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You are on page 1of 32

Phase and Reaction Equilibria

KP8108

Ugochukwu E. Aronu

July, 2009

Table of Contents 2

1.0 Introduction 3

2.2 Partial Molar Gibbs Free Energy 5

2.3 Gibbs-Duhem Equation 6

2.4 Equilibrium in Heterogenous Closed System 7

2.5 Chemical Potential 8

2.6 Fugacity and Fugacity Coefficient 9

2.7 Activity and Activity Coefficient 10

3.3 G E Model for Activity Coefficient 17

4.0 UNIQUAC 18

4.1.2 Acetic Acid-H20 System 21

4.1.3 Other Systems 21

5.0 Results 25

Summary 25

Future Work 25

References 25

2

1.0 Introduction

Design of industrial chemical process separation equipment such as absorption and distillation

columns as well as simulation of chemical plants require reasonably accurate correlation and

prediction of phase equilibria because it is an integral part of vapour liquid equilibrium (VLE)

modeling. It is thus necessary to develope thermodynamic models suitable for practical phase

equilibrium calculations.

In general, VLE models are based on fundamental equations for phase and chemical

equilibria. The basic quantities required for VLE calculations are; chemical reaction

equilibrium constants, Henry’s law constant, fugacity coefficients and activity coefficients

(Poplsteinova, 2004), phase equilibria calculation requires Henry’s law constant, fugacity

coefficients and activity coefficients. The differences in VLE models are mainly in the way

the phase non-idealities are treated. In the vapor phase non-ideality is either neglected or

represented by a fugacity coefficient calculated from one of the well-established equations of

state such as Soave-Redlich-Kwong equation of state, the models will then differ on the type

of equation of state that were applied. These differences, however are of minor importance

since the calculation of vapor phase fugacities are not crucial for the model performance. The

treatment of the liquid phase, on the other hand, is very important. Accurate prediction of the

liquid phase composition plays a key role in the VLE modeling. Since the evaluation of

equilibrium constants and fugacity coefficients are reasonably well established, the activity

coefficients were identified as the most important variables of the VLE model. Thus proper

representation of activity coefficients is desirable (Poplsteinova, 2004).

coefficient model for such system must be able to represent the non-ideality of an electrolyte

solution. Some activity coefficient models for non-electrolyte systems include, Wilson,

NRTL, UNIFAC, UNIQUAC. Some have been modified for electrolyte systems. Review of

electrolyte activity coefficient models were present by Maurer, 1983; Renon, 1986 and

Anderko et al., 2002. For the purpose of this course the universal quasi-chemical

(UNIQUAC) equations proposed by Abrams and Prausnitz, 1975 is used in calculating

activity coefficient for non-electrolyte systems. Further work will involve extending the

model for calculation activity coefficient for electrolyte solutions.

3

2.0 Thermodynamic Frame Work

Vapour liquid equilibria calculation requires simultaneous solution of phase and chemical

equilibria for reactive systems. Ths section shows briefly the mathematical framework for the

VLE calculations which is built around basic concepts of thermodynamic. Most of the

discussions here were taken from Elliot and Lira, 1999; Prausnitz et al., 1999; Kim, 2009;

Hartono, 2009 and Poplsteinova, 2004.

Homogenous Closed system

A homogeneous is a system with a uniform properties ie. properties such as density is same

from point to point, in a macroscopic sense example is a phase. A closed system do not

exchange matter with the surrounding eventhough it may exchange energy (Prausnitz et al.,

1999). An equilibrium state is one with no tendency to depart spontenously (having in mind

certain permissible changes or process such as heat transfer, work of volume displacement

and for open systems mass transfer across phase boundry). It’s properties are independent of

time. A change in equilibrium state of a system is called a process and a reversible process is

one that maintains a state of virtual equilibrium throughout the process, it is often referred to

as one connecting a series of equilibrium states.

For a reversible process, the general condition for thermodynamic equilibrium is derived by

combination of first and second law of thermodynamics as:

dU TdS PdV 1

This condition could be expressed in terms of all extensive thermodynamic functions; internal

energy (U), enthalpy (H), Helmholtz energy (A) and Gibbs free energy (G): The condition for

equilibrium is usually maintained by keeping two of the thermodynamic variables constant.

