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Lecture 6 2022

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38 views37 pages

Lecture 6 2022

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nothingbutrebel
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KMM3531 Chemical Engineering Thermodynamics II

Ideal Solution Lewis-Randall Method


Excess Properties

Prof. Dr. Hasan SADIKOĞLU


Yıldız Technical University
Department of Chemical Engineering
THE IDEAL-SOLUTION MODEL
The chemical potential as given by the ideal-gas-state mixture model

A natural extension of above equation therefore replaces Giig (T, P) with Gi(T, P), the
Gibbs energy of pure i in its real physical state of gas, liquid, or solid. Thus, we define an
ideal solution as one for which:

An ideal solution of gases in the


ideal-gas state, for which xi in this
where superscript id denotes an Equation is replaced by yi.
ideal-solution property. Mole fraction is
here represented by xi to reflect the fact
that this approach is most often applied
to liquids.
If we take derivative wrt P at constant temperature (T) and
composition (x)

Similarly,
The summability relation can be applied to the special case of an ideal solution
LEWIS –RANDALL RULE
❑ The Lewis-Randall rule is simply equation and fugacity of components in gas
mixtures are evaluated .

❑ The Fugacity of solution can be determined by taking in to account deviation of actual


solution from ideal behavior.

❑ As an ideal solution we can consider a gas mixture formed without any volume
change on mixing the components. The volume of mixture is linear function of the
mole number at a fixed temperature and pressure.

The composition dependence of the fugacity of a species in an ideal solution is


particularly simple. Recall following Equations.
Subtraction of the second equation from the first equation yields the general equation

For the special case of an ideal solution,

By Comparing this
Equation with
• The above equation is commonly known as Lewis/Randall rule or Lewis fugacity
rule.

• It states that fugacity of component in an ideal solution is directly proportional to the


mole fraction of the component in the solution.

Division of both sides Substitution Alternative Form Obtained


of above Equation by Pxi

Thus the fugacity coefficient of species i in an ideal solution is equal to the fugacity
coefficient of pure species i in the same physical state as the solution and at the same T
and P.
EXCESS PROPERTIES
❑ The difference between the property of a real solution and an ideal solution is
important in chemical thermodynamics and phase equilibria.

❑ If M represents the molar (or unit-mass) value of any extensive


thermodynamic property (e.g., V, U, H, S, G, etc.), then an excess property 𝑀𝐸
is defined as the difference between the actual property value of a solution
and the value it would have as an ideal solution at the same temperature,
pressure, and composition.
The fundamental excess-property relation
Table 10.1: Summary of Equations for the Gibbs Energy and Related Properties
Example:
(a)1) If is a constant, independent of T, find expression for G E, SE, and HE as
functions of T.

(b) From the equations developed in part (1), fine values for GE , SE, and HE for an
equimolar solution of benzene(1) / n-hexane(2) at 323.15K, given the following
excess-property values for equimolar solution at 298.15K:
=-2.86 J/mol-K, HE = 897.9 J/mol, and GE = 384.5 J/mol
From Table 11.1:

integration
From Table 11.1:

integration
integration

We have values of a, b, c and


hence the excess-properties at
323.15K
The excess Gibbs energy and the activity coefficient

• The excess Gibbs energy is of particular interest:

The activity coefficient of species i in solution. A


factor introduced into Raoult’s law to account for
liquid-phase non-idealities. For ideal solution,

c.f
Experimental accessible values: activity coefficients
from VLE data, VE and HE values come from mixing
experiments.

Important application in phase-equilibrium


thermodynamics.
The Nature of Excess Properties

GE: Gibbs energy comes from experiment through reduction of vapor/liquid


equilibrium data
HE: from mixing experiment
SE = (HE - GE) / T

1. All excess properties become zero as either species approaches purity.

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


exhibit individualistic composition dependencies.

3. When an excess property ME has a single sign (as does GE in all six cases), the
extreme value of ME (maximum or minimum) often occurs near the equimolar
composition.
Excess properties are often strong
functions of temperature, but at
normal temperatures they are not
strongly influenced by pressure.

Their composition dependence is


illustrated in Fig. 10.3 for six
binary liquid mixtures at 50°C and
approximately atmospheric
pressure.

To present SE with the same units


and on the same scale as HE and
GE, the product TSE is shown
rather than SE itself. Although the
systems exhibit a diversity of
behavior, they have common
features
The Excess Gibbs Energy and the Activity Coefficient
Activity coefficient The higher γ , the higher the escaping
tendency of a component from the liquid
phase. Thus;
γ>1 means repulsion of unlike molecules in
This equation gives the a mixture. Like interactions are stronger
liquid phase non-idealities than the unlike ones.
γ<1 means component 1 prefers to remain in
the liquid phase since unlike interactions are
stronger than the like ones

Partial
is partial property of GE/RT properties

Summability of a
Gibbs Duhem at
mixture property constant T and P

Gibbs Duhem
GE/RT is expressed as a function of compositions. Then an expression for activity can be developed
using GE/RT and activity relation.

Fit an expression for activities using Gibbs Duhem

Partial differentiation of GE/RT leads to various excess quantities


Some Expressions of GE/RT

1-Two suffix Margules Equation:

If then

2-Three suffix Margules Equation:

3-Van Laar equation


Models for the Excess Gibbs Energy and Activity
Coefficients for Binary Systems

20
Example: The excess Gibbs energy of a binary liquid mixture at T and P is given by:

(a) Find expressions for Inγl and In γ2 at T and P.


(b) Show that when these expressions are combined in accord with the
given equation for GE/ RT is recovered.
(c) Show that these expressions satisfy the Gibbs-Duhem equation.

(d) Show that

(e) Plot GE/RT, Inγl and In γ2 as calculated by the given equation for GE/RT and
by the equations developed in (a) vs. xl. Label points and show their
values.
(a) Solution

Applying
(b) Applying
(c) Applying

Divide by dx1

These two equations sum to zero in agreement with the Gibbs/Duhem equation
(d)
(e)

g=@(x) -1.8*x+x.^2+0.8*x.^3
g1=@(x) -1.8+2*x+1.4*x.^2-1.6*x.^3
g2=@(x) -x.^2-1.6*x.^3
Property Changes of Mixing

✔Volume change of mixing and enthalpy change of mixing


✔ΔV can be positive or negative regarding to interaction of molecules
✔ΔH can be positive or negative regarding to endothermic or exothermic mixing
Heat of Mixing

ΔH is the heat of mixing while H is the final enthalpy per unit


mole of the solution after mixing

Heats of mixing are similar in many respects to heats of reaction. When a chemical
reaction occurs, the energy of the products is different from the energy of the reactants at
the same T and P because of the chemical rearrangement of the constituent atoms.

When solids or gases are dissolved in liquids, the heat effect is called a heat of solution,
and is based on the dissolution of 1 mol of solute. If species 1 is the solute, then x1 is the
moles of solute per mole of solution.

Concentration-enthalpy diagrams can be used to determine the heat effects. Enthalpy


diagrams are given for a mole or a unit mass of solution.
Construction of a
Hx diagram

Figure 12.17 Hx diagram for H2S04/H20


Hx diagram of NaOH/H2O
Example

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