Electrolyte

Solution

Muhammad Abbas Ahmad Zaini

PhD, CEng
Centre of Lipids Engineering & Applied Research, UTM

Topic Outcomes
Week Topic Topic Outcomes
6-7 Electrolyte Solution It is expected that students are
able to:
•The enthalpy, entropy and
Gibbs energy of Ion formation •Define and determine activities
in solution and activity coefficient.

•Activities and activity •Evaluate mean ionic chemical

coefficient potential in electrolyte and its
characteristic by Debye-Hückel
•The Debye-Hückel theory of limiting law.
electrolyte solution

•Chemical equilibrium in
electrolyte solution
 Introduction

Solutions are homogenous mixtures of 2 or more pure

substances

In solution, the solute is dispersed uniformly

throughout the solvent.

Formation of Solution
Ionic solid dissolving water

Solvent molecules attracted to

surface ions.

Each ion is surrounded by solvent

molecules.

Enthalpy (∆H) changes with each

interaction broken or formed.
 Ions are solvated
(surrounded by solvent)

If the solvent is water, the

ions are hydrated

The intermolecular force

here is ion-dipole

Terminology
Electrolyte – compound that if dissolved in water can
to ionized

Electrolyte solutions – solution that can conduct the

electricity

Ionization process
⇒ Produce +ve and –ve ion.
⇒ Charge of the ions that conduct the electricity from
1 electrode to other electrode
 Solution

Strong
electrolyte

Electrolyte

Weak
electrolyte

Solution

Ideal & real Neutral

Nonelectrolyte
solutions solutes

Strong Electrolyte
Produce ions & conduct electricity;
undergo the completely ionized.

If its test by using electrolyte tester

will produce light lamp and there are
gas bubble
H2O
NaCl(s) → Na+(aq) + Cl–(aq)
H2O
CaBr2(s) → Ca2+(aq) + 2Br–(aq)
100% ions
 Weak Electrolyte
Conduct electricity by weak;
undergo half ionized and produce a
few ions

HF(g) + H2O ↔ H3O+(aq) + F– (aq)

CH3COOH ↔ H+ + CH3COO –
 Non-electrolyte

Solutions that can’t conduct

electricity; do not produce ions

Dissolve as molecules in solution

E.g.

Glucose, urea & alcohol

H, S, G of ion
formation in
solution
 Thermodynamics of Electrolyte
The thermodynamics of electrolyte solutions is
important for a large number of chemical systems

Acid-base Bio-chemical Electrochemical

chemistry processes reactions

Materials that dissociate into positively and negatively

charged mobile solvated ions when dissolved in an
appropriate solvent.

Solvation Shell
1/2 H2(g) + 1/2 Cl2(g) Æ H+(aq) + Cl–(aq) ∆HR=-167.2 KJ/mol

Energy flow into the system is needed to dissociate

and ionize hydrogen and chlorine

Solvation shell is essential in lowering the energy of

the ions thus making the reaction spontaneous
More energy is gained in the reorientation of the
dipolar water molecules around the ions in the
solvation shell
Reaction is exothermic

Note: ∆Hof for a pure element in its standard state = 0; A solvation shell is a shell of any
chemical species that acts as a solvent and surrounds a solute species
 Heat of Reaction

Standard state enthalpy in terms of formation

enthalpies,

Hr

Hf
H
,
a
q
Δ
Hf
C
l
,
a
q
Δ o
=Δ o
( +
)+ o
( −
)
e
a
c
t
i
o
n
No contribution of
H2(g) & Cl2(g) (pure Cannot be measured directly
element) to ∆Hof by calorimetric experiment

How to obtain the information of solvated cations and

anions??

