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CHEMISTRY
NMDCAT
Lecture # 16
Thermochemistry
 Contents
⮚ 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
⮚ Born-Haber cycle
⮚ Hess’s law of constant heat summation
Learning Outcomes
⮚ Define thermodynamics.
⮚ Classify reactions as exothermic or endothermic.
⮚ Define the terms system, surrounding, boundary, state function,
heat, heat capacity, internal energy, work done and enthalpy
of a substance.
⮚ Name and define the units of thermal energy.
⮚ Explain the first law of thermodynamics for energy
conservation.
⮚ Apply Hess’s Law to construct simple energy cycles.
⮚ Describe enthalpy of a reaction.
⮚ Describe Born-Haber cycle.
 1. System, Surrounding and State Function
System:
The portion of universe which is set aside for consideration,
observation, discussion, argumentation or experimentation is
called system. OR
The substance under consideration is called chemical system
Examples:
i. Pb(NO3)2 under consideration is a system
ii. The liquid whose boiling point is to be measured is a system
Surrounding:
The portion of universe except system is called surrounding.
Example:
A chemical reaction happening in a test tube is a system, while the walls of the
test tube and the atmosphere are its surrounding.
State function:
A macroscopic property of a system which has some definite values for
initial and final states, and which is independent of the path adopted
to bring about a change.
Examples:
Pressure (P), Temperature (T), Volume (V), Internal energy (E) and
Enthalpy (H) are all state functions.
• Capital symbols are used for state function
• Heat and work are not state functions
• Internal energy E is a state function
 2. Exothermic and Endothermic reactions. 7

On the basis of 𝚫𝐇 chemical reactions can be classified as

Endothermic reaction Exothermic reaction
• A Chemical reaction in which heat energy is • A Chemical reaction is which heat energy
absorbed is called Endothermic Reaction released is called Exothermic Reaction.
• ∆H for an endothermic reaction is positive. • ∆H for an exothermic reaction is negative.

• Enthalpy of the product is greater than the • Enthalpy of the reactant is greater than the
enthalpy of the reactant. enthalpy of the product.
• Energy is first needed to break bond in the • Energy is when released new bonds are
reactant, bond breaking is an endothermic formed in the product. Bond making is an
process and requires energy. exothermic process and releases energy.

Examples: Examples:
𝑁2 𝑔 + 𝑂2 𝑔 → 2𝑁𝑂 𝑔 𝛥𝐻 = 180.5 𝑘𝐽 𝐶 𝑠 + 𝑂2 𝑔 → 𝐶𝑂2 𝑔 𝛥𝐻 = −393.7 𝑘𝐽
2𝑁𝑂 𝑔 + 𝑂2 𝑔 → 2𝑁𝑂2 𝑔 𝛥𝐻 = 66.36 𝑘𝐽 𝑆 𝑠 + 𝑂2 𝑔 → 𝑆𝑂2 𝑔 𝛥𝐻 = −296.8 𝑘𝐽
 Standard enthalpy of
• It is the amount of heat energy absorbed or evolved when the
certain number of moles of reactants (as indicated by the
8
reaction (∆Hor) balance equation) react together completely to give the
products under standard conditions.
• In an exothermic reaction, the heat contents or enthalpy of the
Enthalpy change for products, H2 (Hproduct) is less than that of the reactants H1
exothermic reactions (Hreactant). Since the system has lost heat, we can say the
enthalpy change for the reaction ∆H is negative H2 – H1 = -∆Hor
• In an endothermic reaction, the enthalpy of products H2, is
Enthalpy change for greater than that of the reactants H1 and the enthalpy change,
endothermic reactions ∆H is positive. These enthalpy changes are represented in figure.
H2 – H1 = -∆Hor

Exothermic reaction Endothermic reaction

H2 – H1 = -∆Hor H2 – H1 = +∆Hor
HP < HR HP > HR
 9

Q:
Reactants have higher energy than products in: 2013
A) Endothermic reactions C) Exothermic reactions
B) Photochemical reactions D) Non-spontaneous reactions

