CHAPTER 3

THERMOCHEMISTRY

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TOPIC LEARNING OUTCOME
 To identify the types and nature of energy.
 To define the law of energy conservation (first law of
thermodynamics).
 To apply the first law of thermodynamics to solve
calculation of energy, heat and work.
 To define enthalpy and calculate the heat involved in a
chemical reaction.

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 CONTENTS

3.1 Nature & Types of Energy

3.2 Introduction to Thermodynamics

3.3 Energy changes in Chemical Reactions

3.4 Enthalpy of Chemical Reactions

3.5 Calorimetry

3.6 Standard Enthalpy of Formation and Reaction

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3.1 NATURE & TYPES OF ENERGY
 Definitionof Energy
- Capacity to do work-

All types of energy are capable of doing work,

however not all types of energy are relevant to
chemistry.

In Chemistry, “WORK” referring to energy

changes resulting from a process.
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 TYPES OF ENERGY
 Kinetic energy
Energy associated with an object by
virtue of its motion.

 Potential energy
Energy an object has by virtue of its
position in a field of force.

 ThermalEnergy
Energy associated with the random
movement of atoms and molecules. 5
 Radiant Energy
Solar energy originated from the sun (primary
energy).

o Chemical Energy
Energy stored within the structural units of
chemical substances.

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UNITS OF ENERGY
 SI unit of energy is the joule (J). This is a derived unit composed of three
basic units:
1 J = 1 kg.m2/s2
Both heat and work are expressed in joules.

See how it applies to work. [ F=force , d = distance ]

Work = F x d . A force changes the velocity of (accelerates) a mass. Velocity

has units of meters per second (m/s) so acceleration (a) has units of m/s 2.
Force therefore has of mass (m in kg) x acceleration

F= m x a in units of kg.m/s2
Therefore w = F x d has units of (kg.m/s2) x m =
kg.m2/s2 =J
1 cal = 4.184 J i.e 1J=1/4.184 = 0.2390 cal
1 kJ =1000J = 0.239 kcal = 239 cal 7
 ENERGY AS STATE FUNCTIONS

E is a state function , a property depends

only on the current state of the system
(its composition, volume, pressure, and
temperature) not on the path the system
took to reach that state.

 What this means is that changes in state

functions depend only on their initial and
final states. 8
3.2 INTRODUCTION TO THERMODYNAMICS
 All forms of energy can be converted from one
form to another.

 Example:

When we performed exercised, chemical

energy which stored in our body is
converted to kinetic energy.

When a ball starts to roll downhill, its potential

energy is converted to kinetic energy.
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 THE FIRST LAW OF THERMODYNAMICS
 Also known as Law of Conservation of Energy.

 Itstates that:
“Energy can be converted from one
form to another form, however cannot be
created or destroy.”

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 Closed
System:
ΔKe + ΔPe + ΔU = Q - W

 OpenSystem:
ΔKe + ΔPe + ΔH = Q - W

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 In order to observe and measure a change in energy,
we must define the:

SYSTEM
part of the universe that we are going to focus
on.

SURROUNDINGS
Every thing else relevant to the change is defined
as the

INTERNAL ENERGY
Each particle in the system has potential and kinetic
energy, and the sum of all energies for all the
particles in the system is the 12
 HEAT & WORK
 Energy transfer can appear in two forms; heat and work.

 Heat : (or thermal energy) usually given the letter q is the energy
transferred between a system and its surroundings as a result of a
difference in their temperatures only. All other forms of energy transfer
(mechanical, electrical, etc) involve some type of WORK (w).

 The total change in a system’s internal energy is the sum of the energy
transferred as heat and / or work.
ΔE = q + w
( value of q and w can be either negative or positive)
We define the sign of the energy transfer from the system’s perspective
only.
Energy coming into the system is positive 13

Energy going out from the system is negative

THERE ARE FOUR SIMPLE CASES:
A-TWO THAT INVOLVE ONLY HEAT TRANSFER
B-TWO THAT INVOLVE ONLY WORK
1. Heat transfer as Heat only. For a system that does no work but transfers
energy only as heat (q). i.e w = 0
therefore :

ΔE = q + w
=q+0
=q

Case 1:
Heat flowing out from a system. e.g. glass of hot water on the table. The
water transfers energy as heat to the surroundings until the T of water
equals that of surroundings. The system’s energy decreases as heat
flows out from the system, so the final energy of the system is less than
its initial energy. Heat was lost by the system , therefore, q is negative

