Physical Chemistry

Lecture 37
Solving Ionic-Equilibrium Problems
Ionic equilibria in solution
Ionic materials dissociate (at least partially) in
solution
An equilibrium problem that can be solved by
estimation of the activity coefficient
Examples
Solubility of sparingly soluble salts
M + X ( solid ) v + M z+ (ai ) + v X z (ai )
Partial dissociation of weak acids and bases
H n A (ao) n H + (ai ) + An (ai )
B(OH ) m (ao) B m + (ai ) + m OH (ai )
Equilibrium constants and free
energies
As with other reactions, a relation between standard
free energy of reaction and the equilibrium constant
G
K a (T ) = exp
RT
Free-energy difference can be found from standard
free energies of formation
G = k k , formation

k
G

Free energies of formation of ions at the Henry-law

standard state are found in tables
Free energies of formation
Free Energies of Formation at 25C
(Henrys Law at 1.0 molal)
Standard state usually the Species fG (kJ/mol)

Henrys Law extrapolation H+ 0.00

at 1 molal
Cu+ 49.98
Cu2+ 65.49

Standard state depends Na+ -261.91

on temperature OH- -157.24

Cl- -131.23
Scale determined by the HCO2- -351.00

free energy of formation CH3CO2- -369.31

of H+ in solution
HCO2H -372.30
CH3CO2H -396.46
CO2 -385.98
H2S -27.83
 Example calculation
Dissolution of AgCl
AgCl ( solid ) Ag + (ai ) + Cl (ai )
Find free energies of formation from tables
GAgCl = 109.789 kJ / mol
GAg + = 77.107 kJ / mol

GCl = 131.228 kJ / mol

Equilibrium constant

55.668 10 joule
3
Ka = exp = 1.77 10 10
8.3144349 joule 298.15 K

K
 Equilibrium solubilities of
sparingly soluble salts
Example: AgCl
AgCl ( solid ) Ag + (ai ) + Cl (ai )
Use
Equilibrium constant
Debye-Hueckel equation
for
Solve iteratively
Use self consistency to
determine convergence
Result
m = 1.34x10-5 mol/kg
= 0.996 Ka = 2 m 2
Two iterations 1.177 m

= exp

1+ m
Presence of other ionic species
Solutions may have several ions present
Presence of other ions changes solubility
Changes ionic strength, which changes the activity
coefficient
Example: solubility of AgCl in a solution containing
NaNO3
Common-ion effect if one of the ions is added
from a separate source
Example: solubility of AgCl in a solution containing NaCl
Must take these factors into account in
determining the solution of the equilibrium
equation
 Ionic-strength effects
Example: Solubility of
AgCl in 0.01 molal
NaNO3
Include NaNO3 in the
ionic strength Ka = 2 m 2
Repeat iterative
procedure to 1.177 m + 0.01
convergence = exp

1 + m + 0.01
Converges to
m = 1.477x10-5 mol/kg
= 0.898
 Common-ion effect
Solubility of AgCl in 0.01
molal NaCl
Presence of NaCl affects
Ionic strength Ka = 2 m(m + 0.01)
Equilibrium expression
Set up and solve iteratively
Use self-consistency test

1.177 m + 0.01
Results = exp
m = 2.18 x 10-8 mol/kg + +

1 m 0 . 01
= 0.899
 Weak-acid dissociation
Example: acetic acid
H 3CCO2 H (ao) H 3CCO2 (ai ) + H + (ai )
Equilibrium constant: Ka = 1.75x10-5
Must consider nonideality
Assume all nonideality lies in the ions
HAc = 1
Solve by methods similar to solubility
problems
Determination of dissociation
of acetic acid
Fractional dissociation, , determines the acid
strength
H 3CCO2 H (ao) H 3CCO2 (ai ) + H + (ai )
(1 )m m m

Solve equilibrium equation iteratively

2
m
Ka =
2

1.177 m
ln =
1 + m
 Dissociation of acetic acid
pH of Acetic Acid Solutions at 25 C

Solve iteratively at each 4

concentration to find 3.5

Dissociation increases as the

pH
3

concentration goes down 2.5

pH of the solution changes 2

with concentration
0 1 2 3 4 5 6

Molality

= log10 (aH + )
Dissociation of Acetic Acid at 25 C
pH 0.07

0.06

Dissociation Fraction
0.05

0.04

0.03

0.02

0.01

0
0 0.02 0.04 0.06 0.08 0.1 0.12
Molality
 Summary
Equilibrium in ionic solutions requires consideration of
activity coefficients of the ions
Solubility of sparingly soluble salts
Weak acid (base) equilibria
Must solve equilibrium equation subject to self-
consistency of the definition of the activity coefficients
At sufficiently low concentrations, the activity
coefficients are determined by the DHG limiting law
Additional complication when other ions are added
Change of ionic strength
Addition of common ion
Calculate concentrations of ions, knowing the activity
coefficients