THERMOCHEMISTRY & ENERGETICS OF CHEMICAL REACTIONS

SUBTOPICS
• 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 ΔH
• Enthalpy of a reaction
• Hess’s law of constant heat summation
LEARNING OBJECTIVES
8.1. Define thermodynamics.
8.2. Classify reactions as exothermic or endothermic.
8.3. Define the terms system, surrounding, boundary, state function, heat, heat
capacity, internal energy, work done and enthalpy of a substance.
8.4. Name and define the units of thermal energy.
8.5. Explain the first law of thermodynamics for energy conservation.
8.6. Apply Hess’s Law to construct simple energy cycles.
8.7. Describe enthalpy of a reaction.

Thermochemistry
The study of heat changes during a chemical reaction is called thermochemistry.
Energy
“Ability of a body to do work is called energy.”
Types of energies
(i) Kinetic energy (K.E) Energy due to motion.
(ii) Potential energy (P.E)Energy due to position, shape and orientation.
(iii) Sound energy
(iv) Heat energy
(v) Magnetic energy
(vi) Mechanical energy
(vii) Solar energy
Units of energy

Units Relation

J=kgm2s-2
Joule (Sl Unit) Unit of heat or thermal
energy. It is defined as the energy required to 1J=1N×1m
move an object or a particle through a distance
of one meter by a force of one Newton.

Calorie: common unit of heat is the calorie. It 1 cal=4.184J

is defined as the heat or thermal energy
required to raise the temperature of one gram
of water from 14.5 to 15.5C.
 1erg =10-7 J
Erg
1BTU=1.055×103 J
British Thermal unit (BTU)
1KWH= 3.6×106 J
Kilowatt Hours (KWH)

SYSTEM,
The part of the universe on which we wish to focus attention is called a system. A system in
chemistry is usually the substance undergoing physical or chemical change.
Types of System
(i) Open system Exchanges matter and energy with surroundings.
(ii) Closed system No exchange of matter but energy with surroundings.
(iii)Isolated system No exchange of matter as well as energy with surroundings.
SURROUNDINGS
The part of the universe except system is called surroundings
BOUNDARY
The real or imaginary surface separating a system from surroundings is called boundary.
UNIVERSE: System+surroundng
STATE FUNCTION
A property of a system that is determined by the state of the system regardless of how that condition
was achieved is called state function. Heat and work are not state functions. E, P, V, S(entropy),
G (free energy), H, are state functions.
HEAT
Heat is the transfer of thermal energy between two bodies that are at different temperature
HEAT CAPACITY
The amount of heat required to raise the temperature of the given quantity of a substance by one
kelvin is called heat capacity
INTERNAL ENERGY(E)
The sum of all kinds of energies of all the particles of a system is called internal energy
WORK
The energy transferred when an object is moved by a force is called work.
ENTHALPY OF A SUBSTANCE (H)
It is defined as the system’s internal energy (e) plus the product of its pressure and volume (pv).
H = E + PV
Spontaneous and non-spontaneous reactions:
Intensive Properties:
Does not depend upon amount e.g., Temp., density, viscosity, surface tension, refractive index,
b.p., f.p.,
Extensive Properties:
Depends upon amount e.g., volume, enthalpy, mass, area,no.of moles,
Thermodynamics
The study of all types of energy changes associated with chemical and physical changes is
known as thermodynamics.
Thermodynamics Processes
(i) Isothermal Process (T=0)
(ii) Adiabatic Process (q=0)
(iii)Isochoric Process (v=0)
(iv) Isobaric Process (P=0)
First Law of Thermodynamics
E = q + w
Where E represents the change in the system’s internal energy, q represents heat and w
represents work.
E = q + w
Since pressure is defined as force per unit area, the pressure of the gas (P) is:

F = P x A ------------ (1)
Work done on the piston is:
Work = force x area
W = F x h ------------ (2)
From equations 1 and 2, we get.
W = P x A x h ------------ (3)
During expansion, the gas changes its volume. This volume change V is equal to the
product of area (A) and displacement (h).
V = A. h
Therefore equation 3 becomes.
W = P x V
The gas (the system) is expanding, pushing back the piston against the pressure. Therefore,
the system is doing work on the surroundings, so the sign of work should be negative.
W = - PV
 Such type of work is done in an automobile engine. Heat from the combustion of the fuel
expands the gases in the cylinder to push back the piston. The piston turns a crankshaft which does
work to move the automobile. This type of work is called as pressure-volume work. Under these
conditions:
E = q - PV
RELATIONSHIP BETWEEN INTERNAL ENERGY OF A SYSTEM AND THERMAL
ENERGY AT CONSTANT TEMPERATURE AND PRESSURE
∆E = qp+ P∆V
Where qp is the heat transferred to the system from the surroundings. P∆V is work done by
the surrounding on the system at constant pressure. If the system does work on the
surrounding then,
∆E = qp - P∆V
Rearranging this equation,
qp= ∆E + P∆V
qp= ∆H = ∆E + P∆V ………………..(1)
qp= ∆H = ∆E + ∆nRT
qp= ∆H = qv + ∆nRT
Since, there is no appreciable volume change in reactions involving solids or
liquids, so ∆V = 0. Therefore, equation (1) becomes,
∆H = ∆E + P(0)
Thus ∆H = ∆E
Standard enthalpy change is enthalpy change at constant pressure (1 atm) and
constant temperature (25oC) and is denoted by ∆Ho.. Under these conditions reactants and
products are in their standard states.
Equation (1) can be written as
qp= ∆Ho = ∆Eo + P∆V

COMPARISON OF EXOTHERMIC AND ENDOTHERMIC REACTIONS

Sr. Properties Exothermic Endothermic

1 Flow of heat energy System to surrounding Surrounding to system

2 Temperature of Increases Decreases

surrounding
 3 Temperature of the Decreases Increases
system

4 Energy of products Low High

5 Energy of reactants High Low

6 Strength of bonds in Strong Weak

products

7 Strength of bonds in Weak Strong

reactants

8 Enthalpy change (ΔH) Negative Positive

C + O2 CO2 N2 + O2 2NO
ΔH=-393.7kJ/mol ΔH = + 180.51kJ/mol
Respiration Thermal
C6H12O6 + 6O2 decomposition
9 Examples 6CO2+6H2O CaCO3(s)
CaO(s)+CO2(g)
Neutralization
Dissolving
NaOH+ HCl
NaCl+H2O NH4NO3(s) NH4NO3(aq)

Graphical representation of exothermic and endothermic reactions

A Exothermic reaction B Endothermic reaction

Energy given off by system Energy absorbed by system

reactants

ΔH ΔH
products reactant
+ve -ve

Progress of reaction Progress of reaction

 ENTHALPY CHANGE AND STANDARD CONDITIONS

Positive or
Enthalpy Definition Symbol negative

The enthalpy change which occurs when the certain

number of moles of reactants as indicated by the
Enthalpy of balanced chemical equation, react together May be positive
reaction completely to give the products under standard or negative
ΔHo
condition.
2H2(g) + O2(g) 2H2O(f)ΔHo = -285.8kJmol-1
The change of enthalpy when one mole of the
Enthalpy of compound is formed from atoms of its elements. May be positive
C(s) + O2(g) CO2(g) ΔHof = -393.7kJmol-1 ΔHof
formation or negative

The enthalpy change when one mole of gaseous

atoms are formed from a molecule or an element o
Enthalpy of under standard conditions. ΔHat Always positive
atomization 1/2H2(g) H(g) ΔHoat= 218kJmol-1
The amount of heat evolved when one mole of
hydrogen ions H+ from an acid, react with one mole
Enthalpy of of hydroxide ions (OH-) from a base to from one mole
neutralization of water. ΔHno Always negative
H+(aq)+ OH-(aq) H2O(l)
Example: The enthalpy of neutralization of strong
acid & base is -57.4kJmol-1
If an acid or base is weak or both the enthalpy of
neutralization will be less than -57.4kJmol-1
The enthalpy change when one mole of a substance is
completely burnt in excess of oxygen under standard
Enthalpy of conditions.
combustion C2H5OH+3O2 2CO2(g)+3H2O(c) ΔHoc=1268kJmol-1 ΔHoc Always negative

The amount of heat absorbed or evolved when one

mole of a substance is dissolved in so much solvent o
Enthalpy of that further dilution results in no detectable heat ΔHsol. May be negative
solution change. or positive
o
NH4Cl(s)+(aq) NH4Cl ΔH(sol) =-1268kJmol-1
The amount of heat evolved or absorbed when one
mole of gaseous ions are dissolved in water is called
Enthalpy of enthalpy of hydration. ΔHho May be negative
hydration H+(g) +H2O(1) H+(aq) or positive

