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Engineering Thermodynamics

CHBE 346
REVIEW NOTES
Introductory Concepts
Definitions of System
Property, State, Equilibrium, Phase Rule
Criteria for Equilibrium
Clausius Clapeyron Equation

Phase Equilibrium in a Pure Fluid


Phase equilibrium is one of the most important and difficult
estimations (designing separation processes).
In most processes the controlled variables are P and T.
Therefore G (Gibbs free energy) is the property to calculate
as it is a function of these two natural variables (P and T).

G U PV TS H TS

and

dG SdT VdP

In a single component system with two phases, we need to


specify 1 state variable (F=C-P+2=1-2+2=1). If we define P
then T is fixed and vice-versa.
2

Criteria for Phase Equilibrium


Example: A piston cylinder contains both propane liquid and vapor at 12oC. The piston is forced down a specified distance under isothermal
conditions. Both phases still remain. How much does the pressure
increase?
Since T and P are fixed:

dG SdT VdP 0

G n LG L nV GV dG n L dG L G L dn L nV dGV GV dnV
Since:

n n L nV dn 0 dn L dn L dn L dnV

Then:

G L GV

pure fluid phase equilibria

Note: None of other thermodynamic properties , U, H, S and A is


equivalent on both phases. In single component phase equilibrium, one
variable at saturation is needed to specify the state.

The Clausiun-Clapeyron Equation


A useful equation to show dependence of vapor pressure on T at low P
L
V
or
V V dP sat S V dT V L dP sat S L dT
We start with: dG dG
Rearranging:

(V V V L )dP sat ( S V S L )dT

Entropy is a difficult property to measure, so we use enthalpy as follows:


By definition:

GV H V TS V H L TS L G L

We can derive:

S S S

Substituting for
entropy:

vap

( H V H L ) H vap

T
T

dP sat
H vap

dT
T (V V V L )

Another form is: d ln P

sat

Clapeyron equation for solid-vapor and solidliquid. Substitute enthalpy of vaporization


with that of fusion or sublimation.

H vap
1 Z stands for compressibility factor in

d

R( Z V Z L ) T ZPV/RT.

For a gas far from the critical point (low


reduced temperatures)
ZV-ZLZV. Also ZV1 (ideal gas near 1 bar)

d ln P

sat

H vap 1

d
R
T

Clausius-Clapeyron equation

Shortcut Estimation of Saturation Properties


Setting PR=PC and TR=Tc, then:

sat
r

ln P

H vap Tc Tc
H vap


RZ vapTc T Tc RZ vapTc

1
1

Tr

In terms of log10:

log10 Prsat

1
H
1
1

2.303 RZTc Tr

1
A 1
Tr

Relating this to the acentric factor, w:

log10 Prsat

Tr 0.7

1
3
7

(w 1) A 1

(1 w )

0.7
7
3

Which results in a shortcut vapor pressure equation:

sat
r

log10 P

7
1
1 w 1
3
Tr

5
Note: This approximation is good above P=0.5 bar. The estimations are based on
the critical pressure which is generally 40-50 bar and acentric factor at Tr=0.7.

The Antoine Equation


The previous equation is appealing. However sometimes we need greater
precision which is based on this equation with the constants fitted from
experimental results. The equation is the Antoine equation:

log10 P sat A B / (T C )
Where T is in Celsius. Constants A, B and C are available for a wide range
of vapor-liquid equilibrium data. The Psat is given in mmHg.

Note: This equation should be only applied over the range recommended
and it should not be extrapolated.

Engineering Thermodynamics
CHBE 346
Phase Equilibrium in a Pure Fluid
Gibbs Free Energy and Fugacity
7

Calculation of Fugacity (Gases)


G G ln f ln
ig

RT

Equations of State

ig 1 and

Ideal Gas

f ig P

The Virial Equation


P

ln
0

B
BP
dP
RT
RT

which becomes when you write the virial coefficient in reduced T and P :

ln

Pr 0
B w B1
Tr

The Peng Robinson equation

Z (1 2) B
ln ln( Z B)
ln
Z 1
B 8 Z (1 2) B
A

Calculation of Fugacity (Liquids)


To introduce the calculation of fugacity for liquids consider Figure 9.5:
f C f B f sat

Any of the methods discussed for gases can be used to calculate fB. The method
to calculate fD defers. Note A: gas, B: sat gas, C: sat liquid, D: liquid

The Poynting Method

D
fD
Apply the following equation: dG VdP RTd ln f RT ln sat VdP
f
P sat

Since liquids are incompressible for Tr<0.9, volume is constant. Then:


V L ( P P sat )
V L ( P P sat )
fD
sat sat
exp
f D P exp

f sat
RT
RT

where:

V satL VC Z C(1Tr )

0.2857

The Rackett Equation

The Poynting correction (exponential) is unity for many


applications and thus:

f sat P sat

or

f P sat

Engineering Thermodynamics
CHBE 346
Introduction to Multicomponent Systems
Phase diagrams
Vapor-Liquid Equilibrium (LVE) Calculations

Principles of Calculations
Standard approaches utilize the ratio of vapor mole fraction to liquid mole fraction,
known as the VLE K-ratio:

