Electrochemistry

Electrochemistry
Outline
•Introduction
•Strong electrolyte
•Weak electrolyte
•Degree of ionization
•factors affecting the degree of ionization
•Arrhenius Theory of Ionization
•Specific conductance
•Molar Conductance
•Faraday’s Law of electrolysis
Introduction
Electrochemistry deals with chemical reactions that produce electricity and
the changes associated with the passage of electrical current through matter.
The reactions involve electron transfer, and so they are oxidation-reduction (or
redox) reactions.
Substances behave differently towards electric current. Some conduct it and
some do not. Substances which conduct electricity are conductors, as for
example, metals, acids, bases etc. and which do not conduct electricity are non
conductors as example, wood, asbestos etc. Again conductors can be divided
into two subdivisions: (i)electrolytes(dissociate when they conduct electricity
i.e., a chemical change occurs)
(ii)non electrolytes(when non electrolytes conduct electricity there is no such
chemical change.
Strong electrolyte
A strong electrolyte is a solution/solute that completely, or almost completely,
ionizes or dissociates in a solution. These ions are good conductors of electric
current in the solution. Originally, a "strong electrolyte" was defined as a
chemical that, when in aqueous solution, is a good conductor of electricity.
• Strong electrolytes like salts are composed of oppositely charged ions. In solid
state, these ions are held by strong electrostatic forces of attractions. When these
electrolytes are dissolved in water, the attraction forces between ions are highly
weakened due to high dielectric constant of water.
General Examples:
• Strong Acids.
• Strong Bases
• Salts
Examples: HCl, H2SO4 , NaOH, KOH, NaCl, KBr, AgCl
H₂O
NaCl(s) Na⁺(aq) +Cl⁻(aq)
100% ions
Weak electrolyte
A weak electrolyte is an electrolyte that does not completely dissociate in aqueous
solution. The solution will contain both ions and molecules of the electrolyte. Weak
electrolytes only partially ionize in water (usually 1% to 10%), while strong
electrolytes completely ionize (100%).
In the aqueous solution of weak electrolytes, the constituent ions are in equilibrium
with un-dissociated molecules of electrolytes.
This type of equilibrium involving ions in aqueous solution is called ionic
equilibrium. The dissociation of weak electrolyte is represented by ⇌
HC2H3O2 (acetic acid), H2CO3 (carbonic acid), NH3 (ammonia), and H3PO4 (phosphoric
acid) are all examples of weak electrolytes.
CH₃COOH(aq) ⇌ CH₃COO⁻(aq) +H⁺(aq)

HCl, HBr, HI, HNO3, HClO3,
strong acids
HClO4, and H2SO4
NaOH, KOH, LiOH, Ba(OH)2,
strong bases
and Ca(OH)2
NaCl, KBr, MgCl2, and many,
salts
many more
HF, HC2H3O2 (acetic acid),

H2CO3 (carbonic acid), H3PO4
weak acids
(phosphoric acid), and many
more
Degree of Ionization
The degree of dissociation α is a way of representing the strength of an acid. It is defined
as the ratio of the number of ionized molecules and the number of molecules dissolved in
water. It can be represented as a decimal number or as a percentage. One can classify
strong acids as those having ionization degrees above 30%, weak acids as those with α
below 30%, and the rest as moderate acids, at a specified molar concentration.
Total no. of molecules ionized
DOI =
Total no. of molecules dissolved
Factors affecting the degree of ionization.

Ionization is the process by which an atom or a molecule acquires a negative or positive
charge by gaining or losing electrons, often in conjunction with other chemical changes.
The resulting electrically charged atom or molecule is called an ion.
The factors of the degree of ionization are:-
•Nature of electrolytes
•Nature of solvent
•Dilution
•Temperature
•Common ion effect
The explanations of the factors affecting the degree of ionization are explained
below:-
1. Nature of electrolytes
2. Nature of solvent
3. Dilution
4. Temperature
5. Common ion effect
1.Nature of electrolytes- Degree of ionization depends upon nature of electrolytes.