Note: ∆Hof for a pure element in its standard state = 0

Thermodynamics Functions for cations and anions

Can be obtained by making an appropriate choice for

the zero of ∆Hof, ∆Gof and Som.
Gf
H
,
a
q

Δ o
( +
)= For all T
Gf
H T
,
a
q

( ) ⎞⎟
S
H
,
a
q

⎛ ∂Δ o +
o
( +
) = −⎜⎜
∂ ⎟ =
⎝ ⎠
P

and
Hf
H
,
a
q

G
H
,
a
q
T
S
H
,
a
q
0

Δ o
( +
) = ∂Δ ( o +
)+ o
( +
)=
f
 ∆Horxn, ∆Gorxn, ∆Sorxn
From previous reaction,

1/2 H2(g) + 1/2 Cl2(g)→ H+(aq) + Cl– (aq)

Hr

Hf
C
l
,
a
q
Δ o
=Δ o
( −
)

x
n
Gr

G
C
l
,
a
q
Δ o
=Δ o
( −
)
x
n

f
Sr

S
C
l
,
a
q
1
/
2
S
H
,2
g
1
/
2
S
C
l2
,
g
Δ o
= Δ o
( −
)− Δ o
( )− Δ o
( )
x
n

m
 Example: NaCl
NaCl (s) → Na+ (aq) + Cl– (aq)
Hr

Hf
C
l 1
,
a 7
q 2

Hf o
N 1
a
,
a 2
q 4

Hf J
N o
a l
C
l
,
s
Δ =Δ ( −
)+ Δ ( +
)− Δ ( )
x
n

6
.
k
J
m
l

0
.
1
k
m

4
1
1
.
2
k
J
m
o
l
( ) − (− )

1
− − −
=− + −
Hr

3
.
9
0
k
J
m
o
l
1
−
Δ =+
x
n

Values of ∆Gof and Som can be determined in similar

manner

Note: ∆Hof, conventional formation enthalpies; ∆Gof, conventional Gibbs energies

formation; So, conventional formation entropies

Note
∆Hof, ∆Gof & Som for ions are defined relative to H+(aq)

∆Hof = –ve; Formation of the solvated ion is more

exothermic than the formation of H+(aq)

Multiply charged ions and smaller ions more

exothermic because stronger electrostatic attraction
with water in the solvation shell

Entropy decreases as the hydration shell is formed

because water molecules are converted to relatively
immobile molecules
⇒ Larger charge-size-ratio than H+(aq).
⇒ E.g. Mg2+(aq), Zn2+(aq), PO3–4(aq)
⇒ Solvation shell is more tightly bound
 Example 1

Calculate ∆Horeaction, ∆Soreaction and ∆Goreaction for

the reaction AgNO3(aq) + KCl(aq) → AgCl(s) +
KNO3(aq)

Check Your Understanding

Calculate ∆Horeaction, ∆Soreaction and ∆Goreaction for the

reaction Ba(NO3)2(aq) + 2KCl(aq) → BaCl2(s) +
2KNO3(aq)
Thermodynamics of Ion Formation & Solvation

Earlier, ∆Hof, ∆Gof & Som cannot be determined for

an individual ion in a calorimetric experiment.

Now, the thermodynamic functions associated with

individual ions can be calculated with reasonable
level confidence using a thermodynamic model.

Allows ∆Hof, ∆Gof & Som values to be converted

to absolute values for individual ions.

Example: Individual Contribution to ∆Gof

Analyze the formation of H+(aq) & Cl– (aq)

1
/
2 /
H C
g g H

H C g C
g l e l a

Gr Gr G Gr Gr Gr

2
0
3
.
3
k
J
m
o
l
1

( )→ ( ) Δ o
= −
2 l2

x
n
1 H
2 g

1
0
5
.
7
k
J
m
o
l

Dissociation
1

( )→ ( ) Δ o
= −
x
n

1
3
1
2
k
J
m
o
l
1

( ) → + ( )+ − Δ o
= −
r
x
n

Formation of
l C
C
g g g
e

3 G G
4
9
k
J
m
o
l C
1

ions ( )+ − → − ( ) Δ o
=− −
x
n
l H

C
l
q

l
,
a a
q q

−
( )→ −( ) Δ o
=Δ o
( −
)
x
n

s
o
l
v
a
t
i
o
n
H
a
q

H
,

+
( )→ +( ) Δ o
=Δ o
( +
)
x
n

s
o
l
v
a
t
i
o
n
1
/
2
H
g
1
/
2
C
l
g

H
a
q
C
l
a
q

Gr

1
3
1
.
2
k
J
m
o
l
1

( )+ ( )→ +
( )+ −
( ) Δ o
=− −
2

x
n

The change in the Gibbs energy for overall process,

Gr

C
l
,
a
q

H
,
a
q
1
2
7
2
k
J
m
o
l

( )+ Δ ( )+
1

− + −
Δ o
=Δ o o
x
n

s
o
l
v
a
t
i
o
n

s
o
l
v
a
t
i
o
n
 Pathway
1/2 H2(g) + 1/2 Cl2 → H+(aq) + Cl– (aq)

