Chapter 1

Thermodynamics of
electrolyte solutions

1
1. Introduction

2
 CONTENT

1. Introduction
2. Thermodynamic properties
3. Debye-Huckel limiting law
4. Electrical conductivity
5. Transport number

3
Introduction
• Electrolytes: chemical compounds that can
generate ionic solution or ionic melting mixtures.

• Electrolyte solutions:
 Homogeneous
 Compositions can vary in a range
 Can allow the electricity current to pass
through by the electron transport by ions
in the solutions.

4
• Electrolytes are substances that
 dissociate into ions when they are dissolved in polar
solvents like water or alcohols (e.g. NaCl, KCl, HCl
solutions).
 molten salts containing ions (e.g. molten NaCl).
• A strong electrolyte will dissociate completely while a weak
electrolyte will only dissociate partly.
• The presence of the charged ions causes the electrolyte
solution to deviate much more from ideal solution behavior than
a non-electrolyte solution does.
• This is the case even at very low electrolyte concentrations.
The reason is that the ions interact with electrostatic forces
which are of much longer range than those involved in the
interaction of neutral molecules. This effect is stronger the
greater the charge on the ions. 5
6
7
 Electro- dissociation
(dissociation)
• Dissociation of electrolyte in the solution.
• a reversible process
M+A- +Mz+ + -Az-
At equilibrium:
 
(n ) .(n ) Dissociation constant KD
KD 
nM A 
 

n: mol, ion-mol concentration

8
 Percent dissociation/Degree of
dissociation ()
• Ratio of dissociated molecules to the total dissolved
molecules.

KD= f()=?
(      1) (     )
n0 .  
KD  .(  ) (  )
(1  )
n0.2
If : + = - = 1 
KD  n0 = initial molar
1 concentration
9
 Van t’Hoff factor i
• Ratio of total particles (ion + molecules) after the
dissociation to total molecules before the dissociation
(dissolved molecules)

(n0  n0 .)    .n0 .    .n0 .

i
n0
with :  = + + -
i 1
i = 1 + (-1). 
 1
• Dilute solutions: i  14
• Weak electrolytes: small  ,  0; i  1
• Strong electrolytes:   1 ; i = 
– Ex: Inorganic soluble salts, acids, bases
10
 Properties of electrolyte solutions

  i  C  R T
• Boiling point elevation
• Freezing point depression Tdd  i  K dd  c2, m
• Increase of osmotic pressure T  i  K  c
s s 2, m

(Numbers of particles in the solution increase due to

the dissociation)

11
 Solvents
• Good solvents for electrolyte dissociation are high –
permittivity solvents (such as water).

• Relative permittivity D: D = /0

0 = 8,8542.10-12 (J.coulomb/m) (F/m): permittivity of
vacuum
: permittivity of the solvent
Solvent Temperature Relative
(oC) permittivity
(D)
Water 0 88
20 80.1
100 55.3
200 34.5 12
Static electrical force between 2 ions

q1.q2 q1.q2
f 2
 2 (Coulomb law)
4r 40Dr

• q1, q2: charge of opposite ions

• Note: The interaction (physical/chemical)
between the solvent and the electrolyte
may exist.

13
 Solvation/ hydration

Kinetic diameter  270 pm

14
 Solvation/ hydration

 Interaction solvent – ions to form relatively stable complex

(solvation). Solvent: H2O  hydration

 Number of water molecules in the complex: ligand.

 For aqua solutions of alkaline/ alkaline earth ions: formed

by the ionic- dipoles interactions which depend on: Ion
electricalal charges, ion radius, and ion weight.

15
 Solvation/ hydration
 Near hydration layer:
coordination bond (donor – accepter
bond): relatively stable.

 Far hydration layer: weak static

electricalal force: relatively unstable.

Solvation/
hydration
release energy
destruct crystalline
solid (break
chemical bonds) 16
 Reverse osmosis (RO)
Water Purification system Water purification
Desalination

Ion Radius
(pm)
Na+ 117
K+ 149 RO membrane pore-size
NH4+
Ca2+
148
100
??
Mg2+ 72
Al3+ 53
Cl- 164
OH- 133
NO3- 179
H2O 135 17
Water treatment in Singapore

18
Ion Unhydrated Hydrated
radius (pm) radius (pm)
Na+ 117 358
K+ 149 331
NH4+ 148 331
Ca2+ 100 412
Mg2+ 72 428
Al3+ 53 480 Kinetic diameter  270
Cl- 164 332
pm
OH- 133 300
NO3- 179 340

Source (Volkov, A. G., S. Paula, and D. W. Deamer (1997))

19
 Classification of electrolytes

• Strong/ weak electrolytes: depend on “”.

