Peter Atkins Julio de Paula

Atkins Physical Chemistry

Eighth Edition

Chapter 5 Lecture 2
Simple Mixtures

Copyright 2006 by Peter Atkins and Julio de Paula

 The Chemical Potential of Liquids

Need to know how Gibbs energy varies with composition

Recall that at equilibrium: A (liq) = A (vapor)

Ideal solutions

Use * to designate pure substances

Fig 5.10 Eqilibrium between liquid and condensed phases

For pure substance A:

*A oA RT ln PA*

When B is added:
A oA RT ln PA
A and B
both
Combining :
volatile
PA
A *A RT ln
PA*
Raoults law:

PA x APA*
Fig 5.11 Ideal binary mixture

PA x APA*

PB x BPB*

A *A RT ln x A

Definition of ideal
solution
Fig 5.12 Near-ideal mixture of benzene and toluene
Pmb
Note:
X mb T ,P

Pb
and
X b T ,P

are straight lines,

indicating a nearly
ideal solution:
* PA
A (liq) A RT ln *
PA
which becomes:

A (liq) *A RT ln X A
Fig 5.13 Molecular basis of Raoults law for a volatile
solvent and volatile solute

solvent molecules
Fig 5.14 Strong deviations from Raoults law

Notice that Raoults law

is obeyed increasingly
closely as the
component in excess
Nonpolar
(solvent) approaches
purity

Polar
 Ideal-dilute solutions

In ideal solutions, both solvent and solute

obey Raoults law.
In real solutions at low concentrations:
Solute = PB Solute
Called an ideal-dilute solution

Raoults law: PA = XAPA* Henrys Law: PB = XBKB

where KB is an empirical
constant in units of P
Fig 5.14 Very dilute solution behavior

Henrys law

PB x BK B mBK B

PB = XBKB

PA = XAPA*
Fig 5.16 Henrys law description of solute molecules in
a very dilute solution

Solvent molecules
environment differs only
slightly from that of pure
solvent

However, solute
molecules are in
an entirely different
environment from that of solvent
the pure solute
Fig 5.17 Experimental vapor pressures of a mixture
of acetone and chloroform
 The Properties of Solutions

Liquid mixtures of ideal solutions

Gmix nRT(x A ln x A x B ln x B )

Smix nR(x A ln x A x B ln x B )

Hmix = 0
 The Properties of Solutions

Liquid mixtures of real solutions

Recall that G = H - TS

Therefore: Gmix < 0 or Gmix > 0

Depends on relative magnitudes of Hmix and Smix and T

Three types of interactions in the mixing process:

solute-solute interaction
solvent-solvent interaction H1
solvent-solute interaction

Hmix = H1 + H2 + H3 H2

H3
 The enthalpy change of the overall process depends on
H for each of these steps

Enthalpy changes accompanying solution processes:

Solutions
Enthalpy is only part of the picture

Increasing the disorder or

randomness of a system tends to
lower the energy of the system

Solutions favored by increase in

entropy that accompanies mixing
 Factors Affecting Gibbs Energy of Mixing

can hydrogen bond with water

Acetone is miscible in water

Gmix < 0

Hexane is immiscible in water C6H14

Gmix > 0
H2O Solutions