∆Gorxn
G G

Δ o
= −131.2 KJ / mol = • Play important role in the
r
x
n

C
l m
, o
a 1
q

H
,
a
q
determination of the Gibbs
Δ o
( −
)+ Δ o
( +
) energies of ion formation
s
o
l
v
a
t
i
o
n

s
o
l
v
a
t
i
o
n
1
2
7
2
k
J
l

• Can be estimated using Born

−
+ model

Determination of ∆Gosolvation
Wnonexp, rev associated with solvation can be calculated,
∆G for the process is known.

Consider, neutral atom A gains the charge q, first in a

vacuum and then in a uniform dielectric medium.

∆Gosolvation of an ion with a charge q = Wrev

(A(g)→Aq(aq))solvation – rev. process (A(g) → Aq(g))vacuum

Electrical potential around sphere,

Q
' ε

Charge Q’
4
r

φ =
π Radius r
Note: Wnon-exp, rev, non-expansion work for a reversible process
 Work
The work in charging a neutral sphere in vacuum to
the charge q’

Q
' 4
d ε0
q
' r

1 ε

Q ε
Q

2
w

Q
'
d
q
'
∫ ∫

4
r0

8
r0
= = =
π π π
0

0
Permittivity of
free space
The work of the same process in a solvent

Q ε0
2 ε
w

rr
=
π
Relative permittivity (dielectric
const.) of the solvent

Born Model (∆Gosolvation)

For an ion of charge Q = ze, ∆Gosolvation

Charge number of the ion Avogadro’s const.

z
e
N r0

1 εr
2 8
2 ε
G

⎛ ⎞
A

Δ o
= ⎜⎜ − ⎟⎟
s
o
l
v
a
t
i
o
n

π ⎝ ⎠
Relative permittivity (dielectric
radius const.) of the solvent

Because εr >1, ∆Gosolvation < 0

⇒ Solvation is spontaneous process

Note: Values for εr for number of solvents, Table 10.2 (App. A, Data Tables)
 Born Model (For Water)

∆Gosolvation < 0 is strongly negative for small, highly

charged ions in media of high relative permittivity.

For water at 25°C,

z
2i i
G

6
.
8
6
1
0
k
J
m
o
l
( )

1
r
−
Δ o
=− × ×
s
o
l
v
a
t
i
o
n

Ref.: Atkins, P., Paula, J. D. (2006). Physical Chemistry. 8th ed. W.H Freeman and Company. N. Y.

Example 2

Calculate ∆Gosolvation in an aqueous solution for Cl– (aq)

using the Born model. The radius of the Cl– ion is 1.81 ×
10–10m.
 Using the Born Equation
To see how closely the Born equation reproduces the
experimental data, we calculate the difference in the
values of ∆Gof for Cl− and I− in water, for which εr=
78.54 at 25°C, given their radii as 181 pm and 220 pm
(Table 20.3*), respectively, is

1 8 7

1 2 o
Gs

C
l

Gs
I

6
.
8
6
1
0
k
J
m
o
l
( )− Δ ( ) = −⎛⎜ ⎞
( )

1
1 6
1 k
2 m
0 l
− − −
Δ o o
− ⎟× ×
o
l
v

o
l
v
⎝ ⎠

1
−
=−

This estimated difference is in good agreement with

the experimental difference, which is −61 kJ mol−1.
*Ref.: Atkins, P., Paula, J. D. (2006). Physical Chemistry. 8th ed. W.H Freeman and Company. N. Y.

Activities &
activity
coefficient for
electrolyte
solution
Thermodynamics of Ions in Solutions

μ
μ

R γc
T c
l
n
a
= o
+

a
= o

Deviations of electrolyte solution from ideal behavior

occur at molalities as low as 0.01 mole/kg
Thermodynamic properties of ionic species in solution?