• True/ potential electrolytes: depend on the nature of chemical
bonds in the molecules/ crystals
– True electrolytes: Ionic bond
– ex: NaCl
– Potential electrolytes: other bonds:
– ex: HCl

20
 A strong electrolyte dissociates completely.
◦ A strong electrolyte is present in solution almost
exclusively as ions.
◦ Strong electrolyte solutions are good conductors.
 A nonelectrolyte does not dissociate.
◦ A nonelectrolyte is present in solution almost
exclusively as molecules.
◦ Nonelectrolyte solutions do not conduct electricity.
 A weak electrolyte dissociates partially.
◦ Weak electrolyte solutions are poor conductors.
◦ Different weak electrolytes dissociate to different
extents. 21
 Classification of solvents

Non- polar Polar

polar aprotic protic
solvents solvents solvents

Increase polarity
- Protic solvents: H+ donor, form hydrogen-
bond between solvent – solute (electrolytes) 
can dissolve/ dissociate/ solvate to form ions (
H2O, ethanol, buthanol,…)
- Aprotic solvents: have common e- pairs 
can solvate cation to form ionic solutions
(Acetone, Acetonitrile,..) 22
2. Thermodynamic
properties

23
• For strong electrolytes:

M+A- +Mz+ + -Az-

m: molality: moles of solute / 1000g of solvent
m+ = +.m m- = -.m

+, - : activity coefficients of ions at molarities m+, m-

a+, a- : activities of ions

a+ = +.m+ a- = -.m-

a1 , a2 : activity of solvent (1) , solute (2)

Standard state: (a+)+.(a-)- = a2 (see more in textbook)

24
 Chemical potential of ions

• + = +0 + RT.lna+
= +0 + RT.lnm+ + RT.ln+

• - = -0 + RT.lna-
= -0 + RT.lnm- + RT.ln-

25
 Mean of ionic chemical-potentials

 .    .   .0   .0

    RT ln(a  .a  )1 / 
 
Mean values: = + + -
 = (++.--)1/
m = (m++.m--)1/ = m(++.--)1/ a = (a++.a--)1/
a =(a++.a--)1/ = .m
(Mean of ionic activities)

In relation to the activity of the solute (a2): a = a2

(Note: (a2) can be obtained by experimental works)

26
 Mean of concentrations & activity coefficients

m = (m++.m--)1/ m = (m++. m--)1/ Molarity

x = (x++.x--)1/ x = (x++. x--)1/ Mole fraction

c = (c++.c--)1/ c = (c++. c--)1/ Mole

concentration
Relations:
m c
x  
m  1000 / M 1 c  (1000   M 2 .c) / M 1

m.M 1  c( M 1  M 2 )
ln  x   ln  m   ln(1  )  ln  c   ln(  )
1000 0 1000 0

 , 0 : density of solution, solvent (g/ml)

27
 Residual chemical-potential

 - lt = .RT.ln
Reason: Difference in interaction of ion – ion,
ion – solvent, solvent – solvent
Significance of : Show the deviation of real solutions
and the ideal solutions

*Very dilute solutions Differences are not significant

  = 1
28
Determination of  by experimental
methods
(Read texbook)

29
 Ionic strength (I)

• Ionic strength of an ionic solution:

Im = 1/2.(mi.Zi2)

• For solutions that consist 02 ions (01 anion, 01 cation):

Im =1/2(m+.Z+2 + m-.Z-2) = 1/2(+.Z+2 + -.Z-2).m
IC = 1/2.(Ci.Zi2)

mi: molarity
Ci: ion-mole concentration

30
 What happen to I ?

• Increase ion
concentrations?
• Increase ion charges?

31
 Ionic strength (I)

Lewis-Randall empirical law

The mean ionic activity coefficients of a strong electrolyte is
similar for all solute solutions which have the same ionic
strength.

For solution of a strong electrolyte,  depends on ion

concentrations and ion charges (not the nature
of ions).

