases co-exist in equilibrium.

Water and steam at 101.325 kPa have exactly the same molar Gibbs energy,

but only at 100oC. This means that pure water and steam can only co-exist in

equilibrium at 100oC when the pressure is 101.325 kPa.

This potential is the so called chemical potential and, for a pure species, it

is denoted by .

species, the chemical potential is equal to the molar Gibbs energy. The

chemical potential, like all driving forces, must be intensive (just like T & P ).

Thus, for a pure species

= g .(1.8)

In order to make the chemical potential and Gibbs free energy compatible, the

intensive versions of the system properties are used, that is g (kJ/mol), h

(kJ/mol) and s (kJ/(mol K)), which leads to

= g = h Ts

In summary, if any two phases & (involving a pure substance) are to co-

exist in equilibrium, then the chemical potential (molar Gibbs free energy)

must be the same in each phase

= ...(1.9)a

g = g (1.9)b

TOPIC 1. Pure Species Phase Equilibrium 9

temperature and vice versa. Only one of these two properties can be varied

(the other is automatically fixed by the above phase constraint). Hence, the

system only has one degree of freedom.

Thus, for any phase change (such as any point on the freezing,

sublimation or vaporisation curves) the chemical potential change and

the Gibbs free energy change g between the co-exiting phases must be

= 0 (1.10)a

g = 0 (1.10)b

Equilibrium State: (G )T , P =0 (S )TOTAL = 0 (Reversible)

Non-Equilibrium State: (G )T , P <0 (S )TOTAL > 0 (Irreversible)

Any Change: (G )T , P 0 (S )T , P 0 (Any process)

The advantage of using the Gibbs free energy is that only system properties

are needed. With entropy, the entropy change of the surroundings is also

needed.

Equation (1.5) was taken directly from Process Engineering B, but, due to its

importance, a quick review of its derivation follows. The total Gibbs energy is

defined as

G = H TS

dG = dH TdS SdT

H = U + PV

dH = dU + PdV + VdP

TOPIC 1. Pure Species Phase Equilibrium 10

dU = dQ + dW = TdS PdV

After cancellation this leads directly to equation (1.5) and shows that Gibbs

free energy fundamentally depends on T & P as follows:

dG = VdP SdT

of the relationship between the isothermal pressure-dependence of total Gibbs

free energy and total system volume, since SdT cancels

G

= V ...(1.11)

P T

g

= v .(1.13)

P T

According to equation (1.8) the molar Gibbs free energy is the chemical

potential, so that equation (1.13) may also be written as

= v .(1.14)

P T

species chemical potential is equal to the molar volume (m3/mol). Consider the

isothermal variation of molar Gibbs energy g (chemical potential) with

pressure, as given by equation (1.12)

d = vdP ...(1.15)

TOPIC 1. Pure Species Phase Equilibrium 11

low pressure state P * and any higher pressure state P

d = vdP

* P*

P

* = vdP

P*

Thus, if is finite at pressure P , then the low pressure value for chemical

potential * , as P * 0 .

Both these features make the chemical potential badly behaved

(mathematically speaking) at low pressure.

gases become ideal at this low-pressure limit. Because of the very non-linear

behaviour and the large negative values (as pressure approaches zero)

chemical potential is difficult to use some other variable would be better.

A good idea would be to seek an auxiliary property, one that depends directly

on but, because of the way the auxiliary property is defined, behaves

differently at low pressure.

isothermal variation of for an ideal-gas. If equation (1.15) is true for any

substance in any state, then it must also be true for an ideal gas

dg ig = v ig dP

ideal gas. If the fluid is an ideal gas, then the ideal gas Equation of state, EOS,

may be substituted into the above to give

RT

d ig = dP ..(1.16)

P

ig = RT ln P + ...(1.17)

TOPIC 1. Pure Species Phase Equilibrium 12

The previous equation may be applied to a real fluid, so long as the real

pressure P is replaced by some new property which allows the equation to

hold for real fluids (not just ideal gases).

This new property is given the symbol f , has the same units as pressure

(kPa) and is called fugacity. Thus, for a real fluid the chemical potential is

given by

= RT ln f + ..(1.18)

potential . Subtract equation (1.17) from equation (1.18), and cancel out the

temperature-dependent constant of integration to get

f

ig = RT ln

P

( )

The term on the left ig is the isothermal change in chemical potential,

between real fluid and ideal gas, and this is related to the ratio f / P . This

expression may also written in differential form as follows:

( )

d ig = RT d ln ...(1.19)

f

= ...(1.20)

P

Integrating equation (1.19) along an isothermal path from some low pressure

state to a higher pressure leads to

( ) = RT ln + ..(1.21)

ig

( )

At P = 0 , corresponding to the ideal gas state, ig = 0 , the constant of

integration will be zero. This means that at P = 0 the fugacity coefficient

must be = 1 and f = P .

( ) = RT ln ..(1.22)

ig

TOPIC 1. Pure Species Phase Equilibrium 13

The term on the left is the difference between the chemical potential of a real

fluid and that of an ideal gas at the same temperature and pressure.

As the pressure P 0 , the chemical potential must approach its ideal gas

( )

value ig 0 , in which case 1 and f P .

This completes the second part of the definition where the fugacity approaches

the system pressure as the pressure approaches zero. Thus, for any ideal gas

(in the limit of zero pressure)

( ) = 0 ..(1.23)

ig

ig = 1 (1.24)

f ig = P ..(1.25)

changes in f through equation (1.18). However, because = 0 , it follows

that f P as P 0 .

behaved. At low pressure f P , whereas at low pressure the chemical

potential tends to minus infinity.

f

=

P

could equally well be defined by

f

= ig

..(1.26)

f

Notice, is a correction factor that corrects the fugacity f between the ideal

gas and real fluid state at the same temperature and pressure.

(Process Industries C), corrects the molar volume v between the ideal gas

state and the real fluid state at the same temperature and pressure.

Thus Z corrects the molar volume and corrects the fugacity between the

ideal gas reference and the real fluid state.

TOPIC 1. Pure Species Phase Equilibrium 14

For a pure species the criterion for phase equilibrium (in terms of chemical

potential) between solid S , liquid L and vapour V phases is expressed by an

equation, similar to equation (1.9a), as follows:

S = L = V ...(1.27)

For instance, this could be applied at the Triple Point for any pure substance.

Simpler expressions (but now for only two co-existing phases) could be used

along the vaporisation, freezing and sublimation curves.

= ig + RT ln

( ig

) ( ) (

+ RT ln S = ig + RT ln L = ig + RT ln V )

However, since the temperature and pressure is the same for all phases this

becomes

ln S = ln L = ln V

S = L = V .(1.28)

f S

= f L

= f V ..(1.29)

Thus, for a pure species in phase equilibrium, equation (1.27) states that the

chemical potential must be the same in all phases.

Again, for a pure species in phase equilibrium, equation (1.29) states that the

fugacity must be the same in all phases. This is the criterion for equilibrium

that is used in practice because it is easier to work in term of fugacity.

When trying to find numerical values for the fugacity f it is better to first find

the fugacity coefficient (it is dimensionless). Once this value has been

found then the fugacity f may be recovered from (1.26).

compressibility factor Z first (it is dimensionless) and then determine the

molar volume v from the definition of Z .

TOPIC 1. Pure Species Phase Equilibrium 15

Equation (1.15) shows how the chemical potential of a real fluid varies with

pressure at constant temperature in accordance with

d = vdP

d ig = v ig dP

( ) ( )

d ig = v v ig dP

higher pressure, where ig 0 , leads to

ig = (v v ig )dP .(1.30)

P

The term on the right v v ig is known as the residual volume (m3/mol) and in

many texts is given the symbol v R . It is just the difference between the real

fluid molar volume and the ideal gas molar volume at the same T & P .

leading to the integral on the right which was used in past papers

P

ig = dP

0

is the more usual notation) to get

P

1

RT 0

ln = v R dP .(1.31)

numerical value for and then, through equation (1.26), a numerical value

may be found for the real fluid fugacity f .

TOPIC 1. Pure Species Phase Equilibrium 16

Estimate the fugacity of gaseous propane at 2.4 MPa. and 344 K using the

following P v T data for propane at 160o F (complete this example by hand

in the workbook).

P v v ig vR P v R P

(MN/m2) (m3/kg) (m3/kg) (m3/kg) (kN/m2) (kJ/kg)

0 --- - - - -

0.1724 0.3691

0.3447 0.1810

0.6895 0.08652

1.0342 0.05512

1.2066 0.04598

1.3790 0.03903

2.4000 0.01783

(v )

1 R

P

RT

TOPIC 1. Pure Species Phase Equilibrium 17

(v v )dP ..(1.32)

P

1

ln = ig

RT 0

P

v v ig

ln = dP

0 RT RT

Pv Pv ig dP

P

ln =

0

RT RT P

the molar volume given by v = V / n) in which case the equation above may

also be written as follows:

P

ln = (Z 1)

dP

..(1.33)

0

P

either using either equation (1.31), in terms of residual volume v R , or equation

(1.33), in terms of compressibility factor Z .

from Z -factor charts or tables. This approach was previously discussed in

Process Industries C.

Broadly there are two types of Z -factor correlations that have been

developed:

1. Two-Parameter correlations.

2. Three-Parameter correlations.

Z = Z (Tr , Pr )

TOPIC 1. Pure Species Phase Equilibrium 18

(also dimensionless) are the two parameters and these have already

previously (Process Industries C) been defined as follows:

T

Tr = ..................................................................(1.34)

TC

P

Pr = ..(1.35)

PC

Where,

T is absolute temperature of the system (K).

TC is absolute critical temperature of the fluid (K).

P is absolute pressure of the system (kPa).

PC is absolute critical pressure of the fluid (kPa).

Corresponding States (also known as the Corresponding States Principle

CSP):

All fluids at same Tr and Pr deviate from ideality to the same extent

and, therefore, have the same compressibility factor Z .

The above statement holds for simple gases with symmetrical charge

distribution (such as noble gases Ar, Kr and Xe).

three-parameter generalised correlation relates some property to reduced

temperature Tr , reduced pressure Pr and a third parameter called the

acentric factor .

takes the general form

Z = Z (Tr , Pr , )

Corresponding States:

All fluids with the same acentric factor and at the same Tr and Pr

deviate from ideality to the same extent and, therefore, have the same

compressibility factor Z

TOPIC 1. Pure Species Phase Equilibrium 19

measurement P sat at a specified reduced temperature of Tr = 0.7 :

r

And,

P sat

Prsat = ....(1.37)

PC

For simple gases (Ar, Kr, Xe) the acentric factor is zero. The three-parameter

correlations are more accurate than two-parameter correlations and have a

good accuracy over a full range of states (particularly when using tables).

chart (sometimes written as Z ( 0 ) ); the Z 1 component chart (sometimes written

as Z (1) ). These two component parts of Z are combined in a simple way:

Z = Z 0 + Z 1 ...(1.38)

Z 0 is the major component of Z due to simple gas behaviour.

Z 1 is the minor adjustment to Z due to non-simple behaviour.

The superscripts are used to identify the component part of the compressibility

factor; note well, they are NOT powers of Z .

TOPIC 1. Pure Species Phase Equilibrium 20

Estimate the fugacity of gaseous propane at 2.4 MPa. and 344 K. Estimate the

compressibility factor Z (at each Pr ) from the charts in Appendix A. Complete

this example by hand in this workbook using the following critical and other

properties for propane:

Critical Temperature TC 369.8 K

Critical Pressure PC 42.48 bar

Acentric Factor 0.152

P Tr Pr Z0 Z 1 Z

(MN/m2)

0 0 1 0 1

0.1724

0.3447

0.6895

1.0342

1.2066

1.3790

2.4000

P Z 1 P Z 1

P

(MN/m2)

P

(kN/m2) P

(kN/m2)-1

0 0 -

0.1724

0.3447

0.6895

1.0342

1.2066

1.3790

2.4000

Z 1

P

P

TOPIC 1. Pure Species Phase Equilibrium 21

reduced pressure as follows:

P = Pr PC dP = dPr PC

T = Tr TC dT = dTr TC

Pr

dPr

ln = (Z 1) P

0 r

..(1.39)

Tr

( )

Pr Pr

dP dPr

ln = Z 1 r

0

+ Z1 (1.40)

0

Pr 0

Pr

Tr Tr

Recognise that the two integrals on the RHS are simply component parts of

ln and, labelling them ln 0 and ln 1 , leads to

ln = ln 0 + ln 1

( )( )

= 0 1 ...(1.41)

temperature and reduced pressure and are also available in the form of

charts/tables.

addition, tabulations are also available (Smith, Van Ness, Abbott, 2005).

TOPIC 1. Pure Species Phase Equilibrium 22

Estimate the fugacity of gaseous propane at 2.4 MPa. and 344 K using the

charts supplied in Appendix B. Complete this example by hand in this

workbook using the following critical and other properties for propane:

Critical Temperature TC 369.8 K

Critical Pressure PC 42.48 bar

Acentric Factor 0.152

Tr =

Pr =

0 =

1 =

TOPIC 1. Pure Species Phase Equilibrium 23

saturated vapour curve on the P T diagram (right hand) corresponds to the

two-phase envelope on P v diagram (left hand). The P v diagram only

shows the vapour/liquid region, the solid region is excluded.

The saturated vapour pressure curve terminates at the upper end at the critical

point, labelled C . At the lower end it terminates at the Triple Point, labelled

TP .

CONSTANT T P

P C

C

4 4

3 2 LIQUID

P sat 2&3

1 1

VAPOUR

A B SOLID TP

v T

3-4 shows one such isotherm:

If P < P sat , then fluid is a single-phase vapour see state 1.

If P > P sat , then fluid is a single-phase liquid see state 4.

If P = P sat fluid state is anywhere within the two-phase envelope, i.e.

anywhere between state 2 and state 3.

State 2 corresponds to a saturated vapour state (dryness fraction

one) where no liquid is present.

State 3 corresponds to a saturated liquid state (dryness fraction zero)

where no vapour is present.

Between state 2 and state 3 the dryness fraction varies continuously

from one to zero.

Within two phase envelope 2 3 the state is continually changing but both

T & P are constant. From point 3 to point 4 notice the steepness of the

isotherm. This is the subcooled liquid region and liquids are nearly

incompressible.

TOPIC 1. Pure Species Phase Equilibrium 24

below point 1), the fugacity increases. When the vapour becomes saturated

at point 2, the fugacity of the saturated vapour may be found from P v T

data using the usual integral:

fV

P2

(Z 1) P

dP

ln V =

P State 2 0

formed. The two phases split into a small amount of saturated liquid (state 3)

and a much larger quantity of saturated vapour (state 2).

These two phases are at the same temperature and pressure and are in

equilibrium. Equation (1.5) shows that dg = 0 (along any tie-line). Integrating

between saturated liquid and saturated vapour states leads to

g 2V g 3L = 0

g 2V = g 3L .....(1.42)

There is always only two equilibrium phases co-existing (just different amounts

of each) and the molar Gibbs energy is the same for each of the two phases.

2V 3L = 0

2V = 3L ....(1.43)

(1.18)) between the same two ends stated leads to

f 2V f 3L = 0

f 2V = f 3L ....(1.44)

Finally dividing equation (1.44) by the pressure (which is the same for both

saturated and saturated vapour states) leads to

V2 3L = 0

V2 = 3L ....(1.45)

TOPIC 1. Pure Species Phase Equilibrium 25

At any point along a horizontal tie-line (linking saturated liquid, point 3, and

vapour, point 2, states) T & P remains constant. This means that there is no

change in Gibbs energy, chemical potential, fugacity or fugacity coefficient

along a tie-line.

Thus, once the fugacity coefficient of the saturated vapour state is known (by

any of the methods discussed previously), it follows that the fugacity coefficient

of the saturated liquid state must have the same numerical value.

When a phase change occurs the fugacity is calculated in three separate steps

as follows:

1. The fugacity of the saturated vapour is found, at the target saturation

temperature, by integrating volumetric data from zero pressure to the

vapour pressure.

2. The fugacity of the saturated liquid in equilibrium, making use of

equation (1.44), must be the same.

3. The fugacity of the compressed (or subcooled) liquid can then be

estimated using the method given in the section below.

Charts may be extended to cover the liquid region but, because liquids are

harder to compress (solids are nearly incompressible), properties such as

molar volume and fugacity, for liquids, are only weak functions of pressure.

The analytical method outlined below is a better approach.

d = vdP

d = RTd ln f

v

d ln f = dP

RT

the compressed liquid region)

f P

1

d ln f =

sat RT v L dP

f P sat

TOPIC 1. Pure Species Phase Equilibrium 26

P

f 1

ln

f sat

=

RT v L dP

P sat

Notice how the lower limit of integration is P sat and not zero pressure, so that

there is no difficulty in terms of the right hand integral tending to infinity (liquid

molar volumes are finite at the saturation pressure).

approximation they may be regarded as constant (this is often taken to be the

saturated liquid volume v Lsat ).

P

f v Lsat

ln

f sat

RT dP

P sat

or

ln

f

=

(

v Lsat P P sat )

.(1.46)

sat

f RT

3 and 4 along the isotherm in the subcooled liquid region. Applying these

subscripts to equation (1.46) leads to

f 4 v Lsat (P4 P3 )

ln = ....(1.47)

f3 RT

numerical value can be placed on the term on the right, then the fugacity f 4

(of the subcooled liquid) may be estimated using equation (1.47).

pressure, P << PC - otherwise the assumption of near constant v Lsat starts to

break down. Equation (1.47) is often written as either

fL v Lsat P P sat

= exp

( )

f sat RT

Or,

f L v sat P P sat

= sat P sat exp L

( )

.(1.48)

RT

TOPIC 1. Pure Species Phase Equilibrium 27

L sat

In which f is the fugacity of the compressed liquid state at T & P and f

is the fugacity of the saturated liquid at T & P sat .

The exponential term on the right hand side of equation (1.48) is known as the

Poynting correction factor. It corrects the fugacity between the saturation

state f sat and the compressed liquid state f L .

Very often the Poynting correction factor adds little to the overall accuracy and

it is often taken to be unity (the dimensionless tem within the square brackets

is usually a very small number).

pressure correction (between saturation and compressed liquid states). In this

case the liquid fugacity becomes f L = sat P sat = f sat .

We will make use of this simplification in Topic 3A, VLE for Polar Liquid

Mixtures.

TOPIC 1. Pure Species Phase Equilibrium 28

Estimate the fugacity of liquid propane at 4.8 MPa. and 344 K using the same

gaseous P v T data for propane at 160oF (344 K) as provided in Example

(1.1). The vapour pressure of propane at 344 K is 2.56 MPa.

P v v ig vR P v R P

(MN/m2) (m3/kg) (m3/kg) (m3/kg) (kN/m2) (kJ/kg)

0 --- - - - -

0.1724 0.3691

0.3447 0.181

0.6895 0.08652

1.0342 0.05512

1.2066 0.04598

1.3790 0.03903

2.4000 0.01783

2.5600

(v )

1 R

P

RT

The specific volume and pressure data for the liquid (past the point of

saturation) is given below:

P v

10 3

(MN/m2) (m3/kg)

2.551 2.446

2.758 2.446

3.447 2.404

4.800 2.338

TOPIC 1. Pure Species Phase Equilibrium 29

EOS may be used to find the fugacity coefficient of a pure species.

pressure using an EOS. This approach is based on the fact that two co-

existing phases must have the same fugacity coefficient.

Experimental Projects. Also, these methods are widely used in Process

Simulators to estimate thermodynamic properties of fluids.

TOPIC 1. Pure Species Phase Equilibrium 30

1.4 Tutorial 1

50.5 bar and 24.95oC using the following data:

Molar mass of ethylene is 28.05 g/mol.

(bar) ( 10 4 m 3 /mol )

1.0 245.00

5.1 47.80

10.1 23.20

15.2 15.00

20.2 10.80

25.3 8.34

30.3 6.66

35.4 5.44

40.4 4.52

45.5 3.78

50.5 3.17

Solutions:

= 0.73854

f = 37.30 bar

275K, using the following methods:

a) At 24.6 bar assuming ideal gas behaviour.

b) At 24.6 bar using the Z factor method.

c) At 24.6 bar using the generalised fugacity coefficient charts.

Critical properties for ethane are given below:

PC = 48.72 bar

TC = 32.17 o C

= 0.100

TOPIC 1. Pure Species Phase Equilibrium 31

Pressure

(bar)

0.0

1.0

2.0

4.0

8.0

12.0

14.8

19.7

24.6

Solutions:

a) f = 24.6 bar

b) f = 18.43 bar

c) f = 18.97 bar

and specific volume of 0.000657 m3/kg. The molar mass of carbon

dioxide is 44.01 kg/kmol

using the following the P v T data for gaseous carbon dioxide.

3

(bar) (m / kg )

0.01020 33.36600

0.03061 13.02200

0.07483 5.32870

0.13605 2.92280

0.37415 1.05870

0.95236 0.41189

2.44897 0.15600

4.09918 0.09120

Solution:

f = 2.83 bar

TOPIC 1. Pure Species Phase Equilibrium 32

1.5 Bibliography

McGraw-Hill, SI ed., 1987.

Wiley 2nd ed., 1993.

ed., 1998.

S.I. Sandler. Chemical and Engineering Thermodynamics. Wiley, 3rd ed., 1999.

Engineering Thermodynamics. McGraw-Hill. 7th ed.,2005.

TOPIC 1. Pure Species Phase Equilibrium 33

Appendix A

State EOS as modified and improved by Lee-Kesler.

TOPIC 1. Pure Species Phase Equilibrium 34

State EOS as modified and improved by Lee-Kesler.

TOPIC 1. Pure Species Phase Equilibrium 35

Reproduced and scanned from Smith, Van Ness, Abbott, 5th. Ed.

TOPIC 1. Pure Species Phase Equilibrium 36

Appendix B

Reproduced and scanned from Smith, Van Ness, Abbott, 5th. Ed.

TOPIC 1. Pure Species Phase Equilibrium 37

Reproduced and scanned from Smith, Van Ness, Abbott, 5th. Ed.

TOPIC 1. Pure Species Phase Equilibrium 38

Reproduced and scanned from Smith, Van Ness, Abbott, 5th. Ed.

TOPIC 1. Pure Species Phase Equilibrium 39

Reproduced and scanned from Smith, Van Ness, Abbott, 5th. Ed.

TOPIC 1. Pure Species Phase Equilibrium 40

Appendix C

This Appendix will be useful since many process simulators find pure species

fugacity coefficients this way.

The PR EOS can also be used to find pure component fugacity coefficients

as follows:

given below; all that is needed are the critical properties of the pure

species (critical temperature, critical pressure and acentric factor).

RTC

b = 0.0778 .(C.1)

PC

2

R 2TC

aT = 0.45724 a (T ) ...(C.2)

PC

[ (

(T ) = 1 + (0.37464 + 1.5422 0.26992 2 ) 1 Tr 0.5 )]

2

..(C.3)

A & B parameters:

aT P

A= .................(C.4)

R 2T 2

bP

B= ...(C.5)

RT

3. Find the three roots of the PR EOS written below in standard cubic

form (notice that all terms in this equation are dimensionless):

Z 3 + ( B 1) Z 2 + ( A 2 B 3B 2 ) Z + ( AB + B 2 + B 3 ) = 0

..(C.6)

TOPIC 1. Pure Species Phase Equilibrium 41

4. Select one of the three roots (see point 5 below) and substitute this

value of Z into expression below to find the pure species :

ln = (Z 1) ln(Z B)

aT ( )

Z + 1+ 2 B

ln

( )

2 2 bRT Z + 1 2 B

..(C.7)

5. The largest root should be selected when P < P sat . Equation (C.7)

then returns the vapour fugacity coefficient.

The smallest root should be selected when P > P sat . Equation (C.7)

then returns the liquid fugacity coefficient.

These equations are normally only used to find the fugacity coefficient of non-

polar/hydrocarbon liquids. For better liquid phase property prediction, special

adjustments are made to the some of the equations listed above.

For liquid and vapour phases to co-exist in equilibrium, equation (1.29) must

be satisfied as follows:

f L

= fV

Since both phases are at the same T & P this is the same as

L = V (C.8)

If the temperature T is fixed and the pressure P is varied and if both the

largest and the smallest roots are substituted into equation (C.7), then both

liquid and vapour phase fugacity coefficients L & V will be returned at the

prevailing temperature T .

corresponding to the pure vapour phase, the other to the pure liquid phase.

The point where the two curves intersect corresponds to equation (C.8).

Referring to point 5 above, when the two phases have the same fugacity

coefficient, the smallest root corresponds to the saturated liquid Z L , the

largest root to the saturated vapour Z V and P = P sat .

Pi sat of a pure species at any temperature T - the temperature must lie

between the Triple Point TP and the Critical Point C of the species.

TOPIC 1. Pure Species Phase Equilibrium 42

The vapour part of the versus P curve is virtual when P > P sat . The liquid

part of the versus P curve is virtual when P < P sat . Where the two curves

meet is the only point where the two phases can co-exist in equilibrium

together; this point corresponds to P = P sat .

For water at 100oC this point will be 101.325 kPa (the vapour pressure of

water at 100oC). Since this vapour pressure corresponds to 1 atm, it means

that the NBP of water is 100oC.

TOPIC 1. Pure Species Phase Equilibrium 43

TOPIC 1. Pure Species Phase Equilibrium 44

TOPIC 2: VLE for Non-Polar Mixtures 1

Topic 2

Contents

TOPIC 2: VLE FOR NON-POLAR MIXTURES

2.1 INTRODUCTION .................................................................................................................. 3

2.1.1 The Apportioning Rule, the Recombination Rule and Gibbs-Duhem.................... 3

2.2 CRITERIA FOR PHASE EQUILIBRIUM .................................................................................... 5

2.2.1 Gibbs Free Energy of a Mixture ........................................................................... 5

2.2.2 Daltons Law........................................................................................................ 7

2.2.3 Fugacity Coefficient of a Component in a Mixture................................................ 7

2.2.4 Ideal Solutions and Lewis-Randall Rule .............................................................. 8

2.2.5 Criterion for Multicomponent Phase Equilibrium ................................................ 10

2.2.6 Fugacity as a Criterion for Mixture Phase Equilibrium........................................ 12

2.2.7 Finding Fugacity Coefficient of a Component in a Mixture ................................. 13

2.3 VLE FOR NON-POLAR SYSTEMS ...................................................................................... 15

2.3.1 Rigorous Phi-Phi Approach to VLE .................................................................... 15

2.3.2 Liquid and Vapour as Ideal Solutions ................................................................ 17

2.3.3 Raoults Law: Liquid as an Ideal Solution and Vapour as an Ideal

Gas........................................................................................................................ 18

2.3.4 Phi-Phi VLE Summary ....................................................................................... 19

2.3.5 Finding K-Values using Charts .......................................................................... 20

2.3.6 Example 2.1 ...................................................................................................... 22

2.3.7 Vapour Pressure Correlation ............................................................................. 25

2.3.8 Temperature-Composition Diagram for Binary System ...................................... 27

2.3.9 Significance of K-Values.................................................................................... 28

2.4 PHASE EQUILIBRIUM CALCULATIONS ................................................................................ 29

2.4.1 Bubble Point Calculations .................................................................................. 29

2.4.2 Dew Point Calculations...................................................................................... 31

2.4.3 Example 2.2 ...................................................................................................... 32

2.4.4 Example 2.3 ...................................................................................................... 34

2.4.5 Flash Calculations ............................................................................................. 36

2.4.6 Example 2.4 ...................................................................................................... 42

2.5 TUTORIAL 2..................................................................................................................... 44

2.6 BIBLIOGRAPHY ................................................................................................................ 51

APPENDIX A.......................................................................................................................... 52

De Priester Charts see next page............................................................................ 52

A1 High Temperature Chart: ...................................................................................... 53

A2 Low Temperature Chart: ....................................................................................... 54

A3 Antoine Coefficient Table ...................................................................................... 55

APPENDIX B.......................................................................................................................... 56

Rigorous Phi-Phi VLE Worksheet ............................................................................... 56

TOPIC 2: VLE for Non-Polar Mixtures 2

APPENDIX C ......................................................................................................................... 61

Review of Partial Molar Properties ............................................................................. 61

C-1 Partial Molar Property Overview .......................................................................... 62

C-2 Definition of Partial Molar Property ...................................................................... 64

C-3 Partial Molar Properties from Correlations ........................................................... 66

C-3 Partial Molar Properties from Diagrams ............................................................... 68

C-4 Recombination Rule ............................................................................................ 71

C-5 Gibbs-Duhem Equation....................................................................................... 72

C-6 Partial Molar Property Relations .......................................................................... 75

Prerequisite knowledge

Process Industries C.

Process Engineering B.

Learning objectives

After studying this VLE for Non-Polar Mixtures topic you should be able to:

Write down definition for a partial molar property

Identify and differentiate nomenclature for mixture property, pure

component properties and partial molar properties.

Review partial molar properties and their importance in terms of

developing phase equilibrium strategies for non-polar systems.

Define the apportioning rule, the recombination rule and the Gibbs-

Duhem rule for partial molar properties.

For any pure component property relation, find the corresponding

partial molar property analogue.

Define the Lewis-Randall Rule and Daltons Law.

Derive the Gibbs free energy in terms of the intensive properties of the

system and then identify the chemical potential.

Define the fugacity coefficient of a component in a mixture and

demonstrate ways of obtaining numerical values.

Derive the criteria for multicomponent phase equilibrium in terms of

chemical potential and the fugacity of a component in a mixture.

Discuss the concept of ideal solutions and derive partial molar

properties of components in an ideal solution.

Define K value and demonstrate how these quantities may be used

to solve VLE problems using a variety of simplifying assumptions.

Demonstrate the use of de Priester charts.

Derive expressions for Raoults Law and Raoults Law K values.

Define and explain the Antoine vapour pressure correlation.

Explain and execute bubble/dew point and flash VLE calculations.

Outline the rigorous phi-phi approach to VLE and how problems may

be solved using an EOS and a maths package.

TOPIC 2: VLE for Non-Polar Mixtures 3

2.1 Introduction

skill that must be mastered by Chemical Engineers. This topic shows how to

derive and solve phase equilibrium expressions to cover such systems.

molar property. A detailed review of partial molar properties is given in

Appendix C, what follows here are the basic partial molar property relations.

property m may be apportioned between the various components in the

solution. For component i the apportioning rule is given by

(nm )

mi = ..(2.1)

ni T , P ,n j

Where,

mi is the partial molar property of species i in the mixture at T & P .

m is the overall solution property at the same T & P .

mi is the pure-component property of i at the same T & P .

n is the total number of mole of the mixture.

partial derivative of the total solution property M = nm with respect to the

mole number of species i :

T & P must be held constant.

Constant n j means that the mole number of all other species except

the i th (the one that is being varied) must be held constant.

Other properties, such as chemical potential, fugacity and fugacity coefficient,

may also be apportioned between the components in the solution and have

their own respective partial molar analogues.

recombine them. Thus, it should be possible to recover some mixture molar

property m from it corresponding partial molar properties mi .

TOPIC 2: VLE for Non-Polar Mixtures 4

n

m = xi mi .(2.2)

i =1

The partial molar properties are functions not only of T & P but also of

composition. If the partial molar properties can be recombined using equation

(2.2), then they cannot vary independently of each other.

The property relation that expresses this dependency is called the Gibbs-

Duhem equation. In its more general form (see Appendix C) it is given by

m m

P dP + T dT xi dmi = 0 (2.3)

T ,x P, x i

However, if T & P are held constant, then equation (2.3) reduces to the most

widely used form of the Gibbs-Duhem equation

x dm

i

i i = 0 ....(2.4)

This can also be expressed at constant T & P , for molar volume, as follows:

n dv = dV

i

i i

i

i =0

Hence, any change in the mole number of a species will change its extensive

partial molar volume so the above expression must sum to zero at equilibrium.

If T and/or P are changed, then this relationship may be used to find

changes in phase equilibrium composition.

In Appendix C it is also shown that for every pure component property relation,

such as, for instance the two well-known expressions below

g i = hi Ts i and, hi = u i + Pvi

properties. Thus, it is possible to immediately write

g i = hi Ts i and, hi = u i + Pvi

TOPIC 2: VLE for Non-Polar Mixtures 5

chemical equilibrium and it needs to be examined closely

Any extensive property M may be expressed in terms of T & P and the mole

number of each species n1 , n 2 ......ni as follows:

M = f (T , P, n1 , n 2 ......ni )

In the same way, the total Gibbs free energy of a mixture G may also be

expressed in terms of T & P and n1 , n 2 ......ni as follows:

G = f (T , P, n1 , n2 ......ni )

G G G

dG = dP + dT + dni

P T ,n T P ,n i ni T , P , n

j

But, since the total Gibbs free energy is G = ng , then this may be written as

d (ng ) = dP + dT + dni ..(2.5)

P T ,n T P ,n i ni T , P , n

j

The first two partial derivatives in the above equation have been shown to be

nv and - ns (Process Engineering B) and this leads to

(ng )

d (ng ) = (nv )dP (ns )dT + dni ...(2.6)

i ni T , P , n

j

Compare the last term with the general definition of a partial molar property

from the apportioning rule, as expressed by equation (2.1) as follows;

(nm )

mi =

ni T , P ,n j

TOPIC 2: VLE for Non-Polar Mixtures 6

(ng )

gi = ..(2.7)

ni T , P , n j

i

Divide through by n , the total number of moles of all species in the mixture

i

variables of the system, namely T , P & xi . Hence, Chemical Engineers can

alter phase equilibrium by changing any of these properties T , P & xi .

In the previous topic the relationship ( g i = i ) was shown to hold for pure

components. Thus, it follows that the partial molar analogue must be

g i = i ...(2.10)

i must also be given by

(ng )

i = ..(2.11)

ni T , P , n

j

i

potential of the species in a mixture at the same T & P . The meaning of the

circumflex over the chemical potential will become apparent later.

criterion for Vapour Liquid Equilibrium (VLE). However, it is better to first

review some fugacity and fugacity coefficient relations.

TOPIC 2: VLE for Non-Polar Mixtures 7

an ideal gas mixture p i is the pressure the species would exert if ni moles of

the species occupied the entire mixture volume V at the same temperature T

as the mixture.

ni RT

pi =

V

While, the total pressure P is related to the total number of moles n of all

species in accordance with the ideal gas EOS below

nRT

P=

V

p i ni

= = yi

P n

p i = Py i .....(2.13)

Equation (2.13) is known as Daltons Law. In many texts the partial pressure is

denoted by p i and the total pressure by P . However, the difference between

uppercase P and lowercase p i can lead to confusion.

uppercase P will be reserved to denote the system (or total) pressure.

fi

i =

f i ig

f i ig = P

TOPIC 2: VLE for Non-Polar Mixtures 8

i and the

fugacity of a component in an ideal gas fi ig are given by their corresponding

partial molar analogues:

= f i (2.14)

i

fi ig

fi ig = y i P ..(2.15)

Substitute equation (2.15) into equation (2.14) to get an alternate definition for

i as follows:

i = f i ..(2.16)

Py i

pressure f i P , while the fugacity of a component in a mixture approaches

its partial pressure fi y i P

Although often used for liquid phase mixtures, the ideal solution concept may

also be applied to gas phase mixtures. Pure-components, when mixed

together, form an ideal-solution whenever there is no heat or volume change

on mixing effects.

This means that the molar volume that a component appears to have in an

ideal solution is the same as its pure component molar volume

viid = vi = vi ...(2.17)

The superscript "id " is used to differentiate an ideal solution from an ideal

gas. These are different models and this should be clearly understood.

For a gas to behave as ideal gas the volume of the molecules, and the forces

of attraction between molecules, must both be negligible. On the other hand,

for a solution to behave as an ideal solution it is only necessary that:

1. Like and unlike molecules have similar size and shape.

2. Like and unlike molecules have similar forces of attraction.

TOPIC 2: VLE for Non-Polar Mixtures 9

homologous series, i.e. an n-hexane/n-heptane mixture.

Not many liquid mixtures behave as ideal solutions principally because, in the

liquid phase, the molecules are closer together and any difference in size,

shape and forces of attraction tends to be significant.

On the other hand, most gas mixtures at low to moderate pressure (although

not ideal gases) may behave as ideal solutions. This is because the molecules

are much further apart and any differences between like and unlike species

are less pronounced.

the limit of very high concentration. The question is: for an ideal solution, how

does the fugacity of a component in a mixture i behave?

In Topic 1 it was shown that the pure component fugacity coefficient may be

calculated by solving the integral on the right of the expression below:

(v v )dP

P

1

ln = ig

RT 0

(v )

P

i = 1

ln i viig dP ....(2.18)

RT 0

But for an ideal solution viid = vi . Substitute this into equation (2.18) to get the

fugacity coefficient of a component in an ideal solution

idi

(v )

P

1

ln

idi = i viig dP

RT 0

In addition, the partial molar volume of an ideal gas, at the same T & P as the

mixture, must be equal to its pure component value viig = viig . Thus, the

previous expression becomes

(v )

P

id = 1

ln viig dP .(2.19)

i i

RT 0

TOPIC 2: VLE for Non-Polar Mixtures 10

Compare this to the pure component fugacity coefficient i that was derived

earlier in Topic 1

(v )

P

1

ln i = i viig dP

RT 0

idi

must be equal to its pure component value i

id = ....(2.20)

i i

idi into the left and the definition of i into

the right and then re-arrange

fi id f

= i

yi P P

fi id = y i f i ....(2.21)

This important equation is known as the Lewis-Randall Rule and shows that

the fugacity of a component fi id depends on the pure component fugacity f i

and the composition y i .

the mixture, as the solution approaches purity in that component. For liquids it

is customary to denote compositions by xi otherwise the Lewis-Randall Rule

is the same.