Explanation: (C) Reactants have higher energy than products

in exothermic reactions.
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0

Q: ∆H will be given a negative sign in: 2012

A) Exothermic reactions C) Dissociation reactions
B) Decomposition reactions D) Endothermic reactions

Explanation: (A) ∆H will be given a negative sign in

Exothermic reactions
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1
Q: If an endothermic reaction is allowed to takes
place rapidly in the air, the temperature of
surrounding air:
A) Remains unchanged
B) Increases
C) Decreases
D) First increases and then decreases

Explanation: (C) If an endothermic reaction is

allowed to takes place rapidly in the air, the
temperature of surrounding air decreases
 3. Standard states 12
Conditions where temperature is 298K, pressure is 1.0atm and concentration of
the substance is maintained at 1M are called standard state of the system.
Under these conditions, any parameter is designated by
∆Ho = standard enthalpy change ∆Eo = standard internal energy change
∆So = standard entropy change ∆Go = standard free energy change
Different forms
of ∆Ho Definition

∆Hor = It is the amount of heat energy absorbed or evolved when the certain number of moles of
( + or - values) reactants (as indicated by the balance equation) react together completely to give the
Enthalpy of products under standard conditions.
reaction 2H2 g + 1/2O2 g → H2 O l ΔHo
r = +285.8kJmol
−1
∆Hof = It is the amount of heat energy absorbed or evolved when one mole of a compound is
( + or - values) formed from its elements under standard conditions.
Enthalpy of Mg s 2 +1/2O2 g → MgO s ΔHof = −692kJmol
−1
formation
 13

Different forms Definition

of ∆Ho
∆Hoat = It is the amount of heat energy absorbed when one mole of gaseous atoms are
( + value) formed from its elements under standard conditions.
Enthalpy of
atomization 1/2H2 g → H g ΔHoat = +218kJmol −1

∆Hon= It is the amount of heat energy evolved when 1 mole of water is formed by the
( - value) reaction of 1 mole of H+ ions from an acid with 1 mole of OH- ions from a base.
Enthalpy of
neutralization HCl aq +NaOH aq ⇌ NaCl + H2 O

H+ aq +OH
−
aq ⇌ H2 Ol ΔHo
n = −57.4kJmol −1
 14

Different Definition
forms of ∆Ho
∆Hoc= It is the amount of heat energy evolved when one of the substance is
( - value) completely burnt in excess of oxygen under the standard conditions.
Enthalpy of C s + O2 g → CO2 g ΔHo
c = −393.7kJmol
−1
combustion

∆Hosol. = It is the amount of heat energy absorbed or evolved when one mole of a
( + or - values) substance is dissolved in excess solvent.
Enthalpy of NH4 Cl s → NH4 Cl aq ΔHo
sol. = +16.2kJmol
−1 ΔH >ΔH
l hyd
solution
 Standard enthalpy change (∆Ho) 15

∆Ho can be measured ∆Ho can be calculated mathematically

experimentally by calorimeter by Hess’s Law

i. Glass calorimeter: It is that ii. Bomb calorimeter: It is that type • Hess’s law: It is applicable for
type of calorimeter which is of calorimeter which is used to a) One step reaction
used to measure to ∆Hon measure to ∆Hoc b) For more than one step reaction
∆Hon = q = m x s x ∆T ∆Hoc = q = c x ∆T
Where, Where,
q = amount of heat evolved or c = heat capacity of a system
absorbed • Heat capacity of a system may be
m = mass of substance defined as the quantity of heat
s = specific heat required to change temperature by
∆H = heat of neutralization 1kelvin.
• Calorimeter is only applicable for one step reaction
 16

