17.

4 Calculating Heats of Reaction >

INTRODUCTION

 Energy exists in different forms.

Some of which can felt or seen. It is
defined by its effect on matter or the
ability of an object or system to do
work on another object or system or
to transfer heat. Let us discuss
each of the six basic forms in which
we use energy in our daily life:

2
17.4 Calculating Heats of Reaction >
THERMOCHEMISTRY

 a branch of chemistry that

describes the energy changes
that occur during chemical
reactions.
 the study of the heat energy
which is associated
with chemical reactions and/or
physical transformations.
3
17.4 Calculating Heats of Reaction >
MECHANICAL ENERGY

 Kinetic mechanical energy is the

energy that a body possesses by
virtue of its motion. On the other
hand, potential mechanical
energy is the energy that a body
possesses by virtue of its
position in relation to a reference
point.
4
17.4 Calculating Heats of Reaction >
CHEMICAL ENERGY

 Chemical energy is the energy stored in

the bonds of chemical compounds in the
form of microscopic potential energy.
This exists due to the electric and
magnetic forces of attraction exerted
between the different parts of each
chemical compound. When these
chemical compounds get rearranged, it
causes this energy to be released or
added.
5
17.4 Calculating Heats of Reaction >
THERMAL / HEAT ENERGY

 Thermal energy is the energy resulting

when atoms or molecules move. If these
particles move faster, the resulting
thermal energy will also be greater. The
temperature of an object is a measure of
how much thermal or heat energy it has.
When the object has a higher
temperature, this also means its
molecules are moving and/or vibrating
faster.
6
17.4 Calculating Heats of Reaction >
ELECTRICAL ENERGY

 Electrical energy is the energy resulting

from the flow of electrically charged
particles or the movement of electrons
among the atoms of matter. It is
considered as one of the most useful
and versatile forms of energy as it is
mostly used in our day to day activities
powering our electronics and machines
in the house.

7
17.4 Calculating Heats of Reaction >
CONVERSION OF EE

8
17.4 Calculating Heats of Reaction >
NUCLEAR ENERGY

 Nuclear energy is the energy produced

when reactions occur in an atom. Fusion
occurs when the two nuclei join together
to form a larger nucleus or particle. With
this process, energy is released in the
form of light and heat. Fission, on the
other hand, occurs when the nucleus of
a larger atom splits into two smaller
atoms. This also produces huge amount
energy in the form of light and heat.
9
17.4 Calculating Heats of Reaction >
RADIATION

 Radiation is the energy

transmitted in the form of rays,
waves, or particles like the
visible light that we can see,
infrared radiation, ultraviolet
radiation, etc.

10
17.4 Calculating
ENERGY Heats IN
CHANGES of CHEMICAL
Reaction > REACTIONS

 The first law of

thermodynamics states that
energy can be converted from
one form to another, but is
neither created nor destroyed.

11
17.4 Calculating
ENERGY Heats IN
CHANGES of CHEMICAL
Reaction > REACTIONS

 In chemical reactions, these involve

change in energy between the reactants
and products. This is because of the
absorption of energy when chemical
bonds broken or the release of energy
when chemical bonds are formed. With
these changes in energy during chemical
reactions, the total energy of a system
shall remain unchanged because of the
Law of Conservation of Energy.
12
17.4 Calculating
ENERGY Heats IN
CHANGES of CHEMICAL
Reaction > REACTIONS

 The energy change in a chemical

reaction is because of the difference in
the amounts of stored chemical energy
between the reactants and the products.
This stored chemical energy, or heat
content, of the system is known as its
enthalpy.

