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Unit 2 - Matter and Energy

Energy Changes in Chemical Reactions

LEARNING OBJECTIVES

• Become acquainted with a new term for energy, called enthalpy.



• Learn ways to measure the heats of reaction or calorimetry, specific

heat and heat capacity.

• Know the standard enthalpies of formation of reactants and products.





1.0 Heat Capacity and Calorimetry

All chemical reactions exhibits the two fundamental laws: the law of conservation of
mass and the law of conservation of energy.
Energy become a word of mouth of everyone especially now we are experiencing
pandemic. To some the feeling of exhaustion, means lack of energy and seeing their special
someone makes them fully charge.
Energy, is defined as the capacity to do work. Energy, unlike matter, cannot be seen,
touched, smelled, or weighed but all of its form are capable of doing work. Chemists define
work as directed energy change resulting from a process. There are different forms of energy
namely: kinetic energy, thermal energy, chemical energy and potential energy. All forms of
energy can be transformed from one form to another. Every time we take our zumba, the
chemical energy stored within our bodies are converted to kinetic energy. Although energy
can be transformed, scientist do believed that it can neither be created nor destroyed. This
phenomenon is summarized by the law of conservation of energy: the total quantity of
energy in the universe is assumed constant.

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Most of the chemical reactions absorb or produce energy in the form of heat. Heat is
the transfer of thermal energy between two bodies that are at different temperatures. When
describing the energy changes that occur during a process, we normally say “heat absorbed”
or “heat released”. Thermochemistry is the study of heat change in chemical reactions.
To study energy changes, we must first define the system, or the specific part of the
universe that is of interest to us. The surroundings are the rest of the universe outside the
system. There are three types of system: open, closed and isolated system. An open system
can exchange mass and energy, usually in the form of heat with its surroundings while a
closed system allows the transfer of energy (heat) but not mass. An isolated system does
not allow the transfer of either mass or energy.
The combustion of hydrogen gas in oxygen is a chemical reactions that releases
considerable amount of energy.
2H2(g) + O2(g) à 2H2O(l) + energy
The reacting mixture (hydrogen, oxygen and water molecules) are the system and the
rest of the universe is the surroundings. Since the energy is cannot be created or destroyed,
any energy lost from the system is gained by the surroundings. The heat released from the
combustion process is transferred from the system to its surroundings. The combustion
reactions is an exothermic process, which is any process that gives off heat.
Let us consider another reaction, the decomposition of mercury (II) oxide (HgO) at
high temperatures:
energy + 2HgO(s) à 2Hg(l) + O2(g)
This is an example of endothermic process, in which heat has to be supplied to the
system by the surroundings.

In the laboratory, heat changes in physical and chemical processes are determined
using a calorimeter which is a closed container designed specifically to measure heat changes.
Calorimetry is the measurement of heat changes. The specific heat (s) of a substance is the
amount of heat required to raise the temperature of one gram of the substance by one degree

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Celsius. It has the units J/g·°C. The heat capacity (C) of a substance is the amount of heat
required to raise the temperature of a given quantity of the substance by one degree Celsius.
Its units are J/°C. Specific heat is an intensive property whereas heat capacity is an extensive
property.
The relationship between the heat capacity and specific heat of a substance is
C = ms
where m is the mass of the substance in grams.

If we know the specific heat and the amount of a substance, then the change in the
sample’s temperature (Δt ) will tell us the amount of heat (q) that has been absorbed or
released in a particular process. Heat (q) is a path function, which values are dependent on
the path taken. The equations for calculating the heat change are given by
q = msΔt
q = CΔt
where Δt is the temperature change:
Δt = tfinal - tinitial
The sign convention for q; positive for endothermic process and negative for
exothermic process.