K i yi / xi

1. For bubble calculations (BP or BT),


all xi are known and we find yi:

K x 1

1 or

i i

2. For dew calculations (DP or DT),


all yi are known and we find xi:

x 1

y /K

or

3. For flash calculations we solve :

x y
i

written in terms of zi and Ki

11

Engineering Thermodynamics
CHBE 346
Vapor-Liquid Equilibrium (LVE) Calculations
using Raoults Law

Binary LVE Using Raoults Law

For such mixtures the K-ratio


for Raoults law is:

Pi sat
Ki
P

or yi P xi Pi sat

1
Note that for such mixtures:
7
(1w )1
T
3
r ,i
(i) K-ratio depends only on T and P (independent of xi)
Pi sat Pc ,i 10
Ki

(ii) Use any method for vapor pressure to calculate K


P
P
(shortcut estimation of the Vapour pressure)
(iii) Later will consider cases where Raoults law does not apply

13

Engineering Thermodynamics
CHBE 346
General Flash Calculations
Adiabatic Flash Calculations

General Flash

Flash drums are used in chemical processes.

For isothermal drum, T and P of drum are known.

F can be either liquid or vapor (partial condenser).

To perform flash calculations (zi, F and the outlet T and P must be known).

Apply mass balances (overall and component)

L / F 1 V / F and zi xi ( L / F ) yi (V / F )
Using

yi xi Ki where K i Pi sat / P

Rearranging

xi

zi
and
1 (V / F )( K i 1)

yi

zi Ki
1 (V / F )( K i 1)

15

Engineering Thermodynamics
CHBE 346
Introduction to Mixture Properties
Property Changes of Mixing
Multicomponent VLE Raoults Law Calculations

Ideal Gas Mixture Properties


For ideal gas (absence of molecular interactions), properties do not change with
mixing (yi is the gas phase composition).
ig
U ig yiU iig or U ig nU
i i
i

The total volume of a mixture is (Amagats law)

V ig RT ni / P
i

Also the enthalpy is:

H ig yi H iig
i

Therefore, we can add the component enthalpies and internal energies for ideal
gas mixtures using the mole fractions as the weighting factors:
ig
U mix
0

ig
Vmix
0

ig
H mix
0

17

Mixture Properties for Ideal Solutions


For ideal solutions, properties do not change with mixing.

U is xU
i i

or U is nU
i i

V is xV
i i

or V is nV
i i

Since

H is U is PV is xi U i PVi xH i
i

H is ni H i

We can add the component enthalpies and internal energies for ideal solution
mixtures using the mole fractions as the weighting factors.
Therefore, an ideal solution has a zero energy of mixing, volume of mixing and
enthalpy of mixing (heat of mixing).
is
U mix
0

is
Vmix
0

is
H mix
0

Examples of ideal solutions are all ideal gases mixtures and liquid mixtures of
family member pairs of similar size such as benzene+toluene, n-butanol+npentanol and n-pentane+n-hexane (n stands for normal to distinguish from isomers).

18

Engineering Thermodynamics
CHBE 346
Phase diagrams of Nonideal Systems
Concepts for Generalized Phase Equilibria
-

Explain nonidealities
Explain deviations from Raoults law

Nonideal Systems

Azeotrope (minimum boiling azeotrope and maximum pressure azeotrope)

Challenges of azeotropes in chemical industry (distillation and extraction)

20

Engineering Thermodynamics
CHBE 346
Equilibrium Criteria
Chemical Potential

Equality of Fugacities as Equilibrium Criteria


The equality of chemical potentials at equilibrium can be interpreted in terms of
fugacities.
iV (T , P) iL (T , P)
Integrating

RTd ln fi d i at fixed T from a state of pure i to a mixed state.


i , pure
V
i

fiV
RT ln
fi

fi and i are for the pure fluid.


Writing an analogous expression for the liquid and equating with the above.

iV iL RT ln fiV / fi L 0

fiV fi L

At equilibrium

This is the starting point for any phase-equilibrium calculations.

Develop methods to calculate chemical potentials and fugacities.

This equation does not look like Raoults equation (we will prove it next).

22

Engineering Thermodynamics
CHBE 346
Introduction to Activity Models
Modified Raoults Law
Excess Gibbs Energy
The One-Parameter Margules Equation

The One-Parameter Margules Equation


The simplest expression for Gibbs excess function is the one-parameter
Margules equation. For a binary system:

GE
A 12 x1 x2
RT
Where A12 is a constant. This equation is symmetrical and it has an extremum at
x1=0.5 and becomes zero at purity of either component. The activity coefficient for
this model is (derive later):

ln i A 12(1 xi )2
Lets fit the model to experimental data.

24

Calculation Using Activity Coefficients


Once the activity coefficient models parameters are known for a given system,
the K-ratio can be calculated of composition using

yi i Pi sat
Ki
xi
P
Then the bubble, dew and flash calculations can be executed. Because the activity
coefficient depends on xi, the algorithms where xi is unknown require an initial guess
to calculate a value for i and an iterative procedure to converge.
The method for bubble pressure does not require iteration because the activity
coefficient depends on the temperature and liquid composition (both are inputs).