13
17.4 Calculating Heats of Reaction >
Exothermic Reactions

 This type of reaction releases heat and light

into their surroundings. In this reaction or
process, the products have less enthalpy
compared to the reactants. This results to a
negative enthalpy of reaction since the energy
required to break the reactants’ bonds is less
than the energy released when new bonds
form in the products. Heat and light are
released as an excess energy from the
reaction. Combustion reactions are common
examples of exothermic reactions.
14
17.4 Calculating Heats of Reaction >
Endothermic Reactions

 This type of reaction absorbs heat and/or

light from their surroundings. In this reaction
or process, the products have more enthalpy
compared to the reactants. This results to a
positive enthalpy of reaction since the energy
required to break the reactants’ bonds is
more than the energy released when new
bonds form in the products. This means that
this reaction requires energy to proceed.
Decomposition reactions are common
examples of endothermic reactions.
15
17.4 Calculating Heats of Reaction >
HESS LAW

 This law states that the

standard reaction enthalpy is the
sum of adding of the standard
enthalpies of the intermediate
reactions into which the overall
reaction can be divided, while
each occurs at the same
temperature
16
17.4 Calculating Heats of Reaction >
HESS LAW

 It is derived directly from the law of

conservation of energy, and its
expression from the first law of
thermodynamics. Since enthalpy is
a state function, its change between
reactants and products in a
chemical system is independent of
the pathway taken from the initial to
the final state of the system.
17
17.4 Calculating Heats of Reaction >
HESS LAW

 It is derived directly from the law of

conservation of energy, and its
expression from the first law of
thermodynamics. Since enthalpy is
a state function, its change between
reactants and products in a
chemical system is independent of
the pathway taken from the initial to
the final state of the system.
18
17.4 Calculating Heats of Reaction >
HESS LAW

 Hess's Law of Constant Heat

Summation (or just Hess's Law)
states that regardless of the multiple
stages or steps of a reaction, the
total enthalpy change for the
reaction is the sum of all changes.
This law is a manifestation that
enthalpy is a state function.

19
17.4 Calculating Heats of Reaction >
HESS LAW

 Hess’s Law can be used to determine

the energy required for a chemical
reaction, especially when the reaction
involves a series of steps. This is very
important because we don’t want any
unexpected explosions when dealing
with chemical reactions. A
thermochemical equation is chemical
equation where it includes the enthalpy
change of the reaction.
20
17.4 Calculating Heats of Reaction >
EXAMPLE

21
17.4 Calculating Heats of Reaction >
HESS LAW

 When reactants are converted to

products involving exothermic reaction
(A), enthalpy is released into the
surroundings, thus the enthalpy change
of the reaction is negative. On the other
side, when reactants are converted to
products involving endothermic reaction
(B), enthalpy is absorbed from the
surroundings and its enthalpy change of
the reaction is positive.
22
17.4 Calculating Heats of Reaction >
THERMOCHEMISTRY

Let us consider the combustion of methane as an example.

Since heat is released by the system, its enthalpy change is
negative. Thus, its overall enthalpy of the system decreases.
The enthalpy of change for a chemical reaction is the heat of
reaction and are measured in kilojoules. With our example,
the heat of reaction is −890.4 kJ. The thermochemical
equation of this reaction can be written in this way:

23
17.4 Calculating Heats of Reaction >
THERMOCHEMISTRY

In endothermic reactions, the energy is absorbed from the

surroundings when the reaction happens. Referring to
Figure 8.31 above in letter B, 177.8 kJ of heat is absorbed
when 1 mol of calcium carbonate decomposes into 1 mol of
calcium oxide and 1 mol of carbon dioxide. This can be
written through thermochemical reaction as:

24
17.4 Calculating Heats of Reaction >
THERMOCHEMISTRY

The way in which the reaction is written influences

the value of enthalpy change for the reaction. When
the reaction is written in the reverse direction, the
sign of the ΔH changes. Let us take a look again at
the reaction of calcium oxide with carbon dioxide to
form calcium carbonate.

25
17.4 Calculating Heats of Reaction >
THERMOCHEMISTRY

The reaction is exothermic so

the enthalpy change is
negative.

26
17.4 Calculating Heats of Reaction >
THERMOCHEMISTRY

How much heat is released when a

diamond changes into graphite?
Diamonds are gemstones
composed of carbon.
Over a time period of
millions and millions of
years, diamond will break
down into graphite, which
is another form of carbon.

27
17.4 Calculating
HESS Heats
LAW of Reaction >

Hess’s Law
How can you calculate the heat of
reaction when it cannot be directly
measured?