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Example 1
A 466-g sample of water is heated from 8.50°C to 74.60°C. Calculate
the amount of heat absorbed (in kilojoules) by the water.
Strategy We know the quantity of water and the specifi c heat of water.
With this information and the temperature rise, we can
calculate the amount of heat absorbed (q).
Solution
𝑞 = 𝑚𝑠∆𝑡
,
= (466𝑔)(4.184 - ∙ .𝐶 )(74.60 .𝐶 − 8.50 .𝐶 )

(/,
= 1.29 𝑥 10# 𝐽 𝑥 (000,

= 129 𝑘𝐽

Practice Exercise 1

An iron bar of mass 869 g cools from 94°C to 5°C. Calculate the heat
released (in kilojoules) by the metal.



Heat of combustion is usually measured by placing a known mass of a compound in a

steel container called a constant-volume bomb calorimeter, which is filled with oxygen at
about 30 atm of pressure. The closed bomb is immersed in a known amount of water and the
sample is ignited electrically, and the heat produced by the combustion reaction can be
calculated accurately by recording the rise in temperature of the water. The heat given off by
the sample is absorbed by the water and the bomb. The special design of the calorimeter
enables us to assume that no heat (or mass) is lost to the surroundings during the time it
takes to make measurements. Therefore, we can call the bomb and the water in which it is
submerged an isolated system. Because no heat enters or leaves the system throughout the
process, the heat change of the system (qsystem) must be zero and we can write
qsystem = qcal + qrxn
qsystem = 0
where qcal and qrxn are the heat changes for the calorimeter and the reaction,
respectively. Thus,
qrxn = -qcal
To determine qcal, we need to know the heat capacity of the calorimeter (Ccal) and the
temperature rise

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qcal = CΔt
The quantity of Ccal is calibrated by burning a substance with an accurately known
heat of combustion.

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Example 2

A quantity of 1.435 g of naphthalene (C10H8), a pungent-smelling
substance used in moth repellents, was burned in a constant-volume
bomb calorimeter. Consequently, the temperature of the water rose
from 20.28°C to 25.95°C. If the heat capacity of the bomb plus water
was 10.17 kJ/°C, calculate the heat of combustion of naphthalene on a
molar basis; that is, find the molar heat of combustion.
Strategy Knowing the heat capacity and the temperature rise, how
do we calculate the heat absorbed by the calorimeter? What
is the heat generated by the combustion of 1.435 g of
naphthalene? What is the conversion factor between grams
and moles of naphthalene?
Solution
𝑞&12 = 𝐶&12 ∆𝑡

= (10.17 𝑘𝐽/°𝐶)(25.95°𝐶 2 20.28°𝐶)

= 57.66 𝑘𝐽

Solution Because qsys = qcal + qrxn. The heat change of the reaction is

257.66 kJ. This is the heat released by the combustion of

1.435 g of C 10 H 8; therefore, we can write the conversion

factor as


3#4.55 /,
(.$+# - 6!" 7#


The molar mass of naphthalene is 128.2 g, so the heat of
combustion of 1 mole of naphthalene is

−57.66𝑘𝐽 128.2 𝑔 𝐶(0 𝐻8
𝑚𝑜𝑙𝑎𝑟 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛 = 𝑥
1.435 𝑔 𝐶(0 𝐻8 1 𝑚𝑜𝑙 𝐶(0 𝐻8

= −5.151 𝑥 10+ 𝑘𝐽/𝑚𝑜𝑙


Practice Exercise 2

A quantity of 1.922 g of methanol (CH 3 OH) was burned in a constant-
volume bomb calorimeter. Consequently, the temperature of the water rose

by 4.20°C. If the heat capacity of the bomb plus water was 10.4 kJ/°C,
calculate the molar heat of combustion of methanol.

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There is a simpler device that the constant-volume calorimeter and that is constant-
pressure calorimeter, which is used to determine the heat changes for noncombustion
reactions. In the laboratory, students can measure heat changes using an improvised
constant-volume calorimeter from two Styrofoam coffee cups. In this improvised
calorimeter, we neglect the small heat capacity of the coffee cups in our calculations. They
used it in measuring the heat effects of a variety of reactions such as acid-base neutralization.
Heat of solution and dilution. The heat changes for the process (qrxn) is equal to the enthalpy
change (ΔH).

