UNIT-5 Thermochemistry & Electrochemistry

CHEMISTRY
PMC TOPICS 8 + 9
KIPS UNIT # 5
THERMOCHEMISTRY
ELECTROCHEMISTRY
(REVIEW LECTURE)
Thermochemistry/Energetics of Chemical Reactions
System, Surrounding and State function
Definitions of terms used in thermodynamics
Standard states and standard enthalpy changes
Energy in chemical reactions
First law of thermodynamics
Sign of H
Enthalpy of a reaction and its Types
Hess’s law of constant heat summation
Born-Haber cycle
CHEMICAL ENERGETIC/THERMOCHEMISTRY
“The study of heat changes accompanying during a chemical reaction is known as thermochemistry or Chemical
energetic”.
1. CONCEPT OF ENERGY CHANGES DURING CHEMICAL REACTIONS

Sr# PROPERTIES EXOTHERMIC ENDOTHERMIC
1 Flow of heat energy Syst. To Surr. (Evolve) Surr. To Syst. (Absorbed)
2 Temperature of surrounding Increase Decrease
3 Temperature of the system Decrease Increase
4 Energy of products Low High
5 Energy of reactants High Low
6 Strength of bonds in the products Strong (stable) Weak
7 Strength of bonds in the reactants Weak Strong (stable)

Sr# PROPERTIES EXOTHERMIC ENDOTHERMIC
8 Enthalpy change (∆H) Negative (-ve) Positive (+ve)
9 Examples C+ O2 CO2 N2 + O2 2NO

∆H = -393.7 KJ/Mol ∆H = +180.51 kJ/mol
NaOH + HCl NaCl + H2O CaCO3 CaO + CO2
∆H = -54.7 kJ/mol ∆H = +176 kJ/mol
10 Graph
2. ENTHALPY CHANGE OF REACTION
ENTHALPY DEFINITION SYMBOL △H
Enthalpy of The enthalpy change which occurs when the certain ∆Ho May be +ve or -
reaction number of moles of reactants as indicated by the ve
balanced chemical equation ,react together completely to
give the products under standard condition.( i.e; 1 atm
pressure and 25 0C temp.)
2H2(g) + O2(g) 2H2O(l) ∆H = -285.8 kJ/mol
Enthalpy of C(s) + O2(g) CO2(g) ∆Hfo= -393.7 kJ/mol ∆Hfo May be +ve or -
formation ve
Enthalpy of ½ H2 (g) H (g) ∆Hato= -218 kJ/mol ∆Hato Always +ve
atomization
Enthalpy of NaOH + HCl NaCl + H2O ∆Hno= -57.4 kJ/mol ∆Hno Always -ve
neutralization
Enthalpy of C2H5OH(l) + 3O2 (g) 2CO2(g) + 3H2O(l) ∆Hco Always -ve
combustion ∆Hco= - 1368 kJ/mol
Enthalpy of NH4Cl(s) + H2O(l) → NH4Cl(aq.) ∆Hsol.o= +16.2kJ/mol ∆Hsol.o May be =ve or -
solution ve
Enthalpy of H+ (g) + H2O (l) H3O+(aq) ∆Hho = - 1075 kJ/mol ∆Hho May be –ve or
3. BOND ENERGY
“The average amount of energy required to break all bonds are present in
one mole of a substance is called bond energy or bond dissociation
energy”
• Energy is always absorb when bond break.
i.e. endothermic process
• Energy is always release when bonds formed
i.e. exothermic process
For a reaction:
• ∆H = Total energy absorbed for breaking bonds in reactants +

