UNIT FOUR
ENERGY CHANGES AND AND
ELECTROCHEMISTRY
⦁ ENERGY CHANGES
⦁ Chemical reactions almost always involve energy change.
⦁ This means, the energy of the reaction mixture is different before and
after the reaction.
Universe = System + Surrounding
⦁ A system is part of the universe that is being studied.
⦁ Surrounding is anything else than the system in the universe.
⦁ Internal energy of a system is the sum of potential energy and kinetic
energies of the components of the system.
(Internal Energy)system = (potential energy + kinetic energy)system
⦁ Potential energy is stored energy. It is stored in chemical bonds.
⦁ Kinetic energy is the energy due to motion. It causes work to be done
through movement.
⦁ When the reactants in a chemical system change to products, the
system’s internal energy is changed.
⦁ This change, ∆E, is the difference between the internal energy after the
change (E final) and before the change (E initial):
∆E = Efinal – Einitial = Eproducts – Ereactants
⦁ Almost all chemical reactions are accompanied by energy changes.
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⦁ This energy is usually in the form of heat, light, or electricity.
⦁ On the basis of energy changes, chemical reactions can be divided into
exothermic and endothermic reactions.
Exothermic and Endothermic Reactions
⦁ A chemical reaction that releases heat energy to the surroundings is
known as an exothermic reaction.
Reactants → Products + Heat
E.g. C + O2 → CO2 + Heat
⦁ A chemical reaction which absorbs heat energy from the surroundings is
known as an endothermic reaction.
Reactants + Heat → products
E.g. C + 2S + Heat → CS2
⦁ The amount of heat energy liberated or absorbed by a chemical reaction
is called heat of reaction or change in enthalpy (∆H) for the reaction
⦁ The change in enthalpy (∆H)is the difference between the energy of the
products(Hp) and the energy of the reactants(Hr);
∆H = Hp – Hr
Energy Diagrams
⦁ For endothermic reactions, ∆H is positive
Hp > Hr, ∆H = positive (∆H > 0)
⦁ For exothermic reactions, ∆H is negative.
Hp < Hr ∆H = negative (∆H < 0)
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⦁ ELECTROCHEMISTRY
⦁ Electrochemistry is a field of chemistry that deals with the relationship
between electrical energy and chemical energy.
⦁ Electrical energy and chemical energy are inter-convertible.
⦁ Electrochemistry is mainly concerned with two processes.
⦁ The generation of electrical energy from chemical reaction.
Chemical reaction Electrical energy.
⦁ The use of electrical energy to produce chemical change.
Electrical energy Chemical change.
⦁ The devices that convert chemical energy to electrical energy or electrical
energy to chemical energy are called electrochemical cells
⦁ Electrochemical cells can be classified as electrolytic cells and galvanic
or voltaic cells.
⦁ Electrolytic cells use electrical energy to bring about chemical changes.
⦁ Galvanic or voltaic cells convert chemical energy to electrical energy.
⦁ Electrochemistry has practical applications in our modern world and in
everyday life.
ELECTRICAL CONDUCTIVITY
⦁ Electrical conductivity is the capacity of a substance to transmit
electricity.
⦁ The materials that allow the passage of electricity through them are called
electrical conductors.
⦁ There are two kinds of electrical conduction.
⦁ Metallic conduction is due to the presence of free electrons.
⦁ Electrolytic conduction is due to the presence of free ions.
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⦁ Metallic or Electronic conductivity
⦁ Metallic conductivity refers to the transmission of electric current
through metals.
⦁ Metals contain electrons that do not have fixed positions and are
relatively free to move. These electrons are called free electrons or
mobile electrons or delocalized electrons.
⦁ In metallic conduction there is no net movement of metal atoms.
⦁Electrons are displaced from one atom but the metal doesn′t
undergoes
chemical change.
⦁ Non-metals are generally non-conductors of electricity, because they do
not have freely moving electrons.
⦁ Graphite is nonmetallic conductor due to free moving electron through
the hexagonal layers.
⦁ Electrolytic or Ionic Conductivity
⦁ The charge-carriers in electrolytic conductivity are ions (anions and
cations).
⦁ In order for a current to flow continuously through an electrolytic
conductor’s chemical change must accompany the movement of the ions.
E.g. Solution of NaCl, HCl, NaOH etc.
⦁ Electrolytes are substances that transmit electricity in a molten state or in
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aqueous solution.
⦁ Based on their degree of ionization electrolytes can be classified as
strong electrolytes or weak electrolytes.
⦁ Strong electrolytes ionize almost completely in aqueous solutions.
⦁ Weak electrolytes ionize only slightly.
⦁ The substances that do not transmit electricity either in solution or in a
molten state are called non-electrolytes.
Examples sugar, ethanol, oil, benzene, and liquid nitrogen.