LEARNING ENRICHMENT ACTIVITIES

Watch the video on the Heat of Neutralization by Ali Hayek

https://youtu.be/eEdqC6hkhRs

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2.0 Enthalpy
Most reactions are prepared under constant pressure (usually atmospheric pressure)
since constant-volume conditions are difficult and impossible to achieve. The reaction is
considered as expansion when there is a net increase in the number of moles of a gas after
the reaction and conversely, it is compression if more gas molecules are consumed than are
produced. The work is done one the surroundings for an expansion process and it is done on
the system for a compression process. There is no work done if there is no net change in the
number of moles of gases from the reactants to products.
In general, for a constant-pressure process we write

*where the subscript “p” means constant-pressure condition.
Enthalphy (H) is defined by the equation
H =E + PV
where E is the internal energy of the system and P and V are the pressure and volume
of the system, respectively. Enthalpy, pressure, energy and volume are all state functions,
that is, the changes depend only on the initial state and final state.

For any process, the change in enthalpy according is given by
ΔH =ΔE + Δ(PV)
If the pressure is held constant, then
ΔH =ΔE + PΔV
The two quantities, ΔE and ΔH, are can be associated with a reaction. If the reaction
occurs under constant-volume conditions, then the heat change, qv , is equal to ΔE. On the
other hand, when the reaction is carried out at constant pressure, the heat change, qp is equal
to ΔH.

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Since most of the reactions are at constant pressure condition, we can use enthalpy
to quantify the heat flow into or out of a system in the process. we can equate the heat change
in these cases to the change in enthalpy. For any reaction of the type
reactants à products
From the reaction, we can compute for the enthalpy of reaction, ΔH, as the difference
between the enthalpies of the products and the enthalpies of the reactants. The enthalpy of
reaction can be positive or negative, depending on the process. For an endothermic process
(heat absorbed by the system from the surroundings), ΔH is positive (that is, ΔH > 0). For an
exothermic process (heat released by the system to the surroundings), ΔH is negative (that
is, ΔH < 0).

At 0°C and a pressure of 1 atm, ice melts to form liquid water. Measurements show
that for every mole of ice converted to liquid water under these conditions, 6.01 kilojoules
(kJ) of heat energy are absorbed by the system (ice). Because the pressure is constant, the
heat change is equal to the enthalpy change, ΔH. Furthermore, this is an endothermic
process, as expected for the energy-absorbing change of melting ice. Therefore, ΔH is a
positive quantity. The equation for this physical change is
H2O(s) à H2O(l) ΔH = 6.01 kJ/mol
The “per mole” in the unit for ΔH means that this is the enthalpy change per mole of
the reaction (or process) as it is written; that is, when 1 mole of ice is converted to 1 mole of
liquid water.

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As another example, consider the combustion of methane (CH4), the principal

component of natural gas:

The natural gas, methane, when burned releases heat to the surroundings exhibiting
an exothermic process. The enthalpy change must have a negative sign since the process
releases heat. The per mole of reaction unit for ΔH means that when 1 mole of CH4 reacts
with 2 moles of O2 to produce 1 mole of CO2 and 2 moles of liquid H2O, 890.4 kJ of heat
energy are released to the surroundings. It is important to remember that the ΔH value does
not refer to a particular reactant or product. It simply means that the quoted ΔH value refers
to all the reacting species in molar quantities. Thus, the following conversion factors can be
created:

Expressing ΔH in units of kJ/mol (rather than just kJ) conforms to the standard
convention; its merit will become apparent when we continue our study of thermodynamics.
Thermochemical equations shows the enthalpy change as well as the mass
relationships. It is essential to specify a balanced equation when quoting the enthalpy change
of a reaction. The following guidelines are helpful in writing and interpreting
thermochemical equations.