Previously, for the H+(aq) ion, we define

o ΔH°f = 0 kJ/mole at all T
o S°m = 0 J/(K mole) at all T
o ΔG°f = 0 kJ/mole at all T

Activities & Activity Coefficient

Activity & activity coefficient of component of real
solution is Not Valid for electrolyte solutions.

Solute-solute interactions are dominated by long range

electrostatic forces present between ions in electrolyte
solutions
N
a
C
l
s
H
O
l

N
a
a
q
C
l
a
q

( )+ ()→ +
( )+ −
( )
2

• NaCl completely dissociated

• Solute-solute interactions are electrostatic
in nature

Activity & activity coefficient must be formulated

differently for electrolytes to include the Coulomb
interactions among ions.
 Activities in Electrolyte Solutions
Consider 1 mole of an electrolyte dissociating into ν+
cations & ν- anions, Gibbs energy of the solution,

G
ns

ns

μs
= +

o
l
v
e
n
t
s
o
l
v
e
n
t

o
l
u
t
e

o
l
u
t
e
A
B
v

v
In general dissociates completely,
G
ns ns

μ μ

n ns
μ
n v
μ μ
+ −

= + +
o
l
v
e
n
t
s
o
l
v
e
n
t
+ + − −

v
μ
= + ( + )
o
l
v
e
n
t
s
o
l
v
e
n
t

o
l
u
t e
+ + − −

v+, v- are stoichiometric coefficients of the cations &

anions, produced upon dissociation of the electrolyte

Note: subscript “+”, cation; “–”, anion

Mean Ionic Chemical Potential

Since, v= v+ + v–
μs

v
μ
v
μ

= +
o
l
u
t
e

+ + − −
for a strong electrolyte

Mean ionic chemical potential μ± for the solute

μs

v
μ
v
μ
μ

+
o
l
u t
e
v

± = = + + − −

Next task is to relate the chemical potentials of the

solute & its individual ions to the activities of these
species.
 Mean Ionic Activity

μ
μ

R
T
l
n
a
Define the activities, = o
+

For the individuals ions

R
T
l
n
a
μ

R
T
l
n μs
a
+ = o
+ + + − = o
− + −

v
μ

v
μ
μ
+

o
l
u t
e
v

v
± = = + + − −

For the ideal dilute solution

μ

R
T
l
n
a
± = o
± + ±

Note: The standard chemical potentials of the ions (μo+ & μo–) are based on Henry’s
law standard state

Relationship between a & a±

a

a
a
o
r
a

a
a
1
/
v

( )
v

v
v

± = +
+
−
−
± = +
+
−
−
μs

μ
μ
R
T
l
n
a
v
μ

R
T
l
n
a

( )
μ

o
l
u t
e

= o
+ = o
+
v

± = ± ±

This gives us the relationship between the electrolyte

activity & the mean activity
a

a
v

± =
Mean ionic activity a± is related to the individual ion
activities by,
 Check Your Understanding

v
μ

v
μ
μ
+

v
± = + + − −

Express µ± in terms of µ+ and µ− for a) NaCl, b) MgBr2, c)

Li3PO4, and d) Ca(NO3)2. Assume complete dissociation.

a
a
1
/
v
( )

v
± = +
+
−
−

Express a± in terms of a+ and a− for a) Li2CO3, b) CaCl2,

c) Na3PO4 and d) K4Fe(CN)6. Assume complete
dissociation.

Ionic Activity
c c
a
γ
a

a
a
1
/
v

( )
v

= + − = o
± + −

If the ionic activities are references to the concentration

units of molality,
m+ = v+m m– = v– m
m m

m m
a

+ = +
o + − = −
o −

Activity is unitless, the molality must be referenced to a

standard state conc. ⇒ m° = 1 mol kg–1

In this standard state, Henry’s law (valid in the limit

m→0), is obeyed up to a conc. of m = 1 molal.
Activities in Electrolyte Solutions