Classification of Solutes in Aqueous Solutions
Strong Weak Electrolyte Non Electrolyte
Electrolyte
HCl HF (NH2)2CO ( urea)
HNO3 HNO2 CH3OH ( methanol)
H2SO4 CH3COOH C6H12O6 ( glucose)
HClO4 H3PO4 CH3CH2OH (Ethanol)
NaOH NH3 C12H22O11 ( sucrose)
Ba(OH)2 H2O
Ionic compound
Difference between metallic conduction and electrolytic
conduction
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Metallic Conduction Electrolytic Conduction
Conduction through metals is due to the Conduction through electrolytes is due to the
movement of electrons. movement of ions.
No change in the chemical properties of It may cause chemical decomposition of the
the conductors is observed. electrolytes.
It does not involve any transfer of matter. It involves the transfer of matter as ions.
It decreases with the increase in It increases with the increase in temperature.
temperature.
It is a physical process It is chemical changes that occur on the
surface of the electrodes.
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Exercise 4.2 (page- 178)
Exercise 4.3 (page- 181)
ELECTROLYSIS
⦁ Electrolysis is a process in which electrical energy is used to produce
chemical changes.
⦁ Electrolysis is carried out in an electrochemical cell known as an
electrolytic or electrolysis cell.
⦁ Electrodes are strips of metal or graphite that allow electrons to leave or
enter the electrolytes.
⦁ They can be chemically active or inert.
⦁ Active electrodes directly take part in reactions.
Examples include zinc and magnesium.
⦁ Inert electrodes do not directly take part in chemical reactions. They
only serve to transfer electrons.
Examples include platinum and graphite.
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⦁ The electrode connected to the positive terminal of the source is positively
charged and is called the anode.
⦁ It is the electrode through which electrons leave the cell.
⦁ The electrode connected to the negative terminal of the source is
negatively charged and is called the cathode.
⦁ It is the electrode through which electrons enter the cell.
⦁ During electrolysis, the ions of the electrolyte migrate to the electrodes of
the opposite charge.
⦁ The positive ions are attracted to the cathode and are called cations.
⦁ The cathode has excess electrons; the cations will discharge by gaining
electrons.
⦁ The process of gaining electrons is called reduction.
⦁ The negative ions are attracted by the positive electrode (anode) and are
called anions.
⦁ Anions are discharged by losing electrons at the anode.
⦁ The process of losing electrons is called oxidation.
⦁ The cathode is the electrode at which reduction occurs and the anode is
the electrode at which oxidation takes place.
⦁ The reaction that takes place at each electrode is known as a half-cell
reaction
⦁ Oxidation half-reactions occur at the anode .
⦁ Reduction half reaction at the cathode.
⦁ The net reaction that takes place in the electrolytic cell is known as a cell
reaction (oxidation-reduction reaction or redox reaction).
⦁ Electrolysis is a process in which electric energy is used to bring about an
oxidation-reduction reaction. It is also defined as the decomposition of an
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electrolyte, using electricity.
ELECTROLYSIS OF MOLTEN (FUSED)
ELECTROLYTES
⦁ When ionic solids melt, they dissociates into positive and negative ions
that are not held in fixed positions.
⦁ Consider a hypothetical electrolyte, MX that dissociate into M+ and X–.
MX melting M+ + X–
⦁ During electrolysis, the cations, M+ ions, move toward the cathode, gain
one electron each and become M atoms.
⦁ The anions, X– ions, move toward the anode, lose one electron and become X
atoms.
Cathode reaction: M+ + 1e– → M (Reduction-half reaction)
Anode reaction: X– → X + 1e– (Oxidation half-reaction)
Cell reaction: M+ + X– electrolysis M + X (Oxidation-
reduction)
⦁ The number of electrons gained by the cations at the cathode is exactly
equal to the number of electrons lost by anions at the anode during
electrolysis.
⦁ Oxidation and reduction reactions proceed simultaneously. Reduction and
oxidation cannot occur separately.
Exercise 4.5 (page- 191)
Exercise 4.6 (page- 193)
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GALVANIC (VOLTAIC) CELLS
⦁ Electrolytic cell is electrochemical cells in which electricity is used to
bring about chemical reactions.
⦁ The chemical reaction in an electrolytic cell is caused by electricity and is
a non-spontaneous redox reaction. This means the reaction can proceed
only in the presence of electricity.
⦁ In a Galvanic cell, the reaction that occurs inside the cell is a
spontaneous redox reaction.
⦁ The reaction that occurs inside the cell will proceed on its own without any
external influence.
⦁ Galvanic cells are electrochemical cells in which spontaneous redox
reactions generate electricity.
⦁ Galvanic or voltaic cells are classified into primary cells, secondary cells,
and fuel cells.
⦁ Primary Cells
⦁ Primary galvanic cells are those cells that are not rechargeable.
⦁ This is because the electrode reaction as well as the entire cell reaction
cannot be reversed on recharging.
⦁ Examples of primary cells are Daniel’s cell, zinc-carbon cell, alkaline
cell, silver oxide cell, and copper oxide cell. Except Daniel’s cell all are
dry cell.
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⦁ The common feature of all Galvanic cells is that they contain two
electrodes in contact with an electrolyte.
⦁ The electrolyte in a Galvanic cell can be in the form of a solution or a
paste.