Q: Neutralization of 50cm3 of 0.5M NaOH at 25oC with

50cm3 of 0.5M HCl 25oC is raised to 31oC. Find enthalpy of
neutralization (∆Hon). Specific heat of water (q) = 5JK-1g-1:
A) -125kJmol-1 C) -120kJmol-1
B) -130kJmol-1 D) -135kJmol-1
Solution (C) 17
Solution: Specific heat of water (s) = 5JK-1g-1
Density of water is around 1gcm3, so 100cm3 (50 cm3+50cm3 =100cm3) of total solution is
approximately = 100g (m = d x V = 1 x 100 =100g) ………… (i)
 Total mass of reaction mixture = 100g
Rise in temperature (∆T) = T2 – T1 = 31.0oC – 25.0oC = 6oC = 6K
Amount of total heat evolved
q = m x s x ∆T ……………………………………………………... (ii)
= 100  5  6
= 3000J
= 3.0kJ ……………………………………………………...…... (iii)
So the reaction is exothermic
q = -3.0kJ
So 50cm3 of 0.5M solution is = 0.05moles of HCl and NaOH respectively
(M1 x 1000 = 0.5 x 50)
𝟓𝟎
∴ M1 = 𝟎. 𝟓 × = 𝟎. 𝟎𝟐𝟓𝐌
𝟏𝟎𝟎𝟎
= 0.025mole …………...…………...…...….. (iv)
When this heat is divided by number of moles, the ∆Hon is for one mole
−𝟑.𝟎𝐤𝐉
Heat of neutralization (∆Hon) = = −𝟏𝟐𝟎𝐤𝐉𝐦𝐨𝐥−𝟏 ………. (v)
𝟎.𝟎𝟐𝟓𝐦𝐨𝐥
 18

Q: Hydrazine (N2H4) is a rocket fuel. It burns in O2 to give N2 and

H 2O
N2H4(l) + O2(g)  N2(g) + 2H2O(g)
1.0g N2H4 is burn in bomb calorimeter. An increase of temperature
recorded is 4.0oC. The heat capacity of calorimeter is 5.0kJk-1g-1.
The heat of combustion of one mole of N2H4 is:
A) -640kJmol-1 C) +620kJmol-1
B) +640kJmol-1 D) -620kJmol-1
Solution (A) The heat of combustion of one mole of 19
N2H4 = -640kJmol-1.
Calculation:
Molar mass of N2H4 = 32gmol-1
Mass of hydrazine burnt = 1g
Heat capacity of bomb calorimeter (c) = 5.0kJK-1g-1
Rise in temperature (∆T) = 4.0oC (4k)
Enthalpy of combustion ∆Hot of hydrazine = ?
q = c x ∆T
q = 5.0 x 4.0
q = -20kJ (exothermic reaction)
1g of N2H4 produces heat = -20.0kJg-1
Heat evolved by 32g = -20.0kJg-1 x 32g mol-1
The heat of combustion of one mole of N2H4 = -640kJmol-1
 4. First law of thermodynamics

