Calculating the Partial Molar Enthalpy

The enthalpy of a binary solution changes with

composition in the manner described by:

Given the expression shown for the enthalpy of a

binary solution as a function of mole fractions x1
and x2,
1. What would be the expression for the partial
molar property of specie 1?
2. What would be the expression for the partial
molar property of specie 2?
Binary mixture Given: H = 12x1x2 Required: H1 and H2
Solution: H = 12x x
1 2
, ,

= +
, ,
n2
1
constant
=
1 0
( )
= =

=
https://www.youtube.com/watch?v=a2XimGRfu3Y
Gibbs-Duhem Equation

=
, ,

Gibbs-Duhem Equation:

, ,
 Implication of the Gibbs-Duhem Equation

At constant T & P, Gibbs – Duhem Equation becomes:

Partial molar properties may not all independently vary.

3 Essential Equations related to Partial Molar Properties

Gibbs-Duhem Equation:
Definition:
, ,

Summability Relations:
 Partial Molar Properties in Binary Mixtures
𝟏 𝟐

Gibbs-Duhem @ const. T&P:

1. Try to work through the above derivation such that
you are able to derive one of the expressions in
the highlighted equations on the left side.
2. Is the relationship between the partial molar
property of species 1 and that of species 2 linear
or or could it be nonlinear?
3. On an M-x diagram, arbitrarily draw the equations
on the left side that you have derived, and show
where the partial molar properties of species 1 and
species 2 lie.
Graphical Illustration of Partial Molar Properties

Const. T&P

or 2

𝑑𝑀
𝑥
𝑑𝑥

𝑑𝑀
𝑑𝑥

𝒙1=(1- 𝒙2)
Partial Properties at the Limits of Dilution

Near-pure solution limit

→ →

Infinite dilution limit

→
Alternative Expression for the Gibbs-Duhem Equation:
Binary Mixture

Gibbs-Duhems at const. T&P:

Derivative Form of Gibbs-Duhems (const. T&P)

or

(provided is finite)
→ →

→
(provided is finite)
→
Relations among Partial Properties

,
,

, ,

Implications?
, ,
 Relations among Partial Properties

, ,
EXPERIMENT measure V at constant
composition, then repeat using
another set of x1, x2

T1, P1 T1,P2 T1, P3

V(x1, x2) V(x1, x2) V(x1, x2)

T2, P1 T2,P2 T2, P3

V(x1, x2) V(x1, x2) V(x1, x2)

T3, P1 T3,P2 T3, P3

V(x1, x2) V(x1, x2) V(x1, x2)
Supplementary Resources

 Learn ChemE Partial Molar Quantity

https://ggle.io/3OTM

 Learn ChemE Partial Molar Properties: Binary Solutions

https://ggle.io/3OTO

 Learn ChemE Partial Molar Enthalpy

https://ggle.io/3OTP
 Ideal Gas Mixture Model

Interviewer: In this job, you may be assigned to

process optimization and control in the various
units of the plant……
If the feed to a distillation unit has changed
slightly and usual process conditions will not be
able to meet the desired product specifications.

What column parameter will you first

Job interview for your
investigate to meet the product specs.?
first job
How will you control that parameter?
 Review: Ideal Gas

Molecules DO NOT occupy volume Molecules DO NOT interact with

one another

Source:
https://chem.libretexts.org/Bookshelves/General_Chemistry/Book%3A_Chemistry_(OpenSTAX)/09%
3A_Gases/9.6%3A_Non-Ideal_Gas_Behavior
 Partial Molar Volume in an Ideal Gas Mixture

Molar volume of any gas:

Partial Molar Volume of species in a mixture in an ideal gas state:

, ,
constant

, ,
Illustrating the Partial Molar Volume in
an Ideal Gas Mixture

= 1 𝑢𝑛𝑖𝑡 𝑣𝑜𝑙𝑢𝑚𝑒
same T & P

=
 Partial Pressure in an Ideal Gas Mixture

Partial pressure of species i

T, P, n Green gas (1)
in an ideal gas mixture: Red gas (2)

T1, P1, n1 T2, P2, n2

T, V are kept constant

 Gibb’s Theorem

For a species i in an ideal gas-state mixture,

pure species ideal gas molar

partial molar property at the same T, but at
property of species i = a pressure equal to its partial
at (T,P) pressure in the mixture Pi
Note: The above relation is true for any partial molar
property M except for partial molar volume.
Illustrating the Partial Molar Property

Partial molar property Pure species molar

of species i in an ideal property at the same T, but
gas mixture at (T,P) at partial pressure P1

Remove all
red molecules

(𝑇, 𝑃) (𝑇, 𝑃 )

Note: The above relation is true for any partial molar

property M except for partial molar volume.
 Partial Molar Enthalpy

Recall: Enthalpy in the ideal-gas state is INDEPENDENT of pressure

or

(const. T&P)
 Partial Molar Entropy

(pure ideal gas i at const. T)

For component i in an ideal gas mixture at the same

temperature and pressure (T,P) as the mixture,

Partial Pure Ideal gas entropy change

molar species due to P-change from Pi
entropy molar
to P at constant T
entropy
Partial Molar Gibbs Energy