25

Engineering Thermodynamics
CHBE 346
Derivation of the Modified Raoults Law
Excess Gibbs Energy
Excess Properties
The Two-Parameter Margules Equation

Deriving Modified Raoults Law


Raoults law is for equilibrium for ideal mixtures.
Staring point for VLE calculations is:

fiV fi L

The Venn diagram below explains the deviations from ideality, going from ideal gas
model to ideal solution model to finally real solution model and the various
equations that hold in each case.
Ideal gas model

fiV yi P
Ideal solution model

fiV i yi P, i 1,

fi L xi fi o

fio is the fugacity at standard state (pure), fi


f / P and f / y P
i

Real Solution Model


Excess properties

fiV i yi P, i 1,

fi L i xi fi o

27

Excess Gibbs Energy


The excess Gibbs energy is:

is
G E G G is G xi Gi G is xiGi Gmix Gmix
Gmix RT xi ln( xi )
i
i
i

Recall that: G xi i

fi
i RT ln o
fi

o
i

The chemical potential relative to a standard state:

fi
ai o xi i
fi

Defining the ratio of fugacities as activity:


Then using io Gi , fi o fi
Gmix

(standard state of pure component), we can derive:

fi
G xi Gi xi ( i Gi ) RT xi ln
f
i
i
i
i

Gmix RT xi ln ai RT xi ln xi i
i

Finally

G E Gmix RT xi ln( xi ) RT xi ln( i )


i

NOTE: The activity coefficients and


GE are coupled. When all activity
coefficients are going to ONE, GE=0
(ideal solution).

28

Activity Coefficients as Derivatives


We have a simple relation between partial molar quantities and molar quantities:
M xi M i
i

G E xi GiE

Apply this for excess Gibbs energy:

E
E
Compare the above with: G RT xi ln( i ) or G / RT xi ln( i )
i

We get:

G E
GiE iE RT ln i

ni T , P ,n j ni

For the one-parameter Margules,

The partial molar excess Gibbs energy


of a component is also the component
excess chemical potential.

GE
n
n ( A12 x1 x2 ) (A12 n2 ) 1
RT
n

n2
1

G
1 n1
For i=1:

ln

A
n

1
12 2
12
2
RT n1 T , P ,n
n
n n
2

ln 1 A12 x22 and ln 2 A12 x12

n1
1 n A12 x2 (1 x1 )

29

The Two-Parameter Margules Equation


The two parameter Margules equation is a simplification of the Redlich-Kister
equation:

GE
x1 x2 ( B12 C12 ( x1 x2 ) D12 ( x1 x2 ) 2 ...)
RT
The two-parameter Margules equation is:
GE
x1 x2 (A 21 x1 A12 x2 )
RT

If A12=A21, the equation reduces to one-parameter Margules equation:


Some important equations for the two-parameter Margules equations are:

ln 1 x22 A12 2( A21 A12 ) x1 and ln 2 x12 A21 2( A12 A21 ) x2


The two parameters can be fitted to a single VLE measurement using

1 ln 2ln 2
A12 2 1
x1
x2 x2

and

1 ln 2ln 1
A21 2 2
x2
x1 x1

30

Engineering Thermodynamics
CHBE 346
Gibbs-Duhem Equation
Lewis-Randall Rule and Henrys Law
Osmotic Pressure

Gibbs-Duhem Equation
An expression known as the Gibbs-Duhem equation is useful
(i) Testing data for experimental errors
(ii) Generating the activity coefficients in a binary for a second component based
on the bahavior of the first component
(iii) Development of theories for G of mixture (models should follow this)
Start with

G ni i or dG ni d i i dni

Using

dG SdT VdP i dni

Combining

0 SdT VdP ni d i

The Gibbs-Duhem equation

n d
i

0 or

n d
i

E
i

0 at T , P constant

Inserting the relation between excess chemical potential and activity coefficient

n d
i

Thus binary at fixed T and P.

E
i

RT ni d ln i 0
i

ln 1
ln 2
x1

0
2
xi T , P
xi T , P

32

Lewis-Randall Rule and Henrys Law


If both components of a mixture are liquids, then the fugacity in solution can be
calculated using the Lewis-Randall Rule, that is:

fi is xi fi or fi xi i fi
The problem is what if one of the components does not exist in these conditions at
pure form to calculate fi . For example for liquid-phase hydrogenation reactions or
oxygenation of water, hydrogen and oxygen are above their critical temperatures As
seen above the Lewis Randal rule requires the fugacity of the pure liquid/component.
In such cases (gases dissolved in liquids at infinite dilutions, Henrys law is used
(outlines the behavior of an ideal solution):

fi is xi hi
The Henry constant, hi is determined
experimentally and depends on P, T and solvent.
The slope in the graph is the Henry constant.
At high concentrations Henrys law breaks
down, however for gases with very low
solubility provides an acceptable approximation.

33

Osmotic Pressure
Consider a membrane separating W from W+C (water or blood purification in dialysis).
If both sides at same pressure, P, W runs from left to right (C cannot permeate) due to higher
potential due to higher mole fraction.

If pressure on the right increases to a level, , where flow stops (osmotic pressure)
If pressure is increased more, a condition of reverse osmosis occur, where flow reverses and W
runs from right to left.