28
17.4 Calculating Heats of Reaction >
HESS LAW

Hess’s law of heat summation states that

if you add two or more thermochemical
equations to give a final equation, then you
can also add the heats of reaction to give
the final heat of reaction.

29 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

17.4 Calculating Heats of Reaction >
HESS LAW

C(s, diamond) → C(s, graphite)

Although the enthalpy change for this reaction
cannot be measured directly, you can use Hess’s
law to find the enthalpy change for the conversion
of diamond to graphite by using the following
combustion reactions.
a. C(s, graphite) + O2(g) → CO2(g) ΔH = –393.5 kJ
b. C(s, diamond) + O2(g) → CO2(g) ΔH = –395.4 kJ

30 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

17.4 Calculating Heats of Reaction >
HESS LAW

C(s, diamond) → C(s, graphite)

a. C(s, graphite) + O2(g) → CO2(g) ΔH = –393.5 kJ
b. C(s, diamond) + O2(g) → CO2(g) ΔH = –395.4 kJ
Write equation a in reverse to give:
c. CO2(g) → C(s, graphite) + O2(g) ΔH = 393.5 kJ

When you reverse a reaction, you must also

change the sign of ΔH.

31 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

17.4 Calculating Heats of Reaction >
HESS LAW

C(s, diamond) → C(s, graphite)

b. C(s, diamond) + O2(g) → CO2(g) ΔH = –395.4 kJ
c. CO2(g) → C(s, graphite) + O2(g) ΔH = 393.5 kJ
If you add equations b and c, you get the equation
for the conversion of diamond to graphite.

C(s, diamond) + O2(g) → CO2(g) ΔH = –395.4 kJ

CO2(g) → C(s, graphite) + O2(g) ΔH = 393.5 kJ
C(s, diamond) → C(s, graphite)
32 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.
17.4 Calculating Heats of Reaction >
HESS LAW

C(s, diamond) → C(s, graphite)

If you also add the values of ΔH for equations b

and c, you get the heat of reaction for this
conversion.

C(s, diamond) + O2(g) → CO2(g) ΔH = –395.4 kJ

CO2(g) → C(s, graphite) + O2(g) ΔH = 393.5 kJ
C(s, diamond) → C(s, graphite) ΔH = –1.9 kJ
33 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.
17.4 Calculating Heats of Reaction >
HESS LAW

C(s, diamond) + O2(g) → CO2(g) ΔH = –395.4 kJ

CO2(g) → C(s, graphite) + O2(g) ΔH = 393.5 kJ
C(s, diamond) → C(s, graphite) ΔH = –1.9 kJ

34 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

17.4 Calculating
StandardHeats of Reaction
Heats >
of Formation

The standard heat of formation (ΔHf°) of

a compound is the change in enthalpy that
accompanies the formation of one mole of a
compound from its elements with all
substances in their standard states.
• The ΔHf° of a free element in its standard
state is arbitrarily set at zero.
• Thus, ΔHf° = 0 for the diatomic molecules
H2(g), N2(g), O2(g), F2(g), Cl2(g), Br2(l), and
I2(s).
35 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.
17.4 Calculating
StandardHeats of Reaction
Heats >
of Formation
Standard Heats of Formation (ΔHf°) at 25°C and 101.3 kPa
ΔHf° ΔHf° ΔHf°
Substance Substance Substance
(kJ/mol) (kJ/mol) (kJ/mol)
Al2O3(s) –1676.0 F2(g) 0.0 NO(g) 90.37
Br2(g) 30.91 Fe(s) 0.0 NO2(g) 33.85
Br2(l) 0.0 Fe2O3(s) –822.1 NaCl(s) –411.2
C(s, diamond) 1.9 H2(g) 0.0 O2(g) 0.0
C(s, graphite) 0.0 H2O(g) –241.8 O3(g) 142.0
CH4(g) –74.86 H2O(l) –285.8 P(s, white) 0.0
CO(g) –110.5 H2O2(l) –187.8 P(s, red) –18.4
CO2(g) –393.5 I2(g) 62.4 S(s, rhombic) 0.0
CaCO3(s) –1207.0 I2(s) 0.0 S(s, monoclinic) 0.30
CaO(s) –635.1 N2(g) 0.0 SO2(g) –296.8
Cl2(g) 0.0 NH3(g) –46.19 SO3(g) –395.7