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Example 3

Given the thermochemical equation

2SO2(g) + O2(g) à 2SO3(g) ΔH = -198.2 kJ/mol

calculate the heat evolved when 87.9 g of SO2 (molar mass 5 64.07

g/mol) is converted to SO3 .


Strategy The thermochemical equation shows that for every 2 moles

of SO2 reacted, 198.2 kJ of heat are given off (note the negative

sign). Therefore, the conversion factor is



−198.2 𝑘𝐽

2 𝑚𝑜𝑙 𝑆𝑂!



How many moles of SO2 are in 87.9 g of SO2? What is the

conversion factor between grams and moles?

Solution We need to first calculate the number of moles of SO2 in

87.9 g of the compound and then find the number of kilojoules

produced from the exothermic reaction. The sequence of

conversions is as follows:

grams of SO2 à moles of SO2 à kJ of heat generated



1 𝑚𝑜𝑙 𝑆𝑂! −198.2 𝑘𝐽
𝛥𝐻 = 87.9 𝑔 𝑆𝑂! 𝑥 𝑥
64.07 𝑔 𝑆𝑂! 2 𝑚𝑜𝑙 𝑆𝑂!

= −136 𝑘𝐽

∴ the heat released to the surroundings is 136 kJ.


Practice Exercise 3

Calculate the heat evolved when 266 g of white phosphorus (P4)
burns in air according to the equation
P4(s) + 5O2(g) à P4O10(s) ΔH = - 3013 kJ/mol

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3.0 Spontaneity
Thermodynamics deals with the interconversion of heat and other forms of energy.
This enables us to use information gained from experiments on a system to draw conclusions
about other aspects of the same system without further experimentation. Studying
thermodynamics will enable us to determine whether or not a reaction will occur when
reactants are brought together under a specific conditions example temperature, pressure
and concentration. This is important for most of the researchers and chemist doing their
synthesis of a particular compounds in the laboratory. A reaction that does occur under the
given set of conditions is called spontaneous reaction. If a reaction does not occur under
specified conditions, it is said to be nonspontaneous.

These examples show that processes that occur spontaneously in one direction
cannot, under the same conditions, also take place spontaneously in the opposite direction.

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Experience tells us that ice melts spontaneously above 0°C even though the process is
endothermic. In this case, the assumption that spontaneous processes always decrease a
system’s energy fails. Exothermicity favors the spontaneity of a reaction but does not
guarantee it. Just as it is possible for an endothermic reaction to be spontaneous, it is possible
for an exothermic reaction to be nonspontaneous. In other words, we cannot decide whether
or not a chemical reaction will occur spontaneously solely on the basis of energy changes in
the system. To make this kind of prediction we need another thermodynamic quantity, which
turns out to be entropy.

Entropy
We have to introduce a new thermodynamic quantity called entropy to determine the
spontaneity of the reaction. Entropy (S) is described as a measure of how spread out or
dispersed the energy of a system is among the different possible ways that system can contain
energy. The greater the randomness, the greater the entropy. Most processes are
accompanied by a change in entropy. A cup of hot water has a certain amount of entropy due
to the dispersal of energy among the various energy states of the water molecules (for
example, energy states associated with the translational, rotational, and vibrational motions
of the water molecules). If left standing on a table, the water loses heat to the cooler
surroundings. Consequently, the entropy of the system increases because closely spaced
energy levels leads to a greater dispersal among the energy levels.
In 1868 Boltzmann showed that the entropy of a system is related to the natural log
of the number of microstates (W):
S = klnW
where k is called the Boltzmann constant (1.38 x 10-23 J/K). Thus, the larger the W,
the greater is the entropy of the system. Entropy is a state function and the change can be
measured as:
ΔS = Sf – Si
where Si and Sf are the entropies of the system in the initial and final states,
respectively.
ΔS = klnWf – klnWi
9
= kln 9$
%
where Wi and Wf are the corresponding numbers of microstates in the initial and final
state. Thus, if Wf . Wi, ΔS > 0 and the entropy of the system increases.

