Module on

Energy Relationships in Chemical Reactions

(Thermochemistry)
The Nature of Energy and Types of Energy
Energy is the capacity to do work or to transfer heats.
Forms
1.
2.
3.
4.
5.

of Energy
Kinetic energy
Radiant energy
Thermal energy
Chemical energy
Potential energy

Energy Changes in Chemical Reactions

Heat is the transfer of thermal energy between two bodies that are at different
temperature.
Thermochemistry is the study of heat change in chemical reactions.
Terms:
System part of the universe set aside for study.
Surroundings part of the universe outside the system
Types of systems:
1. Open system can exchange mass and energy usually in the form of heat
with its surroundings.
2. Closed system allows transfer of energy but not mass.
3. Isolated system does not allow the transfer of either mass or energy.
Types of energy or heat transfer
1. Exothermic process gives off heat to its surroundings
Example:
2H2(g) + O2(g) 2H2O(l) + energy
2. Endothermic process absorbs heat from its surroundings
Example:
Energy + 2HgO(s) 2Hg(l) + O2(g)
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Practice Exercise 6.1: Tell whether the following is an open, closed or isolated system.
a. tree
b. steel
c. rice cooker
d. coleman jug
e. oven
f. electric fan
g. automobile
h. hammer

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Introduction to Thermodynamics
Thermodynamics
- study of the interconversion of heat and other kinds of energy.
Thermodynamic state of a system defined by a set of condition that completely
specifies all the properties of the system, such as temperature, pressure, composition
(identity and amount) and physical state (gas, liquid, solid)

State Function depends only on the state of the system and not on the way in
which the came to be in that state (P,V, T)
- a change in a state function describes a difference between
two states. It is independent of the process or pathway by which the change
occurs.
X = Xfinal - Xinitial
The First Law of Thermodynamics
Statement:
1. Energy ca be converted from one form to another, but cannot be created or
destroyed.
2. The total energy of the isolated system is constant.
3. The sum of all energy changes for all system participating in a process must be zero.
Mathematical Statement:
Energy of the system + Energy of the surroundings = 0
Internal Energy (E) the total energy of the system due to potential and kinetic
energies.
E = Efinal - Einitial
Eststem + surroundings = o
Esystem = -Esurroundings
The change in internal energy, E, is determined by the heat flow, q, and the work, w
E = q + w
Sign Conventions for Work and Heat
Process
Work done by the system on the surroundings
Work done on the system by the surroundings
Heat absorbed by the system from the
surroundings
Heat absorbed by the surroundings from the
system

Sign

+
+

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Practice Exercise 6.2: The work done when a gas is compressed in a cylinder is 462J.
During the process, there is a heat transfer of 128J from the gas to the surroundings.
Calculate the energy change for this process.

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Work
In most chemical and physical changes, the only kind of work is pressure-volume work.
For gas expansion against a constant external pressure
P
P
V

gas

W = - PV
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Practice Exercise 6.3: A sample of gas expands by 22.4L against an average pressure of
2.5atm. How much work (kJ) is done in the process? Is the work done by the system or by
the surrounding?

Special Cases of Processes

1. Constant Volume Process
V = 0;
Therefore:

PV = 0

E = qv

2. Constant Pressure Process

E = q + w
= qp - PV
qp = E + PV
Enthalphy, H the sum of internal energy and work.
H = E + PV
H = E + (PV)
At constant pressure
H = E +
PV

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Enthalphy of Reactions
For any reaction of the type
Reactants Products
H = H (products) H (reactants)
Thermochemical Equations
A thermochemical equation expresses the following:
1. Weight relationships
2. Physical states of reactant and products
3. Temperature
4. Pressure
5. Heat evolved or absorbed in the reaction
Characteristics of Hrxn
1. For any reaction, Hrxn = H (products) H (reactants)
2. It depends on the state of the substance
H2(g) + O2(g) H2O (l)
H = -285.8 kJ
H2(g) + O2(g) H2O (g)
H = -241.8 kJ
3. It is proportional to the amount of reactants and products
H2(g) + O2(g) H2O (l)
H = -285.8 kJ
2H2(g) +
O2(g) 2 H2O (l)
H = -571.6 kJ
4. It changes sign when a process is reverse
H2O (l) H2(g) + O2(g)
H = +285.8 kJ
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Practice Exercise 6.4: Calculate the heat involved when 74.6g of SO 2 (molar mass =
64.07g/mol) is converted to SO3.
Thermochemical reaction: SO2(g) + O2(g) SO3(g) H = -99.1kJ/mol

Calorimetry

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- experimental techniques of determining the amount of energy (heat) associated

with any chemical or physical processes.
- based on observing the temperature change when a system absorbs or releases
energy in the form of heat.
Specific heat of a substance, s amount of heat required to raise the temperature of one
gram of the substance one degree Celsius (or one Kelvin) with no change in phase. It
has a units J/g.oC
Heat capacity of a body, C the amount of heat required to raise its temperature 1 oC. Its
units are J/oC.
Where m = mass of substance in grams.