Conditions for equilibrium is often expressed in terms of Gibbs free energy because the two

constant variables are often the temperature and pressure. Using the fundamental

thermodynamic relation for Gibbs free energy

G U TS PV 2

4

Eq. 1 could be written as

dG SdT VdP 3

dG 0 4

which implies that for thermodynamic equilibrium at constant T and P, the Gibbs free energy

of a closed system reaches its minimum.

Homogenous open System

For a closed system, U is considered a function of S and V only; that is U = U(S, V) but for

open system, there are additional indepedent variables. For these variables we use the mole

numbers of the various compnents present, thus we consider U as the function

U U ( S , V , n1 , n2 ..., nm ) , where m is the number of components present. Total differential is

then

U U U

dU

S V ,ni

dS

V S ,ni

dV S

i

dni 5

S ,V , n j

where subsript ni refers to all mole numbers and nj to all mole numbers other than ith (the

term under differenciation). Writing eq. 5 in the form

dU TdS PdV + dn

i

i i 6

where i U

ni S ,V , n j

Eq. 6 is the fundamental equation for an open system corresponding to eq. 1 for a closed

system. The function μi is an intensive property which depends on temperature, pressure and

composition from its position in the equation as the coefficient of dni it can be refered to as

mass or chemical potential just as T (the coefficient of dS) is a thermal potential and P (the

5

coefficient of dV) is a mechanical potential. Similar expression can be derived in terms of

Gibbs free energy G (and other extentive thermodynamic properties).

dG SdT VdP + dn

i

i i 7

where

U H A G

i 8

ni S ,V , n j ni S , P , n j ni T ,V ,n j ni P ,T ,n j

The quantity i is the partial molar Gibbs free energy, but not partial molar internal energy,

enthalpy, or Helmholtz energy, because the independent variables T and P chosen for defining

of partial molar quantities are also fundamental independent variables for the Gibbs free

G

energy G (Prausnitz et al., 1999). The quantity, i , the partial molar Gibbs free

ni P ,T , n j

At constant temperature and pressure eq. 7 reduces to

dG = i dni 9

i P ,T

For equilibrium, at constant P and T, the Gibbs free energy is minimized (i.e dG = 0) (Elliot

and Lira, 1999). Also for a closed system dni = 0 thus equation 7 equal to zero at equilibrium.

From equation 9, equilibrium condition in terms of chemical potential could then be deduced

dG i dni = 0 10

i P ,T

heterogenous system that is used for experimental data evalution and theory development. It

expresses the fact that among + 2 variables consisting of temperature, pressure and

6

chemical potentials of each component present in the system. Only +1 are independent

variables and the last variable is a dependent variable calculated in such a way that Gibbs-

Duhem equation is satisfied.

In terms of activity coefficient Gibbs-Duhem equation is expressed as

x d ln

i

i i 0 11

Equation 11 is a differential relation between the activity coeffiecients of all the components

in solution (Prausnitz et al., 1999). For a binary solution, the Gibbs-Duhem equation may be

written as:

d ln 1 d ln 2

x1 x2 12

dx1 dx2

A heterogeneous, closed system is made up of two or more phases with each phase considered

an open system within the overall closed system. If the system is in internal equilibrium with

respect to the three processes of heat transfer, boundry displacement and mass transfer,

neglecting special effects such as surface forces; semipermeable membranes; and electric,

magnetic or gravitational forces (Prausnitz et al., 1999), the general result for a closed system

consisting of phases (where two of the phases are liquid (L) and vapour (V)) can be written

as

T v T L ... T

P v P L ... P 13

v L ...

This is the basic criterion for phase equilibrium, which states that at equilibrium, the

temperature, pressure and chemical potentials of all species are uniform over the whole

system.

7

2.5 Chemical Potential

The task of phase-equilibrium thermodynamics is to describe quantitatively the distribution at

equilibrium of every component among all the phases present. Gibbs obtained the

thermodynamic solution to the phase-eqiulibrium problem by introducing the abstract concept

of chemical potential. The task is then to relate the abstract chemical potential of a substance

to physically measurable quantity such as temperature, pressure and composition.