It has been shown that thermal equilibrium occurs when the potential for heat

transfer is zero, i.e. the temperature (the thermal potential) is the same either

side of the system boundary at this point heat transfer stops.

It has also been shown that mechanical equilibrium occurs when the potential

for work transfer is zero, i.e. when the pressure (the mechanical potential) is

the same either side of the system boundary at this point work transfer

stops.

TOPIC 2: VLE for Non-Polar Mixtures 11

It has also been shown that (for a pure species) phase equilibrium occurs

when the potential for mass transfer between the phases is zero, i.e. when the

chemical potential (the mass transfer potential) is the same in either phase:

At this point net interphase mass transfer stops and both phases co-

exist together in equilibrium.

If the pressure is fixed, this can only occur at one temperature (for

water at 1 atm pressure this temperature corresponds to the NBP of

100oC).

approaches zero. The criterion for pure species phase equilibrium was

developed in Topic 1. The derivation for multicomponent phase equilibrium

follows the same steps up to the point where it was shown that, for phase

equilibrium, dG = 0 .

components (these are all contained within a closed system). In addition, all

the phases must be at a uniform T & P .

between these phases and N components occurs whenever

dG = 0

After making the substitution g i = i into equation (2.8), the change in total

Gibbs energy G within any phase, denoted as the -phase, is given by

(

d (ng ) = (nv ) dP (ns ) dT + i dni )

i

Likewise for any other phase, denoted as the -phase, this becomes

(

d (ng ) = (nv ) dP (ns ) dT + i dni )

i

For the moment restrict the case to only two phases, and . In a VLE

system, for instance, could be vapour and could be liquid. This result will

be extended to all phases later).

Adding the above two equations together, at constant T & P , gives the total

change in Gibbs energy dG for both the -phase and the -phase

dG = d (ng ) + d (ng )

TOPIC 2: VLE for Non-Polar Mixtures 12

Thus, the total Gibbs free energy of both phases at constant T & P is given by

( )

dG = i dni + i dni ( )

i i

However, (for the moment) there are only two phases within this closed

system. Thus, any change in the number of moles of any species i in the -

phase must produce an equal and opposite change in the number of moles of

species i in the -phase.

equilibrium between these two phases

( )dn = 0

i

i i i

However, dni is arbitrary, so that the only way the above summation can

always be zero is when the chemical potential (of each species) in both

phases is the same at equilibrium.

i = i (i = 1,2......N ) (2.23)

This reasoning holds for any other pair of phases (taking care to keep one

phase out of each pair of phases the same).

This leads to the following general criterion for phase equilibrium between all

phases (the criterion must hold for each component in the mixture):

When this condition is satisfied net mass transfer of all species, between all

phases, ceases and the phases are all in equilibrium.

It has been shown that all relations between pure component properties have

their partial molar property analogues. Thus, the chemical potential of a

component in a mixture i must be given by

i = RT ln fi + ...(2.25)

TOPIC 2: VLE for Non-Polar Mixtures 13

equation (2.25) into the general criterion for equilibrium, equation (2.24). After

cancelling, since all phases are at the same T & P , this becomes

Equation (2.24) is the general criterion for phase equilibrium in terms of the

chemical potential. However it is difficult to apply since i is mathematically

badly behaved at low pressure.

equilibrium, but now in terms of the fugacity of a component in a mixture fi :

fi behaves in a similar way as i but is easier to deal with.

is related to f through its definition - see equation (2.14) or

i i

equation (2.16)

i is related to measurable P v T data see below.

given by equation (2.18). This equation is shown again below:

(v )

P

i = 1

ln i viig dP

RT 0

in practice) is quite straightforward:

Solve equation (2.18), or similar, to find the fugacity coefficient of a

component in the mixture i for both phases.

Use the definition of

i , equation (2.14) or (2.16), to find the fugacity

of all the components in the mixture fi .

Adjust the intensive properties ( T , P, xi or y i ) until the condition for

phase equilibrium, equation (2.26), is satisfied.

i are complex functions of the

intensive properties of the mixture ( T , P, xi y i ) and this complicates the

problem.

TOPIC 2: VLE for Non-Polar Mixtures 14

1. Make simplifying assumptions that lead either to simpler algebraic

equations (with less complex functional dependency), or to charts

which are straightforward to use.

2. Retain the rigorous approach and use a Mathematics package to help

solve all the equations needed to satisfy the phase equilibrium

condition complex functional dependency is then not an issue.

i , is now

apparent. Compare the expression from Topic 1

P

1

ln =

RT 0

v R dP

P

i = 1 viR dP

RT 0

ln

From the first equation we see that solution property m ln while it partial

molar analogue is mi ln

. In other words the partial molar property

i

includes the logarithm.

i

component in a mixture but not, by themselves, partial molar properties.

but not, by itself, a partial molar property. In fact in this case the partial molar

property is ln( fi / xi ).

The argument for the circumflex above i is a little different. It has been

shown that i = g i , but whereas g i may appear as either intensive or

extensive form, the same is not true of i which, being a potential, may only

be intensive.

Section 2.3 outlines how to solve these phase equilibrium relationships for

non-polar systems (often hydrocarbon mixtures).

TOPIC 2: VLE for Non-Polar Mixtures 15

VLE problems in the hydrocarbon industry have typically been solved using so

called K values. Other methods are now possible but so many K value

charts have been generated that the method is still used.

The original charts have largely been superseded by EOS and computer

simulation packages. However, K value charts are still helpful in terms of

visualising and solving VLE problems.

yi

Ki = .....(2.27)

xi

The most useful criterion for phase equilibrium is given by equation (2.26). For

purely VLE problems equation this becomes

Where the vapour and liquid phases are indicated by superscripts applied to

each fugacity. The vapour phase fugacity coefficient

V is defined as

i

V

Vi = f i

fi ig

fiV =

Vi y i P ....(2.29)

With the phi-phi approach to VLE, the same expression is used to find the

fugacity coefficient of a component in the liquid phase

iL mixture.

fi L =

L x P ..(2.30)

i i

Notice that the ideal-gas is used as reference state for both vapour & liquid

phases. All that changes, for the liquid phase, is that xi is substituted for y i .

TOPIC 2: VLE for Non-Polar Mixtures 16

Substitute equations (2.29) and (2.30) into equation (2.28) then, after

cancellation, the general phi-phi VLE relationship becomes

Vi y i =

iL

Ki = ........................................(2.32)

Vi

Equation (2.31) is suitable for non-polar mixtures and has the distinct

advantage of being predictive (not based on empirical correlations). A single

EOS is used to predict both liquid and vapour

i values.

Rubin BWR equation was popular and many modifications to it were

developed to improve its accuracy.

More recently cubic equations of state have become more popular. The

Redlich-Kwong-Soave RKS and the Peng Robinson PR EOS are now very

accurate, even quite close to the critical point.

VLE problems (for non-polar liquids) are usually solved using equation (2.31).

However, this may be recast as follows:

(v )

P

iL = 1

ln i

L

viig dP

RT 0

(v )

P

V = 1

ln V

viig dP

i i

RT 0

Subtracting the second equation from the first and combining the integral

terms leads to

(v )

iL 1

P

ln = i

L

viV dP .

iV

RT 0

In which case

(v )

P

1

ln K i = i

L

viV dP .(2.33)

RT 0

TOPIC 2: VLE for Non-Polar Mixtures 17

MathCad worksheet is supplied in Appendix B as an example. The answer is

verified in a standard textbook (Smith, Van Ness and Abbott, 2005).

Either equation (2.32) or equation (2.33) may be used to find the species

K i value and hence solve VLE problems. Equation (2.32) is the most direct.

iL = f (T , P, xi ) and

be examined.

If both the liquid phase and the vapour phase can be assumed to be ideal

solutions, then equation (2.20) applies

id = . In this case equation (2.31)

i i

reduces to

iL

K i = V ..........................................(2.35)

i

of writing these expressions are as follows:

f iV y i = f i L x i ...... (i = 1,2,3.....N )

fiL

K i = V ..(2.36)

fi

Equations (2.34) and (2.35) are preferred because equations of state are set

up to calculate dimensionless fugacity coefficients.

TOPIC 2: VLE for Non-Polar Mixtures 18

Gas

fiV = fi L (i = 1,2......N )

fiV =

Vy P

i i

V = 1 and each f V is equal

i i

to the partial pressure of the component in the vapour phase mixture

fiV = y i P ......(2.37)

iL was shown to be given by equation

(2.30) as follows:

fi L =

iL y i P

But if the liquid phase is an ideal solution i i

becomes

fi L = iL xi P

fiL

fi =

L

xi P

P

fi L = x i f i L ..(2.38)

equation (2.37) and (2.38) into (2.28) to get

y i P = x i f i L (i = 1,2......N ) ..(2.39)

At very low pressure the pure component fugacity approached the system

pressure f i P .

TOPIC 2: VLE for Non-Polar Mixtures 19

Thus, the fugacity of a pure liquid f i L (at low pressure) must approach the

pressure exerted by the pure liquid at the same temperature as the mixture.

Thus, for an ideal solution at very low pressure the liquid phase fugacity is

simply f i L = Pi sat and equation (2.39) becomes

This is known as Raoults Law and is the simplest VLE model, often called the

ideal VLE model. It assumes an ideal gas, the vapour phase, in equilibrium

with an ideal solution, the liquid phase.

Raoults Law should be used with caution, since many systems depart from

Raoults Law and it cannot be used to model azeotropic behaviour as shown in

Topics 3A and 3B. Notwithstanding, for non-polar systems Raoults Law is

often applicable.

iL xi ...... (i = 1,2,3.....N )

Vi y i =

and

iL

Ki = V

i

Vi y i = iL xi ...... (i = 1,2,3.....N )

and

iL

Ki = V

i

equivalent to Raoults Law:

y i P = xi Pi sat . (i = 1,2......N )

TOPIC 2: VLE for Non-Polar Mixtures 20

From the last expression, the Raoults Law K values are given by

Pi sat

Ki = ..(2.41)

P

It gets progressively easier to solve VLE problems (and find the K values)

as one moves from case 1 through to case 3.

There is also a 4th case (to be considered in Topic 3). This is the case where

the vapour phase is modelled as an ideal gas mixture (low pressure), but the

liquid phase is modelled as a non-ideal solution.

Raoults Law and will be discussed in the next topic. Many polar systems fit

this model of solution behaviour.

(namely the component K i values) are usually obtained from an Equation of

State EOS.

very accurate for hydrocarbon mixtures the equation is given below:

RT C 1 1 aa 1+ / v2

P= + B0 RT A0 02 2 + (bRT a ) 3 + + c exp 2

v T v v v v

6 3 2

vT

The molar average boiling point was used to take into account the effect of

composition. With this information K i -values were calculated (using the BWR

EOS) for 12 light hydrocarbons, for pressures up to 250 bar.

The results were presented as 324 charts known as Kellogg charts with K i -

values plotted a function of T , P and molar average boiling point. However,

the charts are laborious to use, especially when frequent estimates of K i -

values are needed. As a result, simpler methods have been developed.

De Priester prepared a set of nomographs (from the Kellogg charts) and these

are often used in place of Kellogg charts. In the de Priester nomographs, the

composition dependence of the K i -values has been completely removed

using an averaging process see Appendix A for a copy of these charts.

TOPIC 2: VLE for Non-Polar Mixtures 21

The results are less accurate than using Kellogg charts, but are adequate for

first-order estimates; they are also helpful when trying to visualise how K i -

values change with T & P .

1. Low Temperature Chart -70oC to 20oC 1 bar to 50 bar

2. High Temperature Chart 10oC to 200oC 1 bar to 50 bar

As mentioned above, many EOS have been used to solve VLE problems.

Currently attention has focussed on using cubic EOS. Cubic EOS were

reviewed and discussed in an earlier course (Process Industries C).

It was also explained (in Process Industries C) how cubic EOS may be used to

find not only vapour but also liquid properties; in the past they were used

mainly for vapour phase properties, but recent refinements have led to

improved liquid phase property estimation.

See Appendix B for all the relevant equations and a worked example that

shows how to solve a rigorous VLE problem using the rigorous phi-phi method.

TOPIC 2: VLE for Non-Polar Mixtures 22

component VLE system. Assume that both the liquid and vapour phases

behave as an ideal solution.

Use the generalised fugacity coefficient chart provided over the page. When

using this chart pure i , at these conditions, will be found to be a vapour. This

means that the liquid phase fugacity state is fictitious and, hence, the liquid

phase fugacity coefficient iL must be found by extrapolation from the real

liquid states to this fictitious liquid state.

TOPIC 2: VLE for Non-Polar Mixtures 23

TOPIC 2: VLE for Non-Polar Mixtures 24

TOPIC 2: VLE for Non-Polar Mixtures 25

diagram, for a binary system, will look like the one shown below:

plotted on the y axis.

sat

Subcooled X P1

Liquid P x1 Species 1 is the MVC,

P y1 while 2 is the LVC.

sat L-V

P X

2

The P x1 line (bubble

P

Superheated point curve) is the

Vapour saturated liquid line.

0 1.0

curve) is saturated vapour

x1 & y1

line.

If the system is an ideal VLE system and if the temperature is below the

critical temperature of both components, then the system pressure will vary

from P2sat (LVC) to P1sat (MVC) and the P x1 line will be straight.

To understand why an ideal VLE system behaves in this way write down

Raoults Law twice; first for species 1 and then for species 2:

y1 P = x1 P1sat .(2.42)

y 2 P = x 2 P2sat ....(2.43)

The term on the left of equation (2.42) is the partial pressure of pure

component 1, while the term on the left of equation (2.43) is the partial

pressure of pure component 2.

the partial pressure of 2 is just the total system pressure P which leads to

P = y1 P + y 2 P = x1 P1sat + x 2 P2sat

P = x1 P1sat + (1 x1 )P2sat

TOPIC 2: VLE for Non-Polar Mixtures 26

( )

P = P2sat + x1 P1sat P2sat ....(2.44)

line (saturated liquid line). Clearly, equation (2.44) takes the form y = mx + c .

Thus, is follows that the P x1 line must be straight.

However, this result is only true for ideal systems. For non-ideal systems the

P x1 line is not straight, but the system pressure P must still lie between

P1sat & P2sat (assuming there are no supercritical components present).

Raoults Law K values are given by

y i = K i xi

Pi sat

Ki =

P

good correlation for the vapour pressure P sat is the Antoine equation.

B

ln P sat = A (2.45)

T +C

In which A, B & C are species specific constants which are widely available in

standard reference books see Appendix A3 (Smith, Van Ness and Abbott,

2005). Take note that the Antoine equation is sometimes expressed as

B

log10 P sat = A

T +C

Clearly the numerical value of the constants A, B & C differ (even for the

same species) depending on the units used for T & P sat whether or not

natural logarithms are used.

only. Note that the vapour pressure Pi sat only has physical meaning on the

vaporisation curve between the triple point and critical point temperatures.

TOPIC 2: VLE for Non-Polar Mixtures 27

held constant. A T x y diagram (for the same ideal system) is shown

below; in this case the pressure is fixed:

Constant P

Superheated is LVC.

T2sat Dew Point Vapour Region

Curve

point curve) is saturated

T x1 T y1

L-V Two-phase liquid line.

Region

T

T y1 curve (dew point

Subcooled

Liquid Region Bubble Point T

1

sat

curve) is saturated

Curve

0

vapour line

0 1.0

x1 & y1

Notice that, even though system is still ideal, neither the T x1 curve nor the

T y1 curve is a straight line. This is because the vapour pressure of each

component varies with temperature:

The saturated liquid curve, and the subcooled liquid region, now lies below

the two-phase region. The saturated vapour curve, and the superheated

vapour region, now lies above the two-phase region.

The intercepts T2sat & T1sat are the boiling points of pure 2 and pure 1

respectively (at the fixed pressure P ). The Antoine equation may also be used

to find these two pure component saturation temperatures.

temperature Ti sat is needed to maintain the vapour pressure equal to the

applied pressure Pi sat = P ? The answer to this question is the pure

component saturation temperature Ti sat .

Distillation columns operate with a more or less constant pressure, but with

significant temperature variations along the column. For a binary system, this

type of equipment is best represented by a T x y diagram.

TOPIC 2: VLE for Non-Polar Mixtures 28

y i P = xi Pi sat . (i = 1,2......N )

Pi sat

Ki = . (i = 1,2......N )

P

These Raoults Law K i values depend only on T & P but will vary from

pure species to pure species at the same T & P . Thus, for any pure species:

It is clear that as the pressure decreases the K i values will increase.

And as the temperature increases the K i values will increase.

These findings may be confirmed by running a ruler horizontally up a

de Priester chart (as the ruler goes up, the temperature rises and

pressure drops). As this is done, the K i values for all species will

increase.

Now, keeping T & P constant, read from right to left and note that the de

Priester K i values of each pure species shows an increasing trend. Going

from right to left corresponds to going from heavier to lighter species.

Heavier species have a higher molar mass (molecular weight) than lighter

species. Species with a lower molar mass have a higher value of Pi sat at the

same temperature T .

mixture. An Increasing K i value corresponds to a greater volatility of the

component. Higher volatility is associated with:

1. A decrease in pressure P (releasing more vapour).

2. An increase in temperature T (greater Pi sat for all species).

3. A decrease in molar mass (lighter species have greater Pi sat than

heavier species, at the same T ).

the larger the difference in volatility, the easier the separation. As will be seen

later azeotropes occur when both species have the same volatility. Distillation

alone cannot separate an azeotropic mixture.

TOPIC 2: VLE for Non-Polar Mixtures 29

For bubble point or dew point calculations usually either T or P will be fixed

and either xi or y i will be fixed; the other unknowns may then be found from

the phase equilibrium relationships.

Thus, there are usually four possible combinations (although others are

possible) depending on the unknown variables. For distillation it is often more

realistic to fix the pressure and then calculate the unknown temperature.

If the pressure P and the liquid phase compositions xi are fixed, then this is

known as a bubble point calculation.

composition of the first bubble of vapour y i in equilibrium with this liquid.

The calculations are iterative and may be laid out in the same way whether

Raoults Law or a de Priester chart is used to find the K i values. In either

case proceed as follows:

1. Fix P & x i .

2. Set each Pi sat = P and use the Antoine equation in reverse to calculate

Ti sat these are the boiling points of each component at pressure P :

Bi

Ti sat = C i ..(2.46)

Ai ln Pi sat

T( 0 ) = xi Ti sat (2.47)

i

4. Take a ruler to a de Priester chart, set the left hand side to the specified

pressure P and the right hand end of the ruler to the guessed

temperature T( 0 ) - now read off all K i -values from the chart.

TOPIC 2: VLE for Non-Polar Mixtures 30

If Raoults Law is used, then find all K i -values using the expression

below:

Pi sat

Ki = . (i = 1,2......N )

P

To find these K i -values, Pi sat will needed for each component (use the

Antoine equation at temperature T( 0 ) ).

whether a de Priester chart or Raoults Law is used:

y i = K i xi ..(2.48)

6. Sum up all the vapour phase mole fractions and check whether or not

they sum to one:

y = K x

i

i

i

i i = 1.0 (2.49)

Check is y

i

i 1 0.05 ....(2.50)

7. In all likelihood equation (2.50) will not be satisfied. Return to step 3 and

adjust the guessed temperature T( 0 ) to a new value T(1) . It will be fairly

obvious whether to increase or decrease the temperature.

increased. This means a higher volatility is required; at a fixed pressure,

this means a greater temperature is needed.

8. With this new temperature T(1) repeat steps (4) through (6) until

equation (2.50) is satisfied within the stated tolerance.

This scheme was originally developed for de Priester charts and is purely trial-

and-error. The charts themselves cover only a limited range of hydrocarbon

components and the nomographs are often difficult to read accurately.

When using Raoults Law more efficient schemes have been developed. They

are usually two-stage schemes: the first stage involves iterating on

temperature T (until it converges within some tolerance); the second-stage

involves finding the compositions y i (Smith, Van Ness and Abbot, 2005).

TOPIC 2: VLE for Non-Polar Mixtures 31

A dew point calculation involves fixing the pressure P and the vapour phase

compositions y i . The objective is then to find the temperature T and the

composition of the first drop of liquid xi in equilibrium with this vapour.

Apart from the fact that P and y i are now fixed, step 1, step 2, step 3 and

step 4 are the same. In step 5 equation (2.48) is reversed since y i is fixed and

the purpose of a dew point calculation is to find xi as follows:

yi

xi = ..(2.51)

Ki

yi

x = K

i

= 1.0 ..(2.52)

i i i

Check is x

i

i 1 0.05 ...(2.53)

Repeat steps 4 through 6 until the liquid phase mole fractions all sum to one

within some tolerance thus, T and xi have been estimated. Again, if

Raoults Law is used a more efficient two-stage iteration scheme is available.

In the two cases described above the pressure P was fixed: then either xi

was fixed (bubble point route to estimate T & y i ); or y i was fixed (dew point

route to estimate T & x i ).

Another two cases are possible where the temperature T is fixed together

with one set of phase compositions. Very similar bubble point and dew point

calculations are then possible; these are easier since Pi sat do not change.

It is often better to spend time writing a worksheet (for a maths package) using

the rigorous phi-phi approach see Appendix B (this is a Mathcad worksheet,

although any package may be used).

For a binary, it is also possible to fix T & P and then calculate x i & y i , but

then, to be two-phase, T must lie between T1sat & T2sat at prevailing P .

TOPIC 2: VLE for Non-Polar Mixtures 32

Find the bubble point temperature of the liquid mixture defined below:

Liquid

Component Antoine A Antoine B Antoine C

Mol Fraction

Ethane 0.15 15.6637 1511.42 -17.16

Propane 0.20 15.7260 1872.46 -25.16

i-butane 0.60 15.5381 2032.73 -33.15

n-butane 0.05 15.6782 2154.90 -34.42

Note the data for the Antoine constants have P & T units of (mmHg) and (K)

respectively.

TOPIC 2: VLE for Non-Polar Mixtures 33

TOPIC 2: VLE for Non-Polar Mixtures 34

Find the dew point temperature for the same mixture in Example 2 at the same

pressure.

Liquid

Component Antoine A Antoine B Antoine C

Mol Fraction

Ethane 0.15 15.6637 1511.42 -17.16

Propane 0.20 15.7260 1872.46 -25.16

i-butane 0.60 15.5381 2032.73 -33.15

n-butane 0.05 15.6782 2154.90 -34.42

Note the data for the Antoine constants have P & T units of (mmHg) and (K)

respectively.

TOPIC 2: VLE for Non-Polar Mixtures 35

TOPIC 2: VLE for Non-Polar Mixtures 36

consider that this mixture is gradually expanded at constant temperature. At

some pressure, the liquid becomes saturated at its bubble point:

Constant T

z1

From 12 pressure

1 P x1 X P

1

sat decreases, but fluid

remains entirely liquid.

P 2

P y1

sat

At 2 liquid becomes

P X

2

saturated. The liquid

P

composition is unchanged

at x1 = z1 .

0

x1 y1 Read off to left to find P

0 1.0

then right and down (as

x1 & y1

shown) to find y1 .

Notice that T & x1 are fixed and P & y1 are read-off from the diagram. At

point 2 there is actually no vapour present; however, moving fractionally away

from 2 produces the first bubble of vapour with composition y1 .

vapour is compressed isothermally until it intersects the saturated vapour

curve. Now T & y1 are fixed and P & x1 are read-off the diagram.

On the saturated vapour curve itself there is actually no liquid present, it is only

upon moving fractionally away from this point that the first drop of liquid will be

formed this liquid has composition x1 .

that inside the flash drum a two-phase mixture can be separated. The flash

drum constitutes a single equilibrium stage.

The mixture is separated inside the drum with saturated vapour V leaving

from the top and saturated liquid L leaving from the bottom of the drum. With

flash calculations the unknowns are both the vapour flowrate and composition

V & y1 and the liquid flowrate and composition L & x1 .

TOPIC 2: VLE for Non-Polar Mixtures 37

As well as more unknowns, flash calculations require more equations. Not only

are phase equilibrium relations needed (as in dew point and bubble point

calculations), but also flash calculations require mass balances.

A degree of freedom analysis will show that any flash calculation requires two

variables to be specified; in this case they will be taken to be T & P . For

bubble/dew point calculations the number of variables that need to be

specified is found from the Gibbs phase rule.

Two important types of flash are isothermal and adiabatic flash. In the case

of an isothermal flash, shown below, both T & P are fixed:

Vapour

V, yi

T, P

Feed

Steam

F, zi, T,

PF

If F = 1 , then

Fz i = ni : moles T

entering in the

Condensate

feed.

Liquid

L, xi

The vapour offtake valve controls the pressure within the flash drum while the

steam valve controls the temperature within the drum. Flashing may also

involve cooling of the single phase mixture.

heat is transferred. Thus, the amounts of V and L leaving, the stream

compositions and the final temperature T all depend on the feed enthalpy hF .

decoupled from the mass balances and equilibrium relations. In the case of

adiabatic flash calculations all these relations must be solved simultaneously.

TOPIC 2: VLE for Non-Polar Mixtures 38

condition for an isothermal P T flash is that the pressure P must lie

between PBP (bubble-point pressure) and PDP (dew-point pressure).

composition z i enters the flash drum at a feed rate F kmol/hr.

then be scaled up to the actual feed rate F kmol/hr at the end of the

calculation (in this case Fz i = ni or moles entering in the feed).

Constant T

Subcooled liquid enters

the drum at T & PF

PF 1 P x1 X P1

sat

and composition z1 or

PBP P y1 n1 moles of species 1

P L

2 V

if F = 1 .

P2sat X PDP

P Pressure then drops to

P , while temperature

is kept constant at T .

0

0 x1 z1 y1 1.0 Liquid flashes to V

x1 & y1 kmol/h of vapour and

In a flash drum there is sufficient residence time for the phases to separate

and exit as follows: saturated liquid stream with flowrate L and composition

x1 ; saturated vapour stream with flowrate V and composition y1 .

moles of species 1 if F = 1 ). State 2 corresponds to the mixing point on

the horizontal tie-line.

The horizontal tie-line shows that both streams leaving the drum V & L are at

the same T & P . This must be the case, given that the two exit streams are in

phase equilibrium with each other.

TOPIC 2: VLE for Non-Polar Mixtures 39

Exactly how point 2 bisects the horizontal tie-line fixes the outlet V / L ratio

of the two phases leaving the drum, the exact relationship is known as the

Lever Rule:

As P PBP (bubble-point) then V 0 & L 1 .

As P PDP (dew point) then V 1 & L 0 .

Thus, bubble point and dew point calculations may be thought of as two

special cases of a more general flash calculation:

1. A bubble point calculation can be thought of as a limiting flash

calculation where the liquid exits the drum with the same flow and

composition as the feed entering:

There is actually no vapour leaving the drum; however, any

vapour that tends to leave the saturated liquid will have

composition equal to the bubble point composition.

If P > PBP only subcooled liquid leaves the drum and flash

vaporisation of the liquid into a two-phase mixture cannot occur.

2. A dew point calculation can be thought of as a limiting flash calculation

where the vapour exits the drum with the same flow and composition

as the feed entering:

There is actually no liquid leaving the drum; however, any liquid

that tends to condense from the saturated vapour will have

composition equal to the dew point composition.

If P < PDP only superheated vapour leaves the drum and flash

condensation of vapour into a two phase mixture cannot occur.

With the feed flow initialised to one ( F = 1 kmol/h) there is a single overall

mass balance given by

1 = V + L ......(2.54)

component mass balances

z i = Vy i + L xi ...(2.55a)

Or,

n1 = Vy i L xi ....(2.55b)

y i = K i xi .. (i = 1,2......N )

TOPIC 2: VLE for Non-Polar Mixtures 40

Where, each Raoults Law K values may be found from equation (2.41)

Pi sat

Ki = .. (i = 1,2......N )

P

Substitute equation (2.54) into equation (2.55a) and then eliminate y i using

the expression y i = K i xi to get

z i = (1 L )K i xi + L xi

Or,

ni = (1 L )K i xi + L xi

zi

xi = . (i = 1,2......N ) .(2.56a)

( )

1 L K i + L

Or,

ni

xi = . (i = 1,2......N ) ....(2.56b)

(1 L )K i + L

(2.56b). Note that four different variants of this expression are possible,

depending on which variables are eliminated.

1. Fix F , z i (or ni ), T , PF and initialise F = 1 kmol/h.

2. Ensure flash pressure P lies between bubble point pressure PBP and

the dew point pressure PDP .

3. Knowing T & P calculate all K i from equation (2.41), or look up the

K values on a de Priester chart.

4. Guess a starting value for L . A value of 0.5 is sensible, unless the

pressure is much nearer the bubble point (then set it between 0.5 and

1.0) or the dew point (then set it between 0 and 0.5).

5. Compute all xi from equation (2.56a) or (2.56b).

6. Calculate x

i

i and check if x

i

i 1 0.05 .

TOPIC 2: VLE for Non-Polar Mixtures 41

7. If x

i

i 1 > 0.05 then go back to step (4) and adjust value of L and

8. Once tolerance condition is satisfied the calculation has ended.

Use the converged value for L to calculate fractional vapour flow from

equation (2.54)

V = 1 L

Calculate all the vapour phase compositions y i from the phase equilibrium

relationship:

y i = K i xi

T & P fixed. Finally scale-up L and V based on the actual feed flow F

kmol/h.

If needed the energy balance may be solved for Q (kW). All the enthalpies

are fixed if the system T & P and the stream compositions are known.

This energy balance is derived from the steady flow energy equation. For a

flash drum the work term is zero, the kinetic and potential energy change

terms are zero, there are two exit streams and one inlet stream.

the left side of equation (2.57) is set to zero (adiabatic case). In this case the

energy balance (now an enthalpy balance), the mass balances and all the

phase equilibrium relations must be satisfied simultaneously.

TOPIC 2: VLE for Non-Polar Mixtures 42

A feed stream enters a flash drum at 80oF and 150 psia. The overall molar

composition of this feed stream z i is shown below:

Component zi

CH 4 0.05

C2H8 0.10

C3H8 0.30

i-C 4 H 10 0.55

Calculate the fractional flowrates and compositions of both the exit liquid and

vapour streams leaving the drum.

Conversions:

o

C= ( o

F 32 ) 5

9

TOPIC 2: VLE for Non-Polar Mixtures 43

TOPIC 2: VLE for Non-Polar Mixtures 44

2.5 Tutorial 2

separator at 40oC and 1,000 kPa. Determine what fraction leaves the

separator as liquid and the composition of both product streams.

(Use L = 0.5 for the first iteration).

Methane 0.10

Ethane 0.25

Propane 0.30

n-Butane 0.10

i-Butane 0.20

n-Pentane 0.05

Component xi yi

Methane 0.006 0.108

Ethane 0.067 0.268

Propane 0.194 0.310

n-Butane 0.201 0.090

i-Butane 0.307 0.190

n-Pentane 0.225 0.034

condenser and is partially condensed at 14 bara and 40oC. It is then

passed into a separator where both phase are separated. The mixture

has a composition as given below.

Ethane 0.20

Ethene 0.17

Propane 0.23

n-Butane 0.21

n-Heptane 0.10

n-Octane 0.09

composition of the two phases (Use L = 0.5 for the first iteration).

TOPIC 2: VLE for Non-Polar Mixtures 45

Component xi yi

Methane 0.111 0.333

Ethane 0.071 0.320

Propane 0.221 0.243

n-Butane 0.284 0.099

i-Butane 0.164 0.003

n-Pentane 0.149 0.001

6.5 bara has the following composition and is fed to a total condenser.

Ethane 0.12

Propane 0.26

i-Butane 0.62

pressure drop across the condenser and use 40oC as a first

iteration).

stream, is 5oC higher than that of the condenser. Estimate what

percentage of the liquid stream will re-evaporate (assume no

pressure drop through the reflux drum and use L = 0.5 for the first

iteration).

TOPIC 2: VLE for Non-Polar Mixtures 46

condenser has the following composition:

Ethane 0.15

Propane 0.20

i-Butane 0.60

n-Butane 0.05

condenser. If the material leaves the condenser at 25oC, what is the

pressure required and what is the composition of the vapour product?

(HINT: take a first iteration of 1,000 kPa).

Component yi

Ethane 0.349

Propane 0.255

i-Butane 0.372

n-Butane 0.022

equilibrium with the liquid leaving the top bubble cap plate in the

column, calculate the range of operating temperatures within which the

top plate can be operated. Assume that the pressure drop between the

top plate of the column and the condenser is 50 kPa (HINT: take 40oC

as the first iteration).

TOPIC 2: VLE for Non-Polar Mixtures 47

using a distillation column operating at 15 bara:

Methane 0.17

Ethane 0.24

Propane 0.28

n-Butane 0.31

What is the possible range of feed temperatures (HINT: take -40oC and

50oC as first iterations).

condensed by spraying liquid propane into it.

Methane 0.350

Ethane 0.275

Propane 0.375

If the molar ratio of liquid propane to the vapour stream is 1:4 and the

process is carried out at 30 bara and 5oC, calculate the composition

and quantities of both phases leaving the process (Use L = 0.5 for the

first iteration).

entering, compositions

Component xi yi

Propane 0.227 0.204

i-Butane 0.639 0.160

TOPIC 2: VLE for Non-Polar Mixtures 48

8. A sample of a vapour mixture has been partially analysed and has the

following composition:

Methane 0.08

Ethane 0.17

Propane 0.25

Unknown X 0.50

butane. As a test the vapour is cooled at 1.4 bara and it begins to

condense at -14oC. By the time -26oC is reached, approximately half of

the mixture is condensed. Find Unknown X (HINT: the component may

be a mixture).

and n-butane in a 4:1 ratio. The dew point and liquid fraction

calculations tend point in this direction)

9. The vapour product from the top of a distillation column has the

following composition:

Ethane 0.11

Propane 0.66

n-Butane 0.23

vapour is taken off as a product and the liquid is refluxed to the column.

Estimate the operating temperature of the condenser (HINT: try 40oC) if

the reflux ratio is 5:1 (Note the reflux ratio is the ratio of liquid returned

to the column to the product removed from the condenser). Also

evaluate the composition of the product and reflux streams.

What would be the effect on the K value for propane if the ethane were

replaced by methane?

TOPIC 2: VLE for Non-Polar Mixtures 49

Component xi yi

Propane 0.660 0.660

n-Butane 0.260 0.078

10.

a) Explain the circumstance under which the Lewis-Randall rule and

Raoults law are valid.

flash separator maintained at 10.3 bara and 205oC. Evaluate the

amounts of vapour and liquid formed and the composition of both

phases. Use Raoults law and the vapour pressure given below in

your calculation (Use L = 0.5 as the first iteration).

B

lnP sat = A +

T

(cont)

Component A B

Octane 22.66 -4468.6

Water 24.99 -5068.6

c) Can you see any reasons why your answer should be inaccurate or

invalid?

TOPIC 2: VLE for Non-Polar Mixtures 50

applies to..b) 50 kmol of liquid and 50 kmol of vapour formed,

compositions

Component xi yi

Water 0.368 0.632

TOPIC 2: VLE for Non-Polar Mixtures 51

2.6 Bibliography

Chemistry Data Series, DECHEMA, Frankfurt, 1977-1990.

McGraw-Hill, SI ed., 1987.

Wiley 2nd ed., 1993.

S.I. Sandler. Chemical and Engineering Thermodynamics. Wiley, 3rd ed., 1999.

ed., 1998.

Engineering Thermodynamics. McGraw-Hill. 7th ed.,2005.

TOPIC 2: VLE for Non-Polar Mixtures 52

Appendix A

Engineering, Henley & Seader, Wiley, p277

TOPIC 2: VLE for Non-Polar Mixtures 53

TOPIC 2: VLE for Non-Polar Mixtures 54

TOPIC 2: VLE for Non-Polar Mixtures 55

TOPIC 2: VLE for Non-Polar Mixtures 56

Appendix B

This material will be useful for later Design Projects and Experimental

Projects; see next page for further details.

TOPIC 2: VLE for Non-Polar Mixtures 57

Modified versions of the PR EOS are now very accurate for vapour and liquid

phase property estimation, especially non-polar/hydrocarbon mixtures. The PR

has largely replaced the much more cumbersome BWR EOS and is easy to

program with the help of a mathematics package.