m m
m m

γ
a

γ
+ = +
o + − = −
o −

a
a
v

v
v
± = +
+
−
−

m m

m m
v

v
a

γ
γ
⎛ ⎞ ⎛ ⎞

v
v

+ −

± =⎜ +
o ⎟ ⎜ −
o ⎟ +
+
−
−

⎝ ⎠ ⎝ ⎠

Relationship between a±, m± & γ±

Simplify,
Mean ionic molality, m± Mean ionic activity coefficient, γ±
m

m
m

γ
γ
v

v
v

± = +
+
−
−
± = +
+
−
−
γ

γ
γ
m

v
v

1
/
v
1
/
v

( ) ( )
v

v
v

± = +
+
−
−
± = +
+
−
−

Thus, the mean ionic activity is related to the mean

ionic activity coefficient & mean ionic molality,
m m

m m
v
a

⎛ ⎞ ⎛ ⎞
v

± = ⎜ ±
o ⎟ ± or ± = ⎜ ±
o ⎟ ±
⎝ ⎠ ⎝ ⎠
c c
a

= o
 Chemical Potential Expression

μ v

R
T R
l
n T
a n
± = o
± + ±

μs

l
a
= o
+

o
l
u
t
e
v
± ±

m m
v
a

γ
⎛ ⎞

v
± = ⎜ ±
o ⎟ ±
⎝ ⎠

m m
μs

v
μ

R
T
l
n
v
v

v
R
T
l
n

v
R
T
l
n
γ
[ v ( )] + ⎛ ⎞
v
= o
+ ⎜ ⎟+
o
l
u
t
e

+ −
± + − o ±
⎝ ⎠

“Normal” standard state (usually taken Obtained from the chemical formula for
to be Henry’s law standard state) the solute

This can be factored into 2 parts

m m
μs

v
R
T
l
n

v
R
T
l
n
γ

⎛ ⎞
= oo
+ ⎜ ⎟+
o
l
u
t
e

± o ±
⎝ ⎠
The ideal part Deviations from ideal behavior (γ±
(associated with γ± = 1) can be obtained through exp. or
measurement on electrochemical
cells or theoretical model)
 Check Your Understanding

γ
γ
1
/
v
( )

v
± = +
+
−
−

Express γ± in terms of γ+ and γ− for a) SrSO4, b) MgBr2,

c) K3PO4, and d) Ca(NO3)2. Assume complete
dissociation.

Example 3
Calculate the value of m± in 5.0 x 10–4 molal solutions of
a) KCl, b) Ca(NO3)2, and c) ZnSO4. Assume complete
dissociation.

Calculate the mean ionic molality & mean ionic activity of

a 0.150m Ca(NO3)2 solution for which the mean ionic
activity coefficient is 0.165.

Calculate the mean ionic activity of a 0.0150m K2SO4

solution for which the mean activity coefficient is 0.465.
(Ans: 0.0111)
 The Debye-
Hückel Theory

Estimates of Activity Coefficients

m m
a

⎛ ⎞
± = ⎜ ±
o ⎟ ±
⎝ ⎠
Deviations from ideal solution behavior occur at much
lower concentration for electrolytes
⇒ Long-range electrostatic Coulomb interaction is
more dominant (interaction between the ions)

Cannot be neglected (even for very dilute solutions of

electrolytes)

Allow theoretical estimation of the mean activity

coefficients of an electrolyte.
⇒ Each has a limited range of applicability.
 The Debye-Hückel Limiting Law
0.1
This valid for small concentrations (up to
0.010 molal*)
l
o
g
γ

0
.
5
0
9
2
z
z
I
l
n ± =− + − or
γ

1
.
1
7
3
z
z
I
± =− + −
m 2

1 2
I

vi
z

vi
z

mi
z

mi
z
∑( )= ∑( )
2i

2i

2i

2i
= + + + − − + + + − −
0.06

The Debye-Hückel Extended Law (reliably

estimate the activity coefficients up to a
conc. of 0.10 mole/kg*.
0
.
5 1
1
0
z B
z I
I
l
o
g
γ

− + − B = 1.00
± =
+ (kg/mole)1/2

*Ref: http://people.stfx.ca/gmarango/chem232

The Davies Equation

An empirical modification of Debye-Hückel limiting law
for high concentration
Im
1
/
2

⎡ ⎛ ⎞ ⎤
I m

⎢ ⎜ o ⎟ ⎥
l
o
g
γ

0
.
5
1
0
z
z

0
.
3
0

⎢ ⎝ ⎠ ⎛ ⎞⎥
=− −
Im

⎜ o ⎟
1
/
2
1

± + −
⎢ ⎛ ⎞ ⎝ ⎠⎥
⎢ +⎜ o ⎟ ⎥
⎣ ⎝ ⎠ ⎦

Can reliably estimate the activity coefficients up to a

concentration of 1.00 mole/kg*.