For a pure substance i, the chemical potential is related to the temperature and pressure by the

differential equation

d i si dT vi dP 14

where si is the molar entropy and vi the molar volume. Integrating and solving for i at some

temperature T and pressure P, we have

T P

i (T , P) i (T r , P r ) si dT v dP

i 15

Tr Pr

where superscript r is an arbitrary reference state. The integrals can be solved from thermal

and volumetric data over temperature range T r to T and pressure range P r to P but the

chemical potential i (T r , P r ) is unknown. Chemical potential at T and P can thus only be

evaluated relative to an arbitrary reference states give as T r and P r these refence states are

often known as standard states.

Chemical potential does not have an immediate equivalent in the physical world and it is

desirable to express the chemical potential in terms of some auxilaiary function that might be

more easily identified with physical reality. The term fugacity (f) was introduced by G.N.

Lewis in trying to simplify the equation of chemical equilibrium by first considering the

chemical potential for a pure, ideal gas and then generalized the result to all systems

(Prausnitz et al., 1999). Auxiliary thermodynamic functions such as fugacities and activities

are often used in thermodynamic treatment of phase equilibria.

8

2.6 Fugacity and Fugacity Coefficient

The fugacity of component i in a mixture is defined as (Elliot and Lira, 1999)

RTd In fi d i at constant T 16

where fi is the fugacity of component i in a mixture and i is the chemical potential of the

component. For a pure ideal gas, the fugacity is equal to the pressure, and for a component i in

a mixture of ideal gases, it is equal to its partial pressure yiP. The definition of fugacity is

completed by the limit:

fi

1 as P0 17

yi P

By integrating eq. 16 at constant T for any component in any system, solid, liquid or gas or

pure mixed, ideal or non-ideal. For vapour phase we have

f

o RT ln 18

fo

While either o and fo is arbitrary, both may not be chosen independently; when one is

chosen, the other is fixed. Writing an analogous expression for the liquid and vapour phase

and equating the chemical potentials using equation 13 obtain:

fv

v L RT ln 0 19

fL

isofugacity:

f v f L ... f 20

This tell us that the equilibrium condition in terms of chemical potential can be replaced

without loss of generality by equation in terms of fugacity.

9

Fugacity coefficient, is the ratio of fugacity to real gas pressure. It is a measure of non-

ideality.

fi

i 21

yi P

It is a way of characterizing the Gibbs excess function at fixed T, P. For a mixture of ideal

gases i = 1.

Activity concept is an alternative approach to express the chemical potential in a real solution.

The activity of component i at given temperature, pressure and composition is defined as the

ratio of the fugacity of i at these conditions to the fugacity i at standard state. Activity of a

substance gives an indication of how active a substance is relative to its standard state, it is

expressed as:

fi

ai 22

fi 0

Substituting equation 22 into 18 gives relationship between chemical potential and activity.

i i0 RT ln ai 23

A general expression for the chemical potential in an ideal solution in terms of ideal mixing

could be written as

iid i0 RT ln xi 24

component i to its concentration, usually the mole fraction

ai

i 25

xi

10

In an ideal solution the activity is equal to the mole fraction and the activity coefficient is

equal to unity. Introducing equation (25) into (23)

i i0 RT ln xi RT ln i 26

Activity coefficient relates chemical potential in an ideal solution to the chemical potential in

a real solution, thus representing a measure of non-ideality as illustrated by combining

equations (26) and (24)

i iid RT ln i 27

It is convenient to define activity in such a way that for an ideal solution activity is qual to the

mole fraction or equivalently, that the activity coeffiicent is equal to unity. Because we have

two types of ideality (one leading to Raoult’s law and the other leading to Henry’s law), it

implies there will be two ways of normalizing activity coefficient.

Symmetric Convention

This convention applies when all the components both solutes and solvent at the system

temperature and pressure are liquids in their pure state (reference state). The activity

coefficient of each component i then approaches unity as its mole fraction approaches unity.

This convention leads to an ideal solution in the Raoult’s law sense. It follows that:

i 1 as xi 1 28

Unsymmetric Convention

This convention applies when pure component cannot be used as a reference state for instance

when some component are solid or gaseous at the system temperature and pressure. In this

case it is convenient to define the reference state as the infinite dilute state of the component

at system temperature and reference pressure. This convention therefore leads to an ideal

dilute solution in the sense of Henry’s law.