In the past cubic EOS were not accurate enough to model the behaviour of

polar liquid mixtures. As a result, empirical correlations were developed. These

correlations will be discussed in Topic 3A.

advanced mixing rules, has led to big improvements in their prediction of

polar liquid properties.

should be needed less and less. However, there is likely to be an on-going

need for two different methods: cubic EOS for non-polar liquid mixtures (Topic

2); empirical correlations for polar liquid mixtures (Topic 3A).

parameters. These hark back to the a & b parameters originally developed by

VdW over a hundred years ago.

All that is needed are the critical pressure, the critical temperature and the

acentric factor (for each pure species). From these values pure-component aTi

and bi parameters are found from the following three equations:

2

R 2TCi

aTi = 0.45724 a (T ) i ...(B.1)

PCi

RTC i

bi = 0.0778 .....(B.2)

PCi

[ ( )(

(T ) i = 1 + 0.37464 + 1.5422 i 0.26992 i 2 1 Tr 0.5

i

)]

2

.(B.3)

The bi parameter is a species specific constant, while the aTi parameter is not

only species specific (acentric factor) but also depends on temperature (thus

the subscript T ).

TOPIC 2: VLE for Non-Polar Mixtures 58

predicting vapour pressure data. The next step is to find the dimensionless Ai

and Bi parameters (for each pure species) as follows:

aTi P

Ai = .....(B.4)

R 2T 2

bi P

Bi = ..(B.5)

RT

Once the pure component parameters have been found, mixture parameters

are next (the subscript mix is not really required but is used in order to

emphasise that these are not pure component values).

Use standard mixing rules, as shown below, to calculate mixture aTmix and

bmix parameters. These formulae are just a way of weighting individual aTi and

bi parameters to mixture parameters.

0.5

i j

bmix = y i bi ..(B.7)

i

property prediction so that it better matches experimental results. If BIPs are

unknown then set them to zero, in which case equation (B.6) reduces to

2

0.5

aTmix = y i aT i ..............(B.8)

i

Mixture Amix and Bmix parameters are now calculated from expressions below:

aTmix P

Amix = ....(B.9)

R 2T 2

bmix P

Bmix = ..(B.10)

RT

TOPIC 2: VLE for Non-Polar Mixtures 59

Solve the cubic EOS below for Z = Z mix using the two Amix and Bmix

parameters just found (the mix subscript is now dropped)

Z 3 + ( B 1) Z 2 + ( A 2 B 3B 2 ) Z + ( AB + B 2 + B 3 ) = 0 ..(B.11)

The largest root is the vapour root. Label this root the vapour mixture

compressibility factor Z V . Now solve the equation below for the fugacity

coefficient of the component in the vapour phase mixture:

2 y j Aij

ln i =

Bi

( )

Z 1 ln(Z B mix )

Amix j

B

i ln V

( )

Z V + 1 + 2 B mix

( )

V V V

(B.12)

Notice that

Vi depends not only on T & P but also on the vapour phase

composition y i (this is the complex functional dependency discussed

previously).

Equations (B.6) through (B.11) are now recalculated using liquid phase

compositions xi in place of vapour phase composition y i . Three roots are

again obtained; now choose the smallest root since this will be the liquid root.

Label this root the liquid mixture compressibility factor Z L (again drop the

subscript mix) and then use this value in conjunction with equation (B.13),

shown below, to calculate a value for

iL :

2 x j Aij

ln

= B

( )

Z 1 ln(Z B mix )

A j

B

i ln L

( )

Z L + 1 + 2 B mix

( )

L i L L mix

i

B mix 2 2 B mix Amix B mix Z + 1 2 B mix

(B.13)

Notice that

L

i depends not only on T & P but also on the liquid phase

composition xi - mirroring, once more, the complex functional dependency

discussed previously.

TOPIC 2: VLE for Non-Polar Mixtures 60

(developed earlier) for species any species i in the mixture:

Vy =

i i

Lx

i i

And this in turn finally leads to the K i - value for this species:

iL

Ki = V

i

repeated for all species and the results constrained so that unknown mole

fractions (either liquid or vapour) sum to one.

schemes, since one set of compositions and either the temperature or the

pressure would initially be unknown.

However, all the above equations are readily programed into a maths package

by setting out the known variables and then declaring which parameters are

functions of the unknown variables.

The package then finds a solution (in terms of the unknown variables) that

meets the imposed phase equilibrium constraints. These worksheets may be

shared and adapted to rigorously solve a wide variety of VLE problems.

Below is a fully worked out methane/butane bubble point problem using the

rigorous phi-phi approach to VLE:

The liquid mixture composition and temperature are specified.

The vapour phase composition and pressure are calculated by the

worksheet.

At this temperature the methane is supercritical; that is the system

temperature is above the critical temperature of methane.

Thus, methane cannot exist as a pure liquid at this temperature.

This means that high concentrations of methane cannot co-exist in VLE

beyond some cut-off mixture concentration.

Once the calculation has converged, there is a final run through to find the

numerical values of all parameters as they might appear to verify the answer.

The worked example is rather long to be included in these lecture notes but

may be obtained from the course lecturer, see file below.

Ph-Phi Worked

Example.pdf

TOPIC 2: VLE for Non-Polar Mixtures 61

Appendix C

the various rules associated with partial molar properties and the notation that

is widely used in an engineering context.

Thermodynamics and this was (quite rightly) slanted in favour of a Chemistry

background. The theory was generally applied only to ideal systems.

Students would do well to review the material and pay attention to both

notation and symbols which does vary between disciplines.

and the limiting values of partial molar properties are all particularly important;

of particular importance is the relationship between partial molar properties

and systems at equilibrium.

The solution of both phase and chemical equilibrium problems, for non-ideal

systems, is not possible without a thorough understanding of partial molar

properties, their dependencies and behaviour.

partial molar property) between real mixtures and ideal mixtures is of key

importance.

Also Appendix C, section C-6, is important because it shows that all relations

between pure component properties have their corresponding partial molar

analogues.

How these correction factors are calculated and applied tends to be more

widely used in engineering and industry.

TOPIC 2: VLE for Non-Polar Mixtures 62

component values ( m1 & m 2 ), then we could write

m = x1 m1 + x 2 m 2 >> m = x1 m1 + (1 x1 )m 2

m = m 2 + x1 (m1 m 2 ) (C.1)

the mole fraction weighting rule was obeyed, then equation (C.1) would hold

(the equation of a straight line). If the solution property m were plotted against

x1 , then equation (C.1) must plot as a straight line joining m1 with m 2 :

Constant T & P

X m1

m X

m

m2 X

0

0 x1 1.0

x1

Using this simple mole fraction weight approach, the solution property m lies

between the pure component values m1 & m 2 and approaches them in the

limit as x1 1 and x1 0 respectively.

However, the question is, what experimental evidence is there that the solution

property m varies linearly with composition x1 ?

The answer is, except for special cases (that will be discussed later), the

experimentally-determined variation in solution property is typically a non-

linear function of composition.

TOPIC 2: VLE for Non-Polar Mixtures 63

determined variation in solution property m versus composition x1 is shown

below by the blue curve:

Constant T & P

I1

X m1

m X

m I

2

m2 X

0

0 x1 1.0

x1

shown again below:

m = m 2 + x1 (m1 m 2 )

interest), then the mixture property m could be found using the same rule, but

now the y-axes intercepts of the tangent line (that is I 1 & I 2 ) must be used in

place of m1 & m 2 and this leads to

m = I 2 + x1 (I 1 I 2 )

This in turn may be re-arranged into the same form (as the original mole

fraction weighting formula), to obtain the following expression for the mixture

property m as a function of concentration and the y-axes intercepts:

m = x1 I 1 + x 2 I 2 ..(C.2)

Clearly it is important to identify these y-axes intercepts I 1 & I 2 but first the

partial molar property mi must be defined and explored.

TOPIC 2: VLE for Non-Polar Mixtures 64

the various components in the solution. The rule for quantifying how a solution

property is apportioned to any component i is given by

(nm )

mi = ..(C.3)

ni T , P ,n j

Where,

mi is the partial molar property of species i in the mixture at T & P .

m is the overall solution property at the same T & P .

mi is the pure-component property of i at the same T & P .

partial derivative of the total solution property M = nm with respect to the

mole number of species i :

T & P must be held constant.

Constant n j means that the mole number of all other species except

the i th must be held constant.

If any solution property can be apportioned into partial molar properties, then

it should be possible to recombine partial molar properties back into their

corresponding solution property, see representation below:

T &P

Solution

Property - m

Recombining Apportioning

Route Route

T &P

Partial Molar

Property - mi

The partial molar property mi is the property that component "i" seems to

have in the solution at T & P . The pure component property mi is the

property that the pure species actually has at the same T & P .

TOPIC 2: VLE for Non-Polar Mixtures 65

In the pure state like molecules are completely surrounded by like species

and, as a result, each molecule has an identical size, shape and charge

distribution the forces of attraction on a single molecule are the same in all

directions:

In mixtures like molecules are partially surrounded by unlike species.

The different species all have a different molecular size, shape and

charge distribution.

Thus, the partial molar property (the property it seems to have) is

shifted either above or below its corresponding pure component value

(the property it actually has in the pure state).

The direction in which the partial molar property is shifted (above or

below the pure component value) depends on whether like-unlike

species bond more or less tightly together than like-like species.

The extent to which partial molar properties differ from their pure

component values depends on the extent of these differences

(between like/unlike species) and the concentration of the mixture.

It follows that partial molar properties are not only a function of T & P ,

but also a function of composition.

Pure component properties, on the other hand, depend only on T & P .

It is clear that the partial molar property of any component must approach its

pure component value as the mixture approaches purity in that species.

Equation (C.3) can be used to define the partial molar property of component

1 m1 in a binary mixture as follows:

(nm )

m1 =

n1 T , P ,n2

In the same way we may define the partial molar property of component 2

m 2 in a binary mixture as follows:

(nm )

m2 =

n 2 T , P ,n1

Notice that for component 1 the partial derivative must be with respect to the

mole number of species 1 (while maintaining a constant T & P and a

constant mole number for species 2).

The same situation applies to m 2 in reverse. Notice that it is the mole number

and not the mole fraction that appears in these definitions it is important to

bear this in mind for what follows.

TOPIC 2: VLE for Non-Polar Mixtures 66

The purpose of this section is to derive expressions for the partial molar

properties of each species (in a binary mixture) in terms of mole fractions.

species 1 and 2 was defined as

(nm )

m1 =

n1 T , P ,n2

m n

m1 = n + m

n1 T , P ,n2 n1 T , P ,n2

For a binary mixture, the total moles of the mixture n is simply the moles of

component 1 n1 plus moles of component 2 n 2 . Thus, by material balance

n = n1 + n2

Since the number of moles of species 2 must be held constant, it follows that

n

=1

n1 T , P ,n2

m

m1 = m + n

n1 T , P ,n2

m m m

= 1

n1 T , P ,n2 n

fractions and not mole number. A second partial derivative will be needed to

show how the mole number changes with mole fraction.

TOPIC 2: VLE for Non-Polar Mixtures 67

n1

x1 =

n

Now differentiate this with respect to the mole number of component 1 using

the product rule (a little easier than using the quotient rule)

x 1 n 1 n

1 = 12 = 1 1

n1 T , P ,n2 n n n n

n n

1 =

x1 T , P ,n2 x 2

Use the chain rule for differentiation but recognise that (for a binary), while the

mole number of species1 can vary (keeping the mole number of species 2

constant), the same is not true for mole fractions.

m n dm

1 =

n1 T , P ,n2 x1 T , P ,n2 dx1

constant, then the binary solution property m only depends on x1 . Substitute

the two partial derivatives into the chain rule to get

dm m1 m n

=

dx1 n x 2

dm

m1 = m + x 2 .(C.4)

dx1

dm

m2 = m x1 ...(C.5)

dx1

find the partial molar properties as algebraic function of concentration.

TOPIC 2: VLE for Non-Polar Mixtures 68

Consider once again the relationship between any tangent to the solution

property curve at concentration x1 and the intercepts of this tangent line

I 1 & I 2 at the y-axes:

Constant T & P

I1

X m1

m X

m I

2

m2 X

0

0 x1 1.0

x1

dm m I 2

=

dx1 x1 0

dm

I 2 = m x1 ......(C.6)

dx1

concentration x1 is also given by

dm I 1 I 2

=

dx1 1.0 0

dm

I1 = I 2 +

dx1

TOPIC 2: VLE for Non-Polar Mixtures 69

dm

I1 = m + x2 ...(C.7)

dx1

Compare equation (C.4) with equation (C.7) and equation (C.5) with equation

(C.6) and it is clear that the intercepts of any tangent line (on the y-axes) must

correspond to the partial molar properties as follows:

m1 = I 1

(C.8)

m2 = I 2

Thus, for a binary mixture (at constant T & P ) the following graphical

relationship exists between all the properties mentioned thus far:

Constant T & P

m1

X m1

m X

m m

2

m2 X

0

0 x1 1.0

x1

It follows that the intercepts at either end of any tangent line are the partial

molar properties ( m1 and m2 ) of each species

The partial molar properties ( m1 and m2 ) are the properties that the species

seems to have in the binary mixture. These partial molar properties differ from

the pure component values ( m1 and m 2 ) at the same T & P .

properties of each species may be found by laying off a tangent to the solution

property curve (at the concentration of interest) and reading m1 and m2 from

intercepts at either end of the tangent line this applies to any property m .

TOPIC 2: VLE for Non-Polar Mixtures 70

Notice that the intercepts change as the concentration varies which means

that, even when T & P are held constant, the partial molar properties mi

change with concentration xi . The pure component properties remain fixed.

Constant T & P

I1

I1

I1 m1 m1

X X m1

X

m2 m2 I2

X

I2

I2

m2 X

0

0 x1 x1 x1 1.0

As x1 1.0

The following holds true for all partial molar properties as the concentration

changes:

1. As: xi 1.0 mi mi (pure component value)(C.9)

Hence, the partial molar properties always vary between the pure-component

value and the infinite dilution value:

mi mi as species i becomes completely surrounded by like

molecules, i.e. xi 1 .

molecules, i.e. xi 0 .

The largest departure of the partial molar property m1 from its pure component

value m1 is its infinite dilution value m1 . This is because at this concentration

component 1 is completely surrounded by unlike species (component 2).

TOPIC 2: VLE for Non-Polar Mixtures 71

molar properties mi . The question is how can the constituent mi be

recombined so that the original solution property m is recovered?

(conceptually represented by the drawing below)

T &P

Solution

Property - m

Recombination Apportioning

Rule Rule

(nm )

? mi =

T &P ni T , P ,n j

Partial Molar

Property - mi

In fact the answer is already available. Return to equation (C.2) where it has

been shown that the solution property depends graphically on the y-axes

intercepts of the tangent line.

m = x1 I 1 + x 2 I 2

However, it has already been shown that these intercepts I 1 & I 2 are the

partial molar properties m1 & m 2 of components 1and 2 respectively. Thus,

for a binary mixture the recombination rule is simply

m = x1 m1 + x 2 m 2 (C.11)

In words, the solution property m is the mole fraction weighted partial molar

properties of the components making up the solution. However, there is no

reason why the mixture should be limited to a binary mixture.

Thus, for a multicomponent mixture where i identifies the species and there

are N such species in total ( i = 1, 2.....i......N ), the mixture property m is

given by the more general recombination rule

N

m = xi mi .(C.12)

i =1

TOPIC 2: VLE for Non-Polar Mixtures 72

rule is used to find mi from the solution property m , then equation (2.12) must

be used to recover the original solution property m .

T &P

Solution

Property - m

Recombination Apportioning

Rule Rule

(nm )

m = xi mi mi =

i T &P ni T , P ,n j

Partial Molar

Property - mi

There is yet a third rule which is very useful when using partial molar

properties and it is known as the Gibbs-Duhem equation.

apportioned between the components in a solution:

And that these apportioned partial molar properties mi are known to

vary with composition, as shown by the intercepts at either end of the

tangent line.

Thus, the partial molar properties of the constituent species mi in the

mixture cannot vary independently of each other.

This dependence is shown by the intercepts of the tangent line as

one partial molar property decreases (say the right hand intercept) the

other partial molar property must increase (the left hand intercept).

To find the exact relationship, start with the fact that any property m may be

expressed in terms of T & P and the mole number of each species

n1 , n 2 ......ni as follows.

nm = f (T , P, n1 , n2 ......ni )

TOPIC 2: VLE for Non-Polar Mixtures 73

The total differential can be expressed in terms of all the partial changes in

nm caused by each variable considered separately

d (nm ) = dP + dT + dni

P T ,n T P ,n i ni T , P , n

j

But the last term on the right (within the summation) is defined as the partial

molar property of species i

m m

d (nm ) = n dP + n dT + mi dni

P T , x T P , x i

But,

ni = x i n

dni = xi dn + ndxi

Expand d (nm ) = ndm + mdn on the left and substitute the above expression

into the right to get

m m

ndm + mdn = n dP + n dT + mi ( xi dn + ndxi )

P T , x T P , x i

Bring all the terms to the left and group terms in n and dn together

m m

dm dP dT mi dxi n + m xi mi dn = 0

P T , x T P , x i i

For any system n and dn are independent and arbitrary, so that each of the

terms within the square brackets must individually be zero:

m m

dm dP dT mi dxi = 0 (C.13)

P T , x T P , x i

and

m x i mi = 0 >>>> m = x i mi

i i

This last expression is the recombination rule see equation (C.12). This is

just a more general way of deriving it.

TOPIC 2: VLE for Non-Polar Mixtures 74

as follows:

dm = xi dmi + mi dxi

i i

m m

x dm + m dx P

i

i i

i

i dP dT mi dxi = 0

T P , x i

T ,x

m m

P dP + T dT xi dmi = 0 (C.14)

T ,x P, x i

However, if T & P are held constant, then equation (C.14) reduces to the

most widely used form of the Gibbs-Duhem equation

x dmi

i i = 0 ....(C.15)

It will be shown later just how useful this relationship can be. It is sufficient now

to understand that it restricts how partial molar properties can change relative

to each other.

properties is shown below it includes the apportioning rule (the definition of a

partial molar property), the recombination rule and the Gibbs-Duhem equation:

T &P

Solution

Property - m

Recombination Apportioning

Rule Rule

m = xi mi (nm )

mi =

ni T , P , n j

i

T &P

Partial Molar

Property - mi

Gibbs-Duhem

Equation

x dm

i

i i =0

TOPIC 2: VLE for Non-Polar Mixtures 75

pressure and composition. As an example, take the total solution property ng

ng = f (T , P, n1 , n2 ......ni )

differential is given below, where the summation term includes all the partial

changes in ng caused by changes in the mole number of each component

d (ng ) = dP + dT + dni

P T ,n T P ,n i ni T , P , n

j

(ng )

dGT , P = dni

i n i T , P , n

j

(nh )

dH T , P = dni

i n i T , P , n

j

and

(ns )

dS T , P = dni

i ni T , P , n

j

Now, take definition for the Gibbs free energy and differentiate it at constant

T & P as follows:

G = H TS

dGT , P = dH T , P TdS T , P

dni = dn T dni

i ni T , P ,n

j

i ni T , P , n

j

i ni T , P , n

j

TOPIC 2: VLE for Non-Polar Mixtures 76

According to equation (C.3) each term within the square brackets is a partial

molar property, given by g i hi and s i respectively. Substitute these partial

molar properties into the previous expression to get

g dn = h dn

i

i i

i

i i T s i dni

i

g i = hi Ts i ..(C.16)

g i = hi Ts i ..(C.17)

immediately apparent. In fact, all pure component property relations have their

equivalent partial molar property analogues.

property relations, the right hand column are the corresponding partial molar

property analogues:

Relation Relation

g i = hi Ts i g i = hi Ts i

hi = u i + Pvi hi = u i + Pvi

dg i = vi dP s i dT dg i = vi dP s i dT

d i = RTd ln f i d i = RTd ln fi

This is fortunate because partial molar property relations are, therefore, the

same as pure component property relations.

TOPIC 2: VLE for Non-Polar Mixtures 77

mixture. One might well ask, why not use f i instead of fi ? The answer is

that the fugacity of a component in a mixture is not a partial molar property.

fi mi

( )

ln fi / xi = mi

distinguish it from the pure component fugacity f i the circumflex is added.

and the

i

argument for doing this is similar to that above, namely

m

i i

( )

ln

=m

i i

i often appears by

itself and to distinguish it from the pure component fugacity i the circumflex

is added Thus, if the solution property is m ln , then its corresponding

partial molar property must be mi ln

i and

T &P

Solution

Property - m = ln

Recombination Apportioning

Rule Rule

ln = xi ln i (n ln )

mi = = ln i

ni T , P ,n j

i

T &P

Partial Molar

Property - mi

Gibbs-Duhem

Equation x d ln

i

i i =0

TOPIC 2: VLE for Non-Polar Mixtures 78

TOPIC 3A: VLE for Polar Liquid Mixtures 1

Topic 3A

Contents

TOPIC 3A: VLE FOR POLAR LIQUID MIXTURES

3A.1 INTRODUCTION ............................................................................................................... 3

3A.2 MODELS OF IDEALITY AND STANDARD STATES .................................................................. 4

3.2.1 Lewis-Randall Model of Ideality ........................................................................... 4

3.2.2 Henrys Law Model of Ideality .............................................................................. 5

3A.3 REAL MIXTURES ............................................................................................................. 7

3.3.1 Excess Properties ............................................................................................... 7

3.3.2 Activity Coefficients ............................................................................................. 8

3A.4 THE GAMMA-PHI APPROACH TO VLE ............................................................................. 12

3.4.1 Rigorous Gamma-Phi Approach to VLE ............................................................ 13

3.4.2 Vapour Phase as an Ideal Solution.................................................................... 14

3.4.3 Vapour Phase as an Ideal Gas .......................................................................... 15

3.4.4 Both Phases as Ideal Solutions ......................................................................... 15

3.4.5 Raoults Law...................................................................................................... 16

3A.5 PHASE EQUILIBRIUM DIAGRAMS ..................................................................................... 17

3.5.1 P-x-y Diagrams.................................................................................................. 18

3.5.2 T-x-y Diagrams .................................................................................................. 19

3.5.3 Example 3A.1 .................................................................................................... 22

3.5.4 The x-y Diagram ................................................................................................ 24

3.5.5 Example 3A.2 .................................................................................................... 26

3A.6 MODELS OF SOLUTION BEHAVIOUR ................................................................................ 28

3.6.1 The One Parameter Model ................................................................................ 28

3.6.2 Margules Two Parameter Model ....................................................................... 31

3.6.3 Van Laars Two Parameter Model ..................................................................... 33

3.6.4 Wilsons Local Composition Model .................................................................... 35

3.6.5 Example 3A.3 .................................................................................................... 36

3A.7 TUTORIAL 3A ................................................................................................................ 37

3A.8 BIBLIOGRAPHY .............................................................................................................. 40

APPENDIX A.......................................................................................................................... 41

Real Mixtures ............................................................................................................. 41

A.1 Property Changes on Mixing ................................................................................ 42

A.2 Property Changes on Mixing for Ideal Solutions ................................................... 43

A.3 Activity of a Species in a Mixture.......................................................................... 45

A.4 Excess Properties ................................................................................................ 47

APPENDIX B.......................................................................................................................... 49

B.1 Positive & Negative Deviation from Ideality .......................................................... 49

B.2 Formation of Azeotropes ...................................................................................... 52

APPENDIX C ......................................................................................................................... 54

TOPIC 3A: VLE for Polar Liquid Mixtures 2

Prerequisite knowledge

Process Industries C.

Process Engineering B.

Learning objectives

After studying this VLE for Polar Liquids topic you should be able to:

Define standard states used for VLE purposes.

Define excess property and write down expressions ideal solution

excess properties.

Define the activity coefficient and demonstrate how it is used to correct

the fugacity of a component in a mixture between the ideal solution

state and the real fluid state.

Explain the gamma-phi approach to VLE (polar systems) and compare

and contrast with the phi-phi approach to VLE (non-polar systems).

Derive rigorous VLE relationship for gamma-phi approach to VLE and

successively simplify it to derive Modified Raoults Law and Raoults

Law.

Define K-values in relation to gamma-phi method.

Construct P-x-y, T-x-y and x-y diagrams.

Outline reasons for positive and negative deviation from ideality and

relate this behaviour to activity coefficients.

Draw P-x-y, T-x-y and x-y diagrams involving maximum and minimum

temperature azeotropes and relate this behaviour to activity

coefficients.

Define the relative volatility, calculate and average value over the

boiling point range and use this to plot an x-y diagram.

Use different models of solution behaviour to solve practical problems

involving polar systems. Differentiate between power-law models

Margule and Van Laar and Wilson local composition model.

Show how problems may be solved (involving azeotropes) using a

maths package.

TOPIC 3A: VLE for Polar Liquid Mixtures 3

3A.1 Introduction

fiV = fi L (i = 1,2......N )

leads to the fugacity coefficient of a component in the mixture

i being used

to model the non-idealities in both liquid and vapour phases.

i

ideal gas as a reference state) was defined as follows:

= fi = fi

i

fi ig y i P

As can be seen, the fugacity coefficient corrects the fugacity of a species from

the ideal gas reference state to the real fluid state at the same temperature,

pressure and composition.

Appendix B of Topic 2. This approach works well for non-polar systems, such

hydrocarbon mixtures.

Less rigorously de Priester charts may be used or, if the system can be

assumed to be an ideal gas in equilibrium with an ideal solution, Raoults Law

can be used.

Cubic EOS cannot (as yet) adequately model complex polar liquid mixtures

due to different interactions between like/unlike species in the liquid phase.

Thus, for polar liquid mixtures an empirical approach, called the gamma-phi

approach to VLE has been developed.

namely the activity coefficient i , to model non-idealities in the liquid phase

while retaining

to model non-idealities in the vapour phase.

i

Thus, the gamma-phi approach to VLE uses different correction factors for the

vapour and liquid phases: is predicted using an EOS; is determined

i i

experimentally and the data is regressed to an empirical correlation.

TOPIC 3A: VLE for Polar Liquid Mixtures 4

The ideal solution state requires a model of ideality. In Topic 2 the Lewis-

Randall Rule was developed to find fi id . However, the Lewis-Randall Rule

implicitly uses a standard state which cannot be applied in all cases.

ideal mixture fi id to the fugacity of pure i in its standard state f i 0 . The

simplest relationship for an ideal gas is fi ig = y i P (Daltons Law). Similarly for

an ideal solution we might write::

fi id = xi f i0 ..(3.1)

However, equation (3.1) is only valid when molecular interactions between two

components are weak. In the figure below the experimental behaviour of f1L

(liquid 1 in liquid 2) is described.

The fugacity of component 1 in the real solution f1L is shown by the solid

line. The fugacity of component 1 in an ideal solution f1id ( ) L

is shown by the

dotted line:

Constant T

model of ideality f i 0 = f i

f1L of pure 1 as a liquid at

(kPa) f1L the same T & P as the

mixture.

( f )

1

id

L

solution line f 1L is

0 affected by interactions

0 x1 1.0 with species 2.

1.0 x2 0

TOPIC 3A: VLE for Polar Liquid Mixtures 5

fi id = xi f i ....(3.2)

approaches purity in that species. That is fi L x i f i as x i 1 .

component, then like species are increasingly surrounded by like species and

the species in question behaves as if it were in an ideal solution.

The is why the real solution curve (solid line) becomes a tangent to the ideal

solution line (dotted line) as x1 1 .

Sometimes, as shown below, the right hand side of the real solution curves

stops short of the y-axis intercept; e.g. when a gas dissolves in a liquid, pure

i is not a liquid at mixture T & P and f i does not exist:

Constant T

drawn as a tangent to

the real solution curve at

xi 0 .

f1L

(kPa)

( f )

1

id

L

now f i 0 = k i which is

the Henry Law constant.

f1L

The slope of the ideal

0 solution line is now k i .

0 x1 1.0

1.0 x2 0

fi id = x i k i ....(3.3)

TOPIC 3A: VLE for Polar Liquid Mixtures 6

Notice that the real solution behaves increasingly as an ideal solution as the

solution approaches infinite dilution in that species. That is f1L x1 k1 as

x1 0 (this applies to any species that approaches infinite dilution).

that the prevailing system temperature (assuming room temperature) is well

above their critical temperature; thus O 2 and N 2 cannot exist as pure liquids

under these conditions.

However, oxygen and nitrogen can still dissolve in a liquid (say water) to form

a liquid solution. Henrys Law is a good model of ideality for these

components, because Henry Law constants are available in the literature.

It can be easily shown that when Henrys Law applies to the solute (the

supercritical species), then the Lewis-Randall rule applies to the solvent. As

the solvent approaches purity, the solute approaches purity infinite dilution.

TOPIC 3A: VLE for Polar Liquid Mixtures 7

There are two ways of working out the properties of real mixtures:

1. By measuring the property change relative to the pure components

properties at the same T & P as the mixture.

2. By measuring the property change relative to the property of an ideal

solution at the same T , P & xi as the mixture.

change on mixing m (this could be v , u , h , s or g ) is defined as

m = m xi mi

i

the real solution property m relative the pure component properties mi at the

same T & P as the mixture see Appendix A.

It is by studying these excess properties that the new correction factor for the

liquid phase fugacity can be found.

similar way. However, it is the (experimentally determined) real solution

property m minus the corresponding ideal solution property m id at the same

T , P & xi . Thus, by definition

m E = m m id .....(3.4)

Of particular interest are the expressions for the Gibbs free energy

g E = g g id

And,

g iE = g i g iid ..(3.6)

TOPIC 3A: VLE for Polar Liquid Mixtures 8

equation (2.25). However, it has been shown that i = g i and equation (2.25)

becomes

g i = RT ln fi + i

temperature. Writing this for a component in an ideal solution at the same

T & P gives

g iid = RT ln fi id + i

Subtract the latter equation from the former and, after cancelling out the

constant of integration i , this becomes

fi

( )

g i g iid = RT ln

f id

i

g iE fi

= ln ....(3.7)

RT f id

i

component in an ideal solution at the same T , P & xi is known as the activity

coefficient and is denoted by i . Thus, by definition

fi

i = ..(3.8)

f id

i

or

fi

i = ....(3.9)

xi f i 0

For VLE the usual standard state is the pure component, as a liquid at the

same T & P as the liquid mixture.

TOPIC 3A: VLE for Polar Liquid Mixtures 9

fi

i = (3.10)

xi f i

The activity coefficient i is a correction factor.

It corrects the fugacity of a species from the ideal solution state to the

real liquid state the same T , P & xi as the ideal mixture.

It uses the ideal solution as a reference state.

Activity coefficient i are used to find fi in polar liquid mixtures (many

accurate empirical correlations for i are available in the literature).

To find the fugacity of a component on the real solution curve (see below):

1. Find the corresponding point on the ideal solution straight line, at some

concentration, using the Lewis-Randall Rule fi id = x i f i ; see point 1 on

the diagram below.

2. The activity coefficient shifts point 1, on the ideal solution line, to point

2, on the real solution curve. This is in accordance with a re-arranged

version of equation (3.10), namely fi L = i x i f i .

Constant T

f1L = P1sat

f1L 2 solution curve will lie

above the ideal solution

f1L

( f )

1

id

L line (as shown).

(kPa) 1

If i < 1 , then the real

solution curve lies

below the ideal solution

line (not shown).

0

0 x1 1.0

1.0 x2 0

If i > 1 (as shown) the component will have a greater escaping tendency

from the real solution fi L = i x i f i than it would have from a corresponding

ideal solution fi id ( )

L

= x i f i at same T , P & xi .

TOPIC 3A: VLE for Polar Liquid Mixtures 10

If i < 1 the component will have a lesser escaping tendency from the real

solution fi L = i x i f i than it would have from a corresponding ideal solution

( f )

i

id

L

= xi f i , at same T , P & xi .

Note that as the binary mixture heads towards purity in any component (as

xi 1 ) then the solution moves towards an ideal solution and i 1 . The

solution curve becomes a tangent to the Lewis-Randall line.

Since most binary mixtures do not have i = 1 , the problem will need to be

solved by looking at g iE . Substitute equation (3.8) into (3.7) to get

gE

= ln g i ....(3.11)

RT

g E / RT . Using the general notation, where m is any solution property and mi

is its corresponding partial molar property, then it is clear that

g E / RT m and ln i mi

( )

ng E / RT

ln g i = (3.12)

ni T , P ,n j

g E / RT = xi ln g i (3.13)

i

Duhem equation.

x d ln

i

i i = 0 (3.14)

equilibrium experiments. This data is converted into g E / RT , using equation

(3.13), and then this is regressed to fit some model of solution behaviour.

TOPIC 3A: VLE for Polar Liquid Mixtures 11

then be used to calculate the activity coefficients at other conditions.

models have been developed and much experimental data is available

(Gmehling, J, Onken, U, Arlt, W, Chemistry Data Series, 1977-1990).

One Parameter model.

Margule model.

Van Laar model.

Wilson model.

NRTL model.

UNIQUAC model.

UNIFAC model.

models apply in different situations and the first four of these will be discussed

in Topic 3A. The NRTL model will be reviewed in Topic 3B.

UNIQUAC and UNIFAC are more complex models (not really suitable for

detailed hand calculations). However, simulation packages offer these as more

advanced options.

TOPIC 3A: VLE for Polar Liquid Mixtures 12

Any VLE problem can be solved using the general criterion for phase

equilibrium derived earlier:

the ideal-gas as a reference state) was defined as

V

Vi = f i

fi ig

which leads to

fiV =

Vi y i P

solution as a reference state) was also expressed earlier as

fi L fi L

i = =

fi id xi f i

L

Leading to

fi L = i x i f i L

Substitute these expressions for fi L and fiV into the general criterion for

phase equilibrium leads to the general gamma-phi approach to VLE:

i i i i i

different from the phi-phi approach to VLE:

With the phi-phi approach to VLE, the is used to model the non-

i

idealities in both phases

With the gamma-phi approach, the Vi models non-idealities in the

vapour phase while the i is used to model liquid phase non-idealities.

With gamma-phi, different reference states are used for each phase.

TOPIC 3A: VLE for Polar Liquid Mixtures 13

developed

ln

fiL

=

(

v Lsat P P sat )

sat

f RT

(

v sat P P sat

f i L = f i sat exp L

)

RT

(

v sat P P sat

f i L = isat Pi sat exp L

)

..(3.16)

RT

sat

(

sat

)

Vi y i P = i xi isat Pi sat exp v L P P .......(i = 1,2,3.....N )

RT

..(3.17)

i Pi

sat sat

exp

(

v Lsat P Pi sat )

i

RT

Ki = ..(3.18)

i P

V

If the Poynting correction factor (see Topic 1) is set to unity and the phase

equilibrium relation, equation (3.17), reduces to

i isat Pi sat

Ki = ..(3.20)

Vi P

TOPIC 3A: VLE for Polar Liquid Mixtures 14

V and sat ) may be obtained using a single EOS

i i

(such as PR) but the activity coefficients i must be found from a suitable

empirical correlation.

VLE and are used to model polar liquid mixtures at low to moderate pressure.

By moderate pressure it is meant well removed from the critical point.

Of course it is rigorous only in the sense that the Poynting correction factor is

set to unity. In practice this term adds little to the overall accuracy of the result.

V = V or

i i

V = f / P and,

i i

making use of equation (3.16), then equation (3.17) reduces to

f iV y i = i xi f i L .......(i = 1,2,3.....N )

i f i sat

Ki = ...(3.22)

f iV

And,

i isat Pi sat

Ki = .(3.24)

Vi P

Of course these are the same as the previous case, except that

Vi = Vi .

TOPIC 3A: VLE for Polar Liquid Mixtures 15

At low pressure

Vi 1 & isat 1 and equation (3.19) reduces to

i Pi sat

Ki = ...(3.26)

P

Equation (3.25) is called modified Raoults Law and equation (3.26) defines

corresponding modified Raoults Law K i -values.

The assumption here is that the pressure is low enough for the gas phase to

be an ideal gas. However, the liquid phase remains a non-ideal solution

(because most polar liquid mixtures are non-ideal).

Since not only is the gas phase an ideal solution, but also the liquid phase is

an ideal solution, return to equation (3.21) and set all i = 1

In terms of K i - values

f i sat

Ki = ...(3.28)

f iV

And,

isat Pi sat

Ki = .(3.30)

Vi P

coefficient chart or an appropriate EOS.

TOPIC 3A: VLE for Polar Liquid Mixtures 16

If the pressure is very low then the vapour phase is an ideal gas, then all

V 1 , all sat 1 . As always, if the pressure is low, then the Poynting

i i

correction factor will be unity.

In addition, for an ideal gas in equilibrium with a liquid phase that is an ideal

solution, all the activity coefficients i = 1 and modified Raoults Law reduces

to Raoults Law:

Pi sat

Ki = .....(3.32)

P

However, Raoults Law often fails to accurately model polar systems (even

when the pressure is low). This is because the interactions between like/unlike

species in polar liquid mixtures can be very different.

Most polar liquids exhibit either positive or negative deviation from Raoults

Law and in some cases these deviations are strong enough to lead to the

formation of azeotropes see Appendix B (which is examinable).

In the case of positive deviation from ideality the lack of affinity between unlike

species may be large enough for the liquid phase to spit into two partially

miscible phases see Topic 3B for VLE, LLE and VLLLE.

