UNIT 4

ENERGY CHANGES AND ELECTROCHEMISTRY

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 = E final – E initial = E products – E reactants Where  (Greek
delta) means “change (or difference) in” and refers to the final state minus the initial state. Thus,
E is the final quantity of energy of the system minus the initial quantity.
 Note that the total energy of the universe remains constant. When the system loses a certain
amount of energy, the surrounding gains the same amount of energy.
 This means, energy is simply being exchanged between the two components of the universe
keeping the total energy of the universe constant
 Energy transferred from system to surroundings or vice versa appears in two forms: heat and
work

4.1.1 Exothermic and Endothermic Chemical Reactions

 Exothermic reactions transfer energy to the surroundings and the temperature of the
surroundings increases.
 Endothermic reactions take in energy and the temperature of the surroundings decreases.
 For an exothermic reaction: H is negative, H < 0. For an endothermic reaction: H is positive,
H > 0.
  The device used to measure the heat released (or absorbed) by a chemical reaction is called
calorimeter.
q ∝ ΔT or q = constant x ΔT or q/ΔT = constant
 The proportionality constant in the above equation is called heat capacity.
 Every object has its own heat capacity.
 Heat Capacity of a substance is defined as the quantity of heat required to change its
temperature by 1 K.
 Heat capacity = q/ΔT The unit of heat capacity is Joule per Kelvin (J/K).
 Heat capacity is related to a substance’s ability to retain heat and the rate at which it will heat up
or cool down.
 A related property is specific heat capacity (c). Specific heat capacity (c) of a substance is defined
as the quantity of heat required to change the temperature of 1 gram of the object by 1 K:
Specific heat capacity (c) = (Heat capacity)/mass = q/(mass x ΔT)
 If we know c of the object being heated (or cooled), we can measure the mass and the
temperature change and calculate the heat absorbed (or released): q = c x mass x ΔT Notice that
metals have relatively low values of c and water has a very high value:

Energy Changes in Electrochemistry

Electrochemistry

 Electrochemistry is a field of chemistry that deals with the interconversion of electrical energy
and chemical energy.
 It is concerned with the use of electricity to cause chemical reactions (changes) to happen or
generating electricity from chemical reactions. Thus, electrical energy and chemical energy are
inter-convertible.

Electrical Conductivity

Electrical conductivity is the ability of a substance to transmit electricity.

The materials that allow the passage of electricity through them are called electrical conductors.
Electricity is constituted by movement of charged particles or charge carriers.

Electrons carry negative charge whereas ions may carry positive (cations) or negative (anions) charges.
Depending on the nature of the particles responsible for the flow of electric charges through conductors,
electrical conductivity can be classified as metallic conductivity and electrolytic conductivity.

Metallic conductivity

 Electrical conductivity in metals is a result of the movement of electrically charged particles

called electrons.
 The atoms of metal elements are characterized by the presence of valence electrons; which are
electrons in the outer shell of an atom that are free to move about.
 It is these "free electrons" that allow metals to conduct an electric current. Because valence
electrons are free to move, they can travel through the metallic lattice that forms the physical
structure of a metal.
 Silver is the best electrical conductor.
 Metallic lattice can be described as an atmosphere of positive ions in a sea of mobile electrons
 The electrons entering the metal displace (repel) the freely moving electrons at the point of entry.
 The displaced electrons occupy new positions by pushing neighboring electrons ahead.
 This will continue until electrons are forced out of the wire at the opposite end.
 The charge carriers in metallic conduction are electrons. Hence, metallic conductivity is also
called electronic conductivity.
 Non-metals are generally non-conductors of electricity, because they do not have freely moving
electrons.
 Graphite is a form of carbon in which the carbon atoms are bonded in trigonal planar fashion to
the three other carbon atoms, to form interconnected hexagonal rings.

Electrolytic conductivity

 Electrolytes are substances that transmit electricity in a molten state or in aqueous solution.
 Unlike metallic conductivity, the conductivity of electrolytic solutions depends on the type and
concentration of ions in solution.
 Based on their degree of ionization or the extent to which they produce anions and cations,
electrolytes can be classified as strong electrolytes or weak electrolytes.

Electrolytes and Nonelectrolytes

 All solutes that dissolve in water fall into one of two categories: electrolytes and nonelectrolytes.
 An electrolyte is a substance that, when dissolved in water, results in a solution that can conduct
electricity.
 In order to conduct a current, a substance must contain mobile ions.
 All ionic compounds are electrolytes.
 When ionic compounds dissolve, they dissociate (break apart) into ions, which are then able to
conduct a current.
 Thus, we can represent sodium chloride dissolving in water as NaCl(s) Na+(aq) + Cl- (aq) H2 O
What this equation says is that all the sodium chloride that enters the aqueous solution ends up
as Na+ and Cl- ions; there are no undissociated NaCl units in solution.
 Even insoluble ionic compounds, such as CaCO3, are considered electrolytes because they can
conduct a current in the molten (melted) state.
 Some polar covalent compounds such as acetic acid (CH3 COOH) that can, at least partially,
dissociate into ions when dissolved in water are also classified as electrolytes.
 A nonelectrolyte is a substance that does not conduct an electric current in either aqueous
solution or in the molten state.
 Most polar covalent compounds, such as table sugar (C12H22O11), and all nonpolar covalent
compounds are good examples of nonelectrolytes.
 When these compounds dissolve in water, they do not produce ions. An equation can still be
written that simply shows the solute going into solution without dissociating into ions.

