Thermochemistry

LESSON 1 Energy Changes in Chemical Reactions

After reading and analyzing the lesson, you should be able to:
1. Describe exothermic and endothermic processes and;
2. Classify a process as endothermic or exothermic

Thermochemistry is the study of the energy and heat accompanying a chemical

reaction and/or physical transformations or phase changes. A chemical reaction may release or
absorb energy, and this is also true in phase changes, i.e melting and boiling processes.
Before a chemical reaction takes, energy is either absorbed or released. You have learned
in the early part of inorganic chemistry that in the formation of chemical bonds, energy is
released, thus it is an exothermic reaction.
a. Exothermic reaction is a process that releases energy in the form of heat. Another
example of an exothermic reaction is burning, you can feel the heat that is released during
u process of burning. While the breaking of chemical bond, energy is absorbed, thus it is
an endothermic reaction.

b. Endothermic reaction is process that absorbs energy in the form of heat. One obvious
example is when ice melts, you feel the cold since heat is absorbed or taken away from
the system before the ice melts. The image of some endothermic and exothermic
processes is shown on figure 3.4 and is summarized on table 3.1.

Fig 3.4 Endothermic/Exothermic Processes

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 Endothermic Process Exothermic Process
Melting of ice Freezing of water
Melting solid salts Solidifying liquid salts
Cooking and baking Burning of fuel
Formation of cation from an atom in gas Formation of anion from an atom in gas
phase phase
Splitting gas molecules Splitting of an atom

Fig 3.1 Examples of Endothermic/Exothermic Reactions

First Law of Thermodynamics

The first law of thermodynamics, also known as the law of conservation of energy, states
that’energy cannot be created or destroyed but can simply be converted to other forms of
energy.” It can be written mathematically as follows:
∆U = q + w

where ∆U is the change in internal energy of the system and is determined by the equation:
∆U = Ufinal - Uinitial
or ∆U = = Uf - Ui

Internal energy (U) is the total energy content of the system. Its absolute value difficult to
evaluate, but a change in state can readily be determined. An exothermic reaction is
characterized by a negative ∆U, while an endothermic reaction has a positive ∆U. The symbol q
represents the heat absorbed or evolved by the system. Its value is positive when heat is absorbed
and negative when heat is evolved. The symbol w, represents the work performed by the system
or on the system. Its value is negative when the system performs work on its surroundings and
positive when the surroundings perform work on the system.

Example:
For any chemical reaction carried out in any manner, the quantity of heat absorbed or evolved by
the reaction is determined by the expression __________:
A. ∆U + w B. ∆U - w C. qv D. qp

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Sample Problem:
A system absorbs 50 J of heat during a transformation.Determine the change in internal
energy if the system performs: (a) 15 J and (b) 65 J of work on surrounding.
Solution:
(a) ∆U = q + w
= 50 J + (-15 J) = +35 J

The amount of heat absorbed is greater than the amount of energy used to perform work.
The excess heat energy caused the internal energy of the system to increase which is shown by
the positive value of ∆U.
(b.) ∆U = 50 J + (-65J) = -15 J

Since the amount of heat energy supplied, the additional energy needed is taken from the
internal energy of the system. This causes the internal energy to decrease as shown by the
negative value of ∆U.

Energy can exist in different forms. It can be in any of the following forms:
• Potential energy is stored energy. Matter possesses potential chemical energy.
• Kinetic Energy is energy in motion. Gas particles which are always in motion
possess high kinetic energy. Molecules in a liquid, whose motion are more
restricted compared to gas molecules, possess lower kinetic energy.
• Mechanical energy is energy at work. A man who pedals a running bicycle des
mechanical work.
• Thermal energy is heat energy. The warmth that you feel on a summer day
manifests heat energy caused by the difference in temperature between your body
and your environment.
• Electrical energy is the energy of the mobile electrons that produce electricity.
• Other forms of energy are nuclear energy and geotherrrmal energy, among others.

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Enthalpy of a Chemical Reaction
Enthalpy is the amount of energy possessed by a thermodynamic system for transfer
between itself and its environment. For example, in a chemical reaction, the change in enthalpy
of the system is the heat of the reaction. In a phase change, as from a liquid to a gas, the change
in enthalpy of the system is the latent heat of vaporization. In a simple temperature change, the
change in enthalpy with each degree is the heat capacity of the system at constant pressure. The
German physicist Rudolf J.E. Clausius originated the term in 1850. Mathematically, enthalpy H
is identified as U+ PV, where U is internal energy, P is pressure, and V is volume. H is measured
in joules or British termal units (BTUs).
Enthalpy or heat content is a property related to the heat liberated or absorbed by a
chemical reaction. If the products of a reaction have higher enthalpy than the reactants, then heat
is absorbed in the process. Such type of reaction is said to be endothermic and the change in
enthalpy, ∆H for the reaction is positive. If the products of a reaction have lower enthalpy than
the reactants, ∆H is negative and the reaction liberates heat. Such type or reaction is said to be
exothermic.