TOPIC 3A: VLE for Polar Liquid Mixtures 17

For a binary system that obeys Raoults Law the phase equilibrium

relationships, for both species, are as follows:

The left hand side of each expression are the partial pressures of component

1 and 2 respectively. Adding both equations together gives the total

pressure P as follows:

P = x1 P1sat + x 2 P2sat

P = x1 P1sat + P2sat (1 x1 )

Thus, for ideal VLE systems the partial pressures of each species and the

total pressure must all plot as straight lines. This type of behaviour is shown

below:

Constant T

P1sat

P

(kPa) y1P = x1P1sa t

P2sat

y2 P = x2 P2sa t

0

0 x1 1.0

1.0 x2 0

which means that there are two degrees of freedom F = 2 . The Gibbs Phase

Rule variables are T , P, x1 & y1 (taking 1 to be the independent mole

fractions).

Thus, any two out of these four variables must be fixed in order to solve the

two independent Raoults Law expressions.

TOPIC 3A: VLE for Polar Liquid Mixtures 18

T fixed, then a sequence of pressures P and corresponding compositions y1

may be found; see equation (3.34) and Raoults Law for species 1.

For Raoults Law a plot of P versus x1 produces a straight line, called the

bubble point line this joins P2sat with P1sat . A plot of P versus y1 produces a

curve, called the dew point curve which also joins P2sat with P1sat .

dew point curve ( P y1 curve). As before, both curves meet at the same y-

axis intercepts, corresponding to the vapour pressure of each pure species.

Constant T

Bubble Point

Curve sat For an ideal system,

X P1

P x1 the bubble point

curve will plot as a

P y1

straight line, as

P2

sat

X Dew Point given by equation

Curve

P (3.34)

non-ideal and will

deviate from this.

0 x1 y1 1.0

1.0 x2 y 2 0

If the system is non-ideal, then the P x1 line will either lie above or below the

straight line case: above is positive deviation from ideality; below is negative

deviation from ideality. The dew point line P y1 is always curved.

Positive deviation is associated with activity coefficients greater than one and

is caused by unlike species have less affinity (lower forces of attraction) than

like species. The opposite is the case for negative deviation from ideality.

Ideal solutions will have activity coefficients equal to one and like and unlike

molecules all have the same size and forces of attraction.

If the dew point and bubble point curves meet at some intermediate

composition, forming either a minimum or a maximum, then this is called and

azeotrope more details are available in Appendix B.

TOPIC 3A: VLE for Polar Liquid Mixtures 19

P and then carry out either a sequence of bubble point (fixing x1 finding y1 ),

or a sequence of dew point (fixing y1 finding x1 ) calculations. It is also

possible to fix both T & P (see Example 3A.1).

A typical T x y diagram is shown below. Notice that the bubble point curve

T x1 is below the dew point curve T y1 and, for an ideal system (Raoults

Law) neither curve is straight:

A at constant overall

composition and

T2sat Dew Point D constant pressure.

Line

T x1 follow a vertical line

L V A BC D

M T y1

T

B

Point A corresponds

A Bubble Point T

1

sat to some initial

Line subcooled liquid state.

0

At this point the liquid

0 x1 y1 1.0

is below its BP.

1.0 x2 y 2 0

(to left) gives the bubble point temperature T , while reading horizontally (to

right) and then vertically down gives the bubble point composition y1 .

Further heating leads to point C on the dew point curve. Reading horizontally

(to the left) gives the dew point temperature T , while reading horizontally (to

the left) and then vertically down gives the dew point composition x1 .

Further heating leads to point D , a superheated vapour state with the same

composition y1 . Notice that all states on A B C D have the same overall

composition, even when the system splits into a liquid phase, composition x1

and a vapour phase, composition y1 , between points B & C .

In order to flash a single phase system into the two-phase region, at a fixed

pressure P , the temperature must lie somewhere between the bubble point

and the dew point temperatures.

TOPIC 3A: VLE for Polar Liquid Mixtures 20

The mixing point M lies on a horizontal tie-line L V . It has the same overall

composition as points A, B, C , D , and lies between points B & C . Therefore,

the mixture will split (or flash) into L moles of liquid and V moles of vapour.

The concentration of saturated vapour y1 is read vertically down from V .

To find the amounts of each phase present use the lever rule. The lever rule is

an expression of how the horizontal tie-line L V is bisected by the mixing

point M and is given by

LM V

= (3.35)

MV L

The ratio ( mol V / mol L ) is the same as the ratio ( LM / MV ), i.e. the length

of the tie-line either side of the mixing point. This may also be expressed as

the ratio ( LM / LV ) which leads to

LM V V

= = (3.36)

LV V + L F

then this is vapour fraction). The T x1 y1 plot starts with T2sat on the left

and ends with T1sat on the right. The bubble point and dew point curves

connect to these two points.

Fix the pressure P and split the temperature range up into increments

between T1sat & T2sat ; calculate P1sat & P2sat at each chosen temperature

increment using the Antoine equation.

The total pressure P was initially fixed and is the sum of the partial pressures

and, for an ideal system, each is given by Raoults Law. Now solve for x1 as

follows:

P = x1 P1sat + x 2 P2sat

P = x1 P1sat + (1 x1 ) P2sat

P P2sat

x1 = ..(3.37)

P1sat P2sat

TOPIC 3A: VLE for Polar Liquid Mixtures 21

increment from Raoults Law:

x1 P1sat

y1 =

P

Plot both x1 & y1 versus temperature T , join up all the points that lie on the

bubble point curve T x1 , join up all the points that lie on the dew point curve

T y1 and then connect the two curves at T2sat & T1sat .

Notice that the two degrees of freedom have been fixed by specifying P & T

( P is fixed and then T is incremented). Thus, it is possible to solve for

x1 & y1 directly without iteration.

temperature T is incremented between the pure species BP, that is

T2sat & T1sat . This is the quickest way of plotting a T x y diagram.

The MVC has the lower BP at pressure P , while the LVC has the higher. In

the case of the T x y diagram shown previously, component 1 is the

MVC while 2 is LVC.

as the concentration of MVC increases; not all textbooks follow this

convention.

TOPIC 3A: VLE for Polar Liquid Mixtures 22

Use Raoult's Law and the vapour pressure given below to produce a

T x1 y1 diagram for the ethanol/water system at 2000 mmHg.

o

( C) Vapour Pressure (mmHg)

104.8 2000.00 899.70

110.0 2372.95 1074.41

115.0 2786.81 1267.84

120.0 3257.91 1488.98

125.0 3792.01 1740.72

129.6 4344.22 2000.00

TOPIC 3A: VLE for Polar Liquid Mixtures 23

TOPIC 3A: VLE for Polar Liquid Mixtures 24

temperature. The right hand end of all tie lines join up to form the upper dew

point curve, the left hand end all join up to form the lower bubble point curve.

Constant P

1.0

On the diagonal

line:

y1

x1 = y1

x2 = y 2

0

0 1.0

x1

concentration y1 . A quick way of sketching an x y diagram is as follows:

y1

K1 =

x1

y2

K2 =

x2

TOPIC 3A: VLE for Polar Liquid Mixtures 25

Now for any system the relative volatility 12 of component 1 with respect to

component 2 is defined as

K1 y /x

12 = = 1 1 ..(3.38)

K 2 y 2 / x2

y1 x

= 12 1

y2 x2

y1 x1

= 12

(1 y1 ) (1 x1 )

Further re-arrangement gives y1 as a function of x1 and 12 as follows:

12 x1

y1 = ..(3.39)

1 + ( 12 1)x1

ideal VLE system) using equation (3.31)

P1sat

12 = sat

P2

While the volatility of any species is a strong function of both temperature and

pressure, the relative volatility of an ideal VLE system is independent of

pressure and only a weak function of temperature.

is common practice to use an average value over the pure component

boiling point range.

TOPIC 3A: VLE for Polar Liquid Mixtures 26

Use Raoult's Law to produce an x1 y1 plot for the propane (1)/n-butane (2)

system at a pressure of 400 mmHg.

B

lnP sat = A

T +C

T = temperature (K)

A B C

propane (1) 15.7260 1872.46 -25.16

n-butane (2) 15.6782 2154.90 -34.42

TOPIC 3A: VLE for Polar Liquid Mixtures 27

TOPIC 3A: VLE for Polar Liquid Mixtures 28

When the vapour phase is an ideal gas and the liquid phase is non-ideal

solution then use Modified Raoults Law for VLE calculations, as follows:

quantify the deviation from ideal solution behaviour). It has already been

shown that ln i mi is a partial molar property of g E / RT m :

gE

= ln g i

RT

This means that activity coefficients may be recovered from g E / RT using the

apportioning rule that applies to any partial molar property:

(

ng E / RT

ln g i =

)

ni T , P ,n j

xi only, that is g E / RT does not depend on pressure P (so long as the

pressure is not too high).

series; the one below is called a Redlich-Kister expansion.

gE

= B + C (x1 x 2 ) + D(x1 x 2 ) + ........

2

x1 x 2 RT

The simplest power-series model that could be used is to drop all the higher

order terms, i.e. C = D = .... = 0 , as follows:

gE

= B ..(3.40)

x1 x 2 RT

TOPIC 3A: VLE for Polar Liquid Mixtures 29

composition x1 , then it would plot as a horizontal straight line. Notice that as

purity is approached in either component x i 1 , then g E / RT 0 and

solution becomes ideal.

In order to apply the apportioning rule (and recover the activity coefficients),

then this expression must be re-arranged in terms of mole number

gE nn

= x1 x 2 B = 1 2 2 B

RT n

and

ng E n1 n 2

= B

RT n

n1 n 2

n

ln 1 = B

n1

T , P , n2

n nn n n

ln 1 = B 2 1 2 2 = B 2 1 1

n n n n

ln 1 = Bx 2 (1 x1 )

ln 1 = Bx 22 (3.41)

ln 2 = Bx12 .(3.42)

and i 1 . Once again as the solution approaches purity, in whichever

species, then it starts to behave as an ideal solution.

TOPIC 3A: VLE for Polar Liquid Mixtures 30

and ln 1 ln 1 . Thus, from equation (3.41) the infinite dilution activity

coefficient for species 1 is given by

ln 1 = B ..(3.43)

In exactly the same way, the infinite dilution activity coefficient for species 2

is found from equation (3.42) and is given by

ln 2 = B ..(3.44)

Thus, the infinite dilution activity coefficients (the intercepts of the activity

coefficient curves as x i 0 ) are given by equations (3.43) and (3.44) while

each activity coefficients change with x i in accordance with (3.41) and (3.42).

x1 = x 2 = 0.5 it is easy to show that ln 1 , ln 2 and g E / RT must all pass

through the same point corresponding to a y-axis value of 0.25 B :

Constant T

/ x1 x2 RT = B

E actually behave in

ln 1 = B X X ln 2 = B

this way.

ln 2

only one adjustable

ln 1 parameter B .

Dimensionless

Values all Curves The adjustable

E / RT parameter is called

a Binary Interaction

Parameter BIP.

0

0 1.0

x1

The activity coefficient curves are parabolic and, through equations (3.41) or

(3.42), a single VLE measurement is sufficient to find B .

ln i > 0 and i > 1 . The reverse is the case for negative deviation from

ideality see Appendix B for further details.

TOPIC 3A: VLE for Polar Liquid Mixtures 31

unlikely that both components will behave in the same way. Other, more

complicated models are needed for asymmetric activity coefficients.

If B & C are retained in the Redlich-Kister expansion (and all other higher

order terms are set to zero), then it becomes

gE

= B + C ( x1 x 2 )

x1 x 2 RT

gE

= B( x1 + x 2 ) + C ( x1 x 2 )

x1 x 2 RT

gE

= (B + C )x1 + (B C )x 2

x1 x 2 RT

gE

= A21 x1 + A12 x 2 ....(3.45)

x1 x 2 RT

that this expression has two adjustable BIPs, namely A12 & A21 .

activity coefficient relations first for component 1:

TOPIC 3A: VLE for Polar Liquid Mixtures 32

As before, equations (3.46) and (3.47) yield infinite dilution activity coefficients

ln i as follows:

ln 1 = A12 (3.48)

ln 2 = A21 (3.49)

Constant T

X ln 2 = A21

E / x1 x2 RT

ln 2

ln 1 = A12 X

E / RT

Dimensionless

Values all Curves

ln 1

0

0 1.0

x1

dilution activity coefficients; thus, ln 1 = A12 and ln 2 = A21 .

equations (3.46) and (3.47) may be solved simultaneously:

(x 2 x1 ) 2 ln 2

A12 = 2

ln 1 + (3.50)

x 2 x1

(x1 x 2 ) 2 ln 1

A21 = 2

ln 2 + (3.51)

x 1 x2

Although BIPs may be found in this way for examination purposes, it is poor

industrial practice to use only a single VLE measurement. Better practice is to

regress the BIPs to a complete VLE data set (after it has been checked for

consistency).

TOPIC 3A: VLE for Polar Liquid Mixtures 33

The Van Laar model may also be used to develop the Van Laar activity

coefficient expressions ln i as follows:

2

A x

ln 1 = A12 1 + 12 1 .....(3.52)

x2

A21

2

A x

1 + 21 2

ln 2 = A21 ..(3.53)

A12 x1

are the two adjustable Binary Interaction Parameters

(BIPs). These parameters are again best found by regressing experimental

binary VLE data to this model.

As before, the infinite dilution activity coefficients for Van Laar are given by

ln 1 = A12 (3.54)

(3.55)

ln 2 = A21

and A21

(3.52) and (3.53) could be solved simultaneously to find A12

2

x ln 2

A12 = ln 1 1 + 2 .....(3.56)

x1 ln 1

2

x ln 1

= ln 2 1 + 1

A21 .(3.57)

x 2 ln 2

(as was the case for Margules model) it is recommended that a full data set

be regressed to the Van Laars model in order to find these BIPs.

TOPIC 3A: VLE for Polar Liquid Mixtures 34

Although not recommended, the expressions below show how the BIPs might

be estimated using a single VLE experimental result. First consider modified

Raoults Law written for species 1

y1 P = 1 x1 P1sat

y1 P

1 = ..(3.58)

x1 P1sat

In order to solve equation (3.58) for 1 the T & P will need to be measured, in

addition both liquid and vapour samples must be taken and analysed for

x1 & y1 respectively.

Likewise the activity coefficient 2 is found using the same VLE data

y2 P

2 = ..(3.59)

x 2 P2sat

Or,

(1 y1 ) P

2 =

(1 x1 ) P2sat

If the system forms an azeotrope, then by measuring the T & P and the liquid

phase composition x1 (at the azeotrope), a pair of 1 & 2 values can be

found from the expressions below (at the azeotrope y1 = x1 and y 2 = x 2 ):

P

1 = ..(3.60)

P1sat

P

2 = .....(3.61)

P2sat

Once 1 & 2 are known at liquid composition x1 the BIPs for Margules

model may be found from equations (3.50) and (3.51).

Likewise the BIPs for the Van Laar model may be estimated from equations

(3.56) and (3.57).

TOPIC 3A: VLE for Polar Liquid Mixtures 35

Margule and van Laar equations are simple power-series models that assume

random mixing; although they have been extended there is no theoretical

basis for extending them to multi-component systems at different temperature.

Local composition models take into account that the microscopic local

composition differs from the macroscopic composition. This non-random

mixing effect is caused by:

Differences in molecular size and shape.

Differences in inter-molecular forces of attraction.

A key advantage of all local composition models is that binary pair data at one

temperature may be extrapolated to multi-component systems at a different

temperature the simplest local composition model is Wilsons model:

gE

= x1 ln ( x1 + x 2 12 ) x 2 ln ( x 2 + x1 21 ) ...(3.62)

RT

12 21

ln 1 = ln ( x1 + x 2 12 ) + x 2 .(3.63)

1

x + x

2 12 x 2 + x

1 21

12 21

ln 2 = ln ( x 2 + x1 21 ) x1 .(3.64)

x1 + x 2 12 x 2 + x1 21

The infinite dilution activity coefficients for the Wilson model are given by

ln 1 = ln 12 + 1 21 (3.65)

ln 2 = ln 21 + 1 12 (3.66)

The two BIPs for the Wilson model 12 & 21 are obtained using non-linear

regression techniques; once obtained they are readily extrapolated to multi-

component systems at different temperatures.

Equilibrium LLE is to be modelled, then use the three-parameter NRTL

model (this will be introduced in Topic 3B) or UNIQUAC/UNIFAC models.

A fully worked out solution using the gamma-phi approach to VLE and the

Wilson equation appears in Appendix C. This example features an azeotrope.

TOPIC 3A: VLE for Polar Liquid Mixtures 36

Using the van Laar method and the following vapour pressure data determine

the composition of the vapour stream in equilibrium with a liquid containing a

water mole fraction of 0.5.

Vapour Pressure

Temperature

o (mmHg)

C

Water (1) Ethanol (2)

78.15 330 751

78.4 334 760

80 355 805

90 526 1153

100 760 1648

Take it that an azeotrope exists at 78.13oC and that, for this T x y data

set, the total pressure remains constant at 760 mmHg.

Take it that, under these conditions, the system obeys Modified Raoults Law.

TOPIC 3A: VLE for Polar Liquid Mixtures 37

3A.7 Tutorial 3A

water-phenol system at 1 bar. Compare your calculated data with the

x y diagram provided (below) and comment on the assumptions

implied in the method of calculation.

B

log 10 ( Psat ) = A P sat (mmHg) T (C)

T +C

Component A B C

Water 8.10765 1750.226 235.000

Phenol 7.13301 1516.790 174.954

compositions of the vapour and liquid in equilibrium at 760 mmHg total

pressure and at temperatures of 80oC, 92oC, 100oC and 110.4oC.

Temperature (oC) Benzene Toluene

80.0 760 300

92.0 1078 432

100.0 1344 559

110.4 1748 760

TOPIC 3A: VLE for Polar Liquid Mixtures 38

compositions at atmospheric pressure for a mixture of chloroform and

acetone. Chloroform and acetone form an azeotrope containing 0.666

mole fraction of chloroform at 64.5oC.

Temperature (oC) Acetone Chloroform

45.0 510.5 439.0

50.0 612.6 526.0

55.0 --- 625.2

56.3 760.0 ---

60.0 860.6 739.2

60.9 --- 760.0

70.0 1190.0 1019.0

80.0 1611.0 1403.0

liquid of mole fractions 0.568 n-heptane and 0.432 toluene exists in

equilibrium with a vapour of mole fractions 0.637 n-heptane and 0.363

toluene.

Use Margules model to evaluate the composition of vapour in

equilibrium with a liquid containing mole fractions of 0.185 n-heptane

and 0.815 toluene.

Vapour pressure data at 100.7oC:

n-heptane 780 mmHg

toluene 432 mmHg

41.9oC containing a di-chloroethane mole fraction of 0.769. A

laboratory experiment carried out at 760 mmHg gave the following

equilibrium point:

(Cont..)

TOPIC 3A: VLE for Polar Liquid Mixtures 39

Use the azeotrope data and the Van Laar equations to predict the

composition of the vapour in equilibrium with the liquid above (0.294

mole fraction). Compare the predicted and experimental data and

comment on their accuracy.

B

log 10 ( Psat ) = A

T +C

Component A B C

Di-chloroethane 6.96513 1141.984 231.93

Methanol 7.87863 1473.110 230.00

liquid equilibrium data for the propanol-water system has been found

for two different liquid compositions as shown below:

0.36 0.42 87.7

0.52 0.44 87.9

Using the Van Laar equations evaluate the activity coefficients of both

components and hence the vapour composition in equilibrium with a

liquid with a propanol mole fraction of 0.60 at 760 mmHg.

B

log 10 ( Psat ) = A

T +C

Component A B C

Water (1) 7.96681 1668.21 228.0

Propanol (2) 7.99733 1569.70 209.5

TOPIC 3A: VLE for Polar Liquid Mixtures 40

3A.8 Bibliography

Chemistry Data Series, DECHEMA, Frankfurt, 1977-1990.

McGraw-Hill, SI ed., 1987.

Wiley 2nd ed., 1993.

S.I. Sandler. Chemical and Engineering Thermodynamics. Wiley, 3rd ed., 1999.

ed., 1998.

Engineering Thermodynamics. McGraw-Hill. 7th ed.,2005.

TOPIC 3A: VLE for Polar Liquid Mixtures 41

Appendix A

Real Mixtures

TOPIC 3A: VLE for Polar Liquid Mixtures 42

1. By measuring the property change relative to the pure components

properties at the same T & P as the mixture.

2. By measuring the property change relative to the property of an ideal

solution at the same T , P & xi as the mixture.

The first case leads to the so-called property change on mixing, the second

case leads to the so-called excess properties.

reference works have been compiled for many different mixtures. These data

sets have been regressed to fit a variety of correlations.

m = m xi mi .(A.1)

i

In which m is the real solution property at T , P & xi and mi are the pure

component properties of each species (outside the mixture), but at the same

T & P as the mixture.

(experimentally) when 1 mol of the mixture is formed at constant T & P from

the pure components that make-up the mixture.

However, in Topic 2 it was shown that the real solution property m is the mole

fraction weighted partial molar properties mi of the species making up the

mixture:

m = x i mi

i

m = xi m xi mi

i i

m = xi (mi mi ) .(A.2)

i

TOPIC 3A: VLE for Polar Liquid Mixtures 43

properties, in which m is any property (in this case a property difference)

___ ___

and mi is its corresponding partial molar property ( mi = mi mi )

___

m = xi mi .(A.3)

i

v = v xi vi v = xi (vi vi )

i i

u = u xi u i u = x i (u i u i )

i i

h = h xi hi (

h = x i hi hi )

i i

s = s xi s i s = xi (s i s i )

i i

g = g xi g i g = xi ( g i g i )

i i

The equations on the left enable the various property changes on mixing to be

experimentally measured. The equations on the right may be used in the

section below.

An ideal solution is one where there are no volume change or heat effects

during the mixing process. It follows that the partial molar volume, internal

energy and enthalpy must be equal to their respective pure component values:

viid = vi (A.4)a

u iid = u i (A.4)b

TOPIC 3A: VLE for Polar Liquid Mixtures 44

and,

hi id = hi .(A.4)c

The two properties for which this is not true are entropy and Gibbs free energy.

Standard texts (Smith, Van Ness, Abbott, 2005) show that these expressions

are given by

s iid = s i R ln xi ..(A.4)d

g iid = g i + RT ln xi .(A.4)e

Substitute each partial molar property expression miid (listed above) into its

corresponding m expression (listed on right side of table) to get the following

ideal solution property changes on mixing m id :

v id = 0 (A.5)a

u id = 0 (A.5)b

h id = 0 (A.5)c

Again, the two ideal solution properties that behave differently are the entropy

and the Gibbs free energy as given below:

s id = R x i ln xi ........(A.5)d

i

g id = RT xi ln xi ..(A.5)e

i

(when pure species are mixed together); there are also no enthalpy and

internal energy change on mixing effects (heat effects on mixing).

accordance with the second law s id > 0 (each term within the summation is

negative).

It is also to be expected that the Gibbs free energy should decrease as the

pure components are irreversibly mixed together; equation (A.5e) confirms that

for an ideal solution g id < 0 .

TOPIC 3A: VLE for Polar Liquid Mixtures 45

g i = RT ln fi + i

temperature. Whereas the same expression for a pure species in some

standard state is given by

g i0 = RT ln f i 0 + i

Subtract the latter equation from the former and, after cancelling out the

constant of integration i , this becomes

fi

( )

g i g i0 = RT ln (A.6)

f i0

The activity a i is defined as the ratio of the fugacity of species i in the mixture

fi at T , P & xi to the standard state fugacity f i 0 of pure i . Thus, a i is

defined as follows:

fi

a i = ..(A.7)

f i0

( )

g i g i0 = RT ln a i .(A.8)

Equation (A.7) is a general definition for the activity of a species. However, for

VLE the standard state is chosen to be the pure species at the same T & P

as the mixture. Thus, for VLE equation (A.7) becomes

fi

a i = ..(A.9)

fi

This is because other standard states are used (as will be seen later when

studying chemical equilibrium).

TOPIC 3A: VLE for Polar Liquid Mixtures 46

It has already been shown that the fugacity of component i in an ideal solution

fi id is given by the Lewis-Randall rule; this is one model of ideality.

fi id = xi f i

Substitute the Lewis-Randall rule into equation (A.9) to get the activity of a

species in an ideal solution a iid as follows:

xi f i

a iid =

fi

a iid = xi ..(A.10)

general relationship for a iid is obtained:

xi f i 0

a =

id

i ...(A.11)

fi

concentration but it is better to think of activity in terms of a ratio of two

fugacities; see defining expression for a i - namely equation (A.7).

In this sense the activity of a mixture is the escaping tendency of the

component from the mixture, relative to its escaping tendency from the pure

liquid in some standard state.

The two (escaping tendencies) are different because in a mixture any single

molecule is partially surrounded by like and unlike components. Thus, its

escaping tendency is different (from the pure species) because it is packed

differently and experiences different forces of attraction in the mixture.

TOPIC 3A: VLE for Polar Liquid Mixtures 47

m = m xi mi

i

the real solution property at T , P & x i relative the pure component properties

at the same T & P .

(experimentally determined) real solution property m minus the corresponding

ideal solution property m id at the same T , P & x i . Thus, by definition

m E = m m id .....(A.12)

m id = xi miid

i

Substitute equations (A.4a) through (A.4e) into the equation above to get the

various ideal solution properties listed below:

v id = xi vi ...(A.13)a

i

u id = xi u i ..(A.13)b

i

h id = xi hi ...(A.13)c

i

Thus, the previous three ideal solution properties are just the mole fraction

weighted pure component values. However, entropy and Gibbs free energy

behave differently (due irreversibilities associated with the mixing process):

s id = xi s i R xi ln xi ..(A.13)d

i i

g id = xi g i + RT xi ln xi ..(A.13)e

TOPIC 3A: VLE for Polar Liquid Mixtures 48

given by equation (A.12), leads to the following excess properties:

v E = v xi vi .....(A.14)a

i

u E = u xi u i ....(A.14)b

i

h E = h xi hi .(A.14)c

i

s E = s xi s i + R x i ln xi .(A.14)d

i i

g E = g xi g i RT xi ln xi ...(A.14)e

The above equations may be used to find experimental values for m E . Notice

that in every case (on the right of each expression) there is a common group

of terms given by m i

x i mi .

combination of terms is the property change on mixing m . Thus, as

expected, there is a relationship between m and m E as follows:

v E = v .....(A.15)a

u E = u .....(A.15)b

h E = h ..(A.15)c

In the first three cases m E = m , but the next two are different:

s E = s + R xi ln xi ..(A.15)d

i

g E = g RT x i ln xi .....(A.15)e

literature) may be converted into m E values. The benefit of using excess

properties is that for an ideal solution they are all are zero.

TOPIC 3A: VLE for Polar Liquid Mixtures 49

Appendix B

If the system obeys modified Raoults Law (an ideal gas in equilibrium with a

non-ideal liquid solution), then the partial pressures are given by modified

Raoults Law and may be added together in the usual way:

non-linear functions of composition. Whether the P x1 curve lies above or

below the ideal (straight line) case depends on whether i > 1 or i < 1 .

It must be emphasised that Raoults law (on its own) cannot be used to model

either positive or negative deviation from ideality; activity coefficients are

needed.

When the activity coefficients i > 1 the solution exhibits positive deviation

from Raoults Law; the partial pressures of each species exceed the Raoults

Law case which means the P x1 curve must lie above the straight line case:

Constant T

If i > 1 , then the

Bubble Point

Curve sat Py i = i x i Pi sat

and this

X P1

P x1 must now be larger

P y1 than Py i = x i Pi sat .

P2sat X Dew Point

P

Curve i > 1 means that the

escaping tendency

from a non-ideal

solution exceeds that

0 from an ideal solution.

0 x1 y1 1.0

1.0 x2 y 2 0

If i > 1 (escaping tendency is larger than ideal case), then unlike molecules

attract less strongly (have weaker interactions) than like molecules.

TOPIC 3A: VLE for Polar Liquid Mixtures 50

On the other hand, when the activity coefficients i < 1 the solution exhibits

negative deviation from Raoults Law. This leads to the P x1 y1 diagram

having a completely different shape.

In this case, the partial pressures of each species are below the Raoults Law

partial pressures and the P x1 curve must lie below the straight line case:

Constant T

P y1 X P1

sat

Py i = i x i Pi sat and this

Bubble Point

Curve must now be smaller

P x1 Dew Point

Curve

than Py i = x i Pi sat .

P2sat X

P If i < 1 the escaping

tendency from a non-

ideal solution is less

0 that from an ideal

0 x1 y1 1.0

solution.

1.0 x2 y 2 0

strongly (have stronger interactions) than like molecules.

below the dew point line T y1 :

at constant overall

composition and

T2sat Dew Point D pressure.

Line

T x1 follow a vertical line

L V A BC D

M T y1

T

B

Point A corresponds

A Bubble Point T

1

sat to some initial

Line subcooled liquid state.

0

At this point the liquid

0 x1 y1 1.0 is below its BP.

1.0 x2 y 2 0

TOPIC 3A: VLE for Polar Liquid Mixtures 51

(to left) gives the bubble point temperature T ; reading horizontally (to right)

and then vertically down gives the bubble point composition y1 .

Further heating leads to point C on the dew point curve. Reading horizontally

(to the left) gives the dew point temperature T ; reading horizontally (to the left)

and then vertically down gives the dew point composition x1 .

Further heating leads to point D , a superheated vapour state with the same

composition y1 as the following states: initial subcooled liquid x1 at A ; the

saturated liquid x1 at B ; and the saturated vapour y1 at C .

To flash any two-phase mixture (at this fixed pressure P and the same overall

composition) the temperature must be set somewhere between the (lower)

bubble point temperature and the (higher) dew point temperature.

between these two temperatures; it will separate (or flash) into L moles of

liquid and V moles of vapour, joined by horizontal tie-line L M V .

The concentration of the saturated liquid (that separate out from the mixture) is

read vertically down from L . The concentration of saturated vapour (that

separates from the mixture) is read vertically down from V .

To find the amounts of each phase present use the lever rule. The lever rule

depends on how exactly the horizontal tie-line L M V is bisected by the

mixing point M . The lever rule is given by

LM V

= (B.2)

MV L

The ratio ( mol V / mol L ) is the same as the ratio ( LM / MV ), i.e. the length

of the tie-line either side of the mixing point. This may also be expressed as

the ratio ( LM / LV ) which leads to

LM V V

= = (B.3)

LV V + L F

vapour fraction.

TOPIC 3A: VLE for Polar Liquid Mixtures 52

two-phase mixture (from the initial subcooled liquid) into a heated flash drum;

heating (in turn) then fixes the constant temperature T of the flash.

compressed and then split a two-phase mixture within a cooled drum; cooling

now fixes the constant temperature T of the flash.

Referring back to the previous diagram and the location of mixing point M up

and down the vertical line BC :

As M approaches the bubble point B ; LM 0 and V / F 0 , at

which point L / F 1 . Thus, if the vapour fraction is zero, then the

liquid fraction must be one (remember mass balance F = V + L ).

As M approaches the dew point C ; LM LV and, V / F 1 at

which point L / F 0 . As the vapour fraction approaches one, then

the liquid fraction must approach zero.

It has already been said that negative deviation from ideality reflects a lower

releasing tendency (greater forces of attraction) of a species from a mixture

than from an ideal solution.

If the boiling points of the pure species are not too far apart, then this can lead

to the mixture (at some composition) having a higher boiling point than either

of the pure components.

At the azeotrope, the boiling point of the mixture will be greater than the boiling

points of the two pure species and will, therefore, go through a maximum on a

T x y diagram as shown below:

Constant P

Dew Point

NOTE:

T y1 Line

A maximum temperature

T x1 azeotrope on a T x y

Bubble Point diagram.

T2sat Line

T

..Will plot as a minimum

pressure azeotrope on a

0

T1sat P x y diagram.

0 x1 y1 1.0

1.0 x2 y 2 0

TOPIC 3A: VLE for Polar Liquid Mixtures 53

It has also been said that positive deviation from ideality reflects a greater

releasing tendency (lower forces of attraction) of a species from a mixture than

from an ideal solution.

If the boiling points of the pure species are not too far apart, then this can lead

to the mixture (at some composition) having a lower boiling point than either of

the pure components.

At the azeotrope, the boiling point of the mixture will be less than the boiling

points of the two pure species and will, therefore, go through a minimum on a

T x y as shown below:

Constant P

NOTE:

T2sat

T y1 A minimum temperature

azeotrope on a T x y

Dew Point

diagram..

Curve

T T x1

T1sat ....Will plot as a maximum

Bubble Point pressure azeotrope on a

Curve P x y diagram.

0

0 x1 y1 1.0

1.0 x2 y 2 0

From the above diagram, clearly both species have a K value equal to one.

Thus the composition of species 1 is the same in both phases, likewise for

species 2 ( y1 = x1 and y 2 = x 2 ). It follows that liquid and vapour

compositions must be the same.

An azeotrope is known as a constant boiling mixture; both the vapour and the

liquid phases have identical compositions. Such a mixture cannot be

separated by distillation because its relative volatility 12 = K 1 / K 2 = 1 .

in volatility. If the relative volatility is one, then there is no difference in volatility

between the components and distillation alone cannot separate them.

From this discussion it is clear that the formation of azeotropes depends both

on activity coefficients 1 & 2 and the boiling points T1sat & T2sat . For this

reason it is important to develop suitable correlations for i such as the

Margule, Van Laar and Wilson expressions.

TOPIC 3A: VLE for Polar Liquid Mixtures 54

Appendix C

This file is rather long to be included in these lecture notes but may be

obtained from the course lecturer:

gamma-phi Worked

Example.pdf

TOPIC 3B: VLE, LLE and Miscibility 1

Topic 3B

Liquid Equilibrium and Miscibility

Contents

TOPIC 3B: VAPOUR-LIQUID EQUILIBRIUM, LIQUID-LIQUID EQUILIBRIUM

AND MISCIBILITY

3B.1 INTRODUCTION ............................................................................................................... 3

3B.2 PURE SPECIES ............................................................................................................... 4

3.2.1 P-T Diagrams ...................................................................................................... 4

3.2.2 P-v Diagrams ...................................................................................................... 6

3B.3 BINARY SYSTEMS AND MISCIBLE VLE .............................................................................. 7

3.3.1 P-T Diagrams ...................................................................................................... 8

3.3.2 P-x-y Diagrams.................................................................................................. 13

3.3.3 T-x-y Diagrams .................................................................................................. 14

3.3.4 x-y Diagrams ..................................................................................................... 15

3.3.5 Azeotropes ........................................................................................................ 15

3B.4 PARTIALLY MISCIBLE SYSTEMS ...................................................................................... 20

3.4.1 Liquid-Liquid Solubility Diagrams ....................................................................... 20

3.4.2 VLLE and P-x-y Diagram ................................................................................... 22

3.4.3 VLLE and T-x-y Diagram ................................................................................... 24

3.4.4 VLLE at Higher Temperature ............................................................................. 26

3.4.5 Quantitative Treatment of VLLE ........................................................................ 28

3.4.6 Example 3B.1 .................................................................................................... 34

3B.5 IMMISCIBLE SYSTEMS .................................................................................................... 36

3.5.1 Quantitative Treatment ...................................................................................... 37

3.5.2 Example 3B.2 .................................................................................................... 39

3B.6 TUTORIAL 3B ................................................................................................................ 40

3B.7 BIBLIOGRAPHY .............................................................................................................. 41

APPENDIX A.......................................................................................................................... 42

Rigorous Approach to LLE ......................................................................................... 42

A.1 Liquid-Liquid Equilibrium ...................................................................................... 43

APPENDIX B.......................................................................................................................... 46

Heating or Cooling a VLLE System. ........................................................................... 46

B.1 Isobaric Cooling from A ..................................................................................... 47

B.2 Isobaric Cooling from B ..................................................................................... 48

B.3 Isobaric Cooling from C ..................................................................................... 49

B.4 Isobaric Vaporisation from X .............................................................................. 50

TOPIC 3B: VLE, LLE and Miscibility 2

Prerequisite knowledge

Process Industries C.

Process Engineering B.

Learning objectives

After studying this VLE, LLE and Miscibility topic you should be able to:

Differentiate phase diagrams for pure species from phase diagrams for

mixtures.

Sketch P-T-x-y diagram and show how P-x-y and T-x-y diagrams are

related to the three dimensional P-T-x-y surface.

Sketch diagrams, including x-y diagrams, where one or both of the

species are supercritical.

Sketch P-T diagrams for mixtures and explain retrograde condensation

and the position of the critical point in relation to the cricondenbar and

the cricondentherm.

Explain how changing the mixture composition affects the shape of the

P-T diagram and the importance of these diagrams to Petroleum

Engineers.

Identify which systems can form azeotropes, the location of the

azeotrope and then demonstrate an ability to sketch azeotropic

behaviour on P-x-y, T-x-y and x-y diagrams.