11

for solvent s 1 as xs 1 29

Subscripts s and i refer to solvent and solute respectively while asterisk(*) shows that the

activity coefficient of the solute approaches unity as mole fraction approaches zero. This

convention is said to be unsymmetric because solvent and solute are not normalized in same

way.

Excess functions are thermodynamic properties of a solution that are in excess of an ideal (or

ideal dilute) solution at the same conditions of temperature, pressure and composition. For an

ideal solution all excess properties are zero (Prausnitz, 1999). A general excess function is

defined as

e E ereal eideal 31

One particularly important excess function is the excess Gibbs energy (G E ) defined by

Similar definitions hold for excess volume V E , excess entropy S E , excess enthalpy H E ,

excess internal energy U E , and excess Helmholtz energy AE . Relations between these excess

functions are exactly the same as those between the total functions, for example:

G E H E TS E 33

Also, partial derivative of extensive excess function are analogous to those of the total

functions. For example:

G E

SE 34

T P , x

12

Partial molar excess functions are defined in a manner similar to partial molar thermodynamic

properties. If M is an extensive thermodynamic property, then mi , the partial molar M of

component i, is defined by

M E M E

mi similarly mi 35

ni P ,T ,n j ni P ,T , n j

n m n m

E

M i i

similary ME i i

36

i i

From excess function definition, it can be seen from eq. 27 that RT ln i is equal to excess

chemical potential iE . Since chemical potential at constant T and P is equal to the partial

molar Gibbs free energy as shown in section 2.2, we obtain a very important relationship

between the activity coefficient and the partial molar excess Gibbs free energy:

E

g i RT ln i 37

g E RT xi ln i 38

i

Eq. 38 forms the basis for calculation of activity coefficients from G E models as will

described in section 3.3.

Vapour liquid equilibrium calculation requires simultanoeaus solution of chemical and phase

equilibria, activity and fugacity coefficients is required in chemical equilibria calculations

while fugacity cofficient is required in phase equilibria. Both are used to express chemical

potentials in liquid and vapour phase respectively

13

3.1 Chemical Equilibria

Molecular electrolytes dissociates or react in the liquid phase to produce ionic species to an

extent governed by the chemical equilibrium. Chemical reaction in the liquid phase enhances

the mass transfer rate and the solubility of CO2 and thus affects the phase equilibrium and

vice versa, the distribution of species between the two affects the chemical equilibrium in the

liquid phase. A system is in equilibrium when there is no driving force for a change of

intensive variables within the system. Chemical reaction moves towards a dynamic

equilibrium in which both reactants and products are present but have no further tendency to

undergo net change.

The generalized chemical reaction:

1 A1 2 A2 ... m Am m 1 Am 1 ... 39

A

i

i i 0 40

where the coefficients i are positive for the products of the reaction and negative for the

reactants. The condition for equilibrium in a chemical reaction is given by:

i

i i 0 41

The Gibbs free energy change in the chemical reaction is given by:

i

where Gro is the Gibbs free energy change with reactants in their standard states.

14

3.1.1 Chemical Equilibrium Constant

The chemical equilibrium is traditionally defined by a chemical equilibrium constant. At

equilibrium, Gr = 0 so that equation eq. 42 becomes, (Ott and Goates, 2000):

Gro RT ln K 43

where K is the equilibrium constant and is given by:

K aivi 44

i

The activities in eq. (44) are now the equilibrium activities. An equilibrium constant K

expressed in terms of activities (or fugacities) is called a thermodynamic equilibrium constant.

Equilibrium constants are required for each of the reactions occuring in solutions. They are

related to the activities of each species as:

bB cC dD eE 45

aDd aEe

K 46

aBb aCc

Here the lower case letters are the stoichiometric coefficients, i , and the capital letters are

labels for the chemical species.

The solubility of gas in a liquid is often proportional to its partial pressure in the gas phase,

provided that the partial pressure is not large. The equation that describes this is known as

Henry’s law:

Pi yi P Hxi 47

where Henry’s constant (H) is the constant of proportionality for any given solute and solvent,

depending only on temperature (Prausnitz et al., 1999). At high partial pressures, Henry’s

constant must be multiplied by activity coefficient and pressure by fugacity cofficient.