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Standard entropy is the absolute entropy of a substance at 1 atm and 25°C. (Recall
that the standard state refers only to 1 atm. The reason for specifying 25°C is that many
processes are carried out at room temperature.) The units of entropy are J/K or J/K·mol for
1 mole of the substance. We use joules rather than kilojoules because entropy values are
typically quite small. Entropies of elements and compounds are all positive (that is, S° . 0).
For different substances in the same phase, molecular complexity determines which ones
have higher entropies. Both diamond and graphite are solids, but diamond has a more
ordered structure and hence a smaller number of microstates. Therefore, diamond has a
smaller standard entropy than graphite. Consider the natural gases methane and ethane.

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Ethane has a more complex structure and hence more ways to execute molecular motions,
which also increase its microstates. Therefore, ethane has a greater standard entropy than
methane. Both helium and neon are monatomic gases, which cannot execute rotational or
vibrational motions, but neon has a greater standard entropy than helium because its molar
mass is greater. Heavier atoms have more closely spaced energy levels so there is a greater
distribution of the atoms’ energy among the levels. Consequently, there are more microstates
associated with these atoms.


Example 4

Predict whether the entropy change is greater or less than zero for each of
the following processes: (a) freezing ethanol, (b) evaporating a beaker of
liquid bromine at room temperature, (c) dissolving glucose in water, (d)
cooling nitrogen gas from 80°C to 20°C.

Strategy To determine the entropy change in each case, we examine
whether the number of microstates of the system increases or
decreases. The sign of ΔS will be positive if there is an increase in
the number of microstates and negative if the number of
microstates decreases.
Solution (a) Upon freezing, the ethanol molecules are held rigid in position.
This phase transition reduces the number of microstates and
therefore the entropy decreases; that is, ΔS < 0.
(b) Evaporating bromine increases the number of microstates
because the Br2 molecules can occupy many more positions in
nearly empty space. Therefore, ΔS > 0.
(c) Glucose is a nonelectrolyte. The solution process leads to a
greater dispersal of matter due to the mixing of glucose and
water molecules so we expect ΔS > 0.
(d) The cooling process decreases various molecular motions.
This leads to a decrease in microstates and so ΔS < 0.
Practice Exercise 4


How does the entropy of a system change for each of the following

processes? (a) condensing water vapor, (b) forming sucrose crystals from a

supersaturated solution, (c) heating hydrogen gas from 60°C to 80°C, and (d)

subliming dry ice.

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4.0 Laws of Thermodynamics

The First Law of Thermodynamics states that energy can be converted from one
form to another, but it cannot be created or destroyed. One measure of these changes is the
amount of heat given off or absorbed by a system during a constant-pressure process, which
chemists define as a change in enthalpy (ΔH).
The Second Law of Thermodynamics is defined as the entropy of the universe
increases in a spontaneous process and remains unchanged in an equilibrium process.




The second law of thermodynamics tells us that a spontaneous reaction increases the
entropy of the universe; that is, ΔSuniv > 0. In order to determine the sign of ΔSuniv for a
reaction, however, we would need to calculate both ΔSsys and ΔSsurr. In general, we are usually
concerned only with what happens in a particular system. Therefore, we need another
thermodynamic function to help us determine whether a reaction will occur spontaneously
if we consider only the system itself.
We know that for a spontaneous process, we have

Now we have a criterion for a spontaneous reaction that is expressed only in terms of
the properties of the system (ΔHsys and ΔSsys) and we can ignore the surroundings.

