ChemE 123 Reviewer (LE 2)

IDEAL SOLUTION MODEL

*Pure species behavior defined by , - is unrealistic except for ideal gases

Ideal Solution Model: a thermodynamic model used to apply to systems of gases,

liquids or solids

*In ideal solution model, , - , -

*Ideal gas mixture model is an extension of the ideal solution model

Criteria for an Ideal Solution

 Phases comprised of liquids whose molecules are of similar size and similar
chemical nature
 Mixture of isomers
 Mixture of adjacent members of homologous series
Expression of Different Properties in an Ideal Solution Model

 Volume: , -
 Enthalpy: , -
 Entropy: , -
̂
 Fugacity and Gibbs Energy: , - , - ( )
 Fugacity Coefficient: ̂

Lewis-Randall Rule: for each species in an ideal solution at all conditions of

temperature, pressure, and composition, ̂ ; the fugacity of an ideal
solution is proportional to its mole fraction

*At low to moderate pressures,

*Lewis-Randall rule can be used to determine constants for Henry’s law

~Exercise 1~
EXCESS PROPERTIES
Excess Properties [ME]: the difference between the actual property value of the
solution and the ideal property solution;

*Excess properties are analogous to residual properties for ideal gas mixtures;
both can be related via the equation ( )

*From the ideal gas mixture model and ideal solution model,
∑ ∑ ∑ and ∑

Activity Coefficient [γi]: provides an expression for deviation of real solution from
̂
ideal solution;

̂
Excess Gibbs Energy: . / or

*For an ideal solution, and

*For a real solution, ; for an ideal solution,

; for an ideal gas mixture,

Summary of Mixture Models

Ideal Gas Mixture Ideal Solution Real Solution

̂ gases: ̂ gases: ̂
liquids: liquids:
̂ gases: ̂ gases: ̂ ̂
liquids: ̂ liquids: ̂

̂ ( )
Gamma/Phi Formulation of VLE: ; ( )
 ̂
*At low to moderate pressures,

*If vapor phase is an ideal gas mixture, (modified Raoult’s law:

)

*If liquid phase is an ideal solution, (Raoult’s law: )

*For open systems, . / ∑ and . /

Property Relations Involving Excess Properties

( ⁄ )
 Volume: . /
( ⁄ )
 Enthalpy: . /
( ⁄ )
 Entropy: . /
 ( ⁄ )
*Activity coefficient can be expressed as . /

Property Relations Involving Activity Coefficients

 Volume: . /

 Enthalpy: . /

*Via summability relation, ∑ ∑

*Via Gibbs/Duhem equation at constant T and P, ∑ ( ) ∑ ( )

~Exercise 1~
*All excess properties become zero as either species approaches unity

*Although GE vs. x1 is approximately parabolic in shape, both HE and TSE exhibit

individualistic dependence
*When an excess property ME has a single sign, its minimum or maximum value
often occurs near the equimolar composition; varying signs of the excess property
can signify local minimas and maximas

~Exercise 2~
PROPERTY CHANGES OF MIXING

Property Changes of Mixing: ∑

*Excess properties can be also expressed as

Property Changes of Mixing for an Ideal Solution

  Volume:
 Enthalpy:
 Entropy: ∑
 Gibbs energy: ∑

*Determining and from experimental data using property changes of

mixing can lead to the determination of other properties

~Exercise 1~
~Exercise 2~

~Exercise 3~
*At constant temperature and pressure, the enthalpy change of mixing can be
expressed as ∑

Information from H-x Diagrams

 Enthalpy, concentration of each species, and temperature of solution

 Pure component enthalpies of each species
 Partial molar enthalpies of each species
 Heat of mixing at constant temperature and pressure
 Property of solutions formed by adiabatic mixing of two other solution
(represented by points lying on a straight line connecting the points
representing the initial solutions)
 Energy involved to heat or cool a solution with given composition to
specified temperatures (which may involve phase changes or phase
separation)
ACTIVITY COEFFICIENT MODELS

*For liquids, models are not strong functions of pressure

*In binary systems, variable commonly used is

Rational Function Models: mathematical representations of dimensionless excess

Gibbs energy

*Rational function models have no theoretical and molecular basis for coefficients,
no multicomponent expansion, and no explicit temperature dependence

*Rational function models are accurate models, but are very limited in scope

Types of Rational Function Models

  Redlich/Kister Expansion: . / and

. /; ∑ , ∑ and
; limited to binary systems
 Margules Equation: truncated version of Redlich/Kister Expansion

 van Laar Expansion: . / , . / ,

, and ; and ; derived

⁄
from the van der Waals model; main working equation is

( )
. /

*For Redlich/Kister expansion, at infinite dilution,

∑ ( ) as and ∑ as

*For Redlich/Kister expansion applied to an ideal solution, and

Types of Margules Equation

 1-Parameter Margules Equation: , , and

th
; from the 0 order expansion of Redlich/Kister
equation ( ); appropriate for molecules with little difference
between sizes; main working equation is
 2-Parameter Margules Equation: ( ( ) ),
( ( ) ), , and ;
st
and ; from the 1 order expansion of
Redlich/Kister equation ( ( )); main working equation is
*When using rational function models, experimental data must be
thermodynamically consistent with theoretical values calculated

Thermodynamic Consistency: ;
applies to experimental P*-x-y* data and rational function model