15

A measure of how chemical species distributes itself between liquid and vapour phase, is the

ratio (Perry, 1997):

yi i f i

K 48

xi i P

The condition for phase equilibrium in a closed heterogeneous system at constant temperature

and pressure is given by eq. 20.

fi v fi L 49

Where fi v and f i L are fugacities of component i in the vapor and liquid phase respectrively.

From eq. 48 or by inserting eqs. 21, 22, and 25 into eq. 49 we obtain:

i yi P i xi fi oL 50

where i and i are fugacity and activity coefficient respectively. f i oL is reference state

fugacity coefficient defined either by symmertic conventions Raoult’s law or unsymmetric

convention Henry’s law.

A correction term used to relate fugacities at the different pressures is called Poynting factor,

written as and at constant temperature and pressure change from P1 to P2 can further be

shown to be:

f 2 (T , P2 ) p2 v dP

exp i 51

f1 (T , P1 ) P RT

1

The complete phase equilibria for vapour – liquid equilibrium of solute and solvent at systems

temperature and pressure can thus be respectively written as (Austgen 1989):

vi ( P PHo2O )

For solute: i yi P i xi H i exp 52

RT

16

vi ( P Pso )

For solvent: s ys P x P exp

o o

s s s

o

s 53

RT

where Hi and v i represent Henry’s law constant, partial molar volume of molecular solute i

at infinite dilution in pure water at the system temperature and at saturation water vapour

pressure, PHo2O while vs is the molar volume of pure solvent at system temperature and

saturation pressure. The exponential correction (Poyning factor) here takes into account the

fact that liquid is at a pressure P different from the saturation pressure P o . For molecular

solutes such as carbon dioxide, Henry’s constant represents reference-state fugacities.

To solve the phase equilibrium equation, we need to evaluate the fugacity and activity

coefficients. Gas phase fugacity coefficient can be calculated from equation of state such as

Soave-Redlich-Kwong equation of state. The real modeling task lies in the calculation of

activity coefficient. In this work activity coefficient calculation using, UNIQUAC is

presented.

They are usually obtained from excess Gibbs free energy models using eq.38. An apprioprate

excess Gibbs energy function most take into consideration the molecular interactions between

all species in the system. For electrolyte solutions, diverse species are usually present and

interactions among them must be represented. At high concentrations, interactions between

neutral molecules or between ions and neutral molecules are very short-range in character and

dominates while at low concentrations it is interactions between ions which are very strong

long-range electrostatic interactions that dominates. The usually practice is to assume that the

contributions of the various types of interactions are independent and additive (Poplsteinova,

2004). The excess Gibbs energy is then calculated as the sum of short-range and long-range

contributions:

G E GSR

E

GLR

E

54

17

Most modeling applications combine the Debye-Hückel electrostatic theory for the long-range

term with modifications of well known non-electrolytes models for the short-range term. In

this work the local composition model for non-electrolytes, UNIQUAC will be presented in

more detail since they were applied in this work.

Regular solution theory assumes that the mixture of interactions were independent of each

other such that quadratic mixing rules provide reasonable approximations. However in some

cases, the mixture interaction can be strongly coupled to mixture composition. One way of

treating this is to recognize the possibility that the local compositions in the mixture might

deviate strongly from the bulk composition (Elliot and Lira, 1999). Some of the well-known

local composition models for non-electrolytes are Wilson, NRTL, UNIFAC and UNIQUAC

for these models to be used in electrolyte solutions, several assumptions have to be made

regarding the local composition in the presence of ions.

4.0 UNIQUAC

For this work the UNIQUAC equation described by Abrams and Prausnitz, 1975 was derived,

implemented and used for calculation of activity coefficients for non-electrolyte systems.

Main advantages of UNIQUAC is that it uses only two adjustable parameters per binary to

obtain reliable estimates for both vapor-liquid and liquid-liquid equilibria for a large variety

of multicomponent systems using the same equation for the excess Gibbs energy (Abrams and

Prausnitz, 1975).