32
3. Debye-Huckel
limiting law

33
 Debye-Huckel limiting law

lg  i   A.Z . I C
i
2

Where:
k: Boltzmann constant
8 .e0 N 0
2 2
e0 N0: Avogadro number
A : permittivity of solvent
2,303.2kT  .k .T .1000 e0: electron charge = 4,8 . 10-10

Zi : ion charge
IC = 0.5Ci.Zi2 : ionic strength (ion-gam/l)

34
Activity coefficient of ion in aqua
solutions: i
lg  i   A.Z i2 . I C
For H2O solvent at 25oC:

lg  i  0,509.Z . I C
i
2

• Limitation of the D-H law:

Correct for dilute aqua solutions (C  0.01M, I=
0.01-0.03) and 1-1 electrolytes 35
 Extended Debye-Huckel equation

For H2O solvent at 25oC:

(I 0,1)
a (nm): radius of the hydrated ion
(Second equation)
𝟐
−𝟎,𝟓𝟎𝟗 𝒁𝒊 𝑰
lg i= + 𝑪. 𝑰 (I 0,5)
𝟏+ 𝟑,𝟐𝟗𝒂 𝑰
C: experimental constant(Third equation)36
 Ion Hydrated
radius (pm) (a)
a= 9Å, Z=1  Na+ 358
K+ 331
a= 3Å, Z=1  NH4+ 331
Ca2+ 412
Mg2+ 428
Al3+ 480
Cl- 332
OH- 300
NO3- 340

H3O+  900

a= 3Å, Z=3 

37
 Mean of ionic activity coefficients: 

M   A      M z    A z
 = (++.--)1/ .lg = +lg+ + -lg-
= + + -
  Z 2   Z 2
lg     A IC

Because: + .Z+ = - Z-
(see more in textbook)
lg     Z  Z  A I C   Z  Z  A' I m
( A'  A 0 )

For H2O solvent at 25oC : A A’ = 0,509 (mol/l)-0.5

38
 Mean of ionic activity coefficients: 

lg     Z  Z  A I C   Z  Z  A' I m

For H2O solvent at 25oC: lg    0.509. Z  Z  I

C (mol/l) NaCl ZnSO4

   
(calculated) (Experimental) (calculated) (Experimental)

0.001 0.954 0.965 0.812 0.700

0.002 0.946 0.952 0.812 0.700

0.01 0.840 0.906 0.517 0,387

39
Mean of ionic activity coefficients: 

Davies empirical equation:

(I 0,5)
IC
lg     Z  Z  A  0,1( Z  Z  ) I C
1  IC

(For estimation of  )

40
 Applications

• Equilibrium constants
• pH calculation
• Ionic activity coefficient in solutions
containing many ions

41
4. Electrical conductance

42
 Types of electrical conductors
Type 1 (metals, semi-conductors): electrical conduction
by electrons and holes
Type 2 (electrolyte solutions, molten electrolytes) :
electrical conduction by ions.

ion (+)
(Type 1) q cation q (Type 1)

ion(-)
anion
(+)
(Type 2)
43
 Electrical conductance
• Electrical conductivity  (/’kappa/)
Units: - SI system: S.m-1 [ with S= -1 : /’siemens/]
- or -1.cm-1 with: 1 [-1.cm-1] = 100 [S.m-1]

1
– “type 1” conductors:  ( : resistivity)


– “type 2” conductors: electrical

conductivity of 1cm3 (1ml) solution
between two flat parallel electrodes
which have the same area; the distance
of the two electrodes is 1 cm. 44
 Electrical conductance
• Electrical conductivity  (/’kappa/)

 (-1.cm-1) at
180C

Ag 615000
Solution of KCl 0.0098
(1N)
Paraffin 10-18
45
 Electrical conductance

• Effect of temperature on  :

T = 25 [1- (T-25) + (T-25)2]

T , 25 : Electrical conductivity at T 0C và 250C

, : constants (depend on electrolyte solutions)

Empirical equation:
 = 0,0163 (- 0.0174)
46
 Electrical conductance
• Effect of concentration on :
 (-1.cm-1)
– Strong electrolytes (ex: HCl):
• Low concentrations: Velocity of transportation
of ions are not influenced by the concentration
  increases if C increases.
• High concentrations: Velocity of transportation
of ions decrease due to the “Ion cloud” 
decreases.