*Ref: http://people.stfx.ca/gmarango/chem232
 Check Your Understanding

m 2
I

vi
z

vi
z
∑( )

2i

2i
= + + + − −

Calculate ionic strength, I for 0.05

molal Na2SO4.

Example 4
m 2
I

vi
z

vi
z

∑( )
2i

2i

= + + + − −
l
n
γ

1
.
1
7
3
z
z
I

± =− + −

Using the Debye-Hückel limiting law, calculate the of γ± in

5. 0 ×10–3 m of solutions of
a) KCl (Ans: 0.92)
b) Ca(NO3)2
c) ZnSO4 (Ans: 0.52)
Assume complete dissociation
Equilibrium Constant for Electrolyte Solution

Equilibrium constant in terms of activities

a
vj
( )

ei
q
=∏

i
c ic
The activity of a species relative to its molarity

ai
γi
= o
Activity coefficient of species i

Activities rather than concentration must be taken into

account to accurately model chemical equilibrium

Consider the range of ionic strengths for which the

Debye-Hückel limiting law is valid

The Auto-ionization of Water

Water auto-ionizes (self-dissociates) to a small extent

2H2O(l) ⇌ H3O+(aq) + OH-(aq)

H2O(l) ⇌ H+(aq) + OH-(aq)

These are both equivalent definitions of the

autoionization reaction.

Water is amphoteric.

Note: Amphoteric, can act as either an acid or a base

 The Auto-ionization Equilibrium
The activity equilibrium constant,

a
H 3a
O
a O2
O 2
H
a
H a
a H
O O
H
K
=

o
r
︵ ︶
+ ︵ ︶
−
⎛ ︵ ︶
+ ︵ ︶
−
⎞

H
⎜⎜ ⎟⎟
︵ ︶ ︵ ︶

2
⎝ ⎠

we know a(H2O) is 1.00,

Kw = a(H+) a(OH-)
Ion product const. for water, Kw, is the product of the
activities of the H+ and OH- ions in pure water at a
temperature of 298.15 K

Kw = a(H+) a(OH-) = 1.0x10-14 at 298K

Solubility Product Constant

The equilibrium constant in terms of molarities for ionic

salts is usually given the symbol Ksp

Note: sp, solubility product

Example: Dissociation MgF2
Consider

M
g
F2
s

M
g
a
q
2
F
a
q
2
( )→ +
( )+ −
( )
The activity of the pure solid can be set equal to 1,

c Fc
2
K

a
a

6
.
4
1
0
⎛ ⎞⎛ ⎞

M
g
2 F

9
2
+
=⎜ ⎟⎜

c
−
= ⎟⎟ = × −
s
p

M
g
2
+ −
⎜ o ⎟⎜ o ±
⎝ ⎠⎝ ⎠

From the stoichiometry of the overall equation,

cFγ

2
= c
M
g
2
− +
a
n
d
cF
± − ??

Iteration
Assume
γ± =1
c Mc

a Fc
2
Ks
aM
a

γ
6
.
4
1
0

⎛ ⎞⎛ ⎞
g
2 F

9
2

+
Solve for cF–, = = ⎜ ⎟⎜ −
⎟⎟ = × −
p

g
2

Giving cMg2+
+ −
⎜ o ⎟⎜ o ±
⎝ ⎠⎝ ⎠
1 2
I

z
m

z
m

( )
2

Calculate
ionic strength = + + + − −
l
o
g
γ

0
.
5
0
9
2
z
z
I

Recalculate γ± ± =− + −
Converge

Final γ± & cMg2+

 Tutorial
Calculate the solubility of BaSO4 (Ksp = 1.08 × 10–10) (a) in
pure H2O and (b) in an aqueous solution with I = 0.0010 mol
kg–1.

At 25°C, the equilibrium constant for the dissociation of acetic

acid, Ka, is 1.75 ×10–5. Using the Debye-Hückel limiting law,
calculate the degree of dissociation in 0.100m and 1.00m
solutions. Compare these values with what you would obtain if
the ionic interactions had been ignored.