Strong and Weak Electrolytes

o A strong electrolyte is a substance that when dissolved in water dissociates completely into its
ions.
 All ionic compounds are strong electrolytes. NaCl is a good example.
 A weak electrolyte is a substance that when dissolved in water dissociates partially into its ions.

Electrochemical Cells

 An electrochemical cell is a system that incorporates a redox reaction to produce or use electrical
energy.
 Electrodes are strips of metal or graphite that allow electrons to leave or enter the electrolytes.
 Depending on the purpose or the types of reactions taking place, electrochemical cells are divided
into two. These are Galvanic (Voltaic) cells and Electrolytic cells.
 Galvanic (Voltaic) Cells

 A Galvanic cell or voltaic cell is an electrochemical cell in which chemical energy contained in
reactants is converted into electrical energy via a spontaneous redox reaction.
 Galvanic cell or voltaic cell was so named after the Italian scientists Luigi Galvani and Alessandro
Volta, who constructed early versions of the device.
 Galvanic cells are classified into primary cells, secondary cells, and fuel cells.
 Both primary and secondary cells are batteries that store electrical energy in the form of chemical
energy.
 The chemical energy is converted into electrical energy when we the battery is in use.

Primary Cells (Battery Cells)

 Primary cells or also known as battery cells are galvanic cells that are not rechargeable.
 This is because once the chemicals in the cells that serve as reactants are completely used up, it
is not possible to recover them by charging the cells.
 Examples of primary cells include Daniell’s cell and zinc-carbon (Leclanche) dry cells.
 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 (Daniell cell) or a paste
(Leclanche cell).
 The cells containing electrolytes in the form of solution are called wet cells, and those containing
electrolytes in the form of paste are called dry cells.
 An example of a wet primary cell is the 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
 Each compartment is called a half-cell, and 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, which is then allowed to cool so that it sets in the form of a gel.
 In the anode compartment, 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 (see anode half reaction below).
 This situation causes the zinc electrode to be negative and the solution to have an overall positive
charge.
 In the process the anode (zinc) electrode loses its mass.
 That is why the anode of the galvanic cell is sometimes called sacrificial electrode.
 On the other hand, in the compartment containing the copper electrode, copper ions, Cu2+, 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 (see cathode half reaction below).
 This condition causes the electrode to be positive and the solution to have a negative charge. In
addition, the cathode continuous to grow in masses as more and more copper deposits on it.
 The electron flows from anode to cathode in the external conductor.
 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)
Overall (cell) reaction: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
 Due to the oxidation-reduction reaction in the cell, the Daniell cell generates electricity
 The purpose of the salt bridge is to maintain electrical neutrality between the two solutions.
Although, wet cells like the Daniell cell can serve as a source of electricity, they are not portable
since they contain solutions.
 Due to this practical problem of using wet cells, dry cells were developed. In a dry cell, a moist
electrolyte paste is used instead of solutions.
 This cell was invented by Georges Leclanche, a French chemist.
 We commonly use Leclanche cells as convenient, portable sources of energy.
 Flashlights and radios are examples of devices that are often powered by the zinc–carbon, or
Leclanché, dry cell
 This voltaic cell has a zinc can as the anode; a graphite rod in the center, surrounded by a paste
of manganese dioxide, ammonium and zinc chlorides, and carbon black, as the cathode.
 It produces electricity as a result of spontaneous redox reactions:
 Anode reaction: Zn(s) → Zn2+(aq) + 2e
 Cathode reaction: 2NH4 +(aq) + 2MnO2 (s) + 2e → Mn2 O3 (s) + H2O(l) + 2NH3 (aq)
 Overall (cell) reaction: Zn(s) + 2NH4 +(aq) + 2MnO2 (s) → Zn2+(aq) + Mn2O3 (s) + H2O(l) + 2NH3 (aq)
 A buildup of ammonia gas around the cathode may disrupt the current.
 However, this is prevented by the reaction between Zn2+ and NH3 to form a complex ion,
[Zn(NH3 ) 2 ] 2+ which crystallizes as a chloride salt through reaction with chloride (spectator
ion). Zn2+(aq) + 2NH3 (aq) + 2Cl_ (aq) → Zn(NH3 )2Cl2 (s)
 Therefore, the overall reaction occurring in a Leclanche cell is often written as: Zn(s) + 2NH4
Cl(aq) + 2MnO2 (s) → Zn(NH3 )2Cl2 (s) + Mn2 O3 (s) + H2 O(l)
 The voltage of this dry cell is initially about 1.5 V, but it decreases as current is drawn off.
 The voltage also deteriorates rapidly in cold weather.
 There are other examples of dry cells, such as the alkaline dry cell, silver oxide cell, and copper
oxide cell which are left for interested students to read.
 Secondary (Rechargeable) Cells Unlike primary cells, secondary 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.
 A secondary cell needs to be recharged when it stops producing electricity.
 A lead storage battery is an example of a secondary cell.
 A lead storage battery is the common automobile battery that usually delivers either 6 or 12
volts, depending on the number of cells used in its construction.
 The inside of this Voltaic cell consists of electrodes of lead alloy grids; one electrode is packed
with a spongy lead to form the anode, and the other electrode is packed with lead (IV) oxide to
form the cathode
 Both are bathed in an aqueous solution of 35% sulfuric acid, H2 SO4.
 A single lead-storage cell delivers 2 volts. Therefore, a 12 V battery contains six cells connected in
seriesWhen a lead-storage battery is in operation (on discharge), the following reactions occur at
the electrodes:
Anode reaction: Pb(s) + SO4 2-(aq) → PbSO4 (s) + 2e
Cathode reaction: PbO2 (s) + 4H+(aq) + SO4 2-(aq) + 2e- → PbSO4 (s) + 2H2 O(l)
Overall (cell) reaction: Pb(s) + PbO2 (s) + 4H+(aq) + 2SO4 2-(aq) → 2PbSO4 (s) + 2H2 O(l)
 From the electrode reactions it can be noticed that PbSO4 is produced at both electrodes.
 Lead-storage battery, as a secondary cell, is rechargeable when it runs down.
 The electrode reactions can be reversed by applying a potential across the electrodes that is
slightly larger than that which the battery can deliver.
 The reaction that takes place on recharging a lead storage battery is given by the following
equation. 2PbSO4 (s) + 2H2 O(l) → Pb(s) + PbO2 (s) + 2H2 SO4 (aq)
o The electrode that served as anode during discharging (use) is forced to behave as cathode
during recharging.
o Consequently, the direction of the electron flow that was from left (Pb = anode) to right (PbO2 =
cathode) is changed to right (PbO2 = anode) to left (Pb = cathode).
o Oxidation always takes place at anode and reduction at cathode. The direction of electron flow is
always from anode to cathode.