36 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

17.4 Calculating
StandardHeats of Reaction
Heats >
of Formation

For a reaction that occurs at standard

conditions, you can calculate the heat
of reaction by using standard heats of
formation.
• Such an enthalpy change is called
the standard heat of reaction (ΔH°).

37 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

17.4 Calculating Heats of Reaction >
Calculation of the Heat of Reaction from
Standard Heats of Formation
is based on the following equations:

38 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

17.4 Calculating
StandardHeats of Reaction
Heats >
of Formation

For a reaction that occurs at standard

conditions, you can calculate the heat
of reaction by using standard heats of
formation.
• The standard heat of reaction is the
difference between the standard
heats of formation of all the reactants
and products.

ΔH° = ΔHf°(products) – ΔHf°(reactants)

39 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

17.4 Calculating
StandardHeats of Reaction
Heats >
of Formation

Calculating the Standard Heat

of Reaction
What is the standard heat of
reaction (ΔH°) for the reaction
of CO(g) with O2(g) to form
CO2(g)?

40 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

17.4 Calculating
StandardHeats of Reaction
Heats >
of Formation

1 Analyze List the knowns and the unknown.

Balance the equation of the reaction of CO(g)
with O2(g) to form CO2(g). Then determine
ΔH° using the standard heats of formation of
the reactants and products.
KNOWNS UNKNOWN
ΔHf°CO(g) = –110.5 kJ/mol ΔH° = ? kJ
ΔHf°O2(g) = 0 kJ/mol (free
element)
ΔHf°CO2(g) = –393.5 kJ/mol
41 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.
17.4 Calculating
StandardHeats of Reaction
Heats >
of Formation

2 Calculate Solve for the unknown.

First write the balanced equation.

2CO(g) + O2(g) → 2CO2(g)

42 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

17.4 Calculating
StandardHeats of Reaction
Heats >
of Formation

2 Calculate Solve for the unknown.

Find and add ΔHf° of all the reactants.

ΔHf°(reactants) = 2 mol CO(g)  ΔHf°CO(g) + 1 mol O2(g) 
ΔHf°O2(g)
–110.5 kJ 0 kJ
= 2 mol CO(g)  12 mol CO(g)+ 1 mol O2(g)  1 mol O (g)
2

= –221.0 kJ
Remember to take into
account the number of moles
of each reactant and product.

43 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

17.4 Calculating
StandardHeats of Reaction
Heats >
of Formation

2 Calculate Solve for the unknown.

Find ΔHf° of the product in a similar way.

ΔHf°(products) = 2 mol CO2(g) 
ΔHf°CO2(g)
–393.5 kJ
= 2 mol CO2(g)  1 mol CO (g)
2

= –787.0 kJ
Remember to take into
account the number of moles
of each reactant and product.
44 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.
17.4 Calculating
StandardHeats of Reaction
Heats >
of Formation

2 Calculate Solve for the unknown.

Calculate ΔH° for the reaction.

ΔH° = ΔHf°(products) – ΔHf°(reactants)
= (–787.0 kJ) – (–221.0 kJ)
= –566.0 kJ

45 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

17.4 Calculating
StandardHeats of Reaction
Heats >
of Formation

3 Evaluate Does the result make sense?

• The ΔH° is negative, so the reaction is

exothermic.
• This outcome makes sense because
combustion reactions always release heat.

46 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

17.4 Calculating
StandardHeats of Reaction
Heats >
of Formation

Standard heats of formation are used to

calculate the enthalpy change for the
reaction of carbon monoxide and oxygen.
• 2CO(g) + O2(g) → 2CO2(g)
• The diagram shows the
difference between
ΔHf°(product) and
ΔHf°(reactants) after taking
into account the number of
moles of each.