total energy released during new bond formation in products
• ∆H = (∆H)R – (∆H)P
4.Hess’s Law
If a chemical change takes place by several different routes , the
overall energy change is the same ,regardless of the route by which
the chemical change occurs , provided the initial and final
conditions are the same.
∑∆H(cycle) = 0
∆H = H1 +
H2 + H3……. ∆H0f = ∆H0l + ∆H0x
Born Haber Cycle
Q. 1
Which of the following is correct statement for exothermic
reactions?
A) Reactants are more stable than products
B) Products are more stable than reactants
C) Products are less stable then reactants
D) Reactants are equally stable to products
Q. 2
H2(g) + ½ O2(g) H2O(l)
∆H of the above reaction is
A) Enthalpy of formation
B) Enthalpy of atomization
C) Enthalpy of neutralization
D) Enthalpy of solution
Q. 3
Which of the following compound has highest amount of lattice energy
A) NaI
B) NaCl
C) NaF
D) NaBr
Q. 4
Bond dissociation energy of Cl2 is
A) - 787 kJ/mol
B) - 411 kJ/mol
C) + 242 kJ/mol
D) - 690 kJ/mol
Q.5
C(s) + O2(g) → CO2(g) ∆H = -393.7 kJ/mol
CO(g) + 1/2O2(g) → CO2(g) ∆H2 = -283 kJ/mol
C(s) + 1/2O2(g) → CO(g) ∆H1 = ?
What is ∆H1 ?
A) -676.7 kJ/mol
B) - 787 kJ/mol
C) - 150.3 kj/mol
D) - 110.7 kJ/mol
Q. 6
The internal energy change(∆E) if work(w) done by the system is
20J and heat(q) is absorbed by the system is 50J is
A) + 30
B) - 30
C) + 70
D) - 70
TOPICS
• ELECTROCHEMISTRY
Oxidation number or state
Explanation of electrolysis (Predict the product)
Electrode potential (SHE and Cell Potential)
Balancing of redox equations by ion-electron method
Balancing of redox equations by oxidation number change method
Electrochemical series (ECS)
Oxidation Number:
“Apparent charge on atom or ion in a molecule.”
Products of Electrolysis
When electrodes take part in the reaction(Cu,Ag).
 When inert electrodes of Platinum or graphite

are used.
Voltaic/Galvanic Cell:
• Two half cells are present in voltaic and galvanic cell
a. Oxidation Half Cell:
• Zn electrode in 1M solution of ZnSO4 solution.
b. Reduction Half Cell:
Cu electrode is dipped in 1M CuSO4 solution.
c. Salt Bridge:
Aqueous KCl solution in a gel.
Working:
• Connect both half cells electrolytically.
• Close the external circuit, connecting to Cu and Zn
electrode.
• Flow of electron is from Zn to Cu
• At Anode: oxidation
• Zn(s) → Zn2+ + 2e-
• At Cathode: reduction
• Cu2+ + 2e- → Cu(s)
• emf of the cell: 1.10V
ELECTRODE POTENTIAL
1. Standard Electrode Potential:
Description:
“The potential set up when an electrode is dipped in 1M solution of its own
ions at 298K.”
• Represented by Eo.
2. Standard Hydrogen Electrode:
Construction:
• It consists of Glass tube filled with H2 gas at 1atm.
• Pt-foil coated with finally divided Pt black.
• 1M HCl solution.
APPLICATIONS OF ECS
• SMALLER THE STANDARD REDUCTION POTENTIAL
Higher the position in series.
Greater ability to get oxidize and lesser ability to get reduce.
Stronger reducing agent and weaker oxidizing agent.
Greater the reactivity of metal and also with dilute acid.
Greater the ability to displace the ion from salt.
ECS also help us to find
Feasibility of reaction
Cell potential
MCQ 1
Q. 7
Caustic soda is obtained on Industrial scale by the electrolysis of:
A. Brine
B. Conc. Na2SO4(aq.)
C. Conc. NaNO3(aq)
D. Conc. NaNO3(aq)
MCQ 1
Q. 8
Which of the following metal cannot replace given metal ions from their
salt solutions:
A. Mg
B. Na
C. Al
D. Zn
MCQ 1
Q. 9
Standard reduction potentials are given below. Which of the following
set of electrodes will give maximum emf of cell:
A. +1.5 & -2.5
B. -1.5 & -2.5
C. -1.5 & +2.5
D. Can’t predict

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CHEMISTRY

1. CONCEPT OF ENERGY CHANGES DURING CHEMICAL REACTIONS

2 Temperature of surrounding Increase Decrease

3 Temperature of the system Decrease Increase

4 Energy of products Low High

5 Energy of reactants High Low

6 Strength of bonds in the products Strong (stable) Weak

7 Strength of bonds in the reactants Weak Strong (stable)

9 Examples C+ O2 CO2 N2 + O2 2NO

• ∆H = Total energy absorbed for breaking bonds in reactants +

 When inert electrodes of Platinum or graphite

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