Ideal Gas:
For component i in an ideal gas mixture (IGM) at the
same temperature and pressure (T,P) as the mixture,

Chemical Pure
Partial Tx (ideal gas entropy
potential molar species
of species i molar change due to P-change
entropy
in IGM entropy from Pi to P at constant T
 Property Changes of Mixing Ideal Gas Mixtures

Summability Relations
Summability Relations for Heat Capacity
and Volume of an Ideal Gas Mixture

1
Property Changes of Mixing for an
Ideal Gas Mixture
Alternative Expression for the Chemical Potential

(const. T)

Species-dependent
integration constant



Alternative Expression for Gibbs Energy
of an Ideal Gas Mixture

Apply summability relation:


 Designing an experiment to evaluate G

The Thermodynamic Square:

Fundamental Property Relations for Open Systems
with Variable Amounts and Composition
NATURAL
The Thermodynamic Square: VARIABLES

S&V

T&V

S&P

T&P
 Summary of Relations for Ideal Gas Mixtures
Partial molar properties for ideal gas mixtures
 (except for V)
 (const. T&P)
Summability relations for ideal gas mixtures



Property Changes
of Mixing for Ideal Alternative Expressions
Gas Mixtures for Ideal Gas Mixtures

𝐺 = 𝑦 𝐺̅ = 𝑦  𝑇 + 𝑅𝑇 𝑦 ln(𝑦 𝑃)

𝜇 ≡ 𝐺̅ =  𝑇 + 𝑅𝑇 𝑙𝑛(𝑦 𝑃)
Remarkablysimple
Remarkably simpleexpression
expression
𝐺 = 𝑦 𝐺̅ = 𝑦  𝑇 + 𝑅𝑇 𝑦 ln(𝑦 𝑃)
forthe
for theGibbs
GibbsEnergy:
Energy:
 Activity: Design an experiment to generate an S-x
diagram of a 2-component system

𝜇 ≡ 𝐺̅ =  𝑇 + 𝑅𝑇 𝑙𝑛(𝑦 𝑃)
Remarkably simple expression
𝐺 = 𝑦 𝐺̅ = 𝑦  𝑇 + 𝑅𝑇 𝑦 ln(𝑦 𝑃)
for the Gibbs Energy:

What experiment to do in order to plot S-

x diagram? Plot will be at constant T & P.
Fugacity & Fugacity Coefficient of
Species in Mixtures

Fugacity

 a measure of the tendency of fluid to expand or escape

 a measure of the relative stability of different phases of a

substance under the same conditions.
 Fugacity of Pure Species
 The definition of the fugacity of a species in solution is parallel to the definition of the
pure species fugacity. For a species i in a mixture of real gases or in a solution of liquids,

Where fi is the fugacity of species i
in solution, replacing yiP.


(pure non-ideal gas i)

(pure ideal gas i)
Alternate General Criterion for Phase Equilibrium


 This does not make it a partial molar property, therefore
identified by circumflex rather than by an overbar ( )

fugacity of a specie in solution

(ideal gas mixture)
Clarifying Symbols

fugacity of a specie i in solution

fugacity of a pure species i

fugacity of a specie i in multi-component phases  and , respectively

fugacity of a species i in pure component phases  and , respectively
Alternative General Criterion for Phase Equilibrium

(i = 1,2,….., N)

(i = 1,2,….., N)

For VLE: (i = 1,2,….., N)

Partial Residual Properties & Fugacity
Coefficient of Species in Solution
 Fundamental Residual Property Relation

Fundamental Property Relation

Remarkably simple expression
for the Gibbs Energy:

Differentiate d(nG/RT):
𝜇 ≡ 𝐺̅ =  𝑇 + 𝑅𝑇 𝑙𝑛(𝑦 𝑃)

𝐺 = 𝑦 𝐺̅ = 𝑦  𝑇 + 𝑅𝑇 𝑦 ln(𝑦 𝑃)
Fundamental Residual Property Relation

𝐺 𝐺
𝐺 𝜕(𝑅𝑇) 𝜕(𝑅𝑇)
𝑉 𝜕(𝑅𝑇) 𝐻 𝑙𝑛ϕ =
= = −𝑇 𝜕𝑛
𝑅𝑇 𝜕𝑃 , 𝑅𝑇 𝜕𝑇 , , ,
Fugacity Coefficients for Mixtures from the
Equations of State

Where:

, ,
 Fugacity Coefficients for Mixtures from
Virial Equations of State

Mixing Rules
+ Binary mixture

Binary mixtures:

, , ,
 Fugacity Coefficients for Mixtures from
Virial Equations of State for Multi-component Gas Mixtures
Generalized Correlations for the Fugacity Coefficient

Combining rules:
/ /
 Temperature-Dependence of Fugacity in Mixtures

Generating the Temperature-Composition (Txy) Diagram: Benzene-Toluene Binary System

Raoult’s Law:

all vapor

Benzene Tie Line yb=0.635

𝑦 = 1.0

xb=Zb=0.4
T,Zb 𝑥 = 1.0
Heating
Line
all liquid

Toluene