TOPIC 3B: VLE, LLE and Miscibility 3

3B.1 Introduction

The following types of system will be studied in this topic: fully miscible

systems; partially miscible systems; completely immiscible systems. The

objective is to review, qualitatively and quantitatively, both VLE and LLE.

VLE was studied quantitatively, for fully miscible systems, in Topic 3A. This

was the so-called gamma-phi approach to VLE. The assumptions and the

complexity of the system depended on the pressure and the chemical make-

up of the system.

In real situations, large deviations from ideal behaviour occur in both gas and

liquid phases this is because of forces that exist between molecules:

If forces between like and unlike molecules are the same, then the

solution behaves as an ideal solution.

If these forces are not the same, then deviations from ideality will

occur.

The magnitude of the molecular forces depend on both the nature of

the molecules themselves and the distances between them.

In the liquid phase, the molecules are close together and these forces have a

large effect. Thus, the molecules that make up a liquid phase mixture must be

very similar in shape and size for them to behave as an ideal solution.

Most liquid mixtures have molecules that are sufficiently different to cause

deviations from ideal solution behaviour. Aqueous solutions are nearly always

non-ideal.

In gaseous mixtures, force fields are less strong and ideal solution behaviour

is a good approximation at low pressures. At higher pressures, the molecules

are closer together and difference in molecular shape and size exert an

influence on intermolecular forces.

1. At low pressures, deviations from ideal solution behaviour will occur

primarily in the liquid phase. The gas phase will approach an ideal

solution and may even behave as an ideal gas.

2. At high pressures, both liquid and gas phases may deviate from ideal

solution behaviour. The extent of the deviation will depend on the

dissimilarity of the components.

3. The most difficult problems are dissimilar species at high pressures,

where there are large deviations from ideality in both phases.

topic, but first it is necessary to complete a qualitative review of fully miscible

systems (this was started for polar systems in Topic 3A).

TOPIC 3B: VLE, LLE and Miscibility 4

dimensional P-v-T surface, see below:

C

Liquid Gas

V-L

Psat

Vapour

Three dimensional diagrams are difficult to work with and it is normal to project

the above diagram onto a plane, as in P-T or P-v diagrams shown in topic 2.

Of course these were for pure component systems.

pressure-temperature plane, for a pure species this is given by:

P A region

C

Liquid TP C is the

region vaporisation or boiling

Solid

region Gas point curve.

region

B

TP TP A is the fusion

Vapour or freezing point curve.

region

T TP B is the

sublimation curve.

The areas on this P-T diagram represent single phase regions, while the lines

represent two phases in equilibrium. The Triple Point, denoted by TP , is the

single point on the diagram where three phases are in equilibrium.

TOPIC 3B: VLE, LLE and Miscibility 5

of P sat at any temperature T (along this curve) may be estimated using the

Antoine vapour pressure correlation as discussed in Topic 1.

liquid and vapour may co-exist in equilibrium; any point on this curve must

satisfy f V = f L . Thus, there is one degree of freedom.

Line TP A represents the only combinations of T & P where liquid and solid

may co-exist in equilibrium; any point on this curve must satisfy f L = f S .

Again there is one degree of freedom.

solid may co-exist in equilibrium; any point on this curve must satisfy

f V = f S . Once again there is one degree of freedom.

At the triple point there are zero degrees of freedom. Only one fixed T & P

will simultaneously satisfy the two independent phase constraints.

constant pressure heating process. As heat is added the solid temperature

rises until point 2, the melting point, is reached:

Supercritical

P A region

C

Liquid

region

Solid

region Gas

1 2 3 4

region

TP

B

Vapour

region

Further addition of heat causes the solid to melt; melting, like vaporisation and

sublimation, takes place at constant temperature and pressure.

Eventually all the material is liquid. The amount of heat needed to melt all the

solid is called the latent of fusion or the latent heat of melting. These phase

transitions were mentioned in earlier courses (Process Industries).

TOPIC 3B: VLE, LLE and Miscibility 6

From this point onwards, as more heat is added, the temperature of the liquid

rises from 2 to 3. Liquid between these two points is termed subcooled or

unsaturated liquid.

Point 3 corresponds to the boiling point of the liquid and this is the only

temperature, at this pressure, where vapour and liquid can co-exist in

equilibrium.

complete. The heat needed to completely vaporise all the liquid is called the

latent heat of vaporisation. From 3 to 4 the vapour becomes superheated.

volume plane, then the result is a P-v diagram:

P

TC Supercritical Curve A C is saturated

Fluid liquid curve.

PC C

vapour curve.

Liquid

Vapour

Point C is critical point. The

highest T & P at which

PTP A vapour and liquid can co-

B

exist in equilibrium

The saturated liquid curve A C and the saturated vapour curve B C start

at the triple point TP and meet at the critical point C . At the critical point both

liquid and vapour phase properties become identical.

To the right of the saturated vapour curve (but at temperatures below the fluid

critical temperature TC ) is the superheated vapour region. To the left of the

saturated liquid curve is the subcooled liquid region.

Above the critical temperature TC , but below the critical pressure PC , the fluid

is called a gas because it cannot be liquefied by the action of pressure alone.

Above the critical temperature TC and above the critical pressure PC , the fluid

is called a supercritical. At these high pressure states, gaseous properties

grade into liquid properties without any phase splitting.

TOPIC 3B: VLE, LLE and Miscibility 7

diagram. Thus, the diagram becomes a three dimensional P T x y

diagram. The diagram has thee axes pressure temperature and composition.

Often component 1 is the MVC, so that component 1 will have the higher

vapour pressure P sat , as is shown below:

represents all saturated

liquid states (bubble

point states).

C2 subcooled liquid states.

C1

The lower surface

represents all saturated

sat P1sat

T vapour states (dew

P 2 point states).

0

x1 y1 Below this are all the

1 superheated vapour

states.

The region of space enclosed by these two surfaces is the two-phase region.

The right hand vertical plane is the vapour pressure curve for pure 1; notice

that it terminate at the critical point for component 1, denoted by C1 .

Likewise the left hand vertical plane is the vapour pressure curve for pure 2;

it terminates at the critical point for component 2, denoted by C 2 .

to slice through this 3-D surface using planes where one of the variable is

held constant, as follows:

A P x y diagram is produced by a vertical slice at constant

temperature

A T x y diagram is produced by a horizontal slice at constant

pressure.

A P T diagram is produced by a vertical slice at constant

composition.

TOPIC 3B: VLE, LLE and Miscibility 8

diagram shown below (the pure component vapour pressure curves are added

for convenience):

CP

Curve X C1 is the vapour

P

C1 CM pressure curve for pure

species 1 (MVC).

Liquid CT

Curve S C 2 is the vapour

pressure curve for pure

C2 species 2 (LVC).

X W

V Envelope W-CP-CM-CT-V

S Vapour corresponds to the mixture

phase envelope; all points

T have the same composition.

A pure component critical point (in this case either C1 or C 2 ) is the highest

temperature and pressure at which a pure substance can co-exist as vapour

and liquid in equilibrium.

However, this is not the case for a mixture: the highest pressure is CP which

is called the cricondenbar. On the other hand, the highest temperature is CT

which is called the cricondentherm. Now mixture VLE is represented by an

envelope and not a curve.

The upper and lower parts of this phase envelope W-CP-CM-CT-V represent

all the saturated liquid (bubble point) and saturated vapour (dew point)

states respectively note that these all have the same composition.

The two saturation curves join at the mixture critical point CM. At this point,

saturated vapour and and saturated liquid properties become identical:

Above and to the left of the envelope is the liquid region. Below and to the right

is the vapour region. Inside the envelope is the two-phase region.

Quality lines are lines of constant liquid fraction notice that they are drawn

inside the envelope and all converge at the mixture critical point CM.

TOPIC 3B: VLE, LLE and Miscibility 9

constant T & P . However, this is not the case for a mixture (in this case a

binary mixture) where the initial and a final boiling points are different.

pressure and gradually heated from a subcooled liquid through to a

superheated vapour (as indicated by crosses):

CP bubble point temperature

CM Tbp .

Liquid

CT

Bubble Point

The final boiling point is the

Curve dew point temperature Tdp .

P

Vapour Unlike pure components,

mixtures boil over a definite

Dew Point temperature range, not at a

Curve

fixed temperature.

Tbp T

Tdp

starting starting from point A:

moves the sytem to point

P CP B on the bubble point line.

A CM

Liquid This is also called the

B CT saturated liquid line and the

Bubble Point mixture is 100% liquid.

Curve

Vaporisation begins at a

Dew Point point fractionally below B.

D

Curve

Vapour

Hence, vaporisation or

E boiling of the mixture starts

at B.

T

If the pressure is decreased further (following vertical line B-D), then more

and more liquid vaporises until the system arrives at point D which is on the

dew point curve.

TOPIC 3B: VLE, LLE and Miscibility 10

Fractionally above point D the last drop of liquid will have vaporised, so that

point D itself is 0% liquid hence, vaporisation or boiling stops at D.

As the pressure is decreased further the system moves along path D-E. At

point E, the system is a superheated vapour indeed all states below D are

superheated vapour states (point D itself is a saturated vapour state).

The reverse process starts at E and the system moves up from E-D with

increasing pressure. When the system pressure rises to D it is on the dew

point curve corresponding to 0% liquid.

As the system moves fractionally away from D the vapour starts to condense

and dew will form on any exposed surface (thus dew point) hence, this is

the initial condensation point.

As the pressure increases from D-B, there is a steady increase in the fraction

of liquid until, at the bubble point B where there is 100% liquid. The bubble

point B is where condensation stops.

As the pressure is increased further the system moves along path B-A. At

point A, the system is again a subcooled liquid indeed all states above B

are subcooled liquid states (point B itself is a saturated liquid state).

Thus, the bubble point is the initial boiling point (when pressure is decreasing)

or the final condensation point (when pressure is increasing).

Likewise, the dew point is either the final boiling point (when pressure is

decreasing) or the initial condensation point (when pressure is increasing).

Retrograde Condensation

isothermal decrease in pressure starting from point A along path A-E:

Vaporisation starts

A at B on the

CM

B bubble point curve.

Vaporisation stops

at D on the dew

point curve.

changes smoothly

from 100% to 0%

D Vapour Gas from B to D.

E

TOPIC 3B: VLE, LLE and Miscibility 11

Note the subcooled liquid A is to the left of the mixture critical point CM.

On the other hand, starting with a fluid at point 1, which is a little to the right

of the mixture critical point CM, following a similar vertical path (now 1-2-3),

something completely different happens:

Although point 1 is still above the phase envelope, it does not represent a

subcooled liquid since it lies above the dew point curve. It is really a

supercritical fluid.

The temperature must still be less than the cricondentherm (as shown),

otherwise the vertical line will not intersect the two-phase envelope, but it is

now greater than the mixture critical temperature CM (if the line is to the left

of CM, then the previous scenario will occur).

The main point to notice is that as the pressure is reduced the superheated

vapour, being to the right of the mixture critical point, will now intersect the

two-phase envelope at the dew point curve.

Once fractionally below the dew point curve condensation will start. It is

unusual for a fluid to condense when its pressure is reduced, but this must

happen over a limited temperature range (see shaded region)

formed up to some maximum. In this case, as the pressure drops, the liquid

fraction increases from 0% (at the dew point curve) to a maximum of about 5%

(see point 2 on the diagram).

re-evaporate until the mixture again intersects the lower part of the dew point

curve. At the dew point there is again 0% liquid (or 100% vapour).

Further expansion below the dew point pressure leads to point 3 which again

produces a superheated vapour state.

vaporises. This phenonena, of the mixture condensing with decreasing

pressure, is the opposite of what one would expect and leads to the

expression Retrograde Condensation.

critical point) and phenomena such as retrograde condensation is important to

field development plans; thus, the importance of P T diagrams to them.

more interested in P x y , T x y and x y diagrams; these are

mainly used in the design and operation of distillation columns and flash

drums.

TOPIC 3B: VLE, LLE and Miscibility 12

variety of compositions (the pure ethane and n-heptane vapour pressure

curves are also shown):

phase equilibrium

envelopes for different

mixtures.

critical points is shown by

the outer curve.

are each a tangent to this

outer curve.

critical properties need not

lie between the pure

component values.

ethane. The envelope A 2 B 2 has a mixture critical point C 2 and is 50.25%

(w/w) ethane. The envelope A 3 B 3 has mixture critical point C 3 and is 9.78%

(w/w) ethane.

The curves labelled A are bubble point curves, while all the curves labelled

B are dew point curves.

Also, the relationship between the mixture critical point, the cricondenbar and

the cricondentherm (for each envelope) changes as the composition of the

envelope changes.

Wherever the bubble point curve of one envelope intersects with the dew point

curve of another envelope, then the two phases are in VLE at the same

T & P ; this situation corresponds to two phases in equilibrium at either end of

a tie line on a T x y or a P x y diagram.

TOPIC 3B: VLE, LLE and Miscibility 13

the well-known P x y diagram. There are actually three cases depending

on the selected temperature:

Case 3

The bubble point curve

is above and the dew

Case 2 point curve is below.

P2sat

The liquid region is

sat

Bubble Point X P1

Curve

P P x1 above the two phase L-

P y1 Case 1

V region.

P2sat X Dew Point

Curve

0 The vapour region is

0 1.0 below the two phase

x1 & y1 L-V region.

Case 1 is where the temperature is below the critical temperature of both pure

species. Case 2 is where the temperature is above the critical temperature of

component 1, but below that of 2. Case 3 is where the temperature

exceeds the critical temperatures of both pure species.

pressure while keeping T constant. The process will follow a vertical path

A-B-E-F with no change in the overall composition, as shown:

Constant T

P A P x1 P1sat drops to Pbp , the

B mixture reaches the

Pbp D

Pdp C bubble point line at B.

E

P y1

P

F At B the liquid just

starts to vaporise.

x1

0 1.0 has composition

x1 & y1 composition x1 .

However, the composition of the first bubble of vapour y1 is given by the other

end of the horizontal tie line at D (read y1 vertically below D).

TOPIC 3B: VLE, LLE and Miscibility 14

Notice that this vapour at D is richer in component 1 (the MVC) than the

original saturated liquid at B.

Further reduction of pressure from Pbp Pdp follows vertical path B-E.

However, the liquid composition will now follows the bubble point curve from

B-C, while the vapour composition follows the dew point curve from D-E.

When the pressure drops to Pdp , the mixture reaches the dew point curve at

E where the saturated vapour is in equilibrium with the last drop of liquid.

Any further pressure reduction below Pdp , say to point F, will result in the

vapour becoming superheated. While individual phase compositions may vary,

the overall composition of the mixture always remains the same.

the T x y diagram. Tie-lines are again horizontal and link together phases

in equilibrium. There are three cases depending on the pressure:

Constant P

Case 1: the pressure is

below the critical pressure

of both pure species.

Case 3

Case 2: the pressure is

above the critical pressure

T1sat of component 2, but

Dew Point Case 2

T2satX Curve below the critical pressure

T

T y1 of component 1.

T x1

Bubble Point X T1sat Case 3: the pressure is

Curve Case 1

0 above the critical pressure

0 1.0 of both pure species.

x1 & y1

In a T x y diagram, the dew point curve is above and the bubble point

curve is below. The vapour region is now above the two phase L-V region

while the liquid region is below the two-phase L-V region.

keeping the pressure P constant. The process will follow a vertical path

upward with no change in overall composition. The process is analogous to

that already discussed in the previous P x y diagram.

TOPIC 3B: VLE, LLE and Miscibility 15

P x y diagram, at constant temperature, a plot of liquid phase mole

fraction x1 versus vapour phase mole fraction y1 may be prepared.

simply by plotting the compositions from either end of the tie-lines against

each other. The diagonal x = y line is added for convenience:

Constant P

Plotting a succession of

1.0 points, from a sequence

of tie-lines, produces

the entire case 1

x y diagram.

Case 1

This can be repeated

y1 y1 for case2.

Case 3

And again for Case 3.

Case 2 The result is an x y

diagram at constant

0 pressure.

0 x1 1.0

x1

exercise could be repeated (starting with a P x y diagram) to get an x y

diagram at constant temperature.

multicomponent mixtures (more than two components). However, it is still

possible to plot a P T diagram for such a system.

3.3.5 Azeotropes

Azeotropes are formed when there is a strong departure (both positive and

negative) from ideal solution behaviour. Thus, i will either be i > 1 (positive

deviation) or they will be i < 1 (negative deviation), this was discussed in

Topic 3A and Appendix B.

TOPIC 3B: VLE, LLE and Miscibility 16

If the pressure is low enough for the vapour phase to be an ideal gas then all

V = 1 and, for the liquid phase, f = f sat = P sat . Thus, the appropriate VLE

i i i i

relationship is Modified Raoults Law, as developed earlier in topic 3A:

yi

Ki =

xi

i Pi sat

Ki = ..(3.1)

P

ij , is simply the volatility of i divided by the volatility of j , previously defined

in Topic 2 as

Ki

ij =

Kj

equation (3.1) into the previous expression

i Pi sat

ij = .(3.2)

j Pjsat

For a binary mixture that forms an azeotrope, the volatilities of each species

are the same K 1 = K 2 = 1.0 (literally the mixture boils with a constant

composition y1 = x1 and y 2 = x 2 ).

This means that the relative volatility at the azeotropic composition is one

( ij ) AZ = 1 and distillation alone can no longer separate the mixture; some

other technique, usually in combination with distillation, must be used.

(negative deviation from ideality) or a minimum (positive deviation from

ideality); vice versa for P x y diagrams.

TOPIC 3B: VLE, LLE and Miscibility 17

The diagrams below are taken from Appendix B of Topic 3A where there is a

full discussion of both positive and negative deviation from ideality as well as

the formation of azeotropes please read this appendix carefully:

Constant P Constant P

Dew Point

T y1 Line T2sat

T y1

T x1

Bubble Point Dew Point

T2sat Line Curve

T T T x1

T1sat

Bubble Point

T1sat Curve

0 0

0 1.0 0 1.0

x1 & y1 x1 & y1

1 P1sat

12 = ..(3.3)

2 P2sat

An azeotrope will form when the liquid and vapour have the same composition.

Thus, the relative volatility must be equal to one 12 = 1 , or from (3.3)

1 P1sat

=1

2

sat

AZ P2

P sat

1 = 2sat .(3.4)

2 AZ P1

when equation (3.4) is satisfied. Thus, azeotropic behaviour depends not only

on the activity coefficients but also on the vapour pressure of the pure species.

If the boiling points of the species are not too far apart, and the deviation from

ideal solution behaviour is large enough, and if equation (3.4) is satisfied, then

an azeotrope will form.

1 P1sat

( 12 )x =0 = ...(3.5)

1

P2sat

TOPIC 3B: VLE, LLE and Miscibility 18

P1sat

(12 )x =1.0 = .....(3.6)

1

2 P2sat

Thus, if one limiting value exceeds one while the other limiting value is less

than one, then an azeotrope must exist somewhere in the composition range

0 x1 1.0 .

find the exact azeotropic composition simply search for a value for x1 such

that equation (3.4) is satisfied:

1 P sat

= 2sat

2 AZ P1

shown to have an azeotrope at x1 = 0.7174. The P x y diagram shows a

maximum pressure azeotrope (minimum temperature azeotrope):

At the maximum pressure azeotrope the tie line has zero length and the

mixture boils with a constant composition. At this point x1 = y1 and x 2 = y 2 .

TOPIC 3B: VLE, LLE and Miscibility 19

From this diagram the maximum pressure azeotrope occurs at 99.82 kPa, but

this valve can be found with more accuracy by setting (in modified Raoults

Law) either y1 = x1 or y 2 = x 2 thus for species 1:

equation since, at the azeotrope, equation (3.4) must be satisfied.

x1 = y1 and x 2 = y 2 . For an x y diagram the curve must, therefore, cross

the diagonal line. The three x y diagrams below correspond to three cases

listed below:

1. The mixture is an ideal solution.

2. The mixture has positive deviation from ideality leading to a maximum

pressure azeotrope.

3. The mixture has negative deviation from ideality leading to a minimum

pressure azeotrope.

Constant P

1.0

Curve 1 is the ideal

solution case (no

1 azeotope can occur).

Curve 2 is positive

2

deviation from ideality

case (maximum pressure

3

y1 azeotrope).

Curve 3 is negative

deviation from ideality

case (minimum pressure

0 azeotrope).

0 1.0

x1

Notice that in case 2 before the azeotrope species 1 is MVC, while after the

azeotrope species 1 is LVC; at the azeotrope the volatilities are the same.

TOPIC 3B: VLE, LLE and Miscibility 20

The liquid phase will only split into two immiscible or partially miscible phases

if the system has strong positive deviation from ideality (where unlike species

have little affinity for each other), see Appendix B of Topic 3A.

systems as the non-polar end of the alcohol gets longer, i.e. methanol/water,

ethanol/water, propanol/water and finally butanol/water systems:

All show positive deviation from ideality with increasing activity

coefficients as the non-polar end of the alcohol gets longer.

The methanol/water system does not form an azeotrope, while

ethanol/water and propanol/water do form maximum pressure

azeotropes. However, all of these mixtures are miscible.

As the non-polar end of the alcohol gets longer, the affinity between the

different alcohol/water systems gets less and less.

With the butanol/water system the affinity between the two species is

so low that, depending on the composition, the liquid phase may split

into two partially miscible liquid phases; one butanol-rich, the other

water-rich.

form a so called vapour-liquid-liquid-equilibrium, or VLLE, system.

Below is a system where the miscibility between the two liquid phases

(denoted L 1 and L 2 phases) increases with temperature (phenol/water is an

example). Point U is called the Upper Critical Solution Temperature UCST:

Constant P

Above UCST the two

components are completely

U miscible.

TU

At temperature T < TU , if

Two Phase overall composition x1 < x1

L2 Region L1

T only the L2 - phase exists.

T

L 2 L1

At high overall compositions

REGION

x1 > x only the L1 - phase

exists.

0

x1a

x1

x1 At temperature T two liquid

1.0

1.0 x2

phases L2 L1 exist between

0

these two compositions.

TOPIC 3B: VLE, LLE and Miscibility 21

LCST here miscibility decreases as the temperature rises (a typical system

is trimethylamine/water):

Constant P

Below the LCST the two

components are completely

miscible.

This is explained by the

L 2 L1 two components forming

REGION complexes below LCST.

L2 L1

T

T These complexes help

maintain miscibility below

LCST.

TL L

break down (increased

x1a x1 thermal motion) and

0 x1 1.0

1.0

miscibility decreases.

x2 0

of species 1 in each phase ( x1 and x1 ) varies with temperature T :

Constant P

The left side of this binodal

curve (U-L2-L) is the

TU U solubility of species 1 in

the L2 - phase.

L 2 L1

REGION The right side of the

T

L2

M

L1

binodal curve (U-L1-L) is

T the solubility of species 2

in the L1 - phase.

TL

L

LLE compositions x1 and

x1 are found either side of

x1a x1

0 x1 1.0 the horizontal tie-line.

1.0 x2 0

component 1. The relative amounts of each phase, found using the lever

rule, depends on how the mixing point M bisects the horizontal tie line.

TOPIC 3B: VLE, LLE and Miscibility 22

Temperature TL is the LCST (also called the lower consulate temperature).

For any temperature between TL and TU , the mixture will split into two

partially miscible liquid phases. At points U and L the L 2 - phase and the L 1

- phase will have identical properties.

nicotine/water). Island diagram behaviour is rare, usually either an UCST or a

LCST is observed, the former being the more common.

an upper or lower phase boundary (boiling or freezing), then the remaining

UCST or the LCST nodes may also be absent from the phase diagram.

with temperature, but the UCST is missing because, at lower pressure, the

system boils at temperatures before it reaches an UCST.

diagram below represents a system where the USCT is missing; this is

because the system boils before reaching this point:

Constant T

At constant temperature T :

The lines are nearly vertical here because Three-phase pressure

liquid phase properties are only weak P0 is above the pure

functions of pressure.

component vapour

L 2 L1 pressures.

L2 L1

P0

D E F

HE and GE are the L2

V L2

P V L1

and L1 phase dew point

curves respectively.

H

V HD and GF are the L2

G and L1 phase bubble

point curves respectively.

0 x1 y1 1.0

1.0 x2 y 2 0

Above the three-phase pressure P0 the system has only two liquid phases.

TOPIC 3B: VLE, LLE and Miscibility 23

Below the three-phase pressure P0 the system may either be: single phase,

namely L 2 - liquid, L 1 - liquid or vapour V ; there are also two two-phase

regions, namely V L 2 and V L 1 .

Consider that the system is at the three-phase pressure P0 , but that there is

only pure 2 present (i.e. pure L 2 liquid). Now add small quantities of liquid 1

gradually to this mixture:

in the L 2 - liquid; up to point D. At this stage, there is only a single L 2

rich liquid phase present and the system is miscible.

no more will dissolve. At this point, addition of a little more 1 will

cause a second liquid phase to appear (the L 1 -liquid phase). In addition

a small amount of vapour will form.

3. Applying the phase rule to the line segment DEF. There are three

phases present (L 2 - liquid phase, L 1 - liquid phase and the vapour

phase V ). According to the Phase Rule the system has one degree of

freedom F = 2 + N = 1 (it is univariant).

4. With three phases present, and with the system temperature T fixed,

this means that the state of the system is fixed. Thus, P = P0 must be

fixed, as must the compositions of all three phases; x1 , x1 and y1* .

5. Here y1* is the vapour phase composition at point E. The two liquid

phases will both be saturated solutions with compositions x1 (vertically

below point D) and x1 (vertically below point F).

phases and the pressure P = P0 must be fixed. This applies anywhere

along line segment DEF.

liquids or the vapour phase. The overall composition will change and

thus the quantities of the two liquid phases must change: the L 2 - liquid

phase will decrease, while the L 1 - liquid phase will increase.

becomes saturated and L 2 - liquid phase completely dissolves into the

L 1 - liquid phase.

9. Further addition of species 1, beyond point F, leads to the solution

becoming unsaturated. The overall composition approaches pure 1.

TOPIC 3B: VLE, LLE and Miscibility 24

phases are absent. The system is now miscible.

10. In the single phase regions there are three degrees of freedom

F = 2 + N = 3 ; with the temperature fixed, both pressure and

composition can be varied independently.

11. If the process is reversed and we start with 2 gradually being added

to pure 1, then the process will be repeated, but in reverse.

12. A similar situation will occur at a different fixed temperature, but then

the three-phase pressure P = P0 and the compositions of the two

saturated liquid phases (and the vapour phase) will all be different.

Above the three-phase pressure P > P0 is the liquid phase region, no vapour

is present and only LLE is evident. When the pressure is less than the three-

phase pressure P < P0 , then only VLE phase behaviour is evident. VLLE is

observed only when P = P0 .

the UCST is missing because the LLE region intersects the VLE region before

the UCST is reached (an example would be aniline/water system):

Constant P

Below the three-phase

G temperature T0 the system

V is entirely liquid:

H

Within the L2 L1 region

there are two degrees of

V L2 V L1 freedom and only two

T0 L D E F liquid phases are present.

T 2 L1

L 2 L1 These split into an L2 -

liquid phase and an L1 -

liquid phase.

x1a y1* x1

No vapour is present.

0 x1 y1 1.0

1.0 x2 y 2 0

TOPIC 3B: VLE, LLE and Miscibility 25

Above the three-phase temperature T > T0 is the VLE region. There are three

single-phase regions (two liquid regions and a vapour region). In addition,

there are two two-phase regions; the - V L 2 region and the V L 1 region.

F = 2 + N = 3 , all intensive properties (except the fixed pressure) may be

changed. Thus, temperature and composition can all be varied independently.

In addition to these single phase regions, whenever T > T0 , there are two

vapour-liquid regions. In these two-phase regions F = 2 + N = 2 and there

are two degrees of freedom.

Given that the pressure is fixed, this means that the temperature may

be changed, in which case the composition is fixed, or vice versa;

graphically this situation is represented by horizontal tie-lines.

Here the gamma-phi approach may be used to solve bubble point or

dew point problems. VLE will result in either an L 2 - liquid phase or an

L 1 - liquid phase in equilibrium with the vapour phase (which liquid

phase is present depends on the overall composition).

At T = T0 and for overall compositions that fall within the line segment DEF,

the mixture will split into two liquid and one vapour phase in equilibrium:

The L 2 - liquid phase has a composition x1 , corresponding to a

composition on the x-axis vertically below point D.

The L 1 - liquid phase has a composition x1 , corresponding to a

composition on the x-axis vertically below point F.

The vapour phase has a composition y1* , corresponding to a

composition on the x-axis vertically below point E.

F = 2 + N = 3 = 1 which means the system is univariant. Given that the

pressure is already fixed, this means the temperature and the phase

compositions cannot change.

The removal of heat at constant pressure will cause the system temperature to

drop. How exactly the system will behave depends on the starting point and

the overall composition see Appendix B (this appendix is examinable):

See Appendix B.1: if cooling starts in superheated vapour region with

overall composition to the right of F.

See Appendix B.2: if cooling starts in superheated vapour region with

overall composition that passes exactly through E.

See Appendix B.3: if cooling starts in the superheated vapour region

with overall composition anywhere between E and F (the same

applies to cooling from a superheated vapour state with overall

composition anywhere between D and E).

TOPIC 3B: VLE, LLE and Miscibility 26

increased, then both pure component boiling points will rise.

axis, saturation temperatures T1sat & T2sat , will both rise. Effectively the entire

VLE region will move upwards.

The same effect will occur with a VLLE system. The VLE region will slide up

the LLE region. Thus, the three-phase temperature T0 will also rise.

Due to the higher temperature, the LLE region miscibility will increase (for

systems of this type) and line segment DEF will become shorter see below:

G temperatures and miscibility

V in the liquid region:

H

The three-phase VLLE

behaviour remains the

V L2 V L1 L1

same.

T0 D E F

L2 An azeotrope occurs

L 2 L1 along DEF since the

L 2 L1 mixture boils with

T constant composition.

heterogeneous since

there are two liquid

x1a x1E x1 phases present.

0 x1 y1 1.0

1.0 x2 y 2 0

butanol/water and ethyl acetate/water. Separating these components requires

specialised techniques and equipment.

When this product is totally condensed, it will cool isobarically with to a

temperature below its three-phase temperature T0 .

Thus, a subcooled liquid is formed which, inside a decanter, splits into two

liquid phases. One liquid phase is returned as reflux to the first column while

the other liquid phase is separated in a second column.

TOPIC 3B: VLE, LLE and Miscibility 27

An x y diagram for the VLLE system just discussed is shown below. Notice

the heterogeneous azeotrope and mixture boiling with constant composition:

On the previous T x y

Constant P1

V L 2 region. Notice that

1 is MVC

On the previous T x y

D E F

y1 *

y

1

diagram, GEF is the

V L1 region. Notice that

here 1 is LVC

0 a

x x E

x 1.0 evident on x y diagram

1 1 1

x1 to the left.

the azeotrope is heterogeneous the two liquid phases, in equilibrium with the

vapour phase, have different compositions compared to the vapour phase.

At still higher pressure P3 > P2 the boiling points of the pure species will rise

and the VLE and the LLE regions can separate from each other:

Constant P3

The LLE occurs at lower

Dew Point G

temperatures.

V Curve

Bubble Point temperatures above

Curve L UCST.

Miscible Region

UCST Now there is a minimum

temperature azeotrope

T L2 L 2 L1 L1 and a fully miscible

region between the LLE

and VLE regions.

0 x1 y1 1.0

1.0 x2 y 2 0

azeotrope cannot form. Any distillation column will produce the minimum

temperature homogeneous azeotrope overhead.

TOPIC 3B: VLE, LLE and Miscibility 28

vaporisation effects that are detailed in Appendix B (please note that this entire

appendix is examinable). As seen, these effects can have important

consequences in terms of the design of process plant.

More complex types of phase behaviour can occur and, at a fixed pressure,

this depends not only on the relationship between T0 , T1sat & T2sat but also on

whether or not homogeneous azeotropes can form.

system 3 and system 4 type behaviour. Only system 1 type phase

behaviour is discussed here (and in Appendix B).

It has been said that in the VLE region bubble point and dew point calculations

can be handled using the gamma-phi approach. At low pressure all V =1

i

and all isat = 1 , the rigorous approach reduces to modified Raoults Law:

For VLLE systems, the activity coefficients are best found using the Non-

Random Two Liquid NRTL model. This model, unlike the Wilson model, has

three adjustable BIPs and is recommended for both VLE and LLE.

As stated, in the VLE region use the gamma-phi approach, while in the LLE

region use the approach outlined in Appendix A. This appendix also reviews all

the key NRTL expressions.

using a combination of these methods; again, NRTL is the preferred model of

solution behaviour the Wilson model cannot be used.

In rare circumstances, when the miscibility of each species in the other is very

limited, and when Henry Law constants are available, then simplifying

assumptions may be made. This is what follows in the section below.

If the pressure is very low (ideal gas) and if the liquid phase is also an ideal

solution, then all i = 1 and Raoults Law is obtained which, for species 2 in

a binary mixture may be written

y 2 P = x 2 P2sat ......(3.10)

TOPIC 3B: VLE, LLE and Miscibility 29

A VLE system described by equation (3.9) will only behave in accordance with

equation (3.10) as species 2 approaches purity, that is x 2 1 . At the same

time as species 2 approaches purity then, in a binary mixture, species 1

must approach infinite dilution, that is x1 0 .

Law, species 1 must increasingly be modelled by Henrys Law

y1 P = h12 x1 .(3.11)

In which h12 is the Henry Law constant of species 1 (the low concentration

species often called the solute) in species 2 (the high concentration

species often called the solvent).

Raoults Law while, at the same time, species 1 partial pressures should be

found from Henrys Law:

y 2 P = x 2 P2sat

y1 P = h12 x1

P = x 2 P2sat + h12 x1

P = x 2 P2sat + h12 (1 x 2 )

P h12

x2 = (LINE HD)..(3.12)

P2sat h12

given by Raoults Law

x 2 P2sat

y2 = (LINE HE)....(3.13)

P

either-end of a horizontal tie line within the V L 2 region.

TOPIC 3B: VLE, LLE and Miscibility 30

In the V L 1 region, if the two components have very little solubility, then

species 1 partial pressures may be found using Raoults Law, while species

2 partial pressures are then found using Henrys Law as follows:

y1 P = x1 P1sat

y 2 P = h21 x 2

In which h21 is the Henry Law constant of species 2 (now the low

concentration species) in species 1 (now the high concentration species).

Adding these two equations together leads to

P = x1 P1sat + h21 x 2

P = P1sat (1 x 2 ) + h21 x 2

P P1sat

x2 = (LINE GF)..(3.14)

h21 P1sat

equilibrium is now given by Henrys Law

h21 x 2

y2 = (LINE GE).......(3.15)

P

end of a horizontal tie line within the V L 1 region.

Only where the system behaves ideally (in the limit of very low and high

concentrations) will these expressions apply. It must be noted that not many

systems in practice will behave in this way.

temperature, then only liquid will be present. In order to solve such LLE

problems rigorously please refer to appendix B.

The more difficult case is to solve the VLLE case where the mixture is at the

three-phase temperature and the overall composition falls somewhere along

the line segment DEF.

TOPIC 3B: VLE, LLE and Miscibility 31

1. The saturated L 2 - liquid phase; composition x1 corresponding to point

D on the T x y diagram.

2. The saturated L 1 - liquid phase; composition x1 corresponding to point

F on the T x y diagram.

3. The saturated vapour phase V ; composition y1* corresponding to point

E on the T x y diagram.

Dew point lines HE and GE meet at point E. Where these curves meet

defines the vapour phase composition y 2* . Thus equating (3.13) with (3.15)

leads to

x 2a P2sat h21 x 2

y =

*

2 =

P P

- liquid and L 1 liquid phases respectively. Cancelling and re-arranging gives

x 2a h

= 21 (3.16)

x2 P2sat

y =

* (

h12 1 x 2a

=

)

P1sat 1 x 2 ( )

1

P P

(1 x ) = h

2 12

(1 x ) P

a sat

...(3.17)

2 1

or they be combined to solve for x 2 and x 2 explicitly. Substitute equation

(3.16) into equation (3.17), so as to eliminate x 2 , as follows:

(1 x )

2

=

h12

h P1sat

1 21 x 2

sat

P2

TOPIC 3B: VLE, LLE and Miscibility 32

Or,

(

1 x 2 = ) h12

h

1 21 x 2

P1sat P 2

sat

h21 h12 h

sat sat

x 2 x 2 = 12sat 1

P2 P1 P1

h h12 h

x 2 21sat sat

1 = 12sat 1

P2 P1 P1

h12

1

P1sat

x 2 = ..(3.18)

h21 h12

sat sat 1

P P

2 1

Thus, once a value is available for x 2 from equation (3.18), this may be

substituted into equation (3.16) to find x 2 without any trial-and-error

calculations. A re-arranged version of equation (3.16) is given again below:

h21

x 2 = x 2 ..(3.19)

P2st

The last step is to find the relationship for y 2* . First write down equation (3.12),

representing dew point line HD for the V L 2 region and then re-arrange it

in favour of the total pressure P to get

P h12

x2 =

P2sat h12

P h12

x2 =

P2sat h12

Now do the same for equation (3.13) representing bubble point curve HE

x 2 P2sat

y2 =

P

TOPIC 3B: VLE, LLE and Miscibility 33

Or,

x 2 P2sat

P =

y2

Now eliminate the total pressure P to find the desired relationship between

x & y anywhere in the V L 2 region. These are corresponding points at

either end of any tie-line in the V L 2 region:

x 2 P2sat

= x 2 P2sat x 2 h12 + h12

y2

x 2 P2sat

y2 =

x 2 P2sat x 2 h12 + h12

x2

y2 = ..(3.20)

h

x 2 + 12sat (1 x 2 )

P2

In exactly the same way, starting with equations (3.14) and (3.15) the

relationship between x & y anywhere in the V L 1 region is given by

x

y2 = sat

2

..(3.21)

P

x2 + (1 x 2 )

1

h21

corresponding y 2* (at point E) in equilibrium with this L 2 - liquid.

corresponding y 2* (at point E) in equilibrium with the L 1 - liquid.