Enthalpy of The amount of heat evolved when hydrogen is added Always negative
hydrogenation to one mole of a substance usually unsaturated.
 o
C2H4+H2 C2H6 ΔHhyd =-120kJmol-1
Enthalpy of The amount of heat absorbed when one mole of a Always positive
sublimation substance sublimes.
o
I2(s) I2(g) ΔHsub= 62.3kJmol-1
NOTE:
i) ΔHnº =-57.4Kj / mole (maximum for strong acids and bases)
ii) ΔHnº >-57.4 (not possible)
iii) ΔHnº < -57.4 (when one of the acid or base is strong and other is weaker
BOND ENERGY
The average amount of energy required to break all bonds of a particular type in one mole
of the substance is called bond energy.
• Unit of bond energy is kJ/mole.
Factors affecting bond energy
The bond energy is the measure of the strength of bond. The strength of a bond depends
upon the following factors.
(i) Electronegativity difference of bonded atoms
(ii) Size of the atoms
(iii) Bond length
Applications of bond energy
• Relative strength of bond
• % of ionic character in bond
• Estimation of ΔH
LATTICE ENERGY
Definition:
The amount of energy released when one mole of crystalline solid is formed from the
gaseous ions is called lattice energy.
Example: Na+(g) + Cl-(g) NaCl(s) ΔH = -787 kJmol-1
The lattice energy of the ions depends upon
(i) Size of the ions (ionic radius) (ii) Charge on the ions (ionic charge)
i.e., Charge density (charge/size)
Lattice energy α Charge on the ions
Lattice energy α 1/size of the ions
Lattice energy α [q+q-/r ++ r-]
MEASUREMENT OF ENTHALPY OF A REACTION
A device that measures heat flow is called calorimeter.
There are two basic methods to measure the enthalpy of reactions.
• Experimental methods
(i) Glass Calorimeter (ΔHn and ΔHs) or constant Pressure
calorimeter(qp = ∆H)
(ii) Bomb Calorimeter (ΔHc of food and fuel) or
constant volume calorimeter (qv = ∆E).
• Theoretical methods for calculation of enthalpy
of reaction indirectly
(i) Hess’s Law for constant heat summation
(ii) Born-Haber’s cycle
By glass calorimeter (ΔH=mcΔT)
• Glass calorimeter is used to measure the enthalpy
of solution and enthalpy of neutralization.
• By using following relationship, heat of
reaction is calculated.
Q = m × s × ΔT
Where
m = mass or reactant, Units = ‘g’ or ‘Kg’
s = specific heat of reacting mixture, Units = JK-1g-1
ΔT = change in temperature, Units = K
By bomb calorimeter
• Bomb calorimeter is used to measure enthalpy
of combustion and enthalpy of reaction.
• By using following relationship, heat of
Reaction is calculated.
Q = C × ΔT
Where
C = Heat capacity, Units = kJK-1
ΔT = change in temperature, Units = K
HESS’S LAW OF CONSTANT HRAT SUMMATION (Second Law of Thermochemistry)
Cyclic Process:
Energy contents of a reaction remain constant whether ΔH
Reaction take place in single step or many steps. A
ΔH = ΔH1 + ΔH2 = ΔH3
The sum of enthalpy changes in a cyclic process is zero. ΔH1 ΔH3
Ʃ(ΔH) cycle = 0 B ΔH2
C
Example:
(i) If the enthalpy of combustion for graphite to from CO2 and enthalpy of combustion of
CO to from CO2 are known, then by using Hess’s law we can determine the enthalpy of
formation of CO.
Consider the following cycle.
ΔH
C + O2 CO2
1 1 ΔH ΔH
02 02 1 2
2 2
CO
1
C(s) + 2 02 CO2(g) ΔH (for CO2 from graphite) =-393.7kJmol-
1
1
CO(g) + 2 02 CO2(g) ΔH2(for CO2 from CO) =-283.7kJmol-1
1
C(graphite) + 2 02 CO(g) ΔH1(CO) =?
From Cycle, it is clear that
ΔH =ΔH1 + ΔH2
ΔH1 = ΔH– ΔH2
=-393.7 – (-283)
ΔH1 = -110.7 kJ mol-1
 So, the enthalpy change for the formation of CO(g) is -110 kJmol-1
AVERAGE BOND ENERGIES
• During a chemical reaction, the bonds in the reactants are broken. This is an endothermic
process; energy is required to do this.
• After the bonds have been broken, however, the bonds in the products are formed.
• This is an exothermic process; energy is released when this happens.
• The enthalpy change for a chemical reaction can be deduced from consideration of the
energy required to break bonds in the reactants and the energy released when the bonds in
the products are formed. It can be calculated from the following equation:
ΔH = Energy required to break bonds in reactants – Energy released to make bonds in
products
• This method can be used to calculate the enthalpy changes for any reaction which do
not involve ionic bonds.
• The breaking and making of ionic bonds involve a more complicated sequence of
energetic processes and thus cannot be considered in this way.
Calculation/Estimation of bond Energies:
Hreaction =  B.D.E reactants –  B.E Products.
Example:
2H2 (g) + O2 (g) 2H2O (l)  Ho = ?