This equation says that for a process carried out at constant pressure and
temperature T, if the changes in enthalpy and entropy of the system are such that ΔHsys -
TΔSsys is less than zero, the process must be spontaneous.
In order to express the spontaneity of a reaction more directly, we introduce another
thermodynamic function called Gibbs† free energy (G), or simply free energy:

G = H – TS

All quantities pertain to the system, and T is the temperature of the system. You can
see that G has units of energy (both H and TS are in energy units). Like H and S, G is a state
function.

The change in free energy (ΔG) of a system for a constant-temperature process is

ΔG = ΔH – TΔS

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The standard free-energy of reaction (ΔGo ) is the free-energy change for a reaction
when it occurs under standard-state conditions.

The Third Law of thermodynamics states that entropy of a perfect crystalline
substance is zero at the absolute zero of temperature.


Example 5
Calculate the standard free-energy changes for the following reactions at
25°C.
(a) CH4(g) + 2O2(g) à CO2(g) + 2H2O(l)
(b) 2MgO(s) à 2Mg(s) + O2(g)
Strategy To calculate the standard free-energy change of a reaction, we
look up the standard free energies of formation of reactants and
products. Note that all the stoichiometric coefficients have no units
so ΔG°rxn is expressed in units of kJ/mol, and ΔG°f for O2 is zero
because it is the stable allotropic element at 1 atm and 25°C.
Solution
(a) ΔG°rxn = [ΔG°f(CO2) + 2ΔG°f(H2O)] - [ΔG°f(CH4) + 2ΔG°f(O2)]
=[(-394.4 kJ/mol) + (2)(-237.2 kJ/mol)] - [(-50.8 kJ/mol) + (2)(0
kJ/mol)]
=-818.0 kJ/mol
(b) ΔG°rxn = [2ΔG°f(Mg) + ΔG°f(O2)] - [2ΔG°f(MgO)]
=[(2kJ/mol) + (0 kJ/mol)] - [ (2)(-569.6kJ/mol)]
=1139 kJ/mol

Practice Exercise 5
Calculate the standard free-energy changes for the following reactions at
25°C:

(a) H2(g) + Br2(l) à 2HBr(g)
(b) 2C2H6(g) + 7O2(g) à 4CO2(g) + 6H2O(l)

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ASSESSMENT TASK


1. Define the following terms:

a) Thermodynamics
b) Isolated system
c) Spontaneous
d) Enthalpy
e) Entropy

2. On what law is the first law of thermodynamics based? Explain the sign
conventions in the equation ΔE = q + w.


3. Explain what is meant by a state function. Give two examples of quantities that
are state functions and two that are not.

4. What is the difference between specifi c heat and heat capacity? What are the

units for these two quantities? Which is the intensive property and which is the
extensive property?

5. A sheet of gold weighing 10.0 g and at a temperature of 18.0°C is placed flat on a

sheet of iron weighing 20.0 g and at a temperature of 55.6°C. What is the final
temperature of the combined metals? Assume that no heat is lost to the
surroundings. (Hint: The heat gained by the gold must be equal to the heat lost
by the iron.)

6. State whether the sign of the entropy change expected for each of the following
processes will be positive or negative, and explain your predictions.

a) PCl3(l) + Cl2(g) à PCl5(s)

b) 2HgO(s) à 2Hg(l) + O2(g)
c) H2(g) à 2H(g)
d) U(s) + 3F2(g) à UF6(s)

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References:
Chang, R. and Goldsby, K. A. (2017). Chemistry, (12th International Edition), New York:
McGraw-Hill.

Brown, L., Brown, L. S., & Holme, T. (2011). Chemistry for engineering students. Nelson
Education.

Fahlman, B. D., Purvis-Roberts, K. L., Kirk, J. S., Bentley, A. K., Daubenmire, P. L., Ellis, J. P., &
Mury, M. T. (2018). Chemistry in Context: Applying Chemistry to Society (No. 540
C517cc). McGraw-Hill.

Silberberg, M. (2012). Principles of general chemistry. McGraw-Hill Education.

https://chem.libretexts.org/

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