47 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

17.4 Calculating
StandardHeats of Reaction
Heats >
of Formation
Calculate the standard heat of reaction
for the following:
CH4(g) + Cl2(g) → C(s, diamond) + 4HCl(g)
ΔHf°(CH4(g)) = –74.86 kJ/mol

ΔHf°(C(s, diamond)) = 1.9 kJ/mol

ΔHf°(HCl(g)) = –92.3 kJ/mol

ΔH° = ΔHf°(products) – ΔHf°(reactants)

48 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

17.4 Calculating
StandardHeats of Reaction
Heats >
of Formation
Standard Heats of Formation (ΔHf°) at 25°C and 101.3 kPa
ΔHf° ΔHf° ΔHf°
Substance Substance Substance
(kJ/mol) (kJ/mol) (kJ/mol)
Al2O3(s) –1676.0 F2(g) 0.0 NO(g) 90.37
Br2(g) 30.91 Fe(s) 0.0 NO2(g) 33.85
Br2(l) 0.0 Fe2O3(s) –822.1 NaCl(s) –411.2
C(s, diamond) 1.9 H2(g) 0.0 O2(g) 0.0
C(s, graphite) 0.0 H2O(g) –241.8 O3(g) 142.0
CH4(g) –74.86 H2O(l) –285.8 P(s, white) 0.0
CO(g) –110.5 H2O2(l) –187.8 P(s, red) –18.4
CO2(g) –393.5 I2(g) 62.4 S(s, rhombic) 0.0
CaCO3(s) –1207.0 I2(s) 0.0 S(s, monoclinic) 0.30
CaO(s) –635.1 N2(g) 0.0 SO2(g) –296.8
Cl2(g) 0.0 NH3(g) –46.19 SO3(g) –395.7

49 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

17.4 Calculating Heats
HESSof Reaction
LAW > Hess’s Law
1. Determine the enthalpy change for the
formation of carbon monoxide from its elements.
C(s, graphite)+ 12 O2(g) → CO(g) ΔH = ?
calculate the desired enthalpy change by using
Hess’s law and the following two reactions that
can be carried out in the laboratory

Write reaction enthalpy changes when a process

is reversed.

50 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

17.4 Calculating Heats of Reaction >

Calculate the standard heat of reaction

for the following:
CH4(g) + Cl2(g) → C(s, diamond) + 4HCl(g)
ΔHf°(CH4(g)) = –74.86 kJ/mol

ΔHf°(C(s, diamond)) = 1.9 kJ/mol

ΔHf°(HCl(g)) = –92.3 kJ/mol

ΔHf°(reactants) = [1 mol CH4(g)  ΔHf°CH4(g)] + [1 mol Cl2  ΔHf°Cl2(g)]
= –74.86 kJ + 0.0 kJ = –74.86 kJ
ΔHf°(products) = [1 mol C(s)  ΔHf°C(s, diamond)] + [4 mol HCl  ΔHf°HCl(g)]
= 1.9 kJ + (4  –92.3 kJ) = –367.3 kJ
ΔH° = ΔHf°(products) – ΔHf°(reactants) = –367.3 kJ – (–74.86 kJ) = –292.4 kJ

51 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

17.4 Calculating Heats of Reaction > Hess’s Law

You can calculate the desired enthalpy

change by using Hess’s law and the
following two reactions that can be carried
out in the laboratory:
C(s, graphite) + O2(g) → CO2(g) ΔH = –393.5 kJ
CO2(g) → CO(g) + 12 O2(g) ΔH = 283.0 kJ
C(s, graphite)+ 12 O2(g) → CO(g) ΔH = –110.5 kJ

52 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

17.4 Calculating Heats of Reaction > Hess’s Law

C(s, graphite) + O2(g) → CO2(g) ΔH = –393.5 kJ

CO2(g) → CO(g) + 12 O2(g) ΔH = 283.0 kJ
C(s, graphite)+ 12 O2(g) → CO(g) ΔH = –110.5 kJ

53 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.