It can be proven that the


osmotic pressure is:

RT
ln W
VW

Where w =xww is the activity coefficient of the solvent, W.

34

Engineering Thermodynamics
CHBE 346
The Van der Waals for Mixtures
The Van Laar Model
Scatchard-Hildebarnd Theory
35

Van Der Waals Equation of State


One EOS useful and most influential is the van der Waals Equation of State:
RT
a
RT
P
2
a 2
V b V
1 b

or

1
a

1 b RT

with

PV
RT

Where is the molar density =n/V (moles/cm3), and


27 R 2Tc2
a
64 Pc

; b

RTc
8 Pc

We may rewrite the van der Waals equation as:

Z 1 Z rep Z att 1

b
a

1 b RT

Where 1 denotes the ideal gas law, Zrep denotes deviations from ideal gas law
due to repulsive interactions between the molecules and Zatt denotes
deviations from ideal gas law due to attractive interactions between the
molecules.

36

Van Der Waals for Mixtures

The van der Waals equation of state for mixtures should have the same form.
The key quantities to be considered are van der Waals a and b.
If we know a=a(x) and b=b(x), then we could solve for Z for a mixture and
calculate other functions (departure functions).
The equations to be developed for the compositional dependence into the
mixture constants are termed mixing rules.

The parameter b represents the finite size of the molecules. Thus for similar molecules:

b xi bi
i

For the parameter a we must relate it to the departure function for U, resulting:

U U ig a a / V
In a binary mixtures there are three types of interactions (1+1) and (2+2) between
similar molecules and (1+2) or (2+1) between dissimilar molecules. Thus,

a xi x j aij x12 a11 2 x1 x2 a12 x22 a22


i

Where a11 and a22 are the a in the van der Wall equation of each component and a12

a12 (1 k12 )(a11a22 )

1/2

Where k12 is an adjustable parameter. The default k12=0 gives an estimate of a12.

37

Activity Models for van der Waals


The Gibbs energy, GE=UE+PVE-TSE is composed of three contributions.
The term PVE is small for liquids.
Entropy is related to volume changes and therefore close to ideal, SE negligible.

Under these assumptions:

GE U E
The energetics of a of the mixture are given by the equations presented in the previous page.
ig
Assuming zero excess volume, V xiVi then ( remember that U U a a / V :
i

U U ig

xi x j aij
i

xV

i i

For a pure fluid

Thus for an ideal


mixture/solution

U U ig

U U
ig

is

aii
Vi

( xi aii / Vi )
i

38

Activity Models for van der Waals


To calculate UE, remember that: The deviation of a property from its ideal-solution
value is called the excess property. Thus:

U E U U is
For binary mixtures, we
subtract the ideal solution
result
For

(U U ) a / V
ig

We get

Rearranging

U E (U U ig ) (U U ig )is

Thus,

U U
ig

x12 a11 2 x1 x2 a12 x22 a22


x1V1 x2V2

a11
a22 x12 a11 2 x1 x2 a12 x22 a22
U x1
x2

V1
V2
x1V1 x2V2

UE

x1 x2V1V2 a11 a22


a12

x1V1 x2V2 V12 V22


V1V2

39

The van Laar Model


van Laar found that the parameters from the van der Waals equation were not
accurate enough in predicting the excess energy of mixing. He simplified the
equations as follows:
UE

a
x1 x2V1V2
a
a
Q where Q 112 222 2 12
x1V1 x2V2
V1V2
V1 V2

It appears that this equation contains three parameters (V1, V2 and Q), however van Laar
recognized that these can be rearranged to result only two adjustable parameters.
QV1
QV2
A12 V1
A12
; A21
;

RT
RT
A21 V2
The final results are:

Activity
coefficients

A12 A21 x1 x2
GE U E

RT RT x1 A12 x2 A21
ln 1

A12
A12 x1
1 A x
21 2

and

ln 2

A21
A21 x2
1 A x
12 1

The parameters of the model can be fitted by using a single pair of experimental data (see E. 12.1)
x ln 2
A12 (ln 1 ) 1 2

x1 ln 1

and

x ln 1
A21 (ln 2 ) 1 1

x2 ln 2

40

Scatchard-Hildebrand Theory
This is the theory for nonpolar fluids. Setting a12 (a11a22 )1/2 that is k12 0
a22
x1 x2V1V2 a11 a22
a12
x1 x2V1V2 a11
E
U

x1V1 x2V2 V12 V22


V1V2 x1V1 x2V2 V1
V2

Scatchard and Hilderbrand recognized the unknown parameters in terms of volume fractions
and disperse attraction energies that could be related to the pure component values.

U E 1 2 (1 2 ) 2 ( x1V1 x2V2 )
where

i xiVi / xiVi

is volume fraction

and i aii / Vi is solubility parameter

To calculate these, Scatchard and Hildebrand suggested to use experimental data such that
U ivap
H ivap RT
i

Vi
Vi

Table 12.1 gives values of the solubility parameters and molar volumes.