• Energy can neither be created nor be destroyed, but can be changed

from one form to another
∆E = q + P∆V
∆E = qv
• Enthalpy
The total heat content of system is called enthalpy of a system
• It is a state function
• In a given state, enthalpy cannot be calculated
• Change in enthalpy is equal to heat of reaction at constant pressure
∆H = qp
• Enthalpy change ∆H of a reaction is the change that occurs when certain
number of moles of reactants convert into products under standard
conditions i.e. 25oC and 1atm
• Change in enthalpy, which occurs when one mole of a compound is
produced from reactants, is called molar enthalpy of formation (∆Hf)
e.g.
∆Hof for CO2 = -393.7kJmol-1
∆Hof for MgO = -692kJmol-1
• Standard enthalpy of a substance is chosen “zero”
• qp > qv or ∆H > ∆E
 Enthalpy Definition Symbol
The enthalpy change which occurs when the certain number of moles of
Enthalpy of reactants as indicated by the balanced chemical equation, react together
∆Hof
reaction completely to give the products under standard condition
2H2(g) + O2(g) → 2H2 Ol ∆H o = −285.8kJmol−1
Enthalpy of The change of enthalpy when one mole of the compound is formed from atoms
formation of its elements ∆Hof
C(s) + O2(g) → CO2(g) ∆H o f = −393.7kJmol−1
Enthalpy of The enthalpy change when one mole of gaseous atoms are formed from a
atomization molecule or an element under standard condition ∆Hoat
1/2H2(s) → H(g) ∆H o at = +218kJmol−1
 Enthalpy Definition Symbol
The amount of heat evolved when one mole of hydrogen ions H+ from
an acid, react with one mole of hydroxide ions (OH-) from a base to form
Enthalpy of one mole of water.
∆Hon
neutralization Example: The enthalpy of neutralization of sodium hydroxide by
hydrochloric acid is -57.4kJmol-1
NaOH + HCl → NaCl + H2 O ∆Hn = −57.4kJmol−1
Enthalpy of The enthalpy change when one mole of a substance is completely burnt
combustion in excess of oxygen under standard conditions. ∆Hoc
C2 𝐻5 𝑂𝐻(𝑙) + 3𝑂2 → 2CO2(g) + 3H2 O(𝑙) ∆Hoc = −1368kJmol−1
 Enthalpy Definition Symbol
Enthalpy of The amount of heat absorbed or evolved when one mole of a substance is
solution dissolved in so much solvent that further dilution results in no detectable
∆Hosol.
heat change
NH4 Cl(s) + aq ↔ NH 4 Cl aq ∆Hosol = +16.2kJmol−1

Enthalpy (energy) changes

• ∆ (delta means difference)
• H (means enthalpy)
• ∆H = EIN – EOUT (joules)
 Examples of reactions Examples of reactions Examples of
when ∆Ho = +ve when ∆Ho = -ve reactions when ∆Ho =
i. Enthalpy of i. Enthalpy of +ve or -ve
atomization (∆Hoat) neutralization (∆Hon) i. Enthalpy of
ii. Enthalpy of ionization ii. Enthalpy of formation (∆Hof)
(∆Hof) combustion (∆Hoc) ii. Enthalpy of
solution (∆Hosol)
 5. Sign of H

Any thing added to the

system is taken as
positive and which is give ∆H = ∆E + P∆V
Modes of transference of energy
out from the system is PV = nRT
taken as negative P∆V = ∆nRT
∆H = ∆E + ∆nRT
Heat (q) Work (W)
This mode of transference occurs if there is a difference This mode of transference of energy is possible, if the
of temperature between system and surrounding. system involves gaseous substances and there is a
a) It is a random form of energy difference of pressure between system and surrounding.
b) It is path dependent parameter Such a work is referred to as pressure-volume work (WPV)
c) Units are J, kJ or calories w = +ve if done on system, w = -ve if done by the system
q = +ve if added to system Ergs in CGS system and Joules in SI system
q = -ve if given out the system (1J = 10-7 ergs = 1Nm = 1Kg m2s-2)
 8. Born Haber Cycle

4. Born Haber Cycle:

The amount of heat evolved when gaseous ions of opposite charge combine to form one
mole of ionic solid is called energy.
e.g.
Na+(g) + Cl-(g) → NaCl(s) ∆Hl = -788kJmol-1
Direct determination of the lattice energy is difficult. However Hess’s law is helpful to
determine the lattice energy of binary ionic compounds M+X-. Using this law and Fritz Haber
in 1919 devised a method to calculate the lattice energy called Born Haber cycle. According
to this solid NaCl is formed from two different routes as
Direct route:
Na(s) + ½ Cl2(g) → NaCl(s) ∆Hf = -411kJmol
Second route:
The second route consists of five steps
• Atomization or sublimation of sodium
• Ionization of sodium
• Dissociate of chlorine
• Formation of chloride
• Formation of NaCl
1. Atomization or sublimation of sodium
Na(s) → Na(g) ∆Hat = +108kJmol
 2. Ionization of sodium:
Na(g) → Na+(g) + 1e- ∆H1 = +496kJmol
3. Dissociation of chlorine:
½ Cl2(s) → Cl(g) ∆Hd = +121kJmol
4. Formation of chloride:
Cl(g) + 1e- → Cl-1(g) ∆He = -349kJmol
5. Formation of NaCl
Na+ (from step 2) and Cl- (from step 4) combine to form solid NaCl. The energy released
is lattice energy say the enthalpy change for step 5 is ∆Hf.
ΔH x
= 108 + 496 + 121 - 349