Experimental data for typical binary mixtures are usually not sufficiently plentiful or precise

to yield three meaningful binary parameters, various attempts were made (Abrams and

Prausnitz, 1975; Maurer and Prausnitz, 1978; Anderson, 1978; Kemeny and Rasmussen,

1981) to derive a two-parameter equation for g E that retains at least some advantages of

Wilson equation without restriction to completely miscible mixtures. Abrams derived an

equation that in a sense, extends the quasichemical theory of Guggenheim for

nonrandommixtures to solutions containing molecules of different size. This is called

universal quasi-chemical (UNIQUAC) theory.

18

UNIQUAC equation for g E consists of two parts combinatorial part that describe the

dominant entropic contribution, and residual part that accounts for intermolecular forces

which are responsible for the enthalpy of mixing. The combinatorial part is determined only

by composition and by the sizes and shapes of the molecules, it requires only pure-component

data. The residual part depends on intermolecular forces, thus the two adjustable binary

parameters appear only in the residual part. The UNIQUAC equation is

gE gE gE

55

RT RT combinatorial RT residual

gE z

RT x1 ln 1 x2 ln 2 x1q1 ln 1 x2 q2 ln 2 56

combinatorial x1 x2 2 1 2

gE

x1q1 ln(1 2 21 ) x2 q2 ln( 2 1 12 ) 57

RT residual

where coordination number z is set equal to 10. Segment fraction, , and the area fractions,

, are given by

x1r1 x2 r2

1 2 58

x1r1 x2 r2 x1r1 x2 r2

x1q1 x2 q2

1 2 59

x1q1 x2 q2 x1q1 x2 q2

The parameters r and q are the two pure-component structural parameter per component

representing volume and area respectively. They are dimensionless and are evaluated from

bond angles and bond distances. For a binary mixture, there are two adjustable parameters,

12 and 21 . They are given in terms of charateristic energies u12 u12 u22 ; u21 u21 u11 .

u12 u21

12 exp 21 exp 60

RT RT

19

For many cases eq. 60 gives the primary effect of temperature on 12 and 21 . u12 and u21 are

nT g E RT ni ln i 61

i

where nT is the total number of moles. The final expression for activity coefficient is obtained

by taking the partial derivative of excess Gibbs energy g E with respect to mole number.

n g E

RT ln i T 62

ni T , P , n j ( j ì )

derived to be:

k z k k

k

ln k ln 1

qk ln 1

xk xk 2 k k

63

i ki

qk 1 ln j jk

j i j ji

j

Appendix

The expression for activity coefficient was added to the thermodynamic function library

developed by Tore Haug-Warberg and Bjørn Tore Løvfall at Department of Chemical

Engineering, NTNU. The model was coded in an in-house language called RGrad supporting

automatic gradient calculations, and from there exported to C-code which is compiled into a

set of DLL’s accessible from Matlab, Octave and Ruby (Haug-Warberg, 2008).

20

It has a folder <MODEL>/src/mex that contains two makefiles which compiles and set up the

model called <model>. The model is then simply run as <model>_mexmake or

<model>_octmake depending on whether you want a matlab/MEX interface or an Octave

interface.

Monoethanolamine(MEA) is an important solvent for CO2 absorption, so for this work,

UNIQUAC equation was applied in calculation of activity coefficient in binary system of

MEA and water. In the model, the parameter adjustable energy interaction parameters (uij ) of

the UNIQUAC enthalpy term are assumed to be temperature dependent and are fitted to the

following temperature function

The r and q parameters for MEA and water as well as uijo and uijT were taken from Faramarzi

et al. 2009. Other uijo parameter values were set to large values while uijT parameters were set to

zero. Result from the calculation was compared with literauture data of Tochigi, K et al.,

1999, Belabbaci, A et al. 2009 and Kim, I et al., 2008 in figure 1. Molar Excess Gibbs energy

function was also calculated and presented in figure 5.

The r and q parameters as well as energy interaction parameter aij for acetic acid-water

system were taken from Prausnitz, et al. 1999. The activity coefficient plot for acetic acid-

water system is shown in figure 2. The molar excess Gibbs energy function was also

calculated and presented in figure 6.

The predicted model for formic acid – acetic acid sysems as well as acetone – chloroform

syetems are presented in figure 3 and 4 respectively. All parameters were taken from Prautnitz

et al. 1999. It has not been easy to get experimental data to use to compare the model result

from this work, however the shapes of the plots agrees very well with plots in Prausnitz, et al.