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ENERGY TRANSFER AS HEAT ONLY

q = negative
Hot water, (the
system, sys)
transfers energy
as heat (q) to the
surroundungs
(surr) until
Tsys= Tsurr .
Since Einitial > Efinal
and 15

w=0 ΔE < 0
CASE 2, HEAT FLOWING INTO A SYSTEM
 E.g glass filled with ice-water.
It gains energy as heat from
the surroundings until the
temperature of the water
equals that of the
surroundings. In this case
energy is transferred into the
system, so the final energy of
the system is higher than its
initial energy. Heat was gained
by the system, so q is
positive and ΔE is positive

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• The system is loosing
energy as work is done.
• The internal energy of
the system decreases as
the reactants form
products because the H2
gas does work (w) on

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the surroundings

by pushing back the piston. The reaction vessel is

insulated, so q = 0 since Einitial > E final then
ΔE < 0 , and the sign of w is negative
The H2 gas is doing pressure-volume work (PV
work). This is a type of work in which a volume
changes against an external pressure.
SUMMARY OF THE SIGN CONVENTIONS
E = q + w
E : change in internal energy of a system
Q : heat exchange between the system and the
surroundings
W : work done on (or by) the system

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3.3 ENERGY CHANGES IN CHEMICAL
REACTIONS

 Thermochemistry is the study of the energy changes

taking place during chemical reactions.

 Every substance contains stored chemical energy,

called enthalpy, mainly by virtue of chemical bonds.

 Absolute enthalpy is hard to measure, but enthalpy

changes during reactions are easy to measure
because there will be an observable energy exchange
between the chemicals and the surroundings.

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• It is a branch of thermodynamics that deals with
the heat involved in chemical and physical change
and specially with the concept of enthalpy H.

• H enthalpy means the heat involved at constant

pressure

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3.4 ENTHALPY OF CHEMICAL
REACTIONS

Enthalpy is a STATE FUNCTION

The path taken from reactants to products is

irrelevant

Thermochemical equations are chemical

equations with an added heat term

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 The energy associated with a change such as:
reactants products

 The internal energy E of this system has changed . To determine this

change ΔE we measure the difference between the system’s internal
energy after the change (E final) and before the change (E initial) :

ΔE = E final - E initial = E products – E reactants

 Note that Δ refer to the final state of the system MINUS the initial state.
ALWAYS

 ONE FACT: The total energy of the system and surrounding is constant
(conserved). This means that a change in the energy of the system is
always accompanied by an opposite change in the energy of the
surroundings.
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The energy of the system The energy of the system
increases decreases
ΔE is positive which means: ΔE is negative in other words
E final > E initial ΔE > 0 E final < E initial ΔE < 0
The system is gaining energy The system is loosing energy to the
from the surroundings surroundings
Note that the change in energy is always a transfer of energy from 23
system to surroundings, or vice versa
 HEAT OF REACTION

 In chemical reactions, heat is often

transferred from the system to its
surroundings – or vice versa.

 Heat flows from a region of higher

temperature to one lower temperature . Once
the temperature becomes equal, heat flow
stops.

 Heatof reaction is the value of q required to

return a system to the given temperature at 24

the completion of reaction.

 EXOTHERMIC AND ENDOTHERMIC
PROCESSES
 Because E, P and V are state functions, H is also a state
function which means that ΔH depends on difference
between H final and H initial . The enthalpy of a reaction ,
also called the heat of reaction , ΔH reaction always refer
to [ H final minus H initial ]. Or simply the difference
between enthalpies of products and reactants.

 Because the Hproducts can be either more or less than

Hreactants , the sign of ΔH reaction indicates whether heat is
absorbed or released in the change.

 We determine the sign of ΔH by imagining the heat as

a “reactant” or “product”.

CH 4 ( gas )  O2( gas )  CO2 ( gas )  H 2 O( gas )  heat 25

 Because heat is released to the surroundings, the products (1 mol
of CO2 and 2 mol of H2O ) must have less enthalpy than the
reactants (1 mol CH4 and two mol of O2). Therefore,
 ΔH = (Hproducts- Hreactants) is negative

CO2+2H2O
H final
CH4+2O2
H initial

Enthalpy H
Enthalpy H

Heat in
ΔH > 0
Heat out
ΔH < 0

CH4+2O2
H initial
CO2+2H2O
H final

Endothermic process
Exothermic process

An exothermic (heat out) process releases heat to the

surrounding and always is associated with a decrease
in enthalpy of the system
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For exothermic processes :Hfinal < Hinitial and ΔH < 0

 An endothermic (heat in) process absorbs heat and
results in an increase in the enthalpy of the system. e.g.
Heat + H2O(solid H2O(l) heat flows into the
system from the surroundings. Notice “heat” appears as
a reactant.