4.4 Electrolysis

 In contrast to spontaneous redox reactions, which result in the conversion of chemical energy
into electrical energy, electrolysis is a process by which electrical energy is used to drive an
otherwise nonspontaneous reaction.
 Electrolysis stands for “electro“ means electricity and “lysis” means to separate or break. So in
terms, electrolysis would mean "breakdown via electricity".
 An electrochemical cell in which electrolysis occurs is called electrolytic cell
 It has two components, electrodes (anode and cathode) and electrolyte.
 In electrolytic cell, the electrode connected to the positive terminal of the source (e.g. battery) 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.
 Since the cathode has excess electrons, the cations will discharge by gaining electrons.
 This process of gaining electrons is called reduction. The negative ions are attracted by the
positive electrode (anode) and are called anions.
 These ions are discharged by losing electrons (get oxidized) at the anode.
 This process of losing electrons is called oxidation.
 Thus, the cathode is the electrode at which reduction occurs and the anode is the electrode at
which oxidation takes place.

4.4.1 Electrolysis of Molten (Fused)

 Electrolytes Ionic solids can melt at elevated temperature. NaCl, for instance, melts at 801°C.
 The process is called melting or fusion.
 When ionic solids melt, they dissociate into positive and negative ions that are free to move.
 To understand the chemical reactions that occur during electrolysis of molten (fused) electrolytes,
consider electrolysis of molten NaCl.
 At the electrode connected to the negative pole of the battery, globules of sodium metal form;
chlorine gas evolves from the other electrode.
The half-reactions are Na+(l) + e− → Na(l) Cl− (l) → 1/2Cl2 (g) + e−
 The reduction of Na+ to Na occurs at the cathode, and the oxidation of Cl− to Cl2 occurs at the
anode.
 we obtain the cell reaction by adding the half-reactions. Na+(l) + e− → Na(l) Cl− (l) → 1/2Cl2 (g)
+ e− _______________________________ Na+(l) + Cl− (l) → Na(l) + ½ Cl2 (g)
 As you can see from the cell reaction, the electrolysis of molten NaCl is used commercially to
obtain sodium metal from sodium chloride.
 A number of other reactive metals are obtained by the electrolysis of a molten salt or ionic
compound. Lithium, magnesium, and calcium metals are all obtained by the electrolysis of the
chlorides.