ΔH x
= 376

ΔH l
= Δ H f -Δ H x

ΔH l
= -4 1 1 - 3 7 6
-1
ΔH l
= -7 8 7 k J m o l
 MCQ:
Whenever a reaction is endothermic, then it means that:
A. Heat is transferred from surrounding to the system
B. Heat content of the products is greater than those of the reactants
C. Both A and B
D. Heat content of the reactants is greater than those of the products

Explanation: (C)
• Heat is transferred from surrounding to the system
• Heat content of the products is greater than those of the reactants
 MCQ:
What type of reactions constitute a limiting case between
spontaneous and non-spontaneous reactions:
A. Irreversible reactions B. Reversible reactions
C. Nuclear reactions D. Thermal reactions

Explanation: (B) Reversible reactions

 MCQ:
Mark the incorrect statement:
A. System --- anything which is under observation
B. Beaker --- system
C. Surrounding --- environment of the system
D. Boundary --- the interface (real or imaginary) which separates system and
surrounding

Explanation: (B) Beaker --- system

 MCQ:
Which of the following has minimum heat of neutralization:
A. NH4OH + CH3COOH B. KOH + HNO3
C. NaOH + H2SO4 D. NaOH + HCl

Explanation: (A) NH4OH + CH3COOH

 MCQ:
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. This
is in accordance to:
A. Law of mass action B. Hess’s Law
C. Joule’s Law D. First law of thermodynamics

Explanation: (B) Hess’s Law

 MCQ:
Enthalpy of formation for one mole of carbon dioxide is 200kJ/mol.
What will be enthalpy of combustion for 3g of carbon:
A. 100kJmol-1 B. 50kJmol-1
C. 200kJmol-1 D. 400kJmol-1

Explanation: (B) 50kJmol-1

 MCQ:
One joule is equivalent to _______ calories:
A. 8.14 B. 41.84
C. 1/4.184 D. 4.184

Explanation: (D) One joule is equivalent to 4.184 calories.

 37
9. Hess’s Law

Definition Mathematically representation Applications

with explanation
• Hess’s law can be applied
If a chemical change According to Hess’s law
for one step reaction or
takes place by several mathematically ∆H can be
more than one step
different routes, the calculated as:
reaction. It can be used for
overall energy change is • Let A can be converted into D in
the measurement of
the same, regardless of a single step (first route) and
enthalpy change for:
the route by which the heat evolved is ∆H
i. Heat of combustion
chemical change occurs • If the reaction can have a route
ii. Heat of formation
provided the initial and (second route) from A → B → C
iii. Indirect measurement of
final conditions are the → D as shown below:
enthalpy change
same. This is in • ∆H = ∆H1 + ∆H2 + ∆H3
iv. Lattice energy (by Born
accordance to Hess’s law • ∑∆H (cycle) = 0
Hyber cycle)
 Q: By applying Hess’s law calculate the enthalpy 38
change for the formation of an aqueous solution of
NH4Cl from NH3 gas and HCl gas. The results for the
various reactions and pressures are as follows :

Explanation: (A) According to Hess’s Law ∆Hf = ∆H1 + ∆H2 + ∆H3

∆Hf = -35.16 - 72.41 - 51.48 = -159.05kJmol-1
Note:
FOR FURTHER MCQs SEE PRACTICE BOOK
WITH DETAILED EXPLANATION
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Thank you!