1999.

21

5.0 Results

0.9

0.8

0.7

0.6

Belabbaci A. et al. 2009

Kim I. et al. 2008

0.4 H20 This work

MEA This work

xMEA

0.6

Ellis & Bahari 1956

Sebastiani & Lacquaniti 1967

0.5

Hansen et al. 1955

Arich & Tagliavini 1958

0.4 Marek & Standart 1954

H20 This work

ACETIC This work

0.3

log

0.2

0.1

-0.1

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

xH20

22

Figure 2: Activity coefficient plot for Acetic Acid – H20 system.

1.35

ACETIC

FORMIC

1.3

1.25

1.2

1.15

1.1

1.05

1

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

xFORMIC

Figure 3: Activity Coefficient plot for Acetic Acid – Formic Acid System

0.9

CHLOROFORM

ACETONE

0.8

0.7

0.6

0.5

0.4

xACETONE

23

0

-100

-200

Excess Gibbs Energy (gE)

-300

-400

-500

-600

-700

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

xMEA

Figure 5: Excess molar Gibbs free energy plot for MEA-H20 System

250

200

Excess Gibbs Energy gE

150

100

50

0

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

xACETIC

Figure 6: Excess molar Gibbs free energy plot for Acetic Acid -H20 System

24

Summary

UNIQUAC activity coefficient model was derived and successfully implemented for

calculating activity coefficient for different non-electrolyte systems. Literature activity

coefficient data for MEA-H20 system appear to vary among the different authors presented,

the model appear to fit much better to the data from Tochigi K et al 1999. Activity coefficient

data for acetic acid – H20 system however is more consistent. Model prediction agrees well

with the literature values.

Future Work

Further work will involve the calculation of activity coefficient for electrolyte systems by

extending the UNIQUAC model for electrolyte system through addition of the long-range

term.

References

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26

Derivation of Activity Coecient Expression

Based on UNIQUAC

Ugochukwu Aronu

Combinatorial

z }| {z Residual

}| X {

E

g X i ZX i X

= xi ln + qi xi ln qi xi ln( j ji ) (1)

RT i

xi 2

i

i i j

hu i

where ji = exp ji uii

RT

q xi q ni

i = Pi = Pi (2)

j qj xj j qj nj

r xi r ni

i = Pi = Pi (3)

j rj xj j rj nj

writing eq.1 in terms of the number of moles 'n' and factoring out 'n'.

A B

z }| { z X }| { z C

}| {

ng E X i n Z i X X

= ni ln + qi ni ln qi ni ln( j ji ) (4)

RT i

ni 2

i

i i j

gE

!

@n( RT ) @A @B @C

ln
k = = + +

@nk @nk T;ni6=k @nk T;ni6=k @nk T;ni6=k

T;ni6=k

(5)

1

Simplify Eq. 4A and dierentiate with respect to mole number.

X

i n

A= ni ln

i

ni

X

= ni (ln i n ln ni )

i

X

= ni (ln i + ln n ln ni )

i

A1

zX }| { z A}|2 {

= ni (ln i ln ni ) + n ln n

i

@A @A1 @A2

= + (6)

@nk @nk @nk

P

@A1 @[ i ni (ln i ln ni )]

=

@nk @nk

@A1 X @i 1 1

= (ln i ln ni )ik + ni ( ik )

@nk i

i @nk ni

X ni @i

@A1 k

= ln + 1 (7)

@nk nk i

i @nk

@A2 @ (n ln n)

=

@nk @nk

@n @ ln n

= ln n +n

@nk @nk

1

= ln n + n

n

@A2

= ln n + 1 (8)

@nk

Substituting eq. 7 and eq. 8 back in eq. 6

X ni @i

@A k

= ln + ln n +

@nk nk i

i @nk

X ni @i

@A k

= ln + (9)

@nk xk i

i @nk

2

From 3, i = Prjirnjinj ; thus

P P

@i j rj nj ri ik (ri ni ) j rj jk

@nk

= P 2

j rj nj

@i r ik ri ni rk

= Pi P 2 (10)