If the value of y 2* occurs at a very high concentration, then the latter approach

is correct. If the value of y 2* occurs at very a low concentration, then the

former approach is correct.

With little loss in accuracy, the ratios h12 / P2sat and P1sat / h21 may be treated as

constants.

TOPIC 3B: VLE, LLE and Miscibility 34

Construct a T-x-y diagram for the partially miscible system ether/water system

at 1 atm total pressure using the following data for saturated (i.e. three phase)

vapour-liquid equilibrium at various pressures.

Saturated Saturated

Total

Temperature Water Phase Ether Phase

Pressure

(oC) Composition Composition

(atm)

Mole fraction ether

34.15 1.005 0.0122 0.9451

40.00 1.250 0.0116 0.9416

50.00 1.744 0.0103 0.9348

60.00 2.381 0.0093 0.9271

70.00 3.195 0.0075 0.9212

80.00 4.229 0.0069 0.9158

90.00 5.514 0.0058 0.9107

100.00 7.040 --- ---

Vapour Vapour

Temperature Pressure Pressure

(oC) Water Ether

(atm) (atm)

34.15 0.053 0.983

40.00 0.073 1.212

50.00 0.121 1.679

60.00 0.196 2.271

70.00 0.306 3.018

80.00 0.467 3.935

90.00 0.691 5.040

100.00 1.000 6.390

Assume that Raoults Law is valid for ether in the ether-rich phase and for

water in the water-rich phase.

TOPIC 3B: VLE, LLE and Miscibility 35

TOPIC 3B: VLE, LLE and Miscibility 36

have such positive deviation from ideality, and so little affinity to each other,

that they may (with little loss in accuracy) be considered completely

immiscible:

Constant P

X Y G

H

V

V L2 V L1

T0 F

T D E

L 2 L1

0 x1 y1 1.0

1.0 x2 y 2 0

system by converting HD and GF into vertical lines HD and GF , these lines

also extend (along the two y-axes) vertically into the LLE region.

There is still a VLE region above and a LLE region below the three-phase line

segment DEF. However, the L 2 - liquid is now just pure species 2, while the

L 1 - liquid is now just pure species 1.

compositions (curve HE) to pure liquid 2 while in the V L 1 region,

horizontal tie-lines connect saturated vapour compositions (curve GE) to pure

liquid 1.

with pure L 1 - liquid at F and both of these are in equilibrium with the vapour

phase (composition E).

the dew point curve GE at a point vertically below Y. At this point pure L 1 -

liquid (pure species 1) condenses from the vapour mixture.

TOPIC 3B: VLE, LLE and Miscibility 37

Further cooling and the vapour follows the dew point curve GE while pure L 1

liquid continues to condense out in increasing quantities. This continues until

the vapour composition reaches composition E.

From this point onwards both L 2 - liquid (pure species 2) and L 1 - liquid (pure

species 1) condense out together, until the last bubble of vapour has

condensed. Further cooling leads to both liquids becoming subcooled.

vertical path and behaves in much the same way. Only now L 2 - liquid

condenses out first until the three-phase temperature T0 .

Once cooled to T0 , as before, both liquid phases condense together with all

intensive properties remaining constant until the last bubble of vapour

condenses. Further cooling subcools both liquid phases.

If the vertical line on the previous diagram were to pass through E, then the

same would apply, only now condensation of pure L 2 - liquid and pure L 1 -

liquid will occur simultaneously.

pure 2 and the total pressure above the liquid is simply its vapour pressure

P2sat , this is also equal to its partial pressure Py 2 which leads to

P2sat = Py 2

P2sat

y2 = ...(3.22)

P

liquid is pure 1, so that the same results are obtained in terms of species 1:

P1sat = Py1

P1sat

y1 = .(3.23)

P

TOPIC 3B: VLE, LLE and Miscibility 38

temperature T0 is just the sum of the individual partial pressures at T0

P0 = Py1 + Py 2

The value of P0 is known because the pressure is fixed. If a T P sat data set

is available, then T0 may be estimated by interpolation; varying T0 and hence

Pi sat until equation (3.24) is satisfied (within some tolerance).

The final step is to substitute equation (3.24) into equation (3.23) to get an

expression for y * which is the dew point vapour composition at point E

consistent with T = T0

P1sat (T0 )

y1* = ....(3.25)

P0

meets curve GE. In addition P1sat (T0 ) is the vapour pressure of species 1 at

the interpolated three-phase temperature T0 .

TOPIC 3B: VLE, LLE and Miscibility 39

for the toluene/water system at 760 mm Hg pressure.

B

ln P sat = A

T +C

Where,

P sat is the vapour pressure (mm Hg)

T is the temperature (K)

A B C

Water: 18.3036 3,816.44 -46.13

Toluene: 16.0137 3,096.52 -53.67

TOPIC 3B: VLE, LLE and Miscibility 40

3B.6 Tutorial 3B

pressure of 760 mmHg using the following vapour pressure data and

assuming complete immiscibility.

Temperature (oC)

Benzene (mmHg) Water (mmHg)

50 269 93

60 389 149

70 547 233

75 640 285

80 754 355

90 1016 526

100 1344 760

110 1748 1075

2. Toluene and water are totally immiscible. Use the vapour pressure data

supplied to construct a P x y diagram for the system at 80oC.

Vapour pressure data can be evaluated using:

ln (Psat ) = A

B

T +C

temperature in (K)

Component A B C

Water 18.3036 3816.44 -46.13

Toluene 16.0137 3096.52 -53.67

TOPIC 3B: VLE, LLE and Miscibility 41

3B.7 Bibliography

Chemistry Data Series, DECHEMA, Frankfurt, 1977-1990.

McGraw-Hill, SI ed., 1987.

Wiley 2nd ed., 1993.

S.I. Sandler. Chemical and Engineering Thermodynamics. Wiley, 3rd ed., 1999.

ed., 1998.

Engineering Thermodynamics. McGraw-Hill. 7th ed.,2005.

TOPIC 3B: VLE, LLE and Miscibility 42

Appendix A

The material in this appendix could prove useful for Design Projects and

Research Projects. It deals with non-ideal liquid systems where a combination

of Raoults Law and Henrys Law is invalid.

TOPIC 3B: VLE, LLE and Miscibility 43

fi = fi .( i = 1,2,3.....N ).(A.1)

fugacity of component i in the L 1 - phase (both phases are now liquid

phases). The activity coefficient for a species in the L 2 - phase is defined as

fi

i =

x i f i

fi = i xi f i .(A.2)

fi

i =

xi f i

fi = i xi f i .(A.3)

Substitute equations (A.2) and (A.3) into (A.1) and, if both species exist as

liquids, then at the same T & P the pure component fugacity must be the

same f i = f i . Thus, for LLE

xi i = xi i .( i = 1,2,3.....N )(A.4)

and liquid phase composition:

i = i (xi , T , P )..(A.5)

i = i (xi , T , P ) .(A.6)

N 1 independent mole fractions in each phase). Given that there are N

equilibrium relations, it follows that there must be N degrees of freedom.

TOPIC 3B: VLE, LLE and Miscibility 44

F = N . Thus, N intensive variables must be fixed in order to solve the

equilibrium relationships.

For the special case of a binary LLE system there are two degrees of freedom

F = 2 and equation (A.4) may be written for each species as follows:

x1 1 = x1 1 ...(A.7)

(1 x )

1

2 ( )

= 1 x1 2 ...(A.8)

Often the pressure is fixed or low enough that the activity coefficients are

regarded as being functions of liquid composition and temperature only.

1 = 1 (x1 , T )....(A.9)

2 = 2 (x2 , T ) .(A.10)

If empirical data is available for the activity coefficients, and the temperature T

is fixed, then equations (A.7) through (A.10) may be solved for the liquid phase

compositions ( x1 and x1 ).

In order to avoid tedious iteration schemes, equations (A.7) through (A.10) are

best solved using a mathematics package. To solve equations (A.9) and

(A.10) some model of solution behaviour is needed.

Neither the Wilson equations nor any of the power law models are suitable for

LLE. However, NRTL, UNIQUAC and UNIFAC expressions do model systems

with limited miscibility.

adjustable BIPs and the excess Gibbs function is given by

gE G 21 21 G12 12

= + ...(A.11)

x1 x 2 RT x1 + x 2 G 21 x 2 + x1G12

The NRTL model is widely regarded as one of the most accurate models of

solution behaviour. The adjustable BIPs are found by regressing experimental

data to equation (A.11).

TOPIC 3B: VLE, LLE and Miscibility 45

for ln 1 & ln 2 :

G 21

2

G12 12

ln 1 = x 21

2

+ (A.12)

2

x1 + x 2 G 21 (x 2 + x1G12 )2

G12

2

G 21 21

ln 2 = x 12

2

+ ...(A.13)

1

x 2 + x1G12 (x1 + x 2 G21 )2

Where,

b12

12 = (A.16)

RT

b21

21 = ...(A.17)

RT

The infinite dilution activity coefficients are readily obtained, from equations

(3.12) and (3.13) by setting xi = 0

ln 1 = 21 + 12 exp( 12 ) ..(A.18)

ln 2 = 12 + 21 exp( 21 ) ..(A.19)

The 3 BIPs for the NRTL model are b12 , b21 and . These BIPs are

independent of temperature and composition.

through equations (A.14) through (A.17) while the composition dependence is

expressed through (A.12) and (A.13).

use this approach to LLE, experimental values for the BIPs are needed. Many

values are listed in the literature (Chemical Data Series, Dechema).

TOPIC 3B: VLE, LLE and Miscibility 46

Appendix B

TOPIC 3B: VLE, LLE and Miscibility 47

When the overall composition is A (to the right of point F) the system starts

as a single phase superheated vapour. If this vapour is then cooled (at

constant pressure) it will follow a vertical line indicated below:

Constant P

Further cooling and the

A G system will eventually

V intersect the dew point

H curve (line GE), leading to

the first drop of L1 - liquid.

V L1

V L2

Further cooling and the

T0 L D E F mixture will enter the two-

T 2 L1

phase V L 1 region.

L 2 L1

The compositions of

saturated liquid and vapour

x1a y1* x1

are then located either end

0 x1 y1 1.0 of horizontal tie-lines.

1.0 x2 y 2 0

When the mixture is cooled further, the system will eventually intersect the

bubble point curve (line GF) and the last bubble of vapour will condense.

identical to a miscible VLE system and calculations may be tackled in the

usual way using the gamma-phi approach to VLE. Use either the rigorous or

Modified Raoults Law method depending on pressure.

When the system is either in the superheated vapour region or the subcooled

liquid region it will have three degrees of freedom. Thus, temperature and

composition can be varied independently of each other (assuming a fixed

pressure.

The system will have two degrees of freedom in the V L 1 two-phase region.

Therefore, assuming a fixed pressure, the temperature and composition

cannot be varied independently of each other; they are linked by tie-lines.

ever three phases in equilibrium. The same effect would occur when passing

through the V L 2 region, so long as the starting point was a superheated

vapour state to the left of point D.

TOPIC 3B: VLE, LLE and Miscibility 48

constant pressure starting from B, which has the same overall composition

as point E:

Constant P

G

will cool until point E.

V

H

B At the three-phase

temperature T0 the vapour

V L2 V L1

will start to condense into

T0 L D E F an L2 - liquid at D and a

T 2 L1

L1 - liquid at F.

L 2 L1

Liquids D and F and

vapour E are all in

x1a y1* x1 equilibrium at constant

temperature T0 .

0 x1 y1 1.0

1.0 x2 y 2 0

Now there are three phases in equilibrium; thus, only one degree of freedom.

Since the pressure is already fixed, this means that neither the temperature

nor any of the three phase compositions may change.

into two liquid phases with compositions corresponding to D & F. The

condensation will continue right up to the last bubble of vapour without any

change in any of the intensive variables.

Further cooling will eventually condense the last bubble of vapour and the

system moves into the subcooled region where there are now only two liquid

phases present.

In the L 2 L 1 region, the system will have two degrees of freedom. Therefore,

assuming a fixed pressure, the temperature and composition cannot be varied

independently of each other; horizontal tie-lines link these variables together.

of the vapour phase. This continues from the first drop of liquid right up to the

final bubble of vapour.

TOPIC 3B: VLE, LLE and Miscibility 49

C, then the behaviour is different again:

Constant P

the dew point line GE

C

H where L1 - liquid only starts

V to condense.

V L2 V L1

Further cooling leads to a

T0 L D E F vapour following the dew

T 2 L1

point curve GE and L1 -

L 2 L1 liquid following the bubble

point curve GF.

out until the vapour

0 x1 y1 1.0 composition reaches E

1.0 x2 y 2 0

Once the horizontal tie line drops to EF, then the first L 2 - liquid starts to

condense together with the L 1 - liquid. There are now three phases in

equilibrium (two liquid and one vapour) and one degree of freedom.

liquid phases; one is the L 2 - liquid with composition corresponding to D; the

second liquid is a L 1 - liquid with composition corresponding to F.

The condensation will continue right up to the last bubble of vapour without

any change in any of the intensive variables.

Further cooling will eventually condense the last bubble of vapour and the

system moves into the subcooled region where there are now only two liquid

phases present (and two degrees of freedom).

This same situation prevails if the starting point is superheated vapour with

overall composition between points D and E. Now the L 2 - liquid condenses

first until the tie-line drops to DE and then the two liquid phases condense

together until the last bubble of vapour.

TOPIC 3B: VLE, LLE and Miscibility 50

Consider isobaric heating of subcooled liquid starting from X, well below the

three-phase temperature T0 . Two liquid phases are present at X and initially

there is no vapour phase:

Constant P

the tie line tracks up within

H V the LLE region.

V L2 V L1

L2 - liquid is in equilibrium

T0 L with the L1 - liquid.

D E F

T 2

X

L1

Y

When T = T0 there is liquid

L 2 L1 at D in equilibrium with

liquid at F and both are in

x1a y1* x1 equilibrium with first bubble

of vapour at E

0 x1 y1 1.0

1.0 x2 y 2 0

At this point vaporisation starts. Both the L 2 - liquid and the L 1 - liquid vaporise

together but there is more L 1 - liquid than L 2 - liquid, so that inevitably the L 2 -

liquid is depleted first.

Once the final drop of L 2 - liquid has vaporised, the tie-line is at EF and there

are now two degrees of freedom. As heating continues the temperature is now

free to increase.

and the saturated liquid composition tracking up FG. Once the saturated

vapour composition is the same as the overall composition, then the last drop

of L 1 - liquid will vaporise (this is the dew point).

The mixture then becomes a superheated vapour with the same overall

composition as the original two-phase subcooled liquid at X.

constant) then, once the L 2 - liquid phase has vaporised, vaporisation of L 1 -

liquid continues (with rising temperature) up to the dew point curve.

TOPIC 3B: VLE, LLE and Miscibility 51

The same applies if the overall composition lies between point D and E.

Initially both phases vaporise, but now L 1 - liquid is depleted first leaving the L 2

- liquid to vaporise on its own until the mixture reaches the dew point curve

HE.

point E. In this case both phases vaporise (with constant intensive

properties) until the last drop of liquid then the vapour becomes superheated.

TOPIC 3B: VLE, LLE and Miscibility 52

TOPIC 4: Chemical Equilibrium 1

Topic 4

Chemical Equilibrium

Contents

TOPIC 4: CHEMICAL EQUILIBRIUM

4.1 INTRODUCTION .................................................................................................................. 3

4.2 REACTION STOICHIOMETRY ............................................................................................... 5

4.2.1 Extent of Reaction ............................................................................................... 5

4.2.2 Example 4.1 ........................................................................................................ 7

4.3 EQUILIBRIUM CRITERION .................................................................................................... 9

4.3.1 Equilibrium Constant ......................................................................................... 11

4.3.2 Approximate Temperature Dependence of K ..................................................... 14

4.3.4 Accurate Temperature Dependence of K........................................................... 17

4.3.5 Example 4.2 ...................................................................................................... 20

4.4 GAS PHASE CHEMICAL EQUILIBRIUM ................................................................................ 22

4.4.1 Rigorous Non-Ideal Mixture ............................................................................... 24

4.4.2 Ideal Solution Mixture ........................................................................................ 24

4.4.3 Ideal Gas Mixture .............................................................................................. 25

4.4.4 Effect of Pressure on Chemical Equilibrium ....................................................... 25

4.4.6 Calculation of Equilibrium Conversion ............................................................... 26

4.4.7 Example 4.3 ...................................................................................................... 29

4.5 LIQUID PHASE CHEMICAL EQUILIBRIUM ............................................................................. 31

4.5.1 Rigorous Non-Ideal Mixture ............................................................................... 32

4.5.2 Ideal Solution Mixture ........................................................................................ 33

4.6 HETEROGENEOUS REACTIONS ......................................................................................... 36

4.6.1 Heterogeneous Reactions with Solids ............................................................... 37

4.7 TUTORIAL 4..................................................................................................................... 38

4.8 BIBLIOGRAPHY ................................................................................................................ 44

Prerequisite knowledge

Process Industries C.

Process Engineering B.

Introduction to Kinetics and Thermodynamics (Chemistry)

TOPIC 4: Chemical Equilibrium 2

Learning objectives

After studying this Chemical Equilibrium topic you should be able to:

Differentiate between chemical conversion and rate of reaction.

Define the extent of reaction and show how it can be used to carry out

a material balance within a chemical reactor.

Review and derive the criterion for chemical equilibrium.

Define activity and equilibrium constant.

Write down expressions for enthalpy change and Gibbs free energy

change of reaction.

Outline and derive expressions for the temperature dependence of the

equilibrium constant.

Explain and write down expressions that indicate how the equilibrium

state is affected by pressure and composition.

Solve gas phase chemical equilibrium problems involving ideal and

non-ideal systems then calculate equilibrium composition and the

conversion of limiting reactant.

Solve liquid phase chemical equilibrium problems involving ideal and

non-ideal systems then calculate equilibrium composition and the

conversion of limiting reactant.

Explain how pressure and temperature affect chemical equilibria and

write down the equations that support these arguments.

For heterogeneous reactions write down solution strategies and related

equilibrium relationships.

Explain how solids are handled in a heterogeneous reaction system.

TOPIC 4: Chemical Equilibrium 3

4.1 Introduction

In a chemical reaction the rate of reaction and extent of conversion are both

important. These two variables do not necessarily vary with reaction conditions

(such as temperature and pressure) in the same way.

shown below:

o

= 98,890 J/mol

The reaction is exothermic and an increase temperature will tend to shift the

reaction to the left, which leads to a decrease in the equilibrium conversion of

reactants to products.

However, increasing temperature will increase the rate of reaction. Thus, when

the conversion is low and the rate is high, a smaller reactor is possible but with

more downstream purification.

would decrease the rate of reaction while, at the same time, increase the

equilibrium conversion. Thus, a larger reactor will be needed, but with less

downstream purification.

Hence rate of reaction and extent of conversion are critical parameters for

designing chemical reactors

topic). This has been discussed in various other courses and an overview is as

follows:

Find a numerical value for the equilibrium constant K (usually at

298.15 K).

Knowing the standard enthalpy change of the reaction H o find a

value for the equilibrium constant K at temperature T (the actual

reaction temperature).

Correct this value for the effect of reaction pressure P .

Express chemical equilibrium in terms of the extent of reaction .

Solve for the extent of reaction and find the equilibrium composition.

Calculate the equilibrium conversion.

The basic procedure has already been outlined (for ideal gases) in Process

Engineering B. This material will be reviewed and extended to cover non-ideal

gaseous systems by relating the reaction stoichiometry to the equilibrium

constant K .

TOPIC 4: Chemical Equilibrium 4

Thermodynamics is only concerned about the final equilibrium state, no matter

how fast or slow it takes to reach this state.

chemical kinetics and that these rates are empirically determined; see Y2

course, Introduction to Kinetics and Thermodynamics.

TOPIC 4: Chemical Equilibrium 5

1 A1 + 2 A2 3 A3 + 4 A4

aA + bB cC + dD

Thus,

i are the stoichiometric coefficients of reactant/product species.

Ai are the various chemical species taking part in the reaction.

i is negative for reactant species.

i is positive for product species.

i is zero for inert species.

allows: reactants to be consumed (negative i ); products to be produced

(positive i ); and inerts to pass through the reactor unchanged (zero i ).

In Process Engineering B it was shown that, for any species i in the reaction

mixture, the change in the number of moles of i (that is dni ) depends on its

stoichiometric coefficient i and the extent of reaction :

The extent of reaction (mol) is also called the reaction co-ordinate and has

the same numerical value for all species taking part in the reaction.

Equation (4.1a) may also represent a flowing system. In this case, everything

stays the same except for dots above the following terms:

In this case both the extent of reaction and n will have units (mol/s).

TOPIC 4: Chemical Equilibrium 6

Integrate (4.1a) from the unreacted state, where = 0 , to any later state

where the extent of reaction has a value of (mol)

ni

nii , 0 0

The initial amount of species i present is n = ni , 0 (mol) at any later time this

has changed to ni (mol). Thus, for any species i in the reaction mixture:

Where,

n = ni n 0 = ni , 0 = i ..(4.4)

i i i

leads to the composition of each species y i as a function of :

ni ni , 0 + i

yi = = .....(4.5)

n n0 +

(3), the following table may be prepared for the ammonia reaction:

N2 + 3H 2 2NH 3

Initially n1, 0 n 2, 0 n 3, 0 n0

Reacted 1 2 3

Remaining n1 = n1, 0 + 1 n 2 = n 2, 0 + 2 n 3 = n 3, 0 + 3 n0 +

n1, 0 + 1 n 2, 0 + 2 n 3, 0 + 3

y1 = y2 = y3 =

yi n0 + n0 + n0 + y i =1

Knowing the extent of reaction (and moles of each species initially), the

remaining number of moles and the composition are easily found.

TOPIC 4: Chemical Equilibrium 7

molar fraction of each component of the reaction exiting the system in terms of

extent of reaction.

TOPIC 4: Chemical Equilibrium 8

TOPIC 4: Chemical Equilibrium 9

Irreversible dS TOTAL > 0 dGT , P < 0

Reversible dS TOTAL = 0 dGT , P = 0

For a reaction system, where T & P are fixed and uniform throughout the

system, the Gibbs free energy provides the criterion for chemical equilibrium

dGT , P = 0 ....(4.6)

Clearly the point of chemical equilibrium occurs at minimum Gibbs free energy

as shown in the diagram below:

Constant T & P

Equilibrium may be

approached from either

side.

free energy must

G decrease.

G The point of equilibrium

= 0

T ,P occurs when total Gibbs

EQUIL

0 free energy is a

minimum.

G = G (T , P, n1 , n 2 ,......ni )

G G G

dG = dP + dT + dni

P T , n T P , n i n i T , P , n

j

i

TOPIC 4: Chemical Equilibrium 10

dGT , P = g i dni

i

dGT , P = g i i d

i

G

= g i i

T , P i

The derivative is clearly the gradient of the curve (on the previous diagram)

and the point of equilibrium coincides with this curve passing through a

minimum. Thus, at chemical equilibrium this gradient must be zero

g i i = 0

i

has been shown to be the partial molar Gibbs free energy of the species in the

mixture i = g i .

i

i i = 0 .......(4.7)

(for non-ideal systems) must be expressed in terms of the fugacity. As

introduced in Topic 1, equation (1.18) this is given by

g i = RT ln f i +

The Gibbs free energy of pure i in some standard state g i0 is therefore also

given by the same expression

g i0 = RT ln f i 0 +

TOPIC 4: Chemical Equilibrium 11

mixture as the pure species property at the same temperature as the mixture

T but at a fixed pressure P 0 (now 1 bar but formerly 1 atm), the reason for

this choice will become apparent later.

corresponding relation between the same partial molar properties of a

component in a mixture as given by

g i = RT ln fi +

fi

g i g i0 = RT ln

f i0

and is given the symbol a i

fi

a i = ...(4.8)

f i0

g i = g i0 + RT ln a i

This shows the partial molar Gibbs free energy of a species in a mixture is a

function of its Gibbs free energy in a standard state (its pure form), plus an

adjustment based on its interaction with the other species in the mixture, as

represented by the species activity a i .

However, the chemical potential i of any species i in the mixture has been

shown to be identical to the partial molar Gibbs free energy of the species in

the mixture i = g i . Thus, the previous expression becomes

i = g i0 + RT ln a i .....(4.9)

TOPIC 4: Chemical Equilibrium 12

Substituting equation (4.9) back into the general criterion for chemical

equilibrium (equation 4.7) gives

(g

i

i

0

i + RT ln a i = 0 )

Then, after some re-arrangement it can be separated into its pure-form

contribution and its interaction contribution:

i g i0 + RT i ln a i = 0

i i

g i

0

i

ln (a i ) =

i i

i RT

ln x i = ln x1 + ln x 2 + .... + ln x n = ln ( x1 x 2 .....x n ) = ln ( xi )

i

i

Applying the same reasoning to left side of the previous equation gives

g i

0

i

ln (a i ) =

i i

i RT

or

i g i0

(a i ) = exp i .(4.10)

i

i RT

i g i0

K = exp i .(4.11)

RT

g

i

i

0

i = RT ln K

TOPIC 4: Chemical Equilibrium 13

G 0 = RT ln K ...(4.12)

From equation (4.11), the definition of the equilibrium constant, it is clear that

the equilibrium constant K depends on g i0 (the standard state Gibbs free

energy of each of the pure species), which means that:

K is independent of composition, since g i0 are pure component

properties.

K is independent of pressure, since g i0 are at a fixed pressure of 1

bar (formerly 1 atm).

K is dependent only on temperature, since g i0 depend on the reaction

temperature only.

Notice that defining standard states (in the manner discussed earlier) means

that the equilibrium constant K is dependent on temperature only.

Substituting equation (4.11) into (4.10) gives

K = (a i ) i ........(4.13)

i

be written as follows

K = (a i )

i

i

K = (a C ) (a D ) (a A ) (a B )

c d a b

(a C )c (a D )d

K = .....(4.14)

(a A )a (a B )b

Equation (4.14) is the key to solving chemical equilibrium problems, so long as

a numerical value for K is available. If G 0 is known, then equation (4.12)

provides a value for K . However, G 0 is initially only known at 298.15 K.

Thus, using equation (4.12) usually only provides a numerical value for K at

298.15 K. The next step is to investigate the temperature dependence of the

equilibrium constant K .

TOPIC 4: Chemical Equilibrium 14

Process Engineering B as follows:

g 1 g

d = dg dT

RT RT RT 2

g v s g

d = dP dT dT

RT RT RT RT 2

g

d =

v

dP

1

(g + Ts )dT

RT RT RT 2

g v h

d = dP dT

RT RT RT 2

pressure

( g / RT ) h

T = RT 2

P

For species i in its standard state this becomes (drop partial derivative

notation because mi0 depend only on temperature T ):

h = RT

0 2 (

d g i0 / RT )

i

dT

TOPIC 4: Chemical Equilibrium 15

Multiply both sides by i and then sum over all species in the mixture

d i g i / RT

0

i i hi0 = RT 2 i dT

Where,

h

i

i i

0

= H 0 (standard enthalpy change of reaction)

g

i

i

0

i = G 0 (standard Gibbs energy change of reaction)

H = RT

0 2 (

d G 0 / RT )

dT

into the previous equation.

d (ln K ) H 0

= .(4.16)

dT RT 2

This is the famous Vant Hoff equation which shows how the equilibrium

constant K depends on the reaction temperature.

If H 0 is negative the reaction is exothermic. In this event, as T

increases K decreases and the reaction shifts to the LEFT and the

conversion decreases.

If H 0 is positive the reaction is endothermic. In this event, as T

increases K also increases and the reaction shifts to the RIGHT and

the conversion increases.

is independent of temperature, then equation (4.16) may be integrated.

TOPIC 4: Chemical Equilibrium 16

H

K2 0 T2

d (ln K ) = R T 2

dT

K1 T1

K2 H 0 1 1

ln = ...(4.17)

K1 R T2 T1

may be found at any other temperature T2 . The equilibrium constant K 1 is

best found using equation (4.12), since G 0 is known at 298.15 K.

Alternatively (but less accurately) charts like the one below are available:

Locate 1 / T on the x-

axis (as the temperature

+VE Exothermic increases move to the

Reaction left).

ln K 0 Endothermic

Reaction from the family of curves

(only two are shown).

-VE

Obtain ln K from y-axis

and solve for K .

4 8 12 20

1/ T

graph of ln K versus 1 / T would plot as a perfect straight line.

Experimental data (like the chart above) indicate that the points are nearly

linear over short temperature intervals, but tend to be non-linear over much

longer temperature ranges.

reaction and G 0 , the standard Gibbs free energy of reaction.

TOPIC 4: Chemical Equilibrium 17

H 298

0

= i h f i (4.18)

i

G 298

0

= i g f i ...(4.19)

i

g f i are the Gibbs free energy of formation of each reacting species. All

of these are only listed at 298.15 K.

It has been said that equation (4.17) is only accurate over short temperature

ranges or when interpolating between two closely spaced values, it follows that

some more accurate expression is needed.

The reason why straight lines are not obtained on the previous graph is

because H 0 is actually a function of temperature T . Integrating the Vant

Hoff equation leads to

H 0

ln K = dT + J .....(4.20)

RT 2

state, then pressure is fixed (at 1 bar) which means that the pure species

enthalpy is a function of temperature only and given by

over all reacting species gives

d i hi0 = i C P0i dT

i i

dH 0 = C P0 dT ..(4.22)

TOPIC 4: Chemical Equilibrium 18

heat capacities of constant pressure C Pi are often correlated (Smith, Van

Ness, Abbott, 2005) by polynomials such as:

(

C P0i = R Ai + Bi T + C i T 2 + Di T 2 )

With this type of correlation either the C i or Di coefficient is zero. Multiply

each species heat capacity by its stoichiometric coefficient and then sum over

all species to find C P0 as follows:

( )

C P0 = R A + BT + CT 2 + T 2 .....(4.23)

Where,

A = i Ai ...(4.24a)

i

B = i Bi ...(4.24b)

i

C = i C i ......(4.24c)

i

DD = i Di ......(4.24d)

i

DH 0 = R (DA)T +

(DB ) T 2 + (DC ) T 3 (DD ) + I ..(4.25)

2 3 T

reaction H 0 to be found at any temperature T .

Calculate H 298 0

from equation (4.18), knowing the enthalpy of

formation of each compound at 298.15 K.

Then solve equation (4.25) for the constant of integration I at a

temperature of 298.15 K.

Knowing the constant of integration I solve equation (4.25) for H 0

at any other temperature T .

TOPIC 4: Chemical Equilibrium 19

R (DA)T +

(DB ) T 2 + (DC ) T 3 (DD ) + I

T

ln K =

2 3

dT + J

RT 2

ln K =

I

+ (DA) ln T +

(DB ) T + (DC ) T 2 + (DD ) + J ..(4.26)

RT 2 6 2T 2

for G 0 at any temperature simply multiply through by RT to get

G 0 = I RT (A) ln T +

(B ) T + (C ) T 2 + ( ) + J ..(4.27)

2 6 2T 2

There are at least three ways to find the constants I & J that appear in

equation (4.26):

1. If values of K are known at two different temperatures, then two

versions of equation (4.26) may be solved simultaneously for I & J .

2. If one value of K is known at any T and if a value of H 0 is known at

standard state, then solve equation (4.25) for I , followed by equation

(4.26) for J .

3. If H 0 is known at one T and G 0 is known at another (or the same)

temperature T , then use equation (4.25) to find I followed by

equation (4.27) to find J .

Once the equilibrium constant is known (at the reaction temperature T ) the

chemical equilibrium relationship can be solved to find the equilibrium extent

of reaction E .

may be found; this is what follows in the next section.

TOPIC 4: Chemical Equilibrium 20

Develop expressions for the equilibrium constant and the standard free

energy change as a function of temperature for the reaction:

Dimensionless CO H2O CO 2 H2

a 3.376 3.470 5.457 3.249

b 10 3 0.557 1.450 1.045 0.422

c 10 6 --- --- --- ---

d 10 5 -0.031 0.121 -1.157 0.083

using:

T (oC) K

686 0.534

1309 2.930

(b) The first of the above values and the standard enthalpy change of

reaction.

(c) The standard enthalpy change of reaction and the standard free

energies of formation.

g 0f at 298K

Species

(cal/mol)

CO 2 -94,260

CO -32,808

H2O -54,635

TOPIC 4: Chemical Equilibrium 21

TOPIC 4: Chemical Equilibrium 22

discussion and assume that all species are gaseous, then from equation (4.8)

the activity of a species in a mixture a i was defined as

fi

a i =

f i0

c d

fC fD

f0 f0

K=

C D

...(4.28)

a b

fA fB

f0 f0

A B

fi = i y i f i

c d

C yC f C D yD f D

0 f D0

K=

f C

a b

A yA f A B yB f B

f0 f B0

A

For a gas phase reaction, the standard state is the pure species as an ideal-

gas at the reaction temperature T and P 0 = 1 bar. If the gas is ideal, then

= 1 and it follows that f i 0 = P 0 = 1 (bar).

( C y C f C )c ( D y D f D )d

K=

( A y A f A )a ( B y B f B )b

TOPIC 4: Chemical Equilibrium 23

Cc Dd f Cc f Dd y Cc y Dd

K = a b a b a b

f f y y

A B A B A B

fi

i = fi = i P

P

gives

c d Cc dD y Cc y Dd P c P d

K = Ca Db a b

a b

y y

a b

P P (4.29)

A B A B A B

c d Cc dD y Cc y Dd c + d a b

K = Ca Db a b a b P

y y

A B A B A B

i = c + d a b , then

c d Cc dD y Cc y Dd i

K = Ca Db a b a b P

y y

A B A B A B

K = K K K y P i .(4.30)

However, it must be understood that the pressure P is dimensionless

(Process Engineering B). That is the pressure is actually given by

P P P(bar)

0

0

fi P 1 (bar)

TOPIC 4: Chemical Equilibrium 24

K = K K K y P

i

The term K takes into account the different interactions between like and

unlike species and only applies to the vapour phase when the pressure is high

enough to bring the molecules close together.

differences in interaction between like and unlike species become negligible.

This situation actually applies in the majority of cases.

The pure species fugacity coefficients i are best found using a cubic EOS,

such as Redlich-Kwong-Soave (RKS) or Peng-Robinson (PR).

complex function to temperature, pressure and composition and K is a

function of temperature and pressure. All of this means that lengthy iteration

procedures will be needed to obtain an answer by hand.

is easy to solve using a mathematics package, such as Excel.

assume that the mixture is an ideal-gas. However, the molecules may still be

far enough apart for it to behave as an ideal mixture. For this assumption to be

valid the pressure must not be so high that the mixture is near its critical point.

As stated already, at lower pressure the molecules are further apart and any

differences in interaction between like and unlike species become negligible.

In this event K = 1 and equation (4.30) becomes

K ( i =1) = K K y P i (4.31)

because the pressure is the ratio of two pressures: the numerator is the

system pressure P (bar); the denominator is the standard state pressure of 1

(bar); thus the pressure, as it appears in (4.30) and (4.31) is dimensionless.

TOPIC 4: Chemical Equilibrium 25

If the pressure is very low (below atmospheric pressure), then the mixture will

behave as an ideal gas and both K = 1 and K = 1 . Thus, equation (4.30)

assumes its simplest form:

K p = K y P i ..(4.32b)

whereas K is dimensionless, K P has units. This was fully explained in

Process Engineering B:

Remember the pressure that appears in (4.32a) and (4.32b) is actually

a dimensionless pressure ratio P / P 0 . The numerator goes with K y ,

to unity. However, its units cancel with K P to keep K dimensionless.

depends only on temperature, ratio of mole fractions K y depends only on

composition and the final term on the right depends only on pressure.

The effect of pressure acts through the final term in equation (4.32a) or

equation (4.32b). There are three cases that can arise:

i

i +VE

must decrease to keep K constant. Thus, reaction shifts to the left and

conversion decreases.

