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: μA (liq) = μA (vapor)

• Ideal solutions

• Use * to designate pure substances

Fig 5.10 Eqilibrium between liquid and condensed phases

For pure substance A:

μ*A  μoA  RT ln PA*

When B is added:
μA  μoA  RT ln PA
A and B
both
Combining :
volatile
PA
μA  μ *A  RT ln
PA*
Raoult’s law:

PA  x APA*
Fig 5.11 Ideal binary mixture

PA  x APA*

PB  xBPB*

μA  μ*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
μA (liq)  μ A  RT ln *
PA
which becomes:

μ A (liq)  μ*A  RT ln X A
Fig 5.13 Molecular basis of Raoult’s law for a volatile
solvent and volatile solute

solvent molecules
Fig 5.14 Strong deviations from Raoult’s law

Notice that Raoult’s 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 Raoult’s law.
• In real solutions at low concentrations:
Solute = PB ∝ Solute
• Called an ideal-dilute solution

Raoult’s law: PA = XAPA* Henry’s Law: PB = XBKB

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

Henry’s law

PB  xBKB  mBKB

PB = XBKB

PA = XAPA*
Fig 5.16 Henry’s 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

ΔGmix  nRT(x A ln x A  xB ln xB )

ΔS mix  nR(x A ln x A  xB ln xB )

ΔHmix = 0
 The Properties of Solutions

Liquid mixtures of real solutions

Recall that ΔG = ΔH - TΔS

Therefore: ΔGmix < 0 or ΔGmix > 0

• Depends on relative magnitudes of ΔHmix and ΔSmix and T

Three types of interactions in the mixing process:

• solute-solute interaction
• solvent-solvent interaction ΔH1
• solvent-solute interaction

DHmix = DH1 + DH2 + DH3 ΔH2

ΔH3
 The enthalpy change of the overall process depends on
DH 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

ΔGmix < 0

Hexane is immiscible in water C6H14

ΔGmix > 0
H2O Solutions