Advance Chemical

Engineering Thermodynamics
Instructor: Dr Gunjan Agrahari
Days: Monday, Wednesday, Thursday
Time: 2:00 pm – 3:00 pm
Fugacities
Fugacity calculations

Two main equations are:

Pressure Explicit?
Volume Explicit?
Lewis Rule

• Successfully predicts fugacities of gas mixtures at low

pressures
• For dilute solutions
• At constant temperature and pressure, the molar volume of
mixture is linearly related to its mole fraction
fugacity of ‘i’ in gas mixture

fugacity of pure gaseous ‘i’

Lewis Rule

This rule assumes that

at constant temperature and pressure fugacity coeff is

independent of presence of other components in the mixture

Pure state fugacity, and fugacity coeff are evaluated at the same T & P as that of mixture
Lewis Rule

The above equation gives, finally two simple relations as:

Pure state fugacity, and fugacity coeff are evaluated at the same T & P as that of mixture
Lewis Rule
• Lewis rule encounters practical difficulties—
• At mixture temperature, and for vapor liquid equilibrium,
it often happens that the total pressure, P is higher than
the saturation pressure of i.
• This means at this total P the pure i will not be in gaseous
state
• This requires assumptions of hypothetical conditions
which causes errors in calculations
Thus it has only approximate validity
The VIRIAL EQUATIONS

• Fugacities can be calculated when we have an appropriate

Equation of State
• This means EOS for the gaseous mixture!
• There are several EOS, most of them empirical and rigorous
based on various assumptions
The VIRIAL EQUATIONS

• Can only approximate the physical state of gas!

• Mixing rules are then difficult to apply because constants
used in EOS may not be valid when gas is in mixture form
• This can introduce further assumptions and lead to
significant errors in calculations
The VIRIAL EQUATIONS

• The EOS should be such that the parameters used have

physical significance
• That is, the parameters can be directly related to
intermolecular forces
• Virial EOS are based on compressibility factors
The VIRIAL EQUATIONS
The VIRIAL EQUATIONS

• The above plot shows that as molar density of mixture

increases degree of non-ideality significantly increases
• This means as density increases large variations in
intermolecular forces should occur
• Virial EOS for nonelectrolyte gas represents the correct
theoretical basis – of intermolecular forces
The VIRIAL EQUATIONS

• Virial EOS is given in reciprocal molar volume in a series form

The VIRIAL EQUATIONS

• The coefficients B, C, D … are independent of pressure or

densities
• They are functions of temperature for pure species
• These are directly related to intermolecular forces
The VIRIAL EQUATIONS

• The coefficients B, C, D … depend on compositions ina gas

mixture
• Alternate form:
The VIRIAL EQUATIONS
The VIRIAL EQUATIONS

• The volume form is more convenient to use since truncation

after 3 terms, reproducibilities of experimental data are
applicable over wider range of pressure or densities
The VIRIAL EQUATIONS

• Terms B and C can be estimated from low pressure data as:

The VIRIAL EQUATIONS

• Rewriting virial equation and obtaining B can be done as

shown in the plot
The VIRIAL EQUATIONS
The VIRIAL EQUATIONS

• The isothermal data are plotted, intercept gives the B

• C is found from limiting slope
• Constant temperature, constant composition plots can give
the values of virial coefficients for mixtures
• Virial equations can also give values of critical densities!
The VIRIAL EQUATIONS
The VIRIAL EQUATIONS

• Virial equations are directly related to molecular behavior

• At large intermolecular (mean) distances, real gases tend to
behave ideally
• At low densities, forces are weak
• At high densities forces are strong
The VIRIAL EQUATIONS

• B signifies two molecule interaction

• C takes into account the interactions (forces) between 3
molecules
• … and so on
The VIRIAL EQUATIONS for mixtures

• B C D determinations for mixtures

The VIRIAL EQUATIONS for mixtures

B accounts for two molecule interactions

For binary mixtures:

i-i, j-j, i-j pairs can be regarded for interactions

For each such pair, there is a corresponding B--
The VIRIAL EQUATIONS for mixtures

This B will depend on the corresponding intermolecular

potential
Thus Bii is the second virial coefficient that depends on Гii

Similarly Bjj and Bij

The VIRIAL EQUATIONS for mixtures

For spherically symmetric molecules we have:

B is function of temperature only, independent of pressure/density

The VIRIAL EQUATIONS for mixtures

Further B for mixture can be determined in terms of mole

fractions as:

B is function of temperature only, independent of pressure/density

The VIRIAL EQUATIONS for mixtures

which can be generalized for m-components as:

The VIRIAL EQUATIONS for mixtures

Similarly C is obtained as:

The VIRIAL EQUATIONS: phase equilibria

Fugacities are obtained using B C:

mixture molar volume

MOST IMPORTANT EQUATION OF PHASE EQUILIBRIA

The VIRIAL EQUATIONS: phase equilibria

For binary mixture the above equation becomes

The VIRIAL EQUATIONS: phase equilibria

However if we use only B term then simple expressions are

obtained as:
The VIRIAL EQUATIONS: phase equilibria

Further for volume explicit equation,

Chemical Interpretation for Deviations from
Ideality
At low pressures gases show ideal behavior

As pressure is increased, molecules may form dimer (2-molecule

interaction) or trimer (3-molecule interaction)