*High degree of consistency if average | | across dataset is less than 0.03,

while an average less than 0.10 is deemed acceptable

Barker’s Method: alternative method for determining the activity coefficient of

species using regression that provides better thermodynamic consistency; uses
P*-x* data only to minimize carry-over of systemic errors

Method for Barker’s Method

 Establish model for activity coefficient (typically used is two-parameter

Margules equation)
 Substitute the activity coefficient expressions to
 Determine values of coefficients (for two-parameter Margules equation,
and ) that will minimize the function ∑ ( )
∑ ( ) , where k is a datapoint in the dataset and
is the experimental value of pressure of datapoint k

~Exercise 1~
*If Txy data are given, assuming ideal gas, modified Raoult’s law can still be used
to determine activity coefficients, but would require determination of component
saturation pressures for each temperature at the data set first

*If Txy data are given and Barker’s method is applied, the objective function
becomes ∑ ( ) subject to the constraint , -
, -, and the calculation will be iterative with an initial guess for
temperature

Local Composition Models: a set of activity coefficient models that is applicable

to multicomponent systems and has explicit temperature dependence

*Local composition models are less accurate than rational function models

Types of Local Composition Models

Multicomponent Binary
 ⁄ Expression (Main Working Equation)
Wilson
(
∑ (∑ )
)
(
)
Non-Random Two- ∑
Liquid (NRTL) ∑
∑

Universal
Quasichemical
(UNIQUAC),
∑ ( ) ∑ ( )
UNIQUAC
Functional-Group
Activity Coefficients
∑ (∑ )
(UNIFAC)

∑
Activity Coefficients
Wilson
(∑ ) ( )
(
∑
∑ )

( )
(

)
Non-Random Two-
Liquid (NRTL) ∑
( ( )
∑

∑ ( )
∑ ( )
∑
)
∑ ( ( )
( )
)
( )
( )
( )

UNIQUAC
( )

( ∑ )

∑
∑

∑
. /

UNIQUAC
Functional-Group
Activity Coefficients
( )
(UNIFAC)

( ∑ )

∑
()
∑

()
∑

∑
∑
∑

. /

Activity Coefficients at Infinite Dilution (Applicable for Binary Systems Only)

Wilson

Non-Random Two- ( )
Liquid (NRTL) ( )

LIQUID-LIQUID EQUILIBRIUM

*Phase equilibrium is limited to vapor-liquid equilibrium due to being the most

studied concept with a relative ease of model

Examples of Phase Equilibria

  Vapor-Liquid Equilibrium: most studied with relatively easy-to-understand
model
 Liquid-Liquid Equilibrium: for liquid-liquid extraction
 Solid-Liquid Equilibrium: for crystallization, metallurgy
 Vapor-Liquid-Liquid Equilibrium: simplest 3-phase equilibrium

*For a closed system containing an arbitrary number of species and comprised of

an arbitrary number of phases in which the temperature and pressure are spatially
uniform (though not necessarily constant in time) and is initially in a non-
equilibrium state with respect to mass transfer between phases and chemical
reaction, changes that occur in the system are necessarily irreversible and they
take the system ever closer to an equilibrium state

*A system placed in surroundings such that the system and the surroundings are
always in thermal and mechanical equilibrium will have heat exchange and
expansion work that is accomplished reversibly, and the entropy change of the
surroundings is

*From the first and second laws of thermodynamics,

and , respectively

Phase Stability Criterion: the equilibrium state of a closed system is that state for
which the total Gibbs energy is a minimum with respect to all possible changes at
the given temperature and pressure; ( )

*Determination of stable phase is an optimization problem; to do this, express

in terms of moles of each component and find a set of mole numbers that
minimizes , with constraints of mass and element conservation (to observe
equilibrium state)

*For irreversible processes, ∫ ( )

*For mixing systems, ∑ ∑

*For a stable single phase at constant temperature and pressure,
( ⁄ )

( ⁄ )
*In binary systems, ( ),
( ⁄ ) ( ⁄ ) ( ⁄ )
, and

Binodal Curve: a composition-temperature diagram wherein a two-liquid phase

region is enclosed inside a closed curve with a minima and/or maxima; can act as
a solubility diagram

Upper Critical Solution Temperature//Upper Consulate Temperature: a

temperature at the binodal curve wherein when temperature is further increased,
all components are miscible with one another
Lower Critical Solution Temperature//Lower Consulate Temperature: a
temperature at the binodal curve wherein when temperature is further
decreased, all components are miscible with one another

( ⁄ )
*For a binary system, , ,
( ⁄ )
, and

Phase Stability Criteria of Species of a Binary System as Expressions of Different

Constants

 Activity Coefficient:
̂
 Fugacity:

 Chemical Potential:

*Violation of the phase stability criteria would indicate instability in the single
phase, and would lead to phase-splitting
~Exercise 1~

~Exercise 2~
~Exercise 3~
*For a system with two phases in equilibrium, , ̂ ̂ , and
; both activity coefficients are functions in the two phases are similar but
evaluated at different molar ratio of species i

Ternary Liquid-Liquid Equilibrium Diagram: a three-sided diagram used to

determine the mass fractions of the components of a system based on its position
inside the diagram

Modified Rachford-Rice Equation: an equation used to determine the

components of the two phases of a system in equilibrium; variables set are
usually the temperature and the overall molar ratio of two of the three
( )
components; * + ∑
( )
; ( )
and