– Weak electrolytes (ex: CH3COOH):

• Because of low density of “ion cloud”, 
insignificant effect on 

C (M)
47
 Electrical conductance

• Equivalent conductivity (-1.eq-1.cm2)

Conductivity of a volume containing 1

equivalent (molar equivalent) between 02 flat
parallel same-area electrodes with 1-cm
distance.
.1000

C
Where:
C: equivalent concentration (eq/l)
48
  (
Electrical conductance -1đlg-1.cm 2)

Effect of C on  :
- Strong electrolytes:  slowly decreases
if C increases.
“Kolhrausch 1” law:
 =  - A.C1/2
C (đlg/l)
Where:
 ( -1đlg-1.cm 2)

: limiting equivalent conductivity;

A: empirical constant

- Weak electrolytes:  decrease sharply

if C increases, =f(C1/2) is not a linear
relation.
49
C1/2 (đlg/l)1/2
Transport velocity of ions & electrical conductance

• Symbols:  (upsilon)
+ , - : transport velocity of cation, anion (cm/s)
(depend on nature of ion, concentration,
temperature, viscosity, intensity of electrical field)
0+ , 0- : Absolute velocity of cation, anion (cm2.s-1.V-1)
+ = 0+.(E/l) ;  - = 0-.(E/l)
[E/l: intensity of electrical field]
C, : Equivalent concentration (eq/l), percent dissociation

C. /1000 (eq/cm3) : equivalent of cation, anion

in 1cm3
50
Transport velocity of ions & electrical conductance

C. /1000 (đlg/cm3) C. /1000 (đlg/cm3)

cation
anion

S (cm2)

51
Transport velocity of ions & electrical conductance
• Equivalent of cation, anion transport through
area S (cm2) for 1s:

• Total quantity of electricity transported by cations,

anions through area S (cm2) for 1s:

(   ).S . .C.F (0  0 ).S . .C.F .E

I  I  I  
1000 1000l

• Ohm’s law: E E. .S E..S .C

I  
R l 1000l
• Thus,
 = .F.(0+ + 0-) (F: Faraday’s const.)
52
Transport velocity of ions & electrical conductance

– For strong electrolytes (=1):

 = F.(0+ + 0-) = + + -

– For weak electrolytes (<1):

 =  .F.(0+ + 0-) =  (+ +
- )
+ = 0+F ; - = 0-F : Equivalent conductivity of ions
53
Transport velocity of ions & electrical conductance

Infinitely dilute solutions - “Kohlrausch 2” law:

 = + + -
 , + , - : Limiting equivalent conductivity
of solution and ions (-1.eq-1.cm2)

Note: ∞ (acids) > ∞ (bases) >> ∞ (salts)

54
Transport velocity of ions & electrical conductance

Absolute velocity of H+ and OH-

oH+ and oOH- are very large comparing with
orther ions.

Reason:
Transport of H+ and OH- in aqua solutions under electric
field follow “chain” mechanism.
H+ + H2O  H3O+ H H H H
H-O-H + O-H  H-O + H-O-H
+ +
H H H H
H-O + O  O + H-O
- - 55
Transport velocity of ions & electrical conductance

Ion oi .10 5 (cm2.s-1.V-1)

(for infinitely dilute solutions at 25oC)

H+ 363
OH- 205
Na+ 52
Cl- 79

56
Electrical conductivity VS. solvent

Solvent Relative Max

(HCl)
permittivity (25 oC)
(D)
H2O 81 394
CH3OH 31.2 117
C2H5OH 25.8 27.2
C3H7OH 22.2 9.7
C4H9OH 28.2 4.0
(C2H5)2O 4.4 0.04
57
 Method for electrical conductivity
measurement
- Using “Wheatstone bridge”:
When G=0: R1/R2= R3/Rx

- (In lab) using conductivity meter:

58
 Applications

- Determine energy requirement for electrolysis process

- Determine salt’s concentration in solutions

- Determine solubility of relatively insoluble substances

- In analytical chemistry: Electrical conductivity analysis

59
 Electrical conductivity analysis

HCl by Weak acid Mixtures of KCl by

by NaOH strong/ weak
NaOH acids by AgNO3
NaOH

Principle:
Due to the especially high conductivity of H+
and OH- the equivalent volume can be
recognized. 60
5. Transport number

61
 Transport number, transference number

Ratio of electric quantity carried by the ion to the total

electric quantity pass through an area:
qi
ti 
If the electrolyte solution contains a cation and a anion:  qi

t  1  t
Transport NaCl HCl
number
t-(Cl-) 0.604 0.170
ti depend on the partner ion. 62
Hittorf’s method for transport number determination
Principle: Determine ti via the concentration
change in anode region and cathode region.
Ex: Electrolysis of HCl solution using inert
electrodes
Anode Middle Cathode
region region
Before
electrolysis
During
electrolysis

After
electrolysis
 1 1
t   
   ( /  )  1 (nc / na )  1 63