Standard Enthalpy of Formation and Reaction and Hess’ Law

In 1840, a Russian chemist, Dr German Hess, formulated Hess’ law of constant heat
summation or simply Hess’ law which states that “regardless of a single or multiple steps of a
reaction, the total enthalpy change for a given chemical reaction is the sum of all the changes.”
Mathematically it can be represented as
∆H°reaction = ∆H°fpdt - ∆H°frct

where ∆Hreaction is the change in enthalpy or heat of reaction (also known as enthalpy of
reaction) is the change in the enthalpy of a chemical reaction that occurs at a constant pressure.
∑∆H°fpdt is the sum of the heat of formation (is the change in enthalpy when one
mole of a substance in the standard conditions, 1atm of pressure and 0℃, is formed from its pure
elements under the same conditions) of a substances on the product side
∑∆H°frct is the sum of the heat of formation of substances on the reactant side.

Illustrative example
1. C(s) + 2H2O(g) CO2(g) + 2H2(g)
∆H° of CO2(g) = -393.5Kj/mole
∆H° of H2O(g) = -241.80 Kj/mole

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If we solve for the heat of reaction of the above equation, we shall have:
∆H°R = [ -393.30 – 2(-241.80)] = +90.30 KJ/mole
If the reactions take place in two steps, we shall have:
(1) C(s) + O2(g) CO2(g) ∆H° = -393.5kJ/mole
(2) 2H2(g) +O2(g) 2H2O(g) ∆H° = 2(-241.8kJ/mole)
= -483.60 kJ/mole

If we add the two chemical equations, but first reverse the second, we get

C(s) + O2(g) CO2(g) -393.5kJ/mole

2H2O(g) 2H2(g) + O2(g) + 483.60 kJ/mole
C(s) + O2(g) + 2H2O(g) CO2(g) + 2H2(g) + O2(g)
but we can eliminate O2
∆H°R = [ -393.30 – 2 (-241.80)] = +90.30 kJ/mole
❖ This shows that the heat of reaction is the same whether the reaction takes place in single
or several steps.
2. H2(g) + 1/2O2(g) H2O(l) ∆H° = -285.80 KJ/mole
2H2(g) + O2(g) 2H2O(l) ∆H° = -571.60 KJ/mole
Determine the heat of reaction of the electrolysis of liquid water according to the
equation:
H2O(l) H2(g) + 1/2O2(g)
Using the first equation, we shall have
H2(g) + 1/2O2(g) H2O(l) ∆H° = -285.80 KJ/mole
Using the second equation, we have
2H2(g) + O2(g) 2H2O(l) ∆H° = -571.60 KJ/mole, again

Reverse the equation

2H2O(g) 2H2(g) + O2(g) ∆H° = +571.60 KJ/mole

Add the first and the second equation:
H2(g) + 1/2O2(g) H2O(l) ∆H° = -285.80 KJ/mole

2H2O(l) 2H2(g) + O2(g) ∆H° = +571.60 KJ/mole

H2O(l) H2(g) + 1/2O2(g) ∆H° = +285.80 KJ is needed to electrolyze

one mole of liquid water

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Module: Answer Worksheet A-B,D,E,F on page 39

Activity: How Well Do You Know the First Law?

∆U Q w
+800 J +500 J +300J
-600J +400J
+900J +700J
+500J +800J
+1100J +900J
+750J -500J

Concept Notes

• Endothermic processes involve absorption of energy while exothermic processes involve the
evolution of energy.
• When a system absorbs heat, the surroundings lose the corresponding amount of heat.
• The first law of thermodynamics states that energy cannot be created or destroyed but is simply
converted to other forms of energy.
• The mathematical statement of the first law of thermodynamics is given by the equation: ∆U =q +
w,
where ∆U is the change in internal energy, q is the heat absorbed or evolved, and w is the work
performed on the system or by the system.
• A positive value of ∆U means an increase in internal energy while a negative value means a
decrease in internal energy. A positive value of q means heat is absorbed by the system while a
negative value means heat is evolved by the system. A positive value of work means that the
surroundings performed work on the system while negative value means that the system
performed work on the surroundings.
• The first law of thermodynamics applies to any process.
• In instances where a reaction may be carried indirectly through several steps, the enthalpy change
for the overall process is the sum of the enthalpy changes for the component steps. 6 | P a g e
Direction: Determine which of the following processes are endothermic or exothermic.
A. Cutting of paper ___________________________
B. Rotation of the blades of an electric fan ___________________
C. Digestion of food _______________________
D. Decomposition of waste in a compost heap ______________________

B. Suppose that when you run through a 50-meter distance you perform 2 kJ of work. If
before running, you eat food from which you obtain 800 J, would this activity cause you
to slim down or to increase your weight? Explain
Solution: q = ∆U +w

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