Because heat is absorbed , the enthalpy of the liquid

water is higher than that of solid water, therefore:
For endothermic processes :Hfinal > Hinitial and ΔH > 0

Please note that the value of an enthalpy change refer to the

reactants and products at the same temperature.

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REMEMBER

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 SOME IMPORTANT TYPES OF
ENTHALPY CHANGE
 Some enthalpy changes are frequently studied and,
therefore, they have special names:

 Heat of combustion ΔHcomb:

When one mole of a substance combine with
excess O2 in a combustion reaction

 Heat of formation ΔHf :

when one mole of a compound is produced
from its elements
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 Heat of fusion ΔHfus:
When one mole of a substance melts

 Heat of vaporization ΔHvap:

Heat associated with vaporization of one mole of a
substance.

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STOICHIOMETRY OF THERMOCHEMICAL
EQUATIONS
 A thermochemical equation is a balanced equation that
include the heat of reaction ΔHreaction . Keep in mind that
the ΔHreaction shown refers to amounts (moles) of
substances AND their states of matter in that specific
equation.
The enthalpy changes in any process has two aspects:
1-Sign – the sign of ΔH depends on whether the reaction
is exothermic (-) or endothermic (+). Remember that a
forward reaction has the opposite sign of the reverse
reaction.

2H  O2( g )  2H 2O( g ) H  572 kJ

2( g ) 31

2H 2O( g )  2H  O2( g ) H  572 kJ

2( g )
2- Magnitude: the magnitude of ΔH is proportional to the amount of
substances reacting.
Formation of 1 mole of water from its elements

1
H  O2( g )  H 2O( g ) H  286 kJ
2( g ) 2

Problem: The major source of Al in the world is bauxite

(mostly aluminium oxide). It’s thermal decomposition can be represented
by:
Al2O3 (s) 2Al + ½O2 ΔH =1676 kJ
How many grams of Al can be produced from 1.000 x 103kJ.

Solution: If 1676 kJ produced 2 x 26.98, then 1000 kJ will produce

1676 = 32.20 gm of Al/)x 26.98 x 2 1000(=
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3.5 CALORIMETRY

•Heat changes in physical and chemical

processes are measured with a
calorimeter, which is a closed container
designed for this purpose.

•The measurement of heat changes will

depend on an understanding of specific
heat and heat capacity.
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Specific heat capacity
The heat needed to increase the temperature of 1
g of a substance by 1 C. Symbol: c, units:
J/(gC).

Heat capacity
The heat needed to increase the temperature of
an object by 1 C. Symbol: C (= c x m), units: J/C

Heat of reaction
The heat released during a chemical reaction.
Symbol: none, units: J.

Molar heat of reaction

The heat released during a chemical reaction per 34

mole of reactant. Symbol: H, units: J/mol.

Calculation of Heat :

•To determine the amount of heat a substance produces

or absorbs we often use q = m.cp.T
Where: q: heat in J
cp : specific heat capacity in J/(gC)
m : mass in g
T : temperature change in C

•Sample problem: (must know water = 4.18 J/gC)

•When 12 g of a food was burned in a calorimeter, the

100 mL of water in the calorimeter changed from 20C to
33C. Calculate the heat released by the water.
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q  c.m.T
 4.18 x 100 x 13
 5.4 kJ

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MORE QUESTIONS

1. 5 g of copper was heated from 20C to

80C. How much energy is used to
heat the copper?

2. If a 3.1 g ring is heated using 10.0 J,

it’s temperature rises by 17.9C. Calculate
the specific heat capacity of the ring. Is
the ring pure gold?

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 c = q/mT=

10.0 J/ 3.1 g x 17.9C

= 0.18 J/(g°C)

The ring is not pure. Gold

(for pure gold is 0.13 J/(gC)

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S = SPECIFIC HEAT
C = HEAT CAPACITIES
3.6 STANDARD ENTHALPY OF
FORMATION AND REACTION

3 Methods to calculate (ΔH) :

1. Experimental (Measure it in the lab)

2. Direct method
- Using the enthalpies of formation

3. Indirect method
- Using Hess Law 39
 1.
EXPERIMENTAL
Measuring H in the
lab by bomb
calorimeter

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 The importance of the standard enthalpies of formation is
that, once we know their values, we can readily calculate
the standard enthalpy of reaction, ΔH°rxn, defined as the
enthalpy of a reaction carried out at 1atm.

