PhD.

Bach Thi My Hien

Electrochemistry is part of physical
chemistry focused on the study of
thermodynamic and kinetic
processes in the solutions of
electrolytes and melts, and in
processes related to electrolysis and
those occurring in galvanic cells.
Study of the mutual conversion
between
chemical energy and electrical
energy
chemical reaction and electric
current
 CONTENT

Chapter 1: Electrolyte solution

Chapter 2: Batteries and Electrodes
Chapter 3: Kinetics of electrode processes
Chapter 4: Applications of
electrochemistry
Chapter 1
Electrolyte solution
1.1. Electrolyte solution theory

Electrolyte solution
A solute dissolved in a
solvent forms an
electrically conductive
solution
 1.1. Electrolyte solution theory
1.1.1. Distinguishing characteristics of electrolyte and non-
electrolyte solutions

1. Electrolyte solutions do not obey Raoult's law

Very dilute solutions are

considered ideal Electrolyte solutions do
solutions  obey not obey these laws
Raoult's law, Vant’Hoff’s
law.
1.1.
1.1. Electrolyte
Lý thuyết dung
solution
dịchtheory
chất điện ly
1.1.1. Đặc
Distinguishing
điểm khác biệt
characteristics
của dung dịchofđiện
electrolyte
ly và không
and
điệnnon-
ly
electrolyte solutions

Acid, base, and salt solutions have

osmotic pressure π, saturation vapor
pressure decrease ∆P, boiling point rise
∆ts, and freezing point decrease ∆td
larger than those calculated by the
following the above laws.
1.1.
1.1. Electrolyte
Lý thuyết dung
solution
dịchtheory
chất điện ly
1.1.1. Đặc
Distinguishing
điểm khác biệt
characteristics
của dung dịchofđiện
electrolyte
ly và không
and
điệnnon-
ly
electrolyte solutions

To apply the above laws, a factor i must be added to

their formula. π’=iRCT= iπ
∆P’ = iPoNB = i ∆P
∆t’ = ikCm = i∆t
i – isotonic coefficient ( Vant’Hoff coefficient )
1.1.
1.1. Electrolyte
Lý thuyết dung
solution
dịchtheory
chất điện ly
1.1.1. Đặc
Distinguishing
điểm khác biệt
characteristics
của dung dịchofđiện
electrolyte
ly và không
and
điệnnon-
ly
electrolyte solutions

2. The conductivity is very high compared to that

of a non-electrolyte solution.
Electrolytes are also known as type 2
conductors.
1.1.
1.1. Electrolyte
Lý thuyết dung
solution
dịchtheory
chất điện ly
1.1.2.
1.1.1. Các
Distinguishing
thuyết điện lycharacteristics of electrolyte and non-
electrolyte solutions

To explain the above special features of

solutions of acids, bases, and salts, we use:

Arrhenius ion theory

1.1. Electrolyte solution theory
1.1.2. Electrolyte theories
Arrhenius ion theory content:

• Electrolysis is the process in which electrolytes dissociate into

positively charged particles (cations) and negatively charged
particles (anions).
• When the electrolyte is placed in an electric field, the cations
will move towards the cathode, the anions towards the anode.
• When dissociating into charged particles, the number of
particles in the electrolyte solution increases.
Arrhenius theory explains the first difference
between electrolytes and non-electrolytes.
1.1. Electrolyte solution theory
1.1.2. Electrolyte theories

Arrhenius ion theory content:

• Electrolytes usually do not dissociate completely during
dissolution. Let α be the resolution.

Degree of n

dissociation N
Strong electrolytes: (α=1) strong inorganic acids, bases, most neutral
salts.
Weak electrolytes (α<1) weak inorganic acids, bases, the vast
majority of organic acids and bases, acidic salts, basic salts.
1.1. Electrolyte solution theory
1.1.2. Electrolyte theories

Arrhenius ion theory content:

Relationship between i and dissociation α

i   (   )  1      1  
 

Definition: i is the ratio of the

actual particles in the solution to
the original number of particles.
1.1. Electrolyte solution theory
1.1.2. Electrolyte theories

z

 A

M  A  M
z
 


n  ) 

no 


( 0
) (
Kdl 
(1   ) n 0

   

   
. 
. 
   

n
1
.
Kdl 
0

1
1.1. Electrolyte solution theory
1.1.2. Electrolyte theories

Electrolyte constant

 
 