The final results from these theory are:

G E U E 1 2 (1 2 ) 2 ( x1V1 x2V2 )
RT ln 1 V1 22 (1 2 ) 2

and

RT ln 2 V2 12 (1 2 ) 2

41

Engineering Thermodynamics
CHBE 346
The Flory-Huggins Model
The Wilson Model
THE NRTL Model
42

The Flory-Huggins Model


Polymer-solvent systems differ from usual solutions in that one component
(polymer) is much larger than the other (solvent). This leaves less space for the
solvent, limits the ways that a certain chain can stretch in solution. The FloryHuggins model accounts for these effects (applicable to such systems i.e. polymer
solutions, and polymer blends). The excess Gibbs energy is:
G E RT x1 ln 1 / x1 x2 ln 2 / x2 1 2 ( x1 x2 r ) c RT
Where 1 refer to the solvent and 2 to polymer. The first part reflects the entropic effects
that arise from the number of possible ways that macromolecules and solvent can be
arranged in space. The second part represents the enthalpic contribution that arises from
differences between the polymer-polymer and polymer-solvent interactions and c is a
measure of the interaction between the polymer and solvent.
i xiVi / xiVi

Also

are volume fractions

r V2 / V1 1 (ratio of molecular volumes )

c V1 (1 2 ) 2 / RT

Activity
coefficients

ln 1 ln 1 / x1 (1 1 / x1 )

V1 2
2 (1 2 ) 2
RT

ln 2 ln 2 / x2 (1 2 / x2 )

V2 2
1 (1 2 ) 2
RT

43

Wilson Equation

This theory is based on local composition theory and accounts for intermolecular
interactions between a molecule and its immediate neighbors. Local composition
might differ from bulk composition as molecules might form clusters and not
evenly distributed at a local level. These effects are taken into account using local
composition theories such as the Wilson theory. The excess Gibbs energy is:
GE
x1 ln x1 x2 12 x2 ln x1 21 x2
RT
Activity
coefficients

where

12
21
ln 1 ln x1 x2 12 x2

x1 x2 12 x1 21 x2

12
21
ln 2 ln x1 21 x2 x1

x
1
2
12
1
21
2

12

V2
A
exp 12 and
V1
RT

21

V1
A
exp 21
V2
RT

Where Vi are the molar volume and A12 and A21 are related to the interaction energies
between the components. These are not known and they are treated as adjustable
parameters.
One limitation of the Wilson equation is that it is unable to model liquid-liquid equilibria,
but it is reasonably accurate for modeling the liquid phase when correlating the vapor
liquid equilibria.

44

NRTL (Non-Random Two Liquid)


This theory is based on local composition theory.
The excess Gibbs energy for a binary system is:
G
G
GE
x1 x2 12 12 21 21
RT
x1G12 x2 x1 x2G21

Activity
coefficients

2
G
G21

12 12
ln 1 x
21

2
x

x
G
x1G12 x2
1 2 21
2
2

2
G

G
2
21 21
21
ln 2 x1
12

2
x
G

x
x1 x2G21
2
1 12

where

Gij exp(aij ij ) and ij

gij
RT

Where gij represent the interaction


parameters, available in literature
(units of energy).

For aij =0 , the one-parameter Margules equation is recovered since Gij=1.

For a binary system:

g12 g 22
RT
g g
G21 exp(a 21 ) and 12 21 11
RT
G12 exp( a 12 ) and 12

The NRTL is not appealing from a theoretical perspective, but it is flexibility has led to a
number of applications including elecrolyte models.

45

Engineering Thermodynamics
CHBE 346
The UNIQUAC
The UNIFAC
Project Not for the Final Exam
46

Engineering Thermodynamics
CHBE 346
Engineering Equations of State
for PVT Properties
Phase Equilibria in Mixtures by an
Equation of State

47

The Virial Equation of State for Mixtures


We use a mixing rule to the virial EOS:

B xi x j Bij
i

Which for a binary mixture becomes

B y12 B11 2 y1 y2 B12 y22 B22


Where B11 is the virial coefficient of component 1 and B22 is the virial coefficient of
component 2. B12 is the same as B21 . A way to calculate this (engineering approach) for a
mixture is to calculate first:

Tc12 (Tc1Tc 2 ) (1 k )
1/2

'
12

Vc12

1/3
Vc1/3

1 Vc 2

Z c12 12 (Zc1 Z c 2 )

w12 12 (w1 w2 )

Then these are used in the correlations below to obtain B12 (B of the mixture). If Zc is not
available use: Zc=0.291-0.08w
Z 1 ( B 0 w B1 ) Pr / Tr

or

Z 1 B ( P / RT )

where B(T ) ( B 0 w B1 ) RTC / PC


B 0 0.083 0.422 / Tr1.6
B1 0.139 0.172 / Tr4.2
subject to Tr 0.686 0.439 Pr or Vr 2.0

48

Fugacity and Chemical Potential from an EOS

The tool for LVE is the K-ratio and an expression for the component fugacity
The EOS is capable of representing liquid phases by using the smaller root , we
show both vapor and liquid phases.
Note that for VLE
f L f V
i

The method calculates the Gibbs departure function:

i (T , P) iig (T , P)
RT

G / RT
G ig / RT
(G G ig ) / RT

n
ni
i
i

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

Consider the virial equation:


Then

G G ig BP

RT
RT

fi ( i iig ) (G G ig ) / RT
ln

y P
RT

n
i
i

T , P ,ni j

Define the ratio of the component fugacity to the partial pressure (ideal gas component
fugacity) as the component fugacity coefficient:
fi

i
or fi i yi P
yi P
Differentiation of the Gibbs departure function leads to (binary system):

ln 1 [2 y1 B11 2 y2 B12 B]P / RT

ln 2 [2 y1 B12 2 y2 B22 B]P / RT

The component fugacity coefficient in a mixture may be directly determined at a T and P by


evaluating the virial coefficients at the T.