Strong electrolytes have a high degree of ionization while weak electrolytes have a low
degree of ionization
2.Nature of solvent- The ionizing power of the solvent depends upon its dielectric
constant. Greater the value of dielectric constant greater will ionizing power of solvent
and greater will be the degree of ionization.
3.Dilution- The degree of ionization increases with an increase in dilution. At infinite
dilution, even the weak electrolytes are almost completely ionized.
4.Temperature- Degree of ionization increases with the increase in temperature.
5.Common ion effect- The suppression or degree of ionization of weak electrolyte by
the addition of strong electrolyte having common ion is called common ion effect. Due
to the common ion effect, the degree of ionization of weak electrolyte is decreased or
suppressed.
Arrhenius Theory of Ionization
Arrhenius theory of ionization consists of the following postulates.
The substance called electrolytes are believed to contain electrically charged particles called ions. These
charges are positive for H+ ion or ions derived from metals and negative for the ions derived from non-
metals. Number of electrical charges carried by an ion is equal to the valency of corresponding atom.
Molecules of electrolytes (acids, bases and salts) dissociate into oppositely charged ions on dissolution in
water, e.g.
NaCl Na+ +Cl-
HCl H+ +Cl-
NaOH Na+ + OH-

The number of positive and negative charges on the ions must be equal so that the solution as a whole
remains neutral.
In solution, the ions are in a state of disorderly or random motion. Upon colliding they may combine to
give unionized molecules. Thus ionization is a reversible process in which the solution contains ions of
electrolyte together with unionized molecules.
H2SO4(aq) 2H+(aq) + SO4-2(aq)

. The extent of ionization or the degree of ionization depends upon the nature of electrolyte.
Strong electrolytes such as HCl etc. ionize completely in water. Weak electrolytes such as acetic
acid (CH3COOH) ionize only slightly
. Ionization is not affected by electric current.

.When electric current is passed through an electrolytic solution, charges move towards their
respective electrodes, i.e. cations towards anode and anions towards cathode.When these ions
reached their respective electrodes, they change into neutral species by the gain or loss of
electron.
. The dissociation of electrolyte depend upon

Nature of electrolyte
Degree of dilution
Temperature
.The electrical conductivity depends upon :

The number of ions present in the solution
Speed of ions
Specific conductance
The resistance (R) of a conductor is proportional to its length l and is inversely proportional to its area
of cross-section ’a’
Molar Conductance
Faraday’s Law of electrolysis

The large unit of the quantity of electricity is called Faraday.
One Faraday = 96500 coulombs
Electrochemical equivalent
Electrochemical equivalent of a substance may be defined as “The amount (or

weight) of substance deposited or liberated when one coulomb of electric
charge is passed through an electrolyte” . It is denoted by ‘Z’ and in SI units it
is expressed in Kg/Coulomb.
Example 1:
A current of 0.5 ampere was passed through a solution of CuSO₄ for one hour.
Calculate the mass of copper metal deposited on the cathode.
Electrochemical equivalent of Cu = 0.000329g/c
= 3.294×10⁻⁴ g/C
= 3.294×10⁻⁷K g/C
Data:
1. Current in ampere (C) = 0.5
2. Time in second (1 hour) = 1×60×60
= 3600s
3. Z for Cu metal =3.294×10⁻⁴ g/C
= 3.294×10⁻⁷ Kg/C
Formula:
W= Z × A× t
Solution:
W=Z × A × t
= 3.294×10⁻⁷ × 0.5 ×3600
=5.929×10⁻⁴ ( Mass of copper metal deposited
)
Second law
Eq. Mass of an element =Atomic mass of an element
Valency of element
The current of 96500 coulombs is called one Faraday (F) charge after the name of scientist. Thus,
Faraday is defined as the quantity of charge which deposits or librates exactly one gram
equivalent of substance.

Electrochemistry

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Electrochemistry

CH₃COOH(aq) ⇌ CH₃COO⁻(aq) +H⁺(aq)

HF, HC2H3O2 (acetic acid),

Factors affecting the degree of ionization.

1.Nature of electrolytes- Degree of ionization depends upon nature of electrolytes.

NaOH Na+ + OH-

H2SO4(aq) 2H+(aq) + SO4-2(aq)

. Ionization is not affected by electric current.

. The dissociation of electrolyte depend upon

.The electrical conductivity depends upon :

Faraday’s Law of electrolysis

One Faraday = 96500 coulombs

Electrochemical equivalent of a substance may be defined as “The amount (or

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