@nk j rj nj

j rj nj

2 3

X ni 6 ri ik

@A k ri ni rk 7

@nk

= ln

xk

+

4P r n P 2 5

i j j

i j

j rj nj

P P

k nr i ri ni rk

2

= ln + Pi i i P

xk i j rj nj i ( j rj nj )2

P

k n rk i ri ni rk

2

= ln + Pk P

xk k j rj nj i ( j

2 rj nj )

P

k nr

= ln +1 Pi i k

xk rj nj

j

k nr

= ln +1 P k

xk j rj nj

k nrk nk

= ln +1 P :

xk j rj nj nk

@A k k

= ln +1 (11)

@nk T;ni6=k xk xk

3

Simplify Eq. 4B and dierentiate with respect to mole number.

zX i zX

B = qi ni ln = qi ni (ln i ln i )

2

i

i 2

i

@B zX @i 1 1 @i

= qi (ln i ln i )ik + ni ( )

@nk 2

i

i @nk i @nk

A B

z }| { z }| {

@B z z X ni @i ni @i

= qk ln k + qi (12)

@nk 2 i 2

i

i @nk i @nk

From 10 @i

@nk

= Prjirikj nj (

Prjinrijrnkj 2 ; therefore

)

= P Pi i k 2

i @nk i j rj nj i ( j rj nj )

nr

= ik Pi k (13)

( j rj nj )

Similarly;

P

@i ( qj nj )qi ik qi ni qk

=

j

P

@nk ( j qj nj )2

q qnq

= P i ik Pi i k 2

j qj nj ( j qj nj )

ni @i ni qi ik ni qi ni qk

= P P

i @nk i j qj nj (i j qj nj )2

ni qk

= ik P (14)

( j qj nj )

" ! !#

zX ni qk nr

qi ik P ik Pi k

2

i j qj nj j rj nj

!

zX nr nq

= qi Pi k Pi k

2

i j rj nj j qj nj

P P !

z qnr qi ni qk

= Pi i i k Pi

2 j rj nj j qj nj

4

Multiply numerator and denominator of by nk then factor out k and i .

P P !

z qi ni rk nk qi ni qk

= Pi Pi

2 j rj nj nk j qj nj

Factor out k and i .

P !

z i qi ni k

X

= i qk

2 nk i

P !

z i qi ni k

X

= qk i

2 qk nk i

P

Factoring out k and setting i i = 1 .

z k

= qk 1

2 k

Therefore

@B z k z k

= qk ln + qk ( 1)

@nk 2 k 2 k

@B z k k

= qk ln + 1 (15)

@nk T;ni6=k 2 k k

X X

C = qi ni ln( j ji )

i j

2 0 1 3

@C X X @ni 1 X @j 5

= qi 4ln @ j ji A + ni P ji

@nk i j

@nk j j ji j

@nk

2 B

3

z 0

A

}| {

1 z }| {

6 P @j 7

6 X X n j ji @nk 7

7

6q ln @ A + q i

P (16)

= 6k j jk i 7

6 j ji 7

4 j i j 5

But; j = Pqlj qnljnl . Note that subscript ' ' is used in place of subscript ' ' for

l i

clearity. P

@j ( l ql nl )qj jk

P

qj nj qk

=

@nk ( l ql nl )2

5

@j q jk q nj qk

= Pj Pj (17)

@nk l ql nl ( l ql nl )

2

P h q i

X j ji Pjl qjklnl (

Pqjlnqjlnqkl 2

)

qi ni P

i j j ji

h Pj qj nj qk ji i

X P

qi ni ki qk

l ql nl

qi ni

Pl qlnl 2

) P

( )

i j j ji

P

X i ki X i j ji j

) qk P qk P

j ji j ji

i j i j

2 3

@C X X i ki X

= 4qk ln( j jk ) + qk P qk i 5

@nk j i j j ji i

P

But i i = 1

2 3

X X i ki

@C

= qk 41 ln( j jk ) P 5 (18)

@nk T;ni6=k j i j j ji

Substituting eq. 11, eq. 15 and eq. 18 into eq. 5 and obtain the nal

expression for activity coecient based on UNIQUAC

k k

ln
k = ln +1

xk xk

z

+ qk ln k + k 1

2 k k

2 3

X X i ki

+ qk 41 ln( j jk ) P 5

j i j j ji

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