49

Fugacity coefficients from Peng-Robinson


The method to calculate the fugacity coefficient gives an equation expressed in
terms of the Helmholtz departure function (convenient) - see textbook for details
ln(i )

i iig
RT

( A Aig )T ,V / RT

ni

ln Z

T ,V,ni j

To apply this consider the Peng-Robinson equation as an example. Using the above
relationship, the following equation can be derived:
fiV Bi V
Z V (1 2) BV 2( y1 Ai1 y2 Ai 2 ) Bi
AV
V
V
ln

( Z 1) ln( Z B ) V
ln V
V

V
V

y P BV
A
B
B 8 Z (1 2) B
i

where

AV yi y j Aij
i

BV yi Bi
i

Aij Aii Ajj (1 kij )

The EOS approach encompasses both liquids and vapors. We replace the vapor phase mole
fractions with liquid mole fractions in all formulas.
fi L Bi
Z L (1 2) B L 2(x1 Ai1 x2 Ai 2 ) Bi
AL
L
L
L
ln

( Z 1) ln( Z B ) L
ln L
L
L
L

x P B L
A
B
B
8
Z

(1

2)
B

Recall:

fi L fiV

or

yiiV P xiiL P

or

K i iV / iL

Given Ki for all i, it is straightforward to solve VLE problems using the same procedures as for
ideal solutions.

50

Fugacity coefficients from van der Waals


The method to calculate the fugacity coefficient gives an equation expressed in
terms of the Helmholtz departure function (convenient) - see textbook for details
ln(i )

i iig
RT

( A Aig )T ,V / RT

ni

ln Z

T ,V,ni j

To apply this consider the van der Waals equation. Using the above relationship,
the following equation can be derived:
B
ln k ln( Z B) k
Z B

where

B
a
A
;
;
Z
bRT B

a jk
a

2 x j Akj
j

Ajk
A

bk Bk

b
B

For a binary system i=1,2 and j=1,2. Thus,

ln i ln( Z B)

Bi
2( x1 Ai1 x2 Ai 2 )

Z B
Z

Note that this equation applied for both liquid and vapor phases.

51

Bubble-Pressure Method
For bubble calculations (BP), all xi are known and we need to find yi so that:

1 or

K x 1
i i

Rearranging the above equation using variables of the current method

xiiL
i V P i Ki xi 1
i
Unlike the activity model calculations, we cannot explicitly solve for pressure
because both fugacities, iL and iV depend on pressure. Additionally, iV
depends on the composition of the vapor phase which is not exactly known.
Typically, we use Raoults law with the shortcut vapor pressure equation for
the first guess of yi and P.
Then we determine all Ki and check the sum of yi.
If the sum is greater than 1 , the pressure is increased in the second guess.
If the sum is less than 1 , the pressure is decreased in the second guess.
Complete flow charts on performing these calculations for BP, BT, DP and DT as
well as flash calculations can be found in Appendix C (principles same as before)

52

Engineering Thermodynamics
CHBE 346
Partially Miscible Liquids
Ternary Systems
53

Partially Miscible Blends


When the constituents molecules have low affinity for each other (n-hexane/ethanol).
Both contain CH2 and CH3 which are similar. However ethanol contains OH (hydroxyl)
which has low affinity with the alkyl groups.
At certain compositions the system splits into two separate liquid phases. If such a system
is brought to boiling it becomes a three-phase system: two liquid and a vapor.
Discussion of Figure 8-10 (Matsoukas).
There are three distinct phases: vapor, one
hexane rich liquid phase (L1) and one
ethanol-rich phase (L2).
The rest represents coexistence between
these phases (determined by drawing a tie
line).
Start an experiment at 60oC and start
adding hexane into ethanol. Homogeneous
phase until point C2 is reached. When
solubility of hexane in ethanol is reached, a
second liquid phase appears (reach in
hexane (point C1). When enough hexane is
added and point C1 is reached, L2 phase
disappears as enough hexane exists to
dissolve ethanol (solubility of ethanol in
hexane).

54

Ternary Systems
When a soluble third component is added to two partially miscible liquids we obtain a
ternary system in which the third component (solute) is partitioned between the two liquid
phases (solvents). The phase diagram of such a system is a triangular.
Discussion of Figure 8-13 (Matsoukas).
The three components are placed on the vertices of
the equilateral triangle.
The concentration of a component at any point
inside the triangle is measured by the fractional
distance of that point from the side opposite to the
vertex of the component (explain point A).
Point A lies at 44% of max distance above the
horizontal axis which makes the conc. Acetic acid
44wt%. This can be read from the grid lines placed
on the sides of the triangle (point B). Point C shows
the wt% water and D the wt%of MIBK. These should
add to 100%.
The shaded area represents two liquid system with
the rest one liquid phase.
Point E represents a two phase liquid (L1 which is
mostly water and L2 which contains mostly
methylisobutyl ketone. The lever rule applies (tie
lines are not horizontal).