C = ms

Calculating heat change

q = mst

Where t = tfinal - tinitial

q = Ct
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Practice Exercise 6.5: A 466g sample of water is heated from 8.50 oC to 74.60oC.
Calculate the amount of heat absorbed (in kilojoules) by the water.

Calorimeter -

apparatus used to determine the heat of reaction

TYPES OF CALORIMETER
Constant-Volume Calorimetry used to determine the heat of combustion.

qcal + qrxn = 0

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qrxn = - qcal
qcal = Ccalt
where: Ccal = heat capacity of calorimeter
t = change in temperature
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Practice Exercise 6.6: When 0.7521 g of benzoic acid was burned in a calorimeter

containing 1,000. g of water, a temperature rise of 3.60C was observed.

What is the heat capacity of the bomb calorimeter, excluding the water? The
heat of combustion of benzoic acid is 26.42 kJ/g. (molar mass of C10H8 =
128.2g)

Constant-Pressure Calorimetry used to measure qP for reactions in solution at constant

pressure

Practice Exercise 6.7: A quantity of 1.00 x 102 mL of 0.5M HCl was mixed with 1.00 x 10 2
mL of 0.5M NaOH in a constant-pressure calorimeter of negligible heat capacity. The initial
temperature of the HCl and NaOH solutions was the same, 22.5 oC, and the final temperature
of the mixed solution was 25.86 oC. Calculate the heat change for the neutralization reaction
on a molar basis.
NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l)
Assume that the densities and specific heats of the solutions are the same as for water
(1.00g/mL and 4.184J/g oC, respectively)

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Standard Enthalpy of Formation and Reaction

The thermodynamic standard state of a substance is its most stable pure form under
standard pressure (1 atm) and some specific temperature (25oC or 298 K unless
specified)
Standard molar enthalphies of formation, Hfo - energy released or absorbed when one
mole of a compound is formed from its elements
For element and diatomic elements such as H2, N2, O2, Cl2, F2, Br2 Hfo = 0
Standard enthalpy of reaction, Hrxno - energy released or absorbed as a result of the
complete chemical reaction of the reactants
Hro = Hfo (products) - Hfo (reactants)
The Direct Method
Use of table of Standard Enthalphies of Formation to calculate enthalphies of reactions
Hro = Hfo (products) - Hfo (reactants)
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Practice Exercise 6.8: Calculate the standard heat of reactions, Ho, for the following
using standard heat of formation data Hor.
a. CaCO3(s) CaO(s) + CO2(g)

b. 2NO(g) + O3(g) NO2(g) + O2(g)

The Indirect Method

Based on Hesss Law of heat summation which states that; When a reactants are
converted to products, the change in enthalpy is the same whether the reaction takes
place in one step or in a series of steps.
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Practice Exercise 6.9: Given the following thermochemical equations:
4NH3(g) + 3O2(g) 2N2(g) + 6H2O(l)
Ho = -1531kJ
N2O(g) + H2(g) N2(g) + H2O (l)
Ho = -367.4kJ
H2(g) + O2(g) H2O(l)
Ho = -285.9kJ
o
Calculate the value of H fro the reaction
2NH3(g) + 3N2O(g) 4N2(g) + 3H2O(l)

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Practice Exercise 6.10: Calculate the standard enthalpy change for the reaction
2 Al(s) + Fe2O3(s) 2 Fe(s) + Al2O3(s)
Given that
2 Al(s) + 3/2 O2(g) Al2O3(s)
Ho = -1669.8 kJ/mol
2Fe(s) +

3/2 O2(g)

Fe2O3(s)

Ho = - 822.2 kJ/mol

Solve Problems 6.15, 6.17, 6.25, 6.27, 6.33, 6.37, 6.51, 6.61, 6.63 ; pages 198 201
General Chemistry: The Essential Concepts, 5th edition by Raymond Chang
References:
General Chemistry: The Essential Concepts, 5th edition by Raymond Chang
Chemistry : 8th edition by Whitten, Davis, Peck and Stanley
CHEMISTRY: The Molecular Nature of Matter and Change , 4th ed. by Martin Silberberg

Chemistry: The General Science, 10th ed, by Brown, Le May and Bursten.

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