Simple Mixtures Chapter Outline

Introduction to Simple Mixtures

Thermodynamic description of mixtures
6.1
Partial molar quantities
6.2
Thermodynamics of mixing
6.3
The chemical potential of liquids
The properties of solutions
6.4
Ideal solutions, simple mixtures, and
non-ideal solutions
6.5
Colligative properties
6.6
Activities of regular solutions
6.9
The activities of ions in solution

REVIEW OF BASIC CONCEPTS

Mixtures
Compound

Substance
Element

All matter

Homogeneous

Mixture
Heterogeneous
A mixture of substances can vary in composition and properties from one sample
to another.

What are Solutions?

Solutions are homogeneous
mixtures
of
substances
composed of at least one
solute and one solvent.

Solutions can
liquids, or solids.

be

gases,

GENERAL TYPES
Ideal and non-ideal solutions
Electrolytes and non-electrolytes

How is a solution formed?

Like dissolves like.

1. Breaking up the solute into

individual
components
(expanding the solute).
2. Overcoming intermolecular
forces in the solvent to make
room
for
the
solute
(expanding the solvent).
3. Allowing the solute and
solvent to interact to form the
solution.
Steps that lead to the formation of a liquid solution

Enthalpy (Heat) of Solution

The enthalpy change associated with the formation of a
solution

H soln

H1

H2

H3

Energy is absorbed!
endothermic

Energy is released!
exothermic

???

Enthalpy (Heat) of Solution

Allow solvent
and solute
molecules to mix
H3

Enthalpy. H

Separate solute
molecules H2

(Endothermic)
Separate solvent
molecules H1

Hsoln > 0

Hsoln = 0
Pure
components

Hsoln < 0
(Exothermic)

(a)
(b)

Process is exothermic if Step 3 releases more energy than that required in Step 1 & 2.
Process is endothermic if Steps 1 & 2 require more energy than what is released in Step 3.

Intermolecular forces in a solution

2

(1) Solvent molecules, A-A

(2)Solute molecules, B-B

(3)Solvent and solute
molecules, A-B

3
1

IMFs in Mixtures
Four possibilities for the relative strengths of IMFs:
1.IMFs are of the same type and of the same strength, solute and solvent
mix randomly (Hsoln = 0 ): IDEAL SOLUTIONS.
2.IMFs between unlike molecules exceed IMFs between like molecules, a
solution forms, Hsoln < 0 (exothermic): NON-IDEAL SOLUTIONS
3.IMFs between solute and solvent molecules are somewhat weaker than
between molecules of the same kind, complete mixing may still occur,
Hsoln > 0 (endothermic): NON-IDEAL SOLUTIONS
4.IMFs between unlike molecules are much weaker than those between like
molecules, the components remain segregated in a heterogeneous mixture:
NO SOLUTION FORMS.

Solubility of a Nonpolar Solute and a

Polar Solvent

H2 will be large & positive

because it takes considerable
energy to overcome the
hydrogen
bonding
forces
among the water molecules to
expand.

Large
amounts
of
energy would have to
be expended in order to
form
an
oil-water
solution!

Solubility of an Ionic Solute and a

Polar Solvent
NaCl s
H 2O l

Na

Cl

Na g
g

Na aq

Cl
Cl

H1
aq

786kJ / mol

H hyd

H2

H3

= 783kJ / mol

H soln

Why is NaCl soluble in

water???

3kJ / mol

Solubility of an Ionic Solute and a

Polar Solvent
Increase in
degree of
disorder!

(a)

(b)

(a)Orange & yellow spheres separated by a

partition in a closed container. (b) The
spheres after the partition is removed and the
container has been shaken for some time.

Possible Cases for Solution Formation

Solvent/solute
combination

H1

H2

H3

Hsoln

Outcome

Polar solvent,
polar solute

Large

Large

Large,
negative

Small

Solution forms

Polar solvent,
non polar solute

Small

Large

Small

Large,
positive

No solution forms

Nonpolar
solvent,
nonpolar solute

Small

Small

Small

Small

Solution forms

Nonpolar
solvent, polar
solute

Large

Small

Small

Large,
positive

No solution forms

Processes that require large amounts of energy tend not to occur!!!

Factors Affecting Solubility

Try this.
1. Predict whether or not a
solution will form in
each of the following
mixtures:
a) Ethyl alcohol and water
b) Octanol and water
c) Hexane and octane
2. Benzoic acid is much more
soluble in aqueous NaOH
solution than it is in pure
water. Can you suggest a
reason for this?