Thus virial coefficients B, or C are useful

Chemical Interpretation for Deviations from
Ideality

Dimerization equilibrium constants can be related to B

Trimerization equilibrium constant.. to C

Chemical Interpretation for Deviations from
Ideality

According to chemical interpretation – Forces between

molecules are of chemical nature, i.e. new chemical species are
formed
Chemical Interpretation for Deviations from
Ideality

Thus non-ideal behavior is explained in terms of formation of

these new species

Polymerization reactions that occur result in negative deviations

from ideal gas behavior

Thus Z < 1
Chemical Interpretation for Deviations from
Ideality

At high temperatures, dissociation reactions might occur

Thus Z > 1; positive deviation from ideality, due to dissociation

Chemical Interpretation: Dimerization of
Carboxylic Acid

Two molecules of acetic acid combine as shown:

K
Chemical Interpretation: Dimerization of
Carboxylic Acid
Organic acids, alcohol etc tend to form hydrogen bonding

Considering the mixture of monomers and dimers still as

ideal, the equilibrium constant of the above reaction may
be written in terms of their partial pressures
Chemical Interpretation: Dimerization of
Carboxylic Acid
P: Total pressure
yA: mole fraction of monomer
yA2: mole fraction of dimer
P0: standard state pressure (assigned 1 bar value)
Chemical Interpretation: Dimerization of
Carboxylic Acid
Calculation of equilibrium constant:

Measure volume of 1 mole of acetic acid at total pressure

P and T (1 mole: formula weight of acetic acid monomer)

Let nA be monomer moles

Let nA2 be dimer moles
Chemical Interpretation: Dimerization of
Carboxylic Acid
Calculation of equilibrium constant:

Let α be the fraction of monomer molecules that

dimerizes

Let nT be the total number of moles

Chemical Interpretation: Dimerization of
Carboxylic Acid
Calculation of equilibrium constant: fraction of monomer
that dimerizes

Then: monomer moles dimer moles

True moles
Chemical Interpretation: Dimerization of
Carboxylic Acid
nA+2nA2=1
Calculation of equilibrium constant:
2A A2
1
A A2
2
From material balance: initial total moles = 1
after time t, nA moles remaining,
This means 1-nA moles converted
Since 1 mole of A gives ½ mole of A2, therefore 1 - nA mole gives (1/2)(1-nA) mole of A2
Thus (1/2)(1-nA) = nA2 →1-nA=2nA2 or nA+2nA2=1
Chemical Interpretation: Dimerization of
Carboxylic Acid
Calculation of equilibrium constant:

PV  nRT
 
 PV  nT RT  1   RT
 2
2 PV
  2 
RT
Chemical Interpretation: Dimerization of
Carboxylic Acid
Calculation of equilibrium constant:
Further

nA nA2
yA  ; y A2 
nT nT
Chemical Interpretation: Dimerization of
Carboxylic Acid
As P approaches zero alpha also becomes zero, because
dimerization must become lower and lower as pressure
falls
  0
 1   P
K  2
2 1    P
2
Chemical Interpretation: Dimerization of
Carboxylic Acid

Dimerization
constants for
acetic acid and
propionic acid is
measured
experimentally
Chemical Interpretation: Dimerization of
Carboxylic Acid

At T = 40ᵒC and
P=0.016 bar, α =
0.8 for acetic acid,
and0.84 for
propionic acid
Chemical Interpretation: Dimerization of
Carboxylic Acid
Calculation of equilibrium constant:
Further

  0
 1   P
K  2
2 1    P
2
Chemical Interpretation: Dimerization of
Carboxylic Acid
Cross dimerization of acetic and propionic acid

Equilibrium constant for solvation or cross-dimerization

of these acids can be estimated from that of individual
acids
Chemical Interpretation: Dimerization of
Carboxylic Acid
Cross dimerization of acetic and propionic acid

Assumption: Enthalpy of hydrogen bond formation is

same in mixed dimer as for pure dimer formation
Chemical Interpretation: Dimerization of
Carboxylic Acid
Cross dimerization of acetic and propionic acid

Assumption: Enthalpy of hydrogen bond formation is

same in mixed dimer as for pure dimer formation

i.e. we assume that enthalpy change for the following

reaction is zero
(½)A2+(½)B2→AB
Chemical Interpretation: Dimerization of
Carboxylic Acid
Cross dimerization of acetic and propionic acid
Standard Gibb’s energy of formations are given below
Chemical Interpretation: Dimerization of
Carboxylic Acid
Cross dimerization of acetic and propionic acid
Standard Gibb’s energy of formations are given below

∆g0 is the standard molar Gibb’s energy change

and K AB  2 K A2 K B2
Chemical Interpretation: Dimerization of
Carboxylic Acid
Cross dimerization of acetic and propionic acid

Experimental data have been found to be in good

agreement with the calculated values for the mixture of
acetic acid/propionic acid

K AB  2 K A2 K B2
Chemical Interpretation: Dimerization of
Carboxylic Acid
Cross dimerization of acetic and propionic acid

However the two mixing acids are similar in structure so

solvation data of mixture (calculated from pure species,
and experimentally measured) are in agreement.

K AB  2 K A2 K B2
Theory of Corresponding States

• The equation of state depends only on configurational

integral:

ZN is known as configurational integral