55

Engineering Thermodynamics
CHBE 346
Energy Balance for Reacting Systems
Stoichiometry
Standard State Heat of Reaction
56

Energy Balance for Reacting Systems


Chemical Engineers must be able to include reacting systems into energy balances.
In such systems the number of moles is not conserved (exception).
We use the method of the reaction coordinate (easier to incorporate into the energy balance).
For a reaction (reactants and products Ci), we can write

1C1 2C2 3C3 4C4 0


The Cs represent the species. Reactants have negative s, while products have positive.
The s are called the stoichiometric numbers.

CH 4 H 2O CO 3H 2

For the reaction

1 1; 2 1; 3 1; 4 3
Consider a certain amount of C1 reacts with C2, to produce C3 and C4, we can prove that:

dn1

dn2

dn3

dn4

dni represent differential amount reacted and produced and is the reaction coordinate
and is related to the conversion.

Integrating

d
0

dn

ni

ni

57

Energy Balance for Reacting Systems


In general form

nif nii i

In a flowing system

niout niin i

Where

represents the overall rate of species interconversion.

Moles are not conserved in a chemical reaction. Adding all components in and out.

n out nin i

or

n out n in i
i

In closed systems, the value of is determined by chemical equilibria


calculations; it can be positive or negative. The only limit that it can take is
determined by:

nif 0

for

all i

or

nif 0

for

all i

58

Standard State Heat of Reaction


During a reaction bonds are broken and other form so that there are energy and enthalpy
changes. This has a significant effect on the energy balance, larger than the sensible heat.
Hesss law can be used to calculate the enthalpy change due to reaction.
Suppose that we have to calculate the standard heat (or enthalpy) of the following reaction

We select the standard state which is the reference state at the T of the system, 1 bar. We can write:

H To i H To,i i H ofT ,i

i H ofT ,i

products

i H ofT ,i

reactants

H ofT ,i is the standard heat (or enthalpy) of formation Appendix E.1. (T=298.15 K)
When we know the heat of reaction at a reference temperature we can calculate the heat of reaction
at any temperature.
T
T

H H C P dT H i C P ,i dT

TR
TR i
o
T

o
R

o
R

A reaction with negative heat is called exothermic and one with positive is called endothermic.

59

Engineering Thermodynamics
CHBE 346
Energy Balance for Reactions
(a) Heat of Reaction Method
(b) Heat of Formation Method
60

Energy Balances for Reactions


To calculate heat transfer to or from a reactor system (with a single entrance and a single
outlet) we can use

0 H in n in H out n out Q W S

The enthalpy of each stream is the summation of the


enthalpy of the components plus the enthalpy of
mixing at the stream temperature and pressure.
There are two methods (see Figure 3.5 textbook)

The Heat of Reaction Method (easier to grasp


due to explicit term of heat of reaction)

The Heat of Formation Method (Hesss law, no


need to know the reaction that takes place)

61

Heat of Reaction Method


It is not obvious but the previous expression includes already the heat of reaction.
This is obvious if we write the first difference in the equation as:

H in nin H out n out

components

(niin niout ) H io, R

components

niin H iin

niout H iout

components

niin ( H in H Ro )i

components

niout ( H out H Ro )i

components

The inlet T of all reactants has been assumed the same.


The first term on the right hand side can be related to the heat of reaction using .

(n

in
i

niout ) H io, R

components

i
components

o
i,R

(H Ro )

The steady state balance is:

in
i
components

( H in H Ro ) i

out
i
components

( H out H Ro ) i Q W S H Ro

The enthalpies of the streams should be calculated relative to the reference temperature
where HoR is known. The temperature of 298.15 is almost always the reference
temperature. is calculated on the basis of molar flows.

62

Heat of Formation Method


This method requires a reference state relative to the elements so that the heat of formation
of species is part of the energy balance equation. Thus, the equation becomes.

n [( H H
i

small

) H of ,TR ] n H mix

o
R i

o
ni CP dT H f ,TR
T

i
R
i

When phase change is involved an additional term is needed as discussed before (Example).
The energy balance can be written as:

components

niout ( H out H R0 ) H f , R
i

components

niin ( H in H R0 ) H f , R

out
in
ni C p ,i dT H f , R ni C p ,i dT H f , R

T
components T

components
R

R
i
out

in

If the reference state is gas and reaction is in liquid state, H vap should be taken into
account. See below example problem.