TOPIC 4: Chemical Equilibrium 26

i VE

pressure term must decrease and K y must increase in order to keep K

constant. Thus, reaction shifts to the right and conversion increases.

i

i =0

At equilibrium equation (4.32a) shows that pressure term must then be equal

to one (its exponent is zero). Thus, K y must be constant and, therefore,

pressure can have no effect on the equilibrium composition.

conditions occur (temperature, pressure or composition), then the equilibrium

shifts to counteract the imposed change to the system.

Although the discussion has focussed on an ideal system, the same general

trends hold for non-ideal systems, except that now K or K may also

change K y and affect the equilibrium.

then pressure will have a small effect on equilibrium composition through

these non-ideal adjustment parameters K or K .

concentration) is to find K y from either one of the three expressions below:

K = K K K y P

i

K ( i =1) = K K y P

i

TOPIC 4: Chemical Equilibrium 27

K ( i =1, i =1) = K P = K y P

i

At this point a numerical value for K y should be available 9using any of the

above expressions). For a gas phase reaction aA + bB cC + dD the ratio of

mole fractions is given by the expression below:

( y C )c ( y D ) d

Ky =

( y A )a ( y B )b

At first glance, the previous equation appears to have too many unknowns.

However, each species mole fraction is actually linked to the extent of reaction

as given by equation 4.5:

ni , 0 + i

yi =

n0 +

nC , 0 + C n D , 0 + D

c d

n + n +

= K y .(4.33)

0 0

n A, 0 + A n B , 0 + B

a b

n0 + n0 +

error approach is often needed depending on the stoichiometric coefficients,

alternatively a mathematics package can be used.

Once E is available, equation (4.5) may be solved for each component to find

the equilibrium concentration (these mole fractions must all sum to one,

irrespective of the value of ).

of moles of species i reacted divided by the total number of moles of

species i initially present:

i e

Conversion i = ..(4.34)

ni , 0

TOPIC 4: Chemical Equilibrium 28

Where,

i is stoichiometric coefficient of species i expressed as a modulus.

Usually (but not always) the fractional conversion is based on the limiting

reactant that is initially present.

as a percentage.

TOPIC 4: Chemical Equilibrium 29

C 2 H 4 + 2 H 2 2CH 4

The reaction temperature and pressure are 1,500K and 10 bar respectively. In

the feed stream to the reactor there are 3 moles of ethene to 1 mole of

hydrogen. From the plot of ln K vs. 1 / T for the following two formation

reactions we find:

C + 2 H 2 CH 4 ln K = -6.0

2C + 2 H 2 C 2 H 4 ln K = -12.5

both C 2 H 4 to CH 4 and H 2 to CH 4 . Use the K P approach.

TOPIC 4: Chemical Equilibrium 30

TOPIC 4: Chemical Equilibrium 31

K = (a i ) i

i

(a C )c (a D )d

K=

(a A )a (a B )b

The activity a i is defined in the same way as before

fi

a i =

fi0

For liquid species, the standard state is the pure liquid at the system

temperature T and a pressure of P = 1 bar. In order to find fi start with the

definition of an activity coefficient

fi

i =

f id

i

Then substitute in the Lewis-Randall Rule to get the required expression for fi

fi = i xi f i

fi

a i = i xi ....(4.35)

fi0

while f i is at reaction T & P (both are pure component fugacities).

The ratio f i / f i 0 may be evaluated but, except for high pressure, pure

component liquid phase fugacities are not strongly pressure-dependent.

TOPIC 4: Chemical Equilibrium 32

a i = i xi ...(4.36)

K = ( i xi ) i ......(4.37)

i

As before (for gas phase reactions) the right hand side of equation (4.37) may

be split up as follows:

K = ( x i ) i ( i )

i

i i

i

K = K x K .(4.38)

In which K x is the ratio of liquid phase mole fractions and K is the ratio of

activity coefficients, defined (respectively) as follows:

K x = ( xi ) i ....(4.39)

i

K = ( i ) i ....(4.40)

i

Like gas phase reactions (knowing the equilibrium constant K and the ratio of

activity coefficients K ) the idea is to solve equation (4.38) for K x and then

find the equilibrium composition or equilibrium conversion as before.

using some model of solution behaviour; preferably a local composition model

such as Wilson, NRTL, UNIQUAC or UNIFAC.

However, hand calculations are highly iterative since activity coefficients are

themselves complex functions of temperature and composition and the

pressure if it is very high.

A better approach is to use a mathematics package which can solve all the

equations simultaneously even when some of the variables have complex

dependencies. Often the time spent writing the worksheet is less than the time

spent trying to execute a highly iterative hand-calculation.

TOPIC 4: Chemical Equilibrium 33

If the liquid phase mixtures can be considered an ideal solution, then all the

activity coefficients are individually equal to one, and the ratio of activity

coefficients is also equal to one, so that equation (4.38) reduces to

K = K x = ( xi ) i ..(4.41)

i

written as

( x C )c ( x D ) d

K= .(4.42)

(x A )a (x B )b

Equation (4.42) is known as The Law of Mass Action. Although widely used in

standard textbooks, it rarely models liquid phase reaction equilibrium

accurately; particularly polar liquid mixtures.

Even when the mixture is non-ideal, there are two extreme cases where

ideality may be assumed:

1. When a species is at a high concentration.

2. When a species is at a low concentration.

High Concentration

At high concentration (of a species) the species approaches ideality, the real

solution curve (of that species) becomes a tangent to the Lewis-Randall Rule

and the activity coefficient (of that species) approaches one:

As: xi 1 i 1 .....(4.43)

Equation (4.36) shows that, under these conditions, the activity approaches

the composition

As: xi 1 a i xi .....(4.44)

is as the solution becomes more non-ideal, the activity departs more and more

from the true composition.

TOPIC 4: Chemical Equilibrium 34

Low Concentration

at low concentrations Henrys Law is valid:

Constant T

The Henry Law model

of ideality (dotted line) is

a tangent to the real

solution curve (solid

line) in the limit of very

low concentration

fi fi id = ki mi

(kPa) As: x i 0 the real

fi solution fugacity tends

to the ideal solution

fi 0 = ki

fugacity or fi fi id .

B

0

0 mi0 = 1

molality mi

Notice that the x-axis is the molality of the component in the mixture (not the

mole fraction). The molality is the concentration of the species expressed in

(mol/kg); that is moles of solute per kilogram of solvent.

The law is actually only valid up to about point B, but the procedure is to

assume that this law (dotted line) is valid up to a molality of 1 and then to

choose this y-axis intercept as the standard state fi 0 ; call this intercept k i .

It is important to understand that the standard state is not the pure species but

is taken to be an ideal solution at a composition of 1 molal. Therefore, activity

must now be modified to take into account this new standard state, as follows:

fi

a i =

f 0

i

Clearly from the diagram fi 0 = k i . The slope of the dotted line is then simply

k i so that its equation must be

fi id = k i mi

TOPIC 4: Chemical Equilibrium 35

As the species approaches infinite dilution and, bearing in mind that the

standard state for the species in the mixture was defined as fi 0 = k i , we get

As: xi 0 fi fi id

As: xi 0 fi k i mi

k i mi

As: xi 0 a i

ki

As: xi 0 a i mi (4.45)

This produces a simple result, but the procedure is only useful when G

0

data is available in terms of this fictitious standard state; the state is fictitious

because the real mixture is not ideal at a one molal concentration.

This approach is only accurate for species at very low concentrations when

Henrys Law is valid. Often one component will exist at higher concentration at

which point the accuracy may decline significantly.

required, then there is no option but to use the rigorous approach outlined

earlier (see section 4.5.1). Equation (4.38) is shown again below:

K = K x K

written as

(xC )c (x D )d ( C )c ( D )d

K=

(x A )a (x B )b ( A )a ( B )b

conversion. The added complication is that all the activity coefficients are

needed and the local composition models all have a complex functional

dependency.

TOPIC 4: Chemical Equilibrium 36

problems. For instance, consider a gas B reacting with a liquid A to form a

dilute aqueous solution C:

Gibbs free energy change of reaction G 0 is based on the following mixed

standard states:

B as a pure ideal gas at reaction temperature T and standard state

pressure of f B0 = P 0 = 1 bar.

A as a pure liquid at reaction temperature T and standard state

pressure of P 0 = 1 bar.

C as solute in a hypothetical ideal 1-molal aqueous solution.

(a C )c

K=

(a A )a (a B )b

Where,

a C = mi from equation (4.45)

fB

a B = ..from equation (4.8)

f B0

a B = B B y B P

In view of what has already been said about the choice of standards states this

becomes

(mC )c

K= ....(4.46)

( A x A )a ( B B y B P )b

value for G 0 (and thus K ) will be needed based on these standard states.

TOPIC 4: Chemical Equilibrium 37

K = (a i ) i

i

becomes

(a C )c (a D )d

K=

(a A )a (a B )b

The activity a i is always defined in the same way

fi

a i =

fi0

The standard state for a solid component is the pure solid at reaction

temperature but a pressure of 1 bar. The fugacity of the solid in the mixture is

at the reaction T & P and is equal to fsolid = f solid . Thus, the activity becomes

f solid

a solid = 0

f solid

properties of solids are very weak functions of pressure so that

a S = 1 .(4.47)

TOPIC 4: Chemical Equilibrium 38

4.7 Tutorial 4

1

SO2 ( g ) + O2 ( g ) SO3 ( g )

2

The equilibrium conversion of dioxide to trioxide at 1atm and 500C is

93%. Calculate the reaction equilibrium constant K under these

conditions assuming the gas to be ideal and given an initial

composition as follows:

Component Mole %

Sulphur dioxide 10

Oxygen 11

Nitrogen 79

Sulphur trioxide 0

(Solution: 51.8)

equilibrium constant K for the following gas phase reaction occurring

at 1500 K:

2 H 2 ( g ) + 2 NO ( g ) N 2 ( g ) + 2 H 2 0( g )

Dimensionless H2O N2 H2 NO

a 3.470 3.280 3.249 3.387

TOPIC 4: Chemical Equilibrium 39

compounds taking part in this reaction are listed below:

h 0f g 0f

Component

J/mol

NO 90,374 86,688

CO ( g ) + H 2 O( g ) CO2 ( g ) + H 2 ( g )

of the different sets of conditions described below. Assume the mixture

to be an ideal gas.

4088

K can be calculated from the equation: ln K = 3.59

T

Case

H2O CO N2 CO 2 K bar

a) 1 1 0 0 700 1

b) 1 1 0 0 700 10

c) 1 1 1 0 700 1

d) 1 2 0 0 700 1

e) 2 1 0 2 700 1

f) 1 1 1 0 1366 1

TOPIC 4: Chemical Equilibrium 40

acid is oxidised with 95% pure oxygen according to the reaction:

4 HCl ( g ) + O2 ( g ) 2 H 2 O( g ) + 2Cl 2 ( g )

occurs at 1atm and at temperatures between 450 and 650 C. The

other variable involved is the ratio of the reactants. In view of the

above, determine the following:

(b) The composition of the equilibrium mixture at both 450oC and

650C for feed ratios of both 4 and 12 moles HCl per mole of the

total oxygen stream (including the nitrogen).

(c) The purity of the chlorine produced on an HCl-free and H 2 O-free

basis for each condition in part (b).

(d) The conversion of HCl for each condition in part (b). Use the

thermodynamic data provided below:

H2O Cl 2 HCl O2

a 3.470 4.442 3.156 3.639

h 0f g 0f

Component

J/mol

13905 41150

a) ln K = 0.439 Ln(T ) 0.040 10 3 T 13.01

T T2

TOPIC 4: Chemical Equilibrium 41

depends on the vapour-phase catalytic reaction of methane with steam

according to the reaction:

CH 4 ( g ) + H 2 O( g ) CO ( g ) + 3H 2 ( g ) (1)

The only other reaction which ordinarily occurs to any extent is the

water-gas shift reaction:

CO ( g ) + H 2 O( g ) CO2 ( g ) + H 2 ( g ) .(2)

enthalpies and free energies of formation are available:

T = 600K T = 1300K

Component h 0f g 0f h 0f g 0f

J/mol

CO 2 -393,798 -395,137 -393,798 -396,141

1 atm or 100 atm?

(b) Would it be better to carry out the process so that the maximum

temperature reached in the reactor is 600 or 1300 K?

(c) Using the preferred conditions from parts (a) and (b) estimate the

molar ratio of H 2 to CO in the synthesis gas produced with a feed

ratio of 1 mole steam to 1 mole methane. (NOTE: this is most easily

solved in excel)

(d) Repeat (c) with a feed ratio of 2 moles steam to 1 mole methane.

(NOTE: this is most easily solved in excel)

TOPIC 4: Chemical Equilibrium 42

(e) How would you alter the feed ratio to obtain a lower ratio of H 2 to

CO than is obtained in part (c) without altering the temperature or

pressure.

(Solution

a) 1 atm b) 1300 K c) 3.007 d) 3.600 e) Use a steam to methane

ratio of less than 1).

according to the reaction:

CH 4 ( g ) + Br2 ( g ) CH 3 Br ( g ) + HBr ( g )

This reaction is to be carried out at 1 atm and 800 K with an initial ratio

of methane to bromine of 1:1. In view of the above, calculate the

following:

(a) The equilibrium composition of the product gas stream assuming

that no other reactions occur.

g 0f at 800K

Component

J/mol

CH 4 -2,230

CH 3 Br 27,916

HBr -59,367

TOPIC 4: Chemical Equilibrium 43

methane to bromine ratio of 1:1 and develop expressions for the

equilibrium constant for each reaction.

(Solution

a) CH 4 = 0.05, Br 2 = 0.05, CH 3 Br = 0.45, HBr = 0.45).

( 1 2 )( 1 + 2 + 3 + 4 )

b) K 1 =

(1 1 )(1 1 2 3 4 )

( 2 3 )( 1 + 2 + 3 + 4 )

K2 =

( 1 2 )(1 1 2 3 4 )

( 3 4 )( 1 + 2 + 3 + 4 )

K3 =

( 2 3 )(1 1 2 3 4 )

( 4 )( 1 + 2 + 3 + 4 )

K4 =

( 3 4 )(1 1 2 3 4 )

TOPIC 4: Chemical Equilibrium 44

4.8 Bibliography

McGraw-Hill, SI ed., 1987.

Wiley 2nd ed., 1993.

S.I. Sandler. Chemical and Engineering Thermodynamics. Wiley, 3rd ed., 1999.

ed., 1998.

Engineering Thermodynamics. McGraw-Hill. 7th ed.,2005.

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 1

Topic 5

Fluids and Solids

Contents

TOPIC 5: VOLUMETRIC BEHAVIOUR OF REAL FLUIDS AND SOLIDS

5.1 INTRODUCTION .................................................................................................................. 3

5.1.1 P-T Diagram ........................................................................................................ 3

5.1.2 P-v Diagrams ...................................................................................................... 5

5.1.3 Relation between P-T & P-v Diagrams ................................................................ 7

5.2 VOLUME EXPANSIVITY AND ISOTHERMAL COMPRESSIBILITY ................................................. 8

5.2.1 Liquids and Solids ............................................................................................... 9

5.2.2 Gases................................................................................................................ 10

5.2.3 Worked Example 5.1 ......................................................................................... 11

5.2.4 Worked Example 5.2 ......................................................................................... 12

5.2.5 Reversible Volume Work ................................................................................... 13

5.2.6 Worked Example 5.3 ......................................................................................... 14

5.3 COMPRESSIBILITY FACTOR .............................................................................................. 15

5.3.1 Two-Parameter Generalised Correlations.......................................................... 16

5.3.2 Three-Parameter Generalised Correlations ....................................................... 17

5.4 VIRIAL EOS .................................................................................................................... 20

5.4.1 Truncated Virial EOS ......................................................................................... 22

5.4.2 Worked Example 5.4 ......................................................................................... 23

5.4.3 Worked Example 5.5 ......................................................................................... 24

5.4.4 Worked Example 5.6 ......................................................................................... 25

5.4.5 Worked Example 5.7 ......................................................................................... 26

5.5 SECOND VIRIAL COEFFICIENT B ..................................................................................... 27

5.5.1 Experimental Determination .............................................................................. 27

5.5.2 Generalised Correlations ................................................................................... 29

5.5.3 Worked Example 5.8 ......................................................................................... 30

5.5.4 Worked Example 5.9 ......................................................................................... 31

5.5.5 Worked Example 5.10 ....................................................................................... 32

5.5.6 Worked Example 5.11 ....................................................................................... 33

5.6 CUBIC EOS .................................................................................................................... 34

5.6.1 Manual Iteration Schemes ................................................................................. 34

5.6.2 Generalised Correlations for Cubic Parameters................................................. 36

5.6.3 Worked Example 5.12 ....................................................................................... 37

5.6.4 RKS EOS in Cubic Form ................................................................................... 39

5.6.5 Worked Example 5.13 ....................................................................................... 40

5.7 BIBLIOGRAPHY ................................................................................................................ 42

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 2

Prerequisite knowledge

Process Industries C.

Process Engineering B.

Learning objectives

After studying this Volumetric Behaviour of Real Fluids and Solids topic you

should be able to:

Relate the state of a fluid on a P-T and P-V diagram; identify critical

point and the shape of various isotherms in relation to the phase

boundaries (two-phase envelope).

Define expressions for both the coefficient of volume expansivity and

the coefficient of isothermal compressibility and relate these to the

volume change of a species as a function of temperature and pressure.

Devise strategies for solving problems involving the volume change of

pure solids, liquids and gases.

Define reversible work to compress or expand a fluid and devise

strategies for problem solving.

Derive both forms of the Virial EOS truncated to two terms. Derive both

forms of the Virial EOS truncated to three terms.

Differentiate between experimental determination of the second Virial

coefficient and generalised correlation for the second Virial coefficient.

Write down generalised correlation developed by Pitzer for the second

Virial coefficient in terms of the acentric factor.

Develop strategies and solve problems using the Virial EOS.

List advantages and disadvantages of both Virial EOS and cubic EOS.

Outline solution strategies and solve problems using both original RK

and RKS EOS.

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 3

5.1 Introduction

quick review of some major points of interest are listed below.

temperature TC and the highest pressure PC at which liquid and vapour

phases can co-exist together in phase equilibrium.

Point TP is the Triple Point, a unique point on the diagram where three

phases (solid, liquid and vapour) co-exist together in phase equilibrium.

TP C is the

Supercritical vaporisation or boiling

P

A 1 region

C point curve.

PC

Liquid

Solid

region TP A is the fusion or

region freezing point curve.

Gas

region

TP B is the

TP sublimation curve.

B 2

Vapour

region

TC T

F = 2 + N

phases and N is the number of chemical species present. For a pure species

(as above) there is only one component present and N = 1 .

Areas on this P-T diagram represent single phase regions, which may either

be solid, liquid, or vapour. Anywhere in these regions = 1 and F = 2 . For a

pure species the Gibbs phase rule variables are temperature and pressure.

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 4

states that have two degrees of freedom. This means that both temperature

and pressure may be varied independently of each other:

This is because there are no phase equilibrium relations for a single

phase system.

Two variables (temperature and pressure) and no phase equilibrium

relation leads to two degree of freedom.

From the phase rule, any point on these lines (except the triple point TP ) have

one degree of freedom F = 1 . Thus, either temperature or pressure may be

varied independently, but not both:

This is because there is now a single phase equilibrium relation linking

the two phases together; there is one phase constraint.

Two variables (temperature and pressure), one phase equilibrium

relation f = f leads directly to one degree of freedom.

The triple point is where three phases all co-exist in equilibrium = 3 . At this

point there are zero degrees of freedom (neither temperature nor pressure

may be varied). The system is said to be invariant:

This is because there are now two phase equilibrium relations linking

these three phases together; there are two phase constraints.

Two variables (temperature and pressure), two phase equilibrium

relations, f V = f L and f L = f S , leads to zero degrees of freedom.

Notice that there are three phase equilibrium relations in total, but only

two (any two) are independent.

Following the straight line between 1 and 2 (the dotted line), the process

line must intersect or cross the vaporisation curve. At this point (where they

intersect) there are two phases at equilibrium and the liquid phase changes

completely into a vapour phase as the pressure declines.

Following the curved path between 1 and 2 (the solid line), the process line

never intersects the vaporisation curve. There is always only one phase

present. The properties gradually change from liquid to vapour without the

system ever passing through a phase transition.

solvent used in the production of active pharmaceutical ingredients and in the

extraction of delicate essences from plant material.

need be used, the CO2 may then be removed without any further processing

steps; it is simply a matter of changing the pressure and temperature profiles

to carry out the extraction and purification of complex organic molecules.

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 5

A P-v diagram also differentiates single phase areas from two phase areas. It

also serves to delineate phase boundaries. The critical isotherm TC has a

point of inflection at P = PC (the critical point C ).

To the right of the saturated vapour curve (but at temperatures below the fluid

critical temperature TC ) is the superheated vapour region. To the left of the

saturated liquid curve is the subcooled liquid (compressed liquid) region.

P

TC Supercritical Curve A C is saturated

Fluid liquid curve.

PC C

Liquid vapour curve.

where P = PC , T = TC

PTP A B

and v = vC .

vC v

To the right of the saturated vapour curve (but above the critical temperature

TC and below the critical pressure PC ) is the gaseous region, so-called

because a gas cannot be liquefied by the action of pressure alone.

Above the critical temperature TC and above the critical pressure PC , the fluid

is called a supercritical fluid.

TC

P Supercritical Curve 1-2-3-4 is called a

Fluid subcritical isotherm.

PC 4 C

Liquid subcritical because the

Vapour temperature T < TC .

Psat 3 2

T < TC

If curve 3-4 were a

A B 1 perfect vertical line then

the liquid would be

vC v incompressible.

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 6

At these high pressure states, gaseous properties gradually change into liquid

properties without any phase transition. Notice the discontinuities at the phase

boundary, i.e. points 2 and 3 along the low temperature isotherm 1-2-3-4:

The fact that curve 3-4 is steep (but not perfectly vertical) means that the liquid

actually has small but nearly constant compressibility.

PC C

Q

Gas T4 > TC

N

Liquid

T3 = TC

Vapour

Psat

J K T2 < TC

A Liquid/Vapour B

T1 < TC

vC v

Note the four isotherms: T4 > TC > T2 > T1 . Any isotherm above T3 (say T4 ) is

known as a supercritical isotherm.

Vertical line Q-J represents a constant volume expansion process; notice that

as the pressure drops the vapour fraction increases.

the pressure drops the liquid fraction increases.

Within the two-phase region liquid and vapour co-exist in equilibrium. Any

mixture point along a horizontal tie-line will split into a saturated vapour phase

(less dense/upper phase) and a saturated liquid phase (more dense/lower

phase).

The properties of each of these co-existing phases (either end of the tie-line)

do not change as the mixing point changes, all that changes is the amount of

each phase that is present (as given by the lever rule).

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 7

saturated vapour pressure curve on right hand P T diagram, corresponds to

two-phase envelope on the left hand, P v diagram.

The saturated vapour pressure curve terminates at the upper end at the critical

point C , while at the lower end it terminates at the Triple Point TP .

P CONSTANT T P

C C

4 4

3 2 LIQUID

P sat 2&3

1 1

TP VAPOUR

A B

T

v

P < P sat : fluid is a single-phase vapour (see state 1)

P > P sat : fluid is a single-phase liquid (see state 4).

P = P sat : fluid state is anywhere within the two-phase envelope, i.e.

anywhere along the tie-line between state 2 and state 3.

liquid is present. State 3 corresponds to a saturated liquid state; dryness

fraction zero, no vapour is present.

Between state 2 and state 3 the dryness fraction varies continuously from

one to zero; this corresponds to complete condensation of vapour.

changing but both T & P are constant. Thus, any volume changes along a tie

line cannot be expressed as a function of T & P because they do not change.

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 8

If F is any property and x & y are two other properties then, because of the

two-property rule, F may be expressed as a function of x & y

F = f ( x, y )

For any single phase substance (not within the two phase region), the total

derivative dF is given as the sum of two partial changes: one with respect to

x ; the other with respect to y

F F

dF = dx + dy

x y y x

be expressed as a function of T & P using the total derivative

v v

dv = dT + dP ..(5.1)

T P P T

same equation expressed in terms of V , the total volume (cm3) of the

substance (notice V = nv)

V V

dV = dT + dP ...(5.2)

T P P T

1 V

= .........(5.3)

V T P

1 V

= ......(5.4)

V P T

dV

= dT dP ...(5.5)

V

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 9

equation (5.5) may be integrated choosing some combination of constant

temperature/constant pressure paths.

The exact path chosen between the same two ends states is immaterial since

all paths must yield the same change in volume given by

V2 T

2 P 2

dV

V V T= dT P dP

1 1 1

2T 2P

V2

ln = dT dP (5.6)

V1 T1 P1

For most liquids and solids (not under extreme conditions) & are small

and nearly constant and equation (5.6) is readily integrated to get

2 T 2P

V2

ln = dT dP

V1 T1 P1

V2

ln = (T2 T1 ) (P2 P1 ) ....(5.7)

V1

For liquids and solids undergoing an isothermal process, volume changes are

caused by changes in pressure only and the first term drops out

V2

ln = (P2 P1 ) ....(5.8)

V1

For liquids and solids undergoing an isobaric process, volume changes are

caused by changes in temperature only and the second term drops out

V2

ln = (T2 T1 ) ......(5.9)

V1

These values are often needed for Design Projects.

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 10

5.2.2 Gases

regarded as small and constant.

2 T 2 P

V2

V1 T1

ln = dT dP

P1

However, the above expression may still be used if the coefficient of volume

expansivity is a known function of temperature = (T ) and/or if the

coefficient of isothermal compressibility is a known function of pressure

= (P)

changes in pressure only and the first term drops out

2 P

V

ln 2 = dP ..(5.10)

V1 P1

is a known function of pressure = (P ) .

changes in temperature only and the second term drops out

T

2

V

ln 2 = dT ..(5.11)

V1 T1

known function of temperature = (T ) .

In summary, all these expressions (in sections 5.2.1 and 5.2.2) are only useful

in the following circumstances:

1. When constant (or average) values for & are known for solids or

liquids.

2. For gases when & are known functions of temperature and

pressure respectively.

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 11

pressure that must be applied to increase its density by 0.08%.

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 12

10 atm. The initial volume is 1 m3. Experimental measurements are:

100 1.0

250 2.2

390 3.5

460 4.2

510 4.8

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 13

supplied to the fluid (positive work); the reverse is true if the fluid is expanded.

This type of work is called displacement work or volume work.

Work done on the system by the surroundings is positive and work done by

the system on the surroundings is negative.

by

dw = Pdv (5.12)

pressure (kPa) and v is the molar volume (m3/mol) of the fluid. If a fluid is

compressed dv will be negative and then the negative sign is sign is needed

to keep the work term positive (work transferred to the system.

follows:

dW = PdV (5.13)

In which W is the total work done on or by the fluid (kJ), again P is the

absolute pressure (kPa) and V is now the total volume (m3) of the fluid.

(5.12) or (5.13) will need to be integrated. There are two strategies depending

on how the problem is framed:

1. Eliminate dV and then integrate to find W . This involves using either

equation (5.3) or (5.4). To use this approach for gases or must

be known functions of either temperature or pressure respectively.

2. Eliminate P and then integrate to find W . This approach involves

using an Equation of State (EOS). This will be discussed in the next

section (immediately following this worked example).

In the section that follows the next worked example, the Virial EOS will be

examined. Although the Virial EOS is used here to investigate the volumetric

behaviour of gases v = v(T , P ) , it could equally be used to calculate the

fugacity coefficient behaviour of gases = (T , P ) .

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 14

temperature (298 K) from 1 atm to 200 atm. The isothermal compressibility of

the gas is given as the following linear function of pressure:

= a bP

= 4 10 6 (1.5 10 10 P)

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 15

Pv ig = RT

In the limit of very low pressure (as pressure approaches zero) real gases

approach ideal gas behaviour. A simple way of finding molar volume v for a

real gas is to use a correction factor Z , as follows:

Pv = ZRT ..(5.14)

(5.14) it is clear that Z = Pv / RT . If v is measured in units (cm3/mol), P in

(bar), T in (K) and if R = 83.1447 (cm3 bar/mol K), then Z is dimensionless.

Ideal gases are assumed to consist of point particles occupying zero volume

and with zero forces of attraction. However, Van der Waal reasoned (correctly)

that the departure from ideal gas behaviour was caused by two factors:

1. Gases particles (molecules/atoms) do have a definite volume which

exerts a repulsive force at short-range distances as particles approach

each other.

2. There are longer-range forces of attraction between gas particles which

drop off as particle separation is increased.

increases and these very short-range repulsive forces become insignificant

(the particles effectively act as if they were point particles with zero volume).

The force of attraction for real gases follows an inverse square law. Thus, for

real gases as P 0 the separation between gas particles increases and

these longer-range forces of attraction decline in strength (the particles

effectively act as if they had zero force of attraction).

(5.14) reduces to the ideal gas law. It is clear that if a gas is behaving as a

perfect ideal gas, then the compressibility factor Z = 1 .

On the other hand, the larger the departure of a real gas from ideal gas

behaviour the more the compressibility factor will deviate from unity. In these

cases, the compressibility factor may be greater or less than unity.

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 16

Pv

Z= .(5.15)

RT

obtained from some sort of Z -factor correlation. Two types of Z -factor

correlation have been developed:

1. Two-Parameter correlations.

2. Three-Parameter correlations.

Z = Z (Tr , Pr )

T

Tr = ..................................................................(5.16)

TC

P

Pr = ..(5.17)

PC

Where,

T is absolute temperature of the system (K).

TC is absolute critical temperature of fluid (K).

P is absolute pressure of the system (bar).

PC is absolute critical pressure of the fluid (bar).

Corresponding States (also known as the Corresponding States Principle

CSP):

All fluids at same Tr and Pr deviate from ideality to the same extent

and, therefore, have the same compressibility factor Z .

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 17

The above statement holds for simple gases with symmetrical charge

distribution (such as noble gases Ar, Kr and Xe), but other non-simple gases

depart from the two-parameter Law of Corresponding States.

three-parameter generalised correlation relates some property to reduced

temperature Tr , reduced pressure Pr and a third parameter called the

acentric factor .

takes the general form

Z = Z (Tr , Pr , )

Corresponding States:

All fluids with the same acentric factor and at the same Tr and Pr

deviate from ideality to the same extent and, therefore, have the same

compressibility factor Z .

Experimental results indicate that the data for each fluid falls nearly on a

straight line see below:

1 / Tr

Tr = 0.7

Kr, Xe

log Prsat

Non-Simple

Fluids

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 18

sat

In order to understand the acentric factor plot log( Pr ) versus 1 / Tr for a

number of different fluids; the reduced vapour pressure Prsat is just the vapour

pressure P sat (or the saturation pressure) divided by the critical pressure PC

P sat

Prsat = .....(5.18)

PC

It is also found that Ar, Kr and Xe all lie on a common line (the red line) and

that, for all these noble gases, log Prsat = 1 at a Tr = 0.7 (these gases are

called simple fluids because they have a uniform charge distribution).

Data for other non-simple fluids fall on other straight lines (the dotted blue

lines); the more non-uniform the charge distribution the more the line departs

from the simple fluid case.

may be used to characterise the departure of any non-simple gas from simple

gas behaviour see below:

1 / Tr

Tr = 0.7

Kr, Xe

log Prsat

Non-Simple

Fluids

Thus, the acentric factor, defined below is a measure of how asymmetric the

charge distribution is for any gas:

t

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 19

measurement P sat at a specified reduced temperature of Tr = 0.7 .

For simple gases (Ar, Kr, Xe) the acentric factor is zero. The three-parameter

correlations are more accurate than two-parameter correlations and have a

good accuracy over a full range of states (particularly when using tables).

chart (sometimes written as Z ( 0 ) ) and the Z 1 component chart (sometimes

written as Z (1) ). These two component parts of Z are combined in a simple

way:

Z = Z 0 + Z 1 .(5.20)

minor adjustment to Z due to non-simple behaviour. Charts for the Z 0 and

Z 1 have been discussed in earlier topics.

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 20

Charts and tables are useful ways of finding the compressibility factor.

However, algebraic relationships are often more convenient.

For real gases it is possible to model the shape of isotherms (well to the right

of the critical point) using a power series:

Pv = a + bP + cP 2 + .......

Pv = a (1 + B P + C P 2 + .......) ...(5.21)

nature of the chemical species. The Virial coefficient reflects the chemical

character of species and is a function of molecular interactions: the second

Virial coefficient depends only on two-molecule interactions; the third on three-

molecule interactions. As such they provide a correction for non-interactive

ideal gases.

Pv = Pv * a = RT

is used and this incidentally is defined as follows:

T

=

( )

Pv *

TTP ( )

*

PvTP

value TTP 273.16 K (this value is chosen to align a degree on the centigrade

scale with that on the Kelvin scale). Thus, to find T on the Kelvin scale of

temperature

T = 273.16

(Pv ) ..(5.22)

*

(Pv )

*

TP

*

water to find PvTP . If an ideal gas thermometer is then place in boiling water

(at 101.325 kPa) and Pv * is measured, then equation (5.22) will provide the

boiling point of water on the Kelvin scale T = 373.15 K.

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 21

Bearing this in mind a = RT (using the Kelvin scale) and the value of the

universal gas constant may be taken as R = 8.31447 (J/mol K). In this course

it is more convenient to use R = 83.1447 (cm3 bar/mol K).

obtained:

Pv = RT (1 + B P + C P 2 + .......) ...(5.23)

compressibility factor Z , simply divide through by RT to obtain one form of

the extended Virial EOS

Z = (1 + B P + C P 2 + .......) .(5.24)

B C

Z = 1 + + 2 + ........... ......(5.25)

v v

Where,

B

B ....(5.26)

RT

C B2

C ..(5.27)

R 2T 2

Notice that equations (5.26) and (5.27) are only approximately true. The

equality only hold in the limit of an infinite number of terms.

Either form of the Virial EOS, equation (5.24) or equation (5.25), may be used;

however, the higher the system pressure the more terms that are needed.

Earlier it was shown that Z is dimensionless and this means that each term

on the right of (5.24) and (5.25) must be dimensionless. In which case:

B , equation (5.24) must have the same units as pressure P which

would be (bar-1).

B , equation (5.25) must have the same units as molar volume v which

would be (cm3/mol).

Thus, the units of the second Virial coefficient depend on whether the

expansion is with respect to P or v .

The Virial EOS is always truncated. Often the truncation is to the first two

terms, but sometimes it is truncated to the first three terms.

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 22

The Virial EOS is usually truncated to two terms and as such applies only to

gases or vapours at low to moderate pressure; notice that the molar volume of

liquids cannot be found from these expressions.

Equation (5.24) may be truncated to two terms to get one form of the truncated

Virial EOS

Z = 1 + B P

into the previous expression to get

BP

Z = 1+ ...(5.28)

RT

Equation (5.25) may be truncated to two terms to get a second form of the

truncated Virial EOS

B

Z = 1+ ..(5.29)

v

as follows

Pv B

= 1+

RT v

BRT

Pv = RT +

v

This leads to a quadratic in molar volume v (cm3/mol), but care must be taken

to use the correct units: if universal gas constant is taken to be R = 83.1447

(cm3 bar/mol K); then P must be expressed in (bar); and T must be in (K).

The second Virial coefficient B will have the same units as molar volume, see

equation (5.29) and, therefore, will have units (cm3/mol).

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 23

At still higher pressure (to get a more accurate answer) equation (5.25) may

be truncated to the first three terms as follows:

B C

Z = 1+ + ....(5.31)

v v2

It is clear from equation (5.23) that in the limit as P 0 all higher order terms

drop out and, thus, all forms of the Virial EOS reduce to the ideal gas law:

Pv = RT Z =1

As a rule of thumb the first two terms are reasonably accurate (depending on

temperature) up to about 15 bar, while the first three terms will provide

reasonable accuracy to about 50 bar.

and a pressure of P = 10bar .

Use the Virial EOS truncated to the first two terms and the second Virial

coefficient B is listed in the experimental literature as

B = 194 cm 3 mol 1

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 24

Calculate Z and v for SF 6 at 75oC and 15 bar using the Virial EOS truncated

to two terms. The second Virial coefficient B is listed in the experimental

literature as

B = 194 cm 3 mol 1

Then calculate v at the same conditions using the Virial EOS truncated to

three terms. The third Virial coefficient C is listed in the experimental literature

as

C = 15300 cm 6 mol 2

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 25

temperature of 273 K and a pressure of 100 bar, calculate molar volume v

using:

(ii) Virial EOS truncated to two terms

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 26

volume of 2 dm3 to a final volume of 20 dm3. Given the following Virial

coefficients:

B = 142.2 10 6 m 3 mol 1

C = 7140 10 12 m 6 mol 2

Using the Virial EOS truncated to three terms, calculate how much work is

done by the steam during the expansion

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 27

1. The scientific approach is to find B experimentally or by referencing

peer-reviewed publications and/or data handbooks.

2. The engineering approach is to estimate B using some sort of

generalised correlation.

The scientific approach is more accurate and rigorous. On the other hand, the

engineering approach may be less accurate but is more convenient. Engineers

can allow for inaccuracy by including factors of safety into their designs or

estimates.