If 1

n0 . 2
K đl 
1

If it is a weak electrolyte K đl  n0 . 2

K dl

n0
1.1. Electrolyte solution theory
1.1.2. Electrolyte theories

The influence of solvents

Electrolysis is the interaction between
the solute and the solvent

The presence of ions in a solution

depends on the characteristics of the
solvent
1.1. Electrolyte solution theory
1.1.2. Electrolyte theories

The influence of solvents

A highly polarized medium

will produce an increased
electrolytic capacity. As a
result, the dissociation is
greater.
 1.1. Electrolyte solution theory
1.1.2. Electrolyte theories

Experience shows:
For strong electrolytes: α = 1 (Solution NaCl)

CN 0,001 0,005 0,01 0,05 0,1 0,2

α 0,977 0,953 0,936 0,882 0,852 0,818

K 0,042 0,097 0,137 0,380 0,491 0,735

1.1. Electrolyte solution theory
1.1.2. Electrolyte theories

Conlusion
•The property described above for a solution of a
strong electrolyte is not different from that of a weak
electrolyte.
•However, they contradict the conclusion about
complete dissociation of strong electrolytes and
cannot be explained by the concept of dissociation as
used for weak electrolytes.
1.2. Activity - Activity coefficient
1.2.1. Activity
In solutions of strong electrolytes the number of ions actually
involved in the conduction is not all dissociated ions.
the measured degree of dissociation based on conductivity
will necessarily be less than 1.

From here we call the degree of dissociation defined as the

apparent degree of dissociation because this value does not
reflect the really dissociation that occurs in the solution.

Activity: effective concentration

1.2. Activity - Activity coefficient
1.2.1. Activity

Relationship between activity and concentration C

a = f.C
f – The activity coefficient characterizes the
difference in the properties of the electrolytes
from the ideal solution

For ions: ai = fi .Ci

1.2. Activity - Activity coefficient
1.2.1. Activity

The mean activity of the

electrolyte AB equals to
average multiplication of ions

m n
a AmBn  mn
a A
n .a
B
m
1.2. Activity - Activity coefficient
1.2.1. Activity

Disadvantages of Arrhenius Electrolyte Theory

• Dissociation determined by different methods will give
different results.
• The dissociation constant K is not a fixed quantity, but will
change with the concentration of the electrolyte.
Reasons of disadvantages:

• Arrhenius theory ignores interactions between ions

and polar solvents.
• Neglect interactions between ions.
1.2. Activity - Activity coefficient
1.2.1. Activity
Solvation
• The interaction between the solute and the
solvent is called solvation (the solvent being
water is called hydration).

• MA + (x+y) H2O ↔ M(H2O)xz+ + A(H2O)yz-

• Heat of hydration
1.2. Activity - Activity coefficient
1.2.1. Activity

Debye – Huckel limited theory

Complete dissociation of strong electrolytes in solution 
large ionic concentration  ions are close together  there is
mutual attraction between ions  the ion in solution is
surrounded by ionic atmosphere.

The distance between the ions is larger and there

are solvent molecules between them. The ions are
solvated  the distribution of ions is not uniform
Ions in a solution of strong electrolytes
are not completely free to move

The higher the concentration of strong

electrolyte, the stronger the influence of the
inhibitory factors. Degree of dissociation
will also decrease
When the concentration is high, in
the solution of strong electrolytes, ionic
conjugation occurs.
1.2. Activity - Activity coefficient
1.2.2. Activity coefficient

Based on a theoretical model,

Debye and Huckel derived a
relation for the calculation of the
activity coefficient of an ion i
 Debye-Huckel's limit law equation

I m  0,5. mi zi2
lg f i   A.zi2 . I
I C  0,5. Ci zi2

Based on a theoretical model of a dilute solution of a strong electrolyte

I: ionic strength of the solution

For mean activity coefficient

lg f    A. z  .z  . I
1

f   f v  .f v   v
 Activity coefficients at higher concentrations by
Debye-Huckel (2nd equation)
2 I
lg f i   A.z . i
1  aB I
Mean activity coefficient
I
lg f    A.z  .z  .
1  aB I
Activity coefficients at higher concentrations by Debye-Hucke
(3rd equation)
I
lg f    A.z  .z  .  CI
1  aB I
a: mean effective diameter of the ion
B: constant dependent on the temperature and solvent
C: empirical constant
 The formula for finding the activity and
activity coefficient of an electrolyte
Mv+Av- = v+Mz+ + v-Az-

 Activity : a = a+v+ . a-v-

 Mean activity :
a  v
a  v
av  .av 

 Electrochemistry usually uses molality: ai(m) = mi.fi

a ( m )  m . f 
1 1

m   m  .m 
    
 .  .m
v v