Partial Molar Quantities

The Thermodynamics of Mixing
The Chemical Potentials of Liquids

Partial Molar Properties

The thermodynamic contribution of a substance (per
mole) to an overall property of a mixture

Partial Molar Quantities

Partial pressure
Partial molar volume
Partial molar Gibbs energy (Chemical
potential )
NOTE: Partial molar properties are intensive properties!

The Partial Molar Volume

DEFINITION
The contribution (per mole) of substance, J, to the overall volume, VJ, of
a solution at constant temperature, pressure, and amount of solution
components (Silbey & Alberty, 2001)

1000 mL H2O

1 mol H2O

1018 mL H2O

1000 mL EtOH

1 mol H2O

1014 mL EtOH-H2O soln

The Partial Molar Volume

V(a)

VJ

V
nJ

V(b)

Volume, V

The partial molar volume can also

be regarded as the change in
volume per mole of A added to a
large volume of the mixture.

p ,T , n '(the amount of all other substances present are constant)

b
Amount of A, nA

nAVA nBVB

NOTE:
The partial molar
composition!

volume

is

function

The partial molar volume of a substance is

the slope of the variation of the total volume
of the sample plotted against the
composition.
of

The Partial Molar Volume

1000 mL EtOH

1 mol H2O

1014 mL EtOH-H2O soln

The partial molar volume varies

with composition since the
environment of each type of
molecule changes with each
change in composition.
Does the partial molar volume always have a positive value?

The partial molar volumes of water

and ethanol at 25oC.

Partial Molar Gibbs Energy & Chemical Potential

For a substance in a mixture, the chemical potential is defined
as being the partial molar Gibbs energy
G
nJ

p ,T , n '(the amount of all other substances present are constant)

The slope of a plot of Gibbs energy

against the amount of the component
J, with the pressure and temperature
(and the amounts of other substances)
held constant

Total Gibbs energy of the binary mixture @ constant T & p

nA

nB

Partial Molar Gibbs Energy & Chemical Potential

When composition, T , & p vary
Fundamental equation of chemical thermodynamics

dG Vdp SdT

dnA

dnB ...

At constant pressure and temperature,

dG
dG

dnA

dnB ...

dwe ,max

Non-expansion work takes place due to the changing composition of the

systems!

The Chemical Potential:

On A Wider Scope
The chemical potential also shows how the internal
energy varies with composition.
Recall,

So,

pV

TS

pV

An infinitesimal change in U for a system of variable composition

dU
dU

pdV
pdV

Vdp TdS SdT dG

TdS
...
AnA
B nB

At constant volume and entropy

dU

nA

nB

...

TS

The Chemical Potential:

On A Wider Scope
The chemical potential also shows how the extensive
thermodynamic properties H, U, A, and G vary
with composition.

H
nJ
U
nJ

J
S , p ,n '

J
S ,V , n '

A
nJ

V ,T , n '

G
nJ

p ,T , n '

The Gibbs-Duhem Equation

Illustrates the dependence of the total Gibbs
energy of the system on the composition of the
components
Shows that the chemical potential of one
component of the mixture cannot change
independently of the chemical potentials of the
other components
Allows the determination of the partial molar
volume of one component of a binary mixture
from the measurement of the partial molar
volume of the second component
Pierre Maurice Marie Duhem

The Gibbs-Duhem Equation

j

dG

ni d

i 1

dni

dG Vdp SdT

i 1

i
i 1

At constant p and T

ni d

Vdp SdT

i 1

ni d

i 1

For a binary system

nA
d
nB

The partial molar property of another substance can

be determined from the property of the other.

dni

To ponder on
1. Distinguish ideal solutions
from non-ideal solutions with
respect to chemical
potential?
2. Interpret Raoults and
Henrys laws using the
underlying principle of
chemical potential?

Remember,
The Gibbs energy of the mixture depends on its
composition.
At constant T and p systems tend towards lower
Gibbs energy.

Spontaneous mixing results in

spontaneous change in
composition!

Other Thermodynamic Mixing Functions

Entropy of mixing
mix

mix

nR( x A ln x A

xB ln xB )

p ,n A ,nB

Enthalpy of mixing
There are no
interactions between
the molecules
forming the gaseous
mixture!

G
mix

H T S

At constant T and p

The driving force for mixing is the increasing

entropy of the system as the molecules mingle.
The entropy of the surroundings remain
unchanged.

Thermodynamic Functions of Perfect Gases

Perfect gases mix spontaneously in all proportions since entropy increases

for all compositions and temperatures.
There is no heat transfer to the surroundings when perfect gases mix thus
the entropy of the surroundings remain unchanged.