Consider the following :

aA + bB cC + dD

ΔH°rxn = ∑ n ΔH°f (products) - ∑ m ΔH°f (reactant)

Note : n & m (stoichiometric coefficient) 41

 Problem

Estimate the change in enthalpy, ΔH, for the following

reaction:

H2 (g) + Cl2 (g) → 2 HCl (g)

ΔH°rxn = ∑ n ΔH°f (products) - ∑ m ΔH°f (reactant)

= 2(-92.3 kJ/mol) - [1(0) + 1(0)]
= -184.6 kJ/mol

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 o
1. An element in its standard state is assigned H f =0 Note in
o
the past examples we regarded H f for Na = 0
2. The standard state of diatomic gases is X2 and not X
3. Most compounds have a negative heat of formation.

Standard Heats of Formation H of

Formula
0 Ca
-635.1 CaO
0 Cl2
-92.3 HCl
0 S8 rhombic
0 H2
143 ( note it is positive) O3 43
 3. HESS’S LAW OF HEAT SUMMATION.

 Many reactions are difficult or impossible to

carry out in the labs in order to measure their
enthalpies.

 Yet it is possible to calculate their enthalpies,

because of, when reactant is converted to
products, the changes in enthalpy is the same
whether the reaction takes place in one step
or in a series of steps.

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 HESS’S LAW
• For any chemical change made in several
steps, the net H is equal to the sum of the
H values of the separate steps

Or

• The standard enthalpy of an overall reaction

is the sum of the standard enthalpies of the
individual reactions into which a reaction
may be divided
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 When we burn S in an excess of O2 , SO2 is formed, not SO3

Hess’s law tells us that if we manipulate eqn. 1 and/or 2 so

that they add up to eqn. 3, then ΔH3 is the sum of the
manipulated ΔH values of equation 1 & 2. 46
 47
Once again the key point is that H is a state function
ANOTHER EXAMPLE

e.g. find H for the reaction:

2 CH4(g) + 3 O2(g) 2 CO(g) + 4 H2O(l)

using the following data:

CH4(g) + 2 O2(g)  CO2(g) + 2 H2O(l) …….(1)

H = -890 kJ

2 CO(g) + O2(g)  2 CO2(g) ……(2)

H = -566 kJ
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 IN CLASS ASSIGNMENT
1) Calculate ∆H for the reaction: C2H4 (g) + H2 (g) C2H6 (g), from the
following data.
C2H4 (g) + 3 O2 (g) 2 CO2 (g) + 2 H2O (l) ∆H = -1411. kJ
C2H6 (g) + 3½ O2 (g) 2 CO2 (g) + 3 H2O (l) ∆H = -1560. kJ
H2 (g) + ½ O2 (g) H2O (l) ∆H = -285.8 kJ

2) Find ∆H° for the reaction 2H2(g) + 2C(s) + O2(g) C2H5OH(l), using the
following thermochemical data.
C2H5OH (l) + 2 O2 (g) 2 CO2 (g) + 2 H2O (l) ∆H = -875. kJ
C (s) + O2 (g) CO2 (g) ∆H = -394.51 kJ
H2 (g) + ½ O2 (g) H2O (l) ∆H = -285.8 49kJ
3) Find the ΔH for the reaction below, given the following reactions and
subsequent ΔH values:

PCl5(g)  →  PCl3(g)  +  Cl2(g)

P4(s)  +  6Cl2(g)  →  4PCl3(g) ΔH = -2439 kJ

4PCl5(g)  →  P4(s)  +  10Cl 2(g) ΔH = 3438 kJ

4) Find the ΔH for the reaction below, given the following reactions and
subsequent ΔH values:

H2SO4(l)  →  SO3(g)  +  H2O(g)

H2S(g)  +  2O2(g)  →  H2SO4(l)               ΔH = -235.5 kJ

H2S(g)  +  2O2(g)  →  SO3(g)  +  H2O(l)    ΔH = -207 kJ
H2O(l)  →  H2O(g)                                   ΔH = 44 kJ

50

 
5) Find the ΔH for the reaction below, given the following
reactions and subsequent ΔH values:

CO2(g)  →  C(s) +  O2(g)

H2O(l)  →  H2(g)  +  1/2O2(g)               ΔH = 643 kJ

C2H6(g)  →  2C(s) +  3H 2(g)                 ΔH = 190.6

kJ
2CO2(g) +  3H2O(l)  →  C 2H6(g) + 7/2O2(g) ΔH = 3511.1
kJ

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