⦁ The cells containing electrolytes in the form of solution are called wet
cells.
⦁ The cells containing electrolytes in the form of paste are called dry cells.
⦁ An example of a wet primary cell is the Daniell cell.
⦁ Zn-Cu Voltaic Cell (Daniell Cell)
⦁ It consists of a zinc strip placed in ZnSO4 solution in one compartment
and a copper strip placed in copper sulphate, CuSO4, solution in another
compartment.
⦁ The reactions occurring in each compartment are called half-cell
reactions.
⦁ The solutions in the two compartments are linked by a salt bridge.
⦁ The salt bridge consists of a delivery tube filled with warm mixture of conc.
KCl solution and agar solution.
⦁ The zinc atoms from the zinc electrode lose two electrons each and
become zinc ions, Zn2+. The ions enter into the solution, and the electrons
remain on the electrode and flow through the external wire to the copper
electrode. This situation causes the zinc electrode to be negative and the
solution to have an overall positive charge.
⦁ In the compartment containing the copper electrode, copper ions, Cu 2+,
from the solution move to the cathode and gain two electrons each, to
become copper atoms and deposit on the surface of the copper electrode.
This condition causes the electrode to be positive and the solution to have
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a negative charge.
⦁ The half-cell reactions and the cell reaction in Daniell cells are
represented as
Anode reaction: Zn (s) → Zn2+ (aq) + 2e–
Cathode reaction: Cu2+ (aq) + 2e– → Cu (s)
Cell reaction: Zn (s) + Cu2+ (aq) → Zn2+ (aq) + Cu (s)
⦁ Due to the oxidation-reduction reaction in the cell, the Daniell cell
generates electricity.
⦁ Note; the anode is the negative electrode and the cathode is the positive
electrode in galvanic cells, as opposed to the situation in an electrolytic
cell. But, it is always oxidation that occurs at the anode and reduction at
the cathode.
The purpose of the salt bridge is to:
⦁ Maintain electrical neutrality between the two solutions.
⦁ Allow electrical contact between the two solutions;
⦁ Prevent mixing of the electrode solutions.
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⦁ Zinc-carbon dry cell (Leclanche cell)
⦁ The cell consists of a zinc cup that serves as the anode.
⦁ A graphite rod, serves as the cathode.
⦁ A moist paste of NH4Cl with MnO2 (manganese (IV) oxide), ZnCl2 and
powdered carbon, serves as the electrolyte.
Anode rxn: Zn (s) → Zn2+ (aq) + 2e–
Cathode rxn: 2MnO2 (s) + 2NH+4(aq) + 2e– → Mn2O3 (s) + 2NH3 (aq) + H2O
(l)
⦁ A buildup of ammonia gas around the cathode may disrupt the current.
However, this is prevented by the reaction between Zn 2+ and NH3 to form
a complex ion, [Zn(NH3) 2] 2+ which crystallizes as a chloride salt.
Zn2+ (aq) + 2NH3 (g) + 2Cl– (aq) → Zn(NH3)2 Cl2 (s)
Cell rxn: Zn(s) + 2MnO2(s) + 2NH4Cl(aq) → Zn(NH3)2Cl2(s) + Mn2O3(s) +
H2O
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⦁ Secondary Cells
⦁ Secondary galvanic cells are rechargeable.
⦁ The electrode reactions can be reversed, and the original reactants can
be regenerated. This can be achieved by passing a direct current
through the cell. The process is called charging or recharging.
⦁ In Secondary cell Electrical energy and chemical energy are inter-
convertible.
⦁ When the cell is being charged the electrical energy changes to
chemical energy. The original anode, cathode, & electrolyte are
regenerated. That means chemical energy is stored.
⦁ A secondary cells needs to be recharged when it stops producing
electricity,
⦁ A Lead Storage Battery (car battery) is an example of a secondary cell.
Lead Storage Battery (car battery)
⦁ A lead Storage Battery is delivers either 6 or 12 volts, depending on the
number of cells used in its construction.
⦁ A single lead-storage cell delivers 2 volts. Therefore, a 12 V battery
contains six cells connected in series.
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⦁ When the external circuit is closed & the battery in operation Oxidation-
reduction reaction takes place.
⦁ When a lead-storage battery is in operation (on discharge), the following
reactions occur at the electrodes:
Anode rxn: Pb (s) + SO42– (aq) → PbSO4 (s) + 2e–
Cathode rxn: PbO2 (s) + 4H+ (aq) + SO2– 4 (aq) + 2e– → PbSO4 (s) +
2H2O
Cell rxn: Pb (s) + PbO2(s) + 4H+(aq) +2SO42– (aq) → 2PbSO4(s) +
2H2O
⦁ From the electrode reactions it can be noticed that PbSO 4 is produced at
both electrodes.
⦁ The reaction that takes place on recharging a lead storage battery is given
by the following equation.
2PbSO4 (s) + 2H2O (l) → Pb (s) + PbO2 (s) + 2H2SO4 (aq)
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REVIEW EXERCISE (page 195- 197)
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