 H or = 2 x B.D.E of H2(g) + B.D.E of O2(g) - 4 x B.E of O-H bonds

= 2 x (+436KJ) + 493.6KJ - 4 (460KJ)
= 1365 KJ - 1840 KJ
 H or = - 474.4 KJ.
ENTHALPIES OF REACTIONS FROM ENTHALPIES OF FORMATION
It is often convenient to calculate the  H o values for a reaction from values for the
standard enthalpies of formation H f of the reactants and products. For a given reaction:
o

Ho =  coeffP H of (products) -  Coeffr H of (reactants)

Where coeff = Coefficient
Elements in their standard states are not included in the  Ho reaction calculation i.e.  H of
for an element in its standard state is zero. When balanced equation for a reaction is multiplied by
an integer, the value of  Ho for that reaction should be multiplied by the same integer.
EXAMPLE
Calculate  H of reaction for the following reaction, which take place when gasoline burns
in internal combustion engines. Where the values of  H of are -269Kj, 0Kj, -393.5Kj and -285Kj
for C8H18 (l) , O2(g), CO2(g) and H2O(l) respectively
2C8H18 (l) + 25O2(g) 16CO2(g) + 18H2O(l)
Solution:
  Horeaction =  coeffP H of (products) -  coeffr H of (reactants)

= [16  H of for CO2(g) + 18  H of for H2O(l)] –

[2  H of for C8H18 (l) + 25  H of for O2(g)]

= 16(-393.5KJ) + 18 (-285.8KJ) - 2 (-269KJ) - 25(0)

= -6296 KJ - 5144.4KJ + 538KJ + 0
= -11440.4 KJ + 538KJ
= -10902.4 KJ
= -1.09  104 KJ
BORN-HABER CYCLE

Energy change in cyclic process is always zero. It enables us to calculate the lattice energy of
binary compounds (ionic) this is called Born-Haber cycle.

Na+ (g) + e- + Cl (g)

ΔHatof Cl2(g) + 121 kJ mol-1(Bond dissociation
energy Cl2)

Na+ (g) + e- + ½ Cl2 (g) ΔH•ofCl- (g) = -349 kJ

mol
ΔH1 of Na (g) = + 496 kJ mol-1 (I.E. of Na) (Electron affinity of
Cl)
Na(g) + ½ Na+ (g) + Cl-

(g)

ΔH1 of Na (s) = + 108 kJ mol-1 (heat of alomization of Na)

Na (s) + ½ Cl2 (g) (Reactions)
ΔH of Na+ Cl-

(s) ?
ΔH1of Na+ Cl- (s) = -411 kJ mol -1
(Lettice energy of NaCl)
Na+Cl-
(Final Product)

Lattice energy
 • Lattice energy of an ionic crystal is the enthalpy of Ionic Lattice energy
Formation of one mole of the ionic compound from Compounds (kJ mol-1)
Gaseous ions under STP.
• Lattice energy cannot be obtained by means of LiCl -833
Born-
Haber Cycle. NaF -895
• Lattice energy is helpful in discussing bonding and NaCl -787
Properties of ionic compounds.
Applications KCl -690
It is applied to determine
• Bonding in ionic compounds NaBr -728
• Properties of ionic compound
KBr -665
Lattice energy depends upon charge to size ratio of
ions. Greater the charge to size ratio, greater will be the Nal -690
lattice energy.