For a particular chemical species consider the Virial EOS as given by equation

(5.24), as shown again below:

Z = (1 + B P + C P 2 + .......)

dZ

= B + 2C P + .......

dP

This gives the slope at any point along a Z vs P isotherm. Now find the slope

of any isotherm at zero pressure, i.e. as P 0

dZ

= B

dP P =0

pressure and this provides a method of obtaining B experimentally:

Choose a temperature T which corresponds to one particular

isotherm.

Measure the dZ / dP at pressure P .

Repeat the procedure at successively lower pressures.

Plot dZ / dP on the y-axis against pressure P on the x-axis.

Extrapolate the trend to zero pressure to obtain the y-axis intercept.

This intercept is (dZ / dP ) P =0 which is equal to B .

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 28

At zero pressure all gases behave as idea gases and the compressibility factor

is Z = 1 . Clearly all isotherms must meet at the point Z = 1 and P = 0 :

Z any isotherm.

Z=1

1.0 The blue line is

tangent to the

Slope = B

Isotherm isotherm at Z = 1 and

P = 0.

tangent line is B .

0 P

Z = 1 + B P

This result is identical to the Virial EOS truncated to two terms as given by

equation (5.28) below:

BP

Z = 1+

RT

Thus, the graphical interpretation of the two-term Virial EOS, equation (5.28),

is that it represents the equation of a straight line which is a tangent to the

actual isotherm at Z = 1 and P = 0 .

From this diagram it is clear that the Virial EOS truncated to two terms is a

better fit to the isotherm, at finite pressure, than the ideal gas law ( Z = 1 ).

However, the accuracy of the Virial EOS drops off at higher pressure.

The straight line fits the shape of an isotherm reasonably well at low pressure;

up to about 15 bar.

To improve the accuracy the Virial EOS may be truncated to three terms.

However, more data is available for the second Virial coefficient B than is

available for the third Virial coefficient C .

The accuracy of the two-term Virial EOS (either version of it) also depends on

the gas temperature; the lower the temperature, at any pressure, the lower the

accuracy.

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 29

BP

Z = 1+

RT

BP P / PC

Z = 1 + C

RTC T / TC

BP Pr

Z = 1 + C .....(5.32)

RTC Tr

Pitzer and co-workers then proposed that BPC / RTC consists of two parts:

1. The first component is labelled B 0 and is the simple fluid component

based on Ar, Kr and Xe.

2. The second component is labelled B 1 and is the non-simple fluid

component based on the departure from simple fluid behaviour.

BPC

= B 0 + B 1 ...(5.33)

RTC

t

(

Z = 1 + B 0 + B 1 ) TP r

Pr P

Z = 1+ B0 + B 1 r ...(5.34)

Tr Tr

experimental measurements (by Abbott and Van Ness) as follows:

0.422

B 0 = 0.083 1.6

..(5.35)

Tr

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 30

And,

0.172

B 1 = 0.139 4.2

.(5.36)

Tr

The various forms of the Virial EOS may only be used for gases; they

cannot be used to model liquid phase properties.

The truncated two-term Virial EOS produces reasonable results,

depending on temperature, for gases at pressures up to about 15 bar.

The truncated three-term Virial EOS is reasonably accurate, depending

on temperature, for gases up to about 50 bar.

Since there is much less data available for the third Virial coefficient C

than for B , it is preferable to use a cubic EOS at high pressure.

Cubic EOS have the added advantage that they can model liquid

properties as well as vapour properties.

While the various forms of the Virial EOS are important and must be

remembered, it is not expected that candidates have to remember

correlations, such as equations (5.35) and (5.36).

dV dV

dV = dT + dP

dT P dP T

atm to 500 atm at constant temperature (300K). The coefficient of isothermal

compressibility is known to be

= 4 10 4 atm 1

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 31

cylinder assembly where the molar volume of the gas is given by

RT

v= +b

P

Where,

b = 42.6 cm 3 /mol

calculate the reversible work input per mole (J/mol) needed to compression

the gas.

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 32

Calculate Z and v for gas X at 70oC and 6 bar by applying the Pitzer

correlation to calculate B where:

TC = 330 K

PC = 42 bar

VC = 212 cm 3 /mol

= 0.273

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 33

Calculate Z and v for ethane at 50oC and 15 bar using the following

methods:

B = 156.7 cm 3 /mol

TC = 305 K

PC = 48.7 bar

= 0.10

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 34

Topic 1 of this course. A brief summary is supplied below.

The Van der Waal (VdW) EOS is the root cubic from which all modern

versions are derived. The pressure-explicit form of the VdW EOS is given

below:

RT a

P= 2 ...(5.37)

(v b ) v

In which a & b are species specific parameters. The VdW EOS is now of

historical interest only. A more modern version of VdW is the Redlich-Kwong

(RK) EOS. The pressure-explicit form of the RK EOS is given by

RT a

P= 0.5 ...(5.38)

(v b ) T v(v + b)

In which a & b are again species specific parameters. Notice that VdW a & b

parameters differ from the RK a & b parameters. Notice that when a & b are

zero both of the above expressions revert to the ideal gas law.

Often pressure and temperature are fixed and the objective is to find the molar

volume. Of course all cubic EOS will yield three volume roots and various

manual iteration schemes have been proposed to find these roots.

following expression which efficiently converges to the vapour root (the largest

root):

RT a(v b )

vi +1 = + b 0.5 i .(5.39)

P T Pvi (vi + b)

In which vi +1 is the next molar volume in the iteration cycle and vi is the

current value. A reasonable starting value v 0 is the ideal-gas molar volume

RT

v0 = ..(5.40)

P

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 35

Equation (5.38) may be expanded out as follows (notice that the cubic form of

the RK EOS is now evident):

RT 2 2 bRT a ab

v3 v b + v = 0 .(5.39)

P P PT 0.5 PT 0.5

An iteration scheme designed to converge to the liquid root (the smallest root)

has been developed from equation (5.39)

1 RT 2 ab

vi +1 = vi3 vi ...(5.40)

c P PT 0.5

Where,

bRT a

c = b2 + .(5.41)

P PT 0.5

In which vi +1 and vi are again the molar volumes at successive stages of the

iteration cycle. A good starting value v 0 is b which represents the volume of

the molecules themselves

v0 = b ....(5.42)

The RK EOS yields three roots, select the correct root as follows:

P < P sat : fluid must be a single-phase vapour, choose largest root.

P = P sat : fluid state may be anywhere along a tie-line, choose both the

largest and the smallest roots, since both saturated liquid and vapour

can be present.

to volumetric P v T data; this would be the most accurate approach.

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 36

correlations for the parameters a & b and, for the VdW EOS, these are given

by the expressions below:

2

27 R 2TC

a= ..(5.43)

64 PC

RTC

b= ..(5.44)

8 PC

While the generalised a & b parameters for the RK EOS are as follows:

2.5

R 2TC

a = 0.42748 .(5.45)

PC

RTC

b = 0.08664 ..(5.46)

PC

factor Z which can then be re-arranged to get

Pv v ab

=

RT (v b ) bRT (v + b)

3/ 2

1 a h

Z =

1 h bRT 1.5 1 + h

Where,

b bP

h= =

v ZRT

Substituting (5.45) and (5.46) into the last two equations then gives

1 4.934 h

Z = 3/ 2 ...(5.47)

1 h Tr 1 + h

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 37

And,

0.08664 Pr

h= ..(5.48)

ZTr

Equations (5.47) and (5.48) are solved together to find the vapour root. The

following procedure is used:

Set Z = 1 and then find then find h from equation (5.48).

Substitute this value of h into equation (5.47) and find a new value for

Z.

Repeat this procedure until Z converges within some tolerance.

The worked example below will not appear as an examination question since it

just involves substituting supplied data into supplied equations. However,

these equations are very useful (in Design projects) for finding properties of

real fluids.

Therefore, it is important to understand how cubic EOS work, when they are

appropriate and how they may be solved.

Calculate Z and v for gas X at 90oC and 10 bar. Use the Redlich-Kwong

EOS together with the following data:

TC = 319 K

PC = 38 bar

vC = 198 cm 3 mol 1

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 38

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 39

The original RK EOS was updated by Soave in 1972 and is now much more

accurate. In textbooks this is either called the Soave-Redlich-Kwong (SRK)

EOS or the Redlich-Kwong-Soave (RKS) EOS.

The two cubic EOS used most frequently by chemical engineers are the Peng-

Robinson (PR) EOS and the RKS EOS. The Peng-Robinson EOS was

discussed in detail towards the end of Topic 1.

The best approach for solving the RKS EOS is to re-arrange it into cubic form

(in terms of the compressibility factor Z ) and then find all three roots either

using an advanced hand calculator, an on-line calculator, or using any

mathematics package.

Find first step is to find the pure component aT & b parameter from the three

equations given below:

RTC

b = 0.08664 .(5.49)

PC

2

R 2TC

aT = 0.42748 a (T ) .....(5.50)

PC

[ (

(T ) = 1 + (0.48 + 1.57 0.17 2 ) 1 Tr 0.5 )]

2

....(5.51)

Notice that an alpha function has been incorporated into the aT parameter

making it a function of temperature and acentric factor (thus the subscript).

These refinements provide much better vapour pressure prediction.

A & B parameters as follows:

aT P

A= .................(5.52)

R 2T 2

bP

B= ...(5.53)

RT

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 40

The cubic form of the RKS EOS is then expressed in terms of these

dimensionless A & B parameters:

The final steps are to find all three roots, select the correct root and find the

molar volume from the definition of Z - see below:

Pv

Z=

RT

Repeat the previous problem using the approach outlined above. To make this

consistent with the original RK EOS, simply use the following expression for

the alpha-function.

1

(T ) = 0.5

Tr

If the same critical properties are used then the same answer should be

obtained. If the RKS alpha-function is used, then a more accurate result

should be obtained.

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 41

TOPIC 5 Volumetric Behaviour of Real Fluids & Solids 42

5.7 Bibliography

McGraw-Hill, SI ed., 1987.

Wiley 2nd ed., 1993.

ed., 1998.

S.I. Sandler. Chemical and Engineering Thermodynamics. Wiley, 3rd ed., 1999.

TOPIC 1: Glossary 1

Topic 7

Glossary

Azeotrope

present at a particular composition only if the volatility of each species is the

same, which is the same as saying that the K-value of each species is unity, or

that the relative volatility of one species with respect to the other is unity.

Since the volatility of each species is the same, then the vapour and liquid

phases must both have the same composition. Distillation separates

component by exploiting difference in volatility and, therefore, distillation alone

cannot separate an azeotropic mixture.

Azeotrope form when the liquid phase deviates from ideality either positively or

negatively. Azeotropes form when the species have close boiling points (close

vapour pressures at prevailing temperature) and when there are sufficient non-

ideality for the relative volatility to be unit.

ideality and corresponds to a minimum temperature azeotrope. On the other

hand, a minimum pressure azeotrope is caused by strong negative deviation

from ideality and this corresponds to a maximum temperature azeotrope.

Chemical Equilibrium

occur within a reaction system. This means that the temperature, pressure and

composition are all absolutely uniform throughout the system.

Such a system will experience no heat transfer, no work transfer and no net

change in composition. Of particular interest in a chemical reaction, where the

temperature and pressure are constant, is that the composition is then fixed

and cannot change.

Chemical equilibrium for a reaction system does not imply that conversion

between reactants and products has stopped; it implies a dynamic equilibrium

where the rate of inter-conversion of species is the same in either direction.

That is the forward and the reverse reactions are operating at the same rate

and, therefore, the composition cannot change.

GLOSSARY 2

Chemical equilibrium occurs at a point where the total Gibbs free energy of the

reaction mixture is a minimum. This in turn leads to the species activity, raised

to the power of its stoichiometric coefficient, summed over all species taking

part in the reaction, is equal to the equilibrium constant.

Chemical Potential

The chemical potential of a species in a mixture is the partial molar Gibbs free

energy that that component has in a mixture (this is different from the molar

Gibbs free energy that a component has as a pure species). The chemical

potential, like all potentials must be an intensive property. Thus, unlike the

Gibbs free energy, it does not have an extensive form and this is why,

although equal to partial molar Gibbs free energy, the chemical potential has a

different symbol.

Closed system

A closed system in one where the same quantity of matter remains within the

boundary for all times that is matter cannot cross the boundary. In this case,

only energy in the form of heat or work can cross the boundary.

the US a closed system is often referred to as a Control Mass.

Compressed Liquid

larger than the vapour temperature. Thinking about it the other way around, it

also means that, at a fixed pressure, the temperature is less than the species

boiling point. Thus, a compressed liquid is the same as a subcooled liquid.

Compressibility Factor

The compressibility factor is the ratio of the molar volume of the real fluid to

the molar volume of an ideal gas at the same temperature and pressure. The

compressibility factor corrects the molar volume between the ideal gas state

and the real fluid state. Both liquids and gases may have compressibility

factors and the ideal gas is the reference state for both. As pressure tends to

zero, the compressibility factors tend to unity.

GLOSSARY 3

Energy Balance

general principle is that energy is conserved and the total energy entering a

system must be equal to the total energy leaving a system (whatever the

system). As well as energy associated with inlet and exit streams, energy can

also enter or leave the system as either heat or work. The energy content of

streams is expressed in terms of enthalpy.

Batch systems are handled in much the same way as continuous systems, so

long as the energy content of the charge material and discharge material is

considered in place of streams. The energy content charge and discharge

material is expressed in terms of internal energy.

Enthalpy

The enthalpy represents the energy content of a system and as such is the

energy that is stored in the system. The enthalpy is the sum of the internal

energy plus the combination Pv . Both terms have units (J/kg), in the case or

specific enthalpy or (J/mol) in the case of molar enthalpy.

Enthalpy is often associated with steady-flow processes, but also occurs when

the heat transferred to or from a non-flow constant pressure process.

Enthalpy balance

For the special case of a steady-flow process, without any work or heat and

with negligible kinetic and potential energy effects, the steady-flow energy

equation reduces to an enthalpy balance.

An enthalpy balance simple states that the total rate at which enthalpy enters

the device, summed over all inlet streams, is equal to the total rate at which

enthalpy leaves the device, summed over all exit streams.

The rate at which enthalpy enters or leaves with a stream (kW) is the product

of the stream specific enthalpy (kJ/kg) times the mass flow (kg/s) of the

stream. Alternatively it can also be the product of the stream molar enthalpy

(kJ/kmol) times the mole flow (kmol/s).

Enthalpy balances can be applied to mixing and splitting points, flow through

expansion valves or any item of equipment where no heat or work is either

supplied or removed.

GLOSSARY 4

Enthalpy of formation

one mole of a compound from its constituent elements. The elements should

be as they commonly occur in nature, e.g. Cl 2 rather than Cl.

standard enthalpies of formation are usually listed for pure species at 298.15 K

and at the reference pressure.

Enthalpy of reaction

The enthalpy of reaction is the pure component enthalpy of each species, in its

standard state, times its stoichiometric coefficient and then summed over all

reacting species.

aggregation of the pure species at the reaction temperature and a reference

pressure of 1 bar. Thus, the standard enthalpy of reaction depends on

temperature only (and is independent of pressure).

of formation of individual species and these are usually listed in tables at

298.15 K.

reactions will have a positive enthalpy of reaction. Whether heat is actually

given out or taken in also depends on the design of the reactor. The enthalpy

of reaction varies depending on the temperature and the state of aggregation

of both reactants and products. Although over short temperature ranges it may

be considered constant.

coefficients are doubled or halved then, through Hesss Law, the same must

apply to the standard enthalpy of reaction.

The enthalpy of reaction has units of (J/mol) and while this looks like a molar

property it is not one in the usual sense. The enthalpy of reaction is the heat

effect pre mole of reaction, that is to get the heat released, or absorbed (J), the

enthalpy of reaction must be multiplied by the extent of reaction, not the total

number of moles present or flowing through the system.

reaction. This is because heat does not reside within a system, it is an energy

exchange term.

GLOSSARY 5

Entropy

the more disorder the larger the system entropy; the less disorder the lower

the system entropy.

isolated system at best (reversible process) stays constant or increases

(irreversible process). As a system spontaneously moves towards its

equilibrium state, the entropy change is always positive and when it reaches

equilibrium the entropy of the system will be a maximum. Therefore, at

equilibrium the entropy change will be zero.

The same law applies to systems that are not isolated, but now both the

entropy change of the system and the surroundings must be considered

together. For a reversible process the total entropy change (both system and

surroundings) is zero. However, for irreversible processes the total entropy

change (system and surroundings) is greater than zero. An increase in entropy

during any process is associated with energy being degraded and a loss in

capacity to do work.

Once this capacity to do work has been lost it may never be recovered and

this is the meaning of the expression that the process is irreversible, literally-

speaking something irrevocable has occurred that can never be undone. Once

work has been lost as random thermal energy it may never be completely

recovered.

integrating the incremental heat added (positive entropy change) or removed

(negative entropy change) from the system divided by the absolute

temperature of the system at the instant that the heat is added or removed.

The requirement is that this integration must be carried out from the initial state

to some final state using an imaginary reversible process that connects the

two states.

Entropy was first identified when it was discovered that this integral summed to

zero over a cycle. Entropy is, therefore, a thermodynamic property (all state

functions, thermodynamic properties, must sum to zero over a cycle) and its

existence is a consequence of the second law of thermodynamics.

The entropy change of the surroundings is found in the same way. However,

for an infinite heat reservoir the surroundings temperature may be taken as

fixed. Thus the entropy change of the surroundings is just the heat added

(positive entropy change) or removed (negative entropy change) divided by

the absolute fixed temperature of the surroundings. The second law then

becomes the entropy change of the system plus surroundings must be greater

(irreversible) or equal to (reversible) zero. It is impossible to have any process

that results in a total entropy change of less than zero.

GLOSSARY 6

Equation of State

volume, temperature and the number of moles. The simplest EOS is the ideal

gas law. A better Equation of State, although now out of date, is the Van der

Waal EOS. Many accurate EOS have been developed over the years.

Chemical Engineers often use Redlich-Kwong-Soave (RKS) EOS or the Peng-

Robinson (PR) EOS.

These are popular because they can model both liquid and vapour properties,

although vapour properties tend to be more accurately modelled than liquid

properties. Polar liquids are especially difficult to model and empirical

correlations are used to find the properties of these mixtures.

Equilibrium Conversion

that has reacted, once the system is at chemical equilibrium, divided by

moles of the same component in feed. It may be expressed as a percentage or

as a fraction.

The equilibrium conversion can be calculated for any reactant species. However,

it is usually the conversion of the limiting reactant that is of interest (see also

limiting reactant and excess reactant in this glossary). The moles of a

reactant which has reacted is equal to the extent of reaction times the species

stoichiometric coefficient.

be insufficient residence time for the reaction system to reach equilibrium. In

this event the fraction conversion, defined the same way, will be less than the

equilibrium fractional conversion.

The equilibrium extent of reaction is the amount of a species that has reacted,

when the reaction system is at chemical equilibrium, divided by its

stoichiometric coefficient. The equilibrium extent of reaction is always positive

if the reaction proceeds in the forward direction. It either has units of (mol), for

non-flow processes, or (mol/s), for steady-flow processes. It is the same for all

reacting species in the mixture.

Naturally, the equilibrium extent of reaction must lie somewhere between zero

and some maximum value and this in turn is moles of limiting reactant initially

present divided by its stoichiometric coefficient.

GLOSSARY 7

equilibrium constant is very small (several orders of magnitude less than one)

then the equilibrium extent of reaction will be close to zero. If the equilibrium

constant is very large (several orders of magnitude greater than one), then the

equilibrium extent of reaction will be close to its maximum value (mentioned

above).

reaction will have a value somewhere near the middle of its possible range.

This information is very useful when a starting value is needed for the

equilibrium extent of reaction (often the case when a trial-and-error approach

is adopted).

Excess reactant

stoichiometric proportion. In practice one reactant is always supplied in

excess to force the reaction to the right and to ensure that as much as

possible of the limiting reactant actually reacts at equilibrium.

Extent of reaction

The extent of reaction is the amount of a species that has reacted divided by

its stoichiometric coefficient. The extent of reaction is always positive (so long

as the reaction proceeds in the forward direction) and either has units of (mol),

for non-flow processes, or (mol/s), for steady-flow processes.

The extent of reaction is the same for all species and is the key variable

needed when balancing all material flows entering and leaving a chemical

reactor. It is also a vital component when balancing all the energy flows

entering and leaving a reactor (see also equilibrium extent of reaction in this

glossary).

Fractional Conversion

species that has reacted divided by moles of the same component in feed; it

may also be expressed as percentage conversion. The conversion of any

reactant may be found, but it is usually the conversion of the limiting reactant

that is of interest.

GLOSSARY 8

Fugacity

potential tends to minus infinity as pressure tends to zero. Changes in fugacity

are directly linked to changes in chemical potential but, because of the way it

is defined, the fugacity tends to the system pressure as pressure tends to

zero, because of this the fugacity is often called an effective pressure. The

fugacity of an ideal gas is equal to the ideal gas pressure.

Fugacity Coefficient

The fugacity coefficient is defined as the fugacity of the real fluid divided by its

pressure. But due to what has been discussed under fugacity (this glossary)

the fugacity coefficient is also the fugacity of the real fluid divided by the

fugacity of an ideal gas.

Thus, the fugacity coefficient is a correction factor that corrects the fugacity

from the ideal gas state to the real fluid state at the same temperature and

pressure. As the fluid pressure approaches zero the fugacity coefficient

approaches unity. For an ideal gas the fugacity coefficient is unity. Fugacity

coefficients may be applied to both vapour and liquid phases.

The fugacity coefficient does exactly the same job for the fugacity as the

compressibility factor does for the molar volume.

Gas

may be liquefied by the action of pressure. If a gas is at a temperature above

its critical temperature it may not be liquefied by the action of pressure and is

called supercritical.

energy) is the maximum amount of non-expansion work that may be

recovered from a closed system, undergoing a reversible process at constant

temperature and pressure. The energy is free only in the sense that it is the

energy left over or available (after accounting for expansion/compressive

work).

then the total Gibbs free energy is a minimum. Thus, changes in the total

Gibbs free energy must be equal to zero at equilibrium.

GLOSSARY 9

pressure, must be minimised at equilibrium. The direction for spontaneous

change, as the system heads towards equilibrium, is always in the direction of

decreasing Gibbs free energy. These facts apply to both phase and chemical

equilibrium.

The derivative of the total Gibbs free energy with respect to the extent of

reaction (at constant temperature and pressure) is zero and this condition

defines the equilibrium extent of reaction.

The gamma-phi approach to VLE is used for polar mixtures which exhibit

strong differences in forces between like/unlike species in the liquid phase.

With this approach to VLE the ideal gas state is used as the reference state for

the real vapour phase and the ideal solution state is used as the reference

state for the real liquid phase. The fugacity coefficient corrects the fugacity in

the vapour phase, while the activity coefficient corrects the fugacity in the

liquid phase.

The fugacity coefficients are usually found using an EOS (often a cubic EOS),

while the activity coefficients are obtained from an empirical correlation (called

a model of solution behavior).

The Gibbs free energy change of reaction is the pure component Gibbs free

energy of a species, in its standard state, times its stoichiometric coefficient

and then summed over all reacting species.

aggregation of the pure species at the reaction temperature and a reference

pressure of 1 bar. Thus, the standard Gibbs free energy of reaction depends

on temperature only (and is independent of pressure).

The equilibrium constant is defined directly in terms of the Gibbs free energy

change of reaction and thus also depends on temperature only.

Gibbs free energy of formation of individual species and these are usually

listed in tables at 298.15 K. Thus, it is always possible to find the equilibrium

constant at a temperature of 298.15 K.

GLOSSARY 10

The standard Gibbs free energy of formation g of is the Gibbs free energy

change associated with forming one mole of a compound from its constituent

elements. The elements should be as they commonly occur in nature, e.g. Cl 2

rather than Cl.

Pure elements are defined as having a Gibbs free energy of formation of zero.

The standard Gibbs free energy of formation is usually listed for pure species

at 298.15 K and at the reference pressure.

Heat

energy exchange term, not an energy storage term. Heat is energy crossing

the boundary only while the system is actually changing state.

In this sense heat is energy in transit and is only observed when there is a

temperature difference across the boundary. Since heat does not reside in the

system, it is not good practice to use the term heat content. What is stored in

the system is energy, either as internal energy or enthalpy.

Heat is positive when transferred to and negative when transferred from the

system.

Heterogeneous Azeotrope

When a VLE system has large positive deviation from ideality like and unlike

species will have little affinity with each other. If this lack of affinity is large

enough, the liquid phase can split into two co-existing liquid phases.

temperature then a heterogeneous azeotrope can form (depending on the

overall composition). Vaporisation or condensation, under these conditions,

will occur with no change in liquid or vapour composition, and at constant

temperature, until one or other of the phases disappear.

The system is azeotropic because the compositions of vapour and liquid are

fixed and heterogeneous because the liquid splits into two phases.

GLOSSARY 11

An ideal VLE system is one that obeys Raoults Law. The vapour phase

mixture is an ideal gas while the liquid phase mixture, in equilibrium with this

vapour, is an ideal solution. The fugacity coefficients of all species in the

vapour phase are unity, the activity coefficients of all species in the liquid

phase are unity and the fugacity of the pure liquid is equal to its pressure (the

vapour pressure of the species).

Immiscible Systems

When two species have large positive deviation from ideality they may have so

little affinity for each other that they can split into two liquid phases. Depending

on this lack of affinity the two liquid phases may be partially miscible or

immiscible: partial miscibility is where unlike components may dissolve a little

in each phase (up to the point that the phase becomes saturated in the unlike

species); immiscibility is where unlike species have so little affinity that they

cannot dissolve in each phase; each phase is a pure species.

It is probably the case that no system is truly immiscible, but the miscibility

may be so low that (from an engineering point of view) the two liquid phases

may be considered immiscible.

Internal energy

quantity sums to zero across a cycle and, any quantity that behaves in this

way, must be a thermodynamic property.

potential and vibrational energies of all the particles making up the system.

For a monoatomic ideal gas internal energy is the average kinetic energy of all

the gas particles, since a monoatomic gas can only store energy in the form of

translational kinetic energy.

For any species internal energy depends on the temperature and the pressure

of a pure species. For an ideal gas internal energy is a function of temperature

only this is because only temperature affects the translational kinetic energy

of ideal gas particles.

GLOSSARY 12

Limiting reactant

Limiting means that one reactant is supplied in quantities less than the

theoretical stoichiometric proportion this is often the more valuable reactant.

Le Chateliers Principle

whenever the temperature, pressure or concentration of the reacting mixture is

changed, the equilibrium will adjust to oppose the change until a new

equilibrium state is eventually established.

Molar

A mole is the amount of any substance that contains the same number of

entities (ions, electrons, atoms or molecules) as 12 g of 12 C. This is the same

as Avogadro's number (6.02210 23 entities).

the substance. This is because a molar property is based on 1 mole of a

substance (containing Avogadros number of particles), see also molar mass

(this glossary).

Molar Mass

that substance. In SI units it is expressed as (g/mol). T hus, the molar mass,

in SI units, is the mass in (g) of 1 mole of the substance.

The molar mass of a species is found by adding the atomic masses of all the

atoms in a molecule. The molar mass of a species is often referred to be engineers

(incorrectly) as the molecular weight.

system is examined. The number of equations less the number of variables (in

these equations) is the number of degrees of freedom of the system. It is the

number of variables that must be specified in order for the number of unknown

variables to equal the number of equations available.

GLOSSARY 13

When used in the context of the Gibbs Phase Rule the general meaning in the

above paragraph is the same, but now the number of degrees of freedom

applies to phase equilibrium problems (bubble point and dew point problems).

Now the number of equations is the number of independent phase equilibrium

relations, while the number of variable is the number of intensive variables of

the system (temperature, pressure, composition).

If these are counted correctly (not all variables and equations are

independent), then the famous Gibbs Phase Rule formula is obtained.

For flash calculations the number of equations is larger (mass balances are

included) and the number of variables is larger (the amount of each phase is

needed). Thus, if these are counted properly, the number of degrees of

freedom is two. Notice this does not come from the phase rule.

Open system

In an open system matter can cross the boundary. Therefore, both matter and

energy, in the form of heat or work, may cross the boundary.

Processes occurring within an open system are called flow processes; either

steady-flow or unsteady flow. Steady-flow processes arise when the mass

flow entering the system is equal to the mass flow leaving the system. In the

US an open system can be called a Control Volume.

When two species have large positive deviation from ideality they may have so

little affinity for each other that they can split into two liquid phases. Depending

on this lack of affinity the two liquid phases may be partially miscible or

immiscible. Partial miscibility is where unlike components may dissolve a little

in each phase (up to the point that the phase becomes saturated in the unlike

species), see also immiscible systems (this glossary).

The phi-phi approach to VLE is used for non-polar mixtures (often hydrocarbon

mixtures). With this approach to VLE the ideal gas state is used as the

reference state for both the real vapour phase and the real liquid phase. The

fugacity coefficient corrects the fugacity in both vapour and liquid phases.

This approach works well for hydrocarbons because like/unlike species are

more similar in the liquid phase that fugacity coefficients (usually found from

an EOS) adequately model liquid phase properties.

GLOSSARY 14

The Poynting correction factor is the name often given to the exponential term

that correct the pure species liquid fugacity between vapour pressure of the

pure species and the system temperature. In many calculations this correction

factor has a negligible on the overall accuracy of the result. If this is the case

then it may be ignored.

Process

A system undergoes a process when its state is altered in some way. The

state may be altered in some arbitrary way or it may be altered in some well-

defined way, i.e. isothermal, isobaric, isochoric isenthalpic or adiabatic

processes.

The process may involve a definite change in state (two different end states)

or may trace out a cycle where, after passing through a sequence of states,

the initial and final states are the same.

Quasi-static Process

Work is done by moving an external force through some distance under the

action of an unbalanced force. A quasi-static process is when the system

exchanges work with the surroundings but the unbalanced force becomes

infinitesimally small (which is not to say that it is zero).

Under these circumstances internal and external forces acting over the

(slowly) moving boundary can be equated. Thus, the work done by moving the

external force through a distance becomes equal to a combination of internal

system properties.

the system changes state and is then returned to its original state, there will be

no evidence (in either the system or surroundings) that the process ever

occurred. In essence no work done on or by the system will be lost as heat at

any time during a quasi-static (reversible) process.

GLOSSARY 15

Reversible Process

A reversible process is one with only infinitesimal driving forces. This means

for work to be transferred reversibly the unbalanced force, causing the

boundary to move (the external force) through a distance, must be

infinitesimal. For heat transfer to be reversible, the temperature difference

across the boundary must be infinitesimal.

For a reversible process all intermediate states are equilibrium states and in

most textbooks such processes are represented by a solid line. Taking a solid

line to be an infinite series of dots, then any single dot represents one of these

intermediate equilibrium states.

If a reversible process is stopped and returned to its original state, then there

will be no evidence, either in the system or surroundings that the process had

ever occurred. All the heat and work exchanged in one direction will be exactly

equal to the heat and work exchanged when the system is returned to its

original state in the other direction.

irrevocable has been done during a reversible process, see quasi-static

processes (this glossary).

Saturated liquid

A saturated liquid, in the sense of VLE, is a liquid mixture at its boiling point.

The mixture is still completely liquid but has a tendency to generate vapour.

When moved incrementally (in the correct direction) the liquid phase will

generate this first bubble of vapour. This is why the saturated liquid curve is

also known as the bubble point curve. In this sense the liquid is saturated

because, at the prevailing temperature and pressure, it can no longer dissolve

or contain the vapour phase, thus, two different phases may co-exist at this

point.

At any prevailing pressure, the liquid mixture becomes saturated at its bubble

point temperature (this depends not only on the pressure, but also on the

overall composition). Below the bubble point temperature the liquid is

subcooled or unsaturated.

This sense of a saturated liquid also applies to LLE. The system is miscible

until the liquid is saturated. At this point the single liquid phase can no longer

dissolve the unlike species and (upon further addition of the unlike species)

the single liquid splits into two liquid phases, each of which is saturated in the

unlike species.

GLOSSARY 16

Saturated Vapour

condensation. The mixture is still completely vapour but has a tendency to

generate liquid. When moved incrementally (in the correct direction) the

vapour phase will generate this first drop of liquid. This is why the saturated

vapour curve is also known as the dew point curve. In this sense the vapour is

saturated because, at the prevailing temperature and pressure, it can no

longer contain the vapour phase, thus, two different phases may co-exist at

this point.

At any prevailing pressure, the liquid mixture becomes saturated at its dew

point temperature (this depends not only on the pressure, but also on the

overall composition). Above the dew point temperature the vapour is

superheated (thus also unsaturated).

Spontaneous process

will occur naturally by itself without any outside assistance. Thus heat flows

from a high to a low temperature occurs spontaneously, while a wheel that is

sent spinning will spontaneously slow down and eventually stop.

any real process, there must be an increase in entropy (both system and

surrounds considered together)

Gibbs free energy and ultimate reach equilibrium when this thermodynamic

potential is minimised.

Standard conditions

and products are in specified states of aggregation at the reaction

temperature, but a reference pressure of 1 bar. Thus, standard state

properties only depend on temperature.

GLOSSARY 17

Steady-flow

A steady-flow process is associated with open systems where mass can cross

the boundary. If an open system changes its state, then it properties must

change, such a process is called a flow process.

A flow process is called a steady-flow process if the flow is steady and this

means that at any point within the system the thermodynamic properties do

not change with time although, in all likelihood, they will change with position.

Steady-flow conditions prevail when the total mass flow entering the device is

equal to the total mass flow leaving the device. Obviously, when starting up or

shutting down an item of equipment, the operation will be transient and, during

such time, flow will be unsteady.

Stoichiometric Coefficients

Stoichiometric coefficients are the numbers that appear beside each reactant

or product in a properly balanced chemical equation. Stoichiometric

coefficients have no units and simply relate the number of reactant molecules

that are consumed to the number of product molecules that are produced.

Stoichiometric coefficients are positive for products, negative for reactants and

zero for inert species. This allows, using algebraic equations, products to be

produced, reactants to be consumed and inerts to pass through unchanged.

absolute quantities (without any sign). This is because it is known that

reactants are on the LHS, while products are on RHS. Thus, in chemical

reactions signs are omitted.

species summed over the reaction mixture. This is an important quantity since

it determines whether the number of moles in the reaction mixture will

increase, decrease or stay the same as the reaction proceeds.

are generally not conserved; moles will only be conserved if the overall

stoichiometric coefficient is zero. This means that the number of moles of

reactants being consumed exactly equals the number of moles of products

being produced.

GLOSSARY 18

Surrounding

affected by changes occurring within the system.

Thermodynamic system

has been separated from its environment and its behaviour is being

investigated.

being linked to the quantities heat and work.

The boundary envelops only the system itself and should exclude any

mechanical components that support or contain the system. Thus, for most

chemical engineering applications, the system is restricted to the fluid itself

(and not the equipment it is passing through).

Thermodynamics properties

this state all the thermodynamic properties must return to their original values.

reach a particular end state. It is said that the properties are not path

functions. Since thermodynamic properties depend only on the current state

they are called state functions or more commonly state variables.

Three-Phase Pressure

When a VLE system has large positive deviation from ideality like and unlike

species will have little affinity with each other. If this lack of affinity is large

enough, the liquid phase can split into two co-existing liquid phases.

pressure then a heterogeneous azeotrope can form (depending on the overall

composition). Vaporisation or condensation, under these conditions, will occur

with no change in liquid or vapour composition, and at constant pressure, until

one or other of the phases disappear.

GLOSSARY 19

Above the three-phase pressure is the LLE region, below the three-phase

pressure is the VLE region. VLLE can only occur at the three-phase pressure

and when the overall system composition lies within a band corresponding to

the saturated liquid compositions of each phase.

Three-Phase Temperature

When a VLE system has large positive deviation from ideality like and unlike

species will have little affinity with each other. If this lack of affinity is large

enough, the liquid phase can split into two co-existing liquid phases.

temperature then a heterogeneous azeotrope can form (depending on the

overall composition). Vaporisation or condensation, under these conditions,

will occur with no change in liquid or vapour composition, and at constant

temperature, until one or other of the phases disappear.

Above the three-phase temperature is the VLE region, below the three-phase

temperature is the LLE region. VLLE can only occur at the three-phase

temperature and when the overall system composition lies within a band

corresponding to the saturated liquid compositions of each phase.

Work

Work is force times distance moved. Hence, work can only be transferred

when the system boundary is actually moving and, thus, while the system is

changing state. Whenever the boundary stops moving then no work can be

done

boundary. Work cannot be exchanged if the boundary is fixed or rigid.

Movement of the boundary only occurs when there is an unbalanced force.

Thus, work is only done by moving the boundary against an external force

while under the action of an unbalanced force. Work is an energy exchange

term. Work does not reside within the system and is only manifest at a moving

boundary as the system is changing state. When the state is fixed the system

is in equilibrium and work transfer stops.

Work is positive when transferred into the system and negative when

transferred out of the system.

GLOSSARY 20

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