63

Engineering Thermodynamics
CHBE 346
Equilibrium Constant
Reaction Equilibrium Constraint
The Standard State Gibbs Energy of Reaction
64

Reaction Equilibria
Equilibrium thermodynamics tells us the direction and extend to which a reaction will go.
The constraint of minimum Gibbs energy dictates the equilibrium results at fixed T and P.
Select the following reaction:

1C1 2C2 3C3 4C4 0

CH 3OH ( g )
CO( g ) 2 H 2( g )

or

The Cs represent the species and reactants have negative s, while products have positive.
The s are called the stoichiometric numbers.
If we consider ideal gases, then the equilibrium constant (P always in bars, prove that later):

K a yi P i

The major steps to solving an equilibrium problem are as follows:


1. Ascertain how many phases are present and the method to be used for equilibrium
calculations. We will start with gases and then introduce the method for liquids and
solids.
2. Use standard state properties to obtain the value of the equilibrium constant or for
Gibbs minimization energy method find the Gibbs energies of the species.
3. Perform a material balance and relate composition to Ka.
4. Solve for the equilibrium compositions.
Steps (1) and (2) are lengthy. Easier to start illustrating examples by using steps (3) and (4).

65

The Standard State Gibbs Energy of Reaction

i Gi is the standard state Gibbs energy of reactions which is denoted by G o


The term,
T
i
and can be calculated from (using the Gibbs energies of formation):

Example:

GTo i Gio

products

i G of ,i

i G of ,i

rea cta cts

CH 4( g ) H 2O( g ) CO( g ) 3H 2( g )

GTo i Gio G of ( CO( g ) ) 3G of ( H 2( g ) ) G of ( CH 4 ( g ) ) G of ( H 2O( g ) )


i

This path of calculation implies the Hesss law:

GTo i G of ,i
i

The Gibbs energies of formation are tabulated at 298.15 K and 1 bar (E.1). This energy is taken
as zero for elements that naturally exist at 298.15 and 1 bar (similar to enthalpies of formation).
The standard state Gibbs energy of reaction is related to the equilibrium constant through:

exp(GTo / RT ) K a
The standard state is at fixed pressure Po. Thus GTo is independent of pressure. The
standard states are also at fixed composition (pure state) and therefore independent of
equilibrium composition. Looking at the above equation we can conclude that Ka is
independent of equilibrium composition and pressure.

66

Engineering Thermodynamics
CHBE 346
Effects of P, Inerts and Feed Ratios
Temperature Dependence of Ka
Estimation of Temperature Effects
67

Effects of Pressure, Inerts and Feed Ratios


The equilibrium constant, Ka, depends only on T (independent of concentration and pressure)
because GoT is at a fixed pressure, Po and state. The reaction coordinate (equilibrium
conversions) is affected by pressure, inerts and feed ratios (Le Chateliers principle).

Pressure Effects
Pressure has important effects when both 1) gas species are involved in reactions and 2) the
stoichiometric numbers of gas species are different for reactants and products.

To see this, we can write the equilibrium constant for ideal gases using partial pressures as:

K a yi P i yi i P

When the stoichiometry is the same then Si=0 and the pressure drops out.
When Si<0 an increase in pressure will drive the reaction to higher conversions.
When Si>0 a decrease in pressure will drive the reaction to higher conversions.
Essentially the pressure squeezes the reaction towards the side with fewer moles.

Inerts and Nonstoichiometric Feed


A component that does not participate in the reaction is called inert. Inert gas components
have important effects on the equilibrium reaction coordinate. When Si>0 addition of an
inert will increase conversion at a fixed total pressure. Similar is the effect of stoichiometry. An
excess of one reactant will increase conversion of the other reactant.

68

Temperature Dependence of Ka
o
Always remember that GT depends on the standard state, which changes with
temperature. To calculate this change the Gibbs-Helmholtz relation is used.

(G / RT )
1 G
G
S H S

2
2
T
RT T P RT
RT RT
RT

RT 2

Which results in the vant Hoff equation:

(GTo / RT ) ( ln K a ) H To

T
T
RT 2
GTo
H To
GRo
H To

dT
ln K a
dT ln K aR
2
2
RT
RT
RTR
RT
TR
TR
T

To calculate this, we take into account the heat capacities of the reactants and products (full
calculation) and substitute into the vant Hoff equation (see example below).

GTo J 1 1 a T b
GRo
c 2
d 3
2
3

ln
(T TR )
(T TR )
(T TR )
RT
R T TR R TR 2 R
6R
12 R
RTR
or

GTo
J
a
bT cT 2 dT 3
ln K a

ln T

I
RT
RT R
2R
6R
12 R

o
Where I may be evaluated from a knowledge of G298 by plugging in T=298.15 on the righthand side as illustrated below (example). J can be found from the corresponding eqn of H To

69

Shortcut Estimation of Temperature Effects


H To is independent of temperature, that is:
Cp=a=b=c=d=0, which means that the sensible heat effects for the reactants and
products are the same, then the shortcut vant Hoff equation is obtained:
If we make the assumption that

Ka
ln
K aR

GRo GTo H Ro

RT
RT
R
R

1 1

T TR

Ka

From this equation, exothermic reactions (HT<0) lead to Ka decreasing as temperature


increases, and endothermic reactions (HT >0) lead to Ka increasing with temperature.
This effects is illustrated in Fig 17.1. Industrial applications of exothermic reactions are
almost run at elevated temperatures even though equilibrium constant decreases at high
temperature. The benefit of faster reaction rates at higher temperature outweighs the
smaller equilibrium constant of exothermic reactions when economics are considered.

70

Engineering Thermodynamics
CHBE 346
Liquid Components in Reactions
Solid Components in Reactions
71

72

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