ENERGY AND ENERGY CHANGES

SYSTEM AND SURROUNDINGS

To be able to understand the energy changes associated with chemical reactions, it is important
to be familiar with the terminologies system and surroundings.
System: This is defined as the part of the universe under study or of interest. For example, an
acid – base neutralization reaction taking place in a beaker can be the system.
Surroundings: This is defined as anything outside the system including the universe. In the
example above, the surrounding becomes the beaker in which the reaction(system) is taking
place and everything else around.

Types of systems
There are three types of system depending on the exchange that takes place between itself and
its surroundings. These are:
Open system: A system that exchanges both matter(mass) and energy with its surroundings.
For example, a hot in an open container from which both matter (water vapour) and heat
energy can escape into its surroundings.
Closed system: A system that exchanges only energy but not mass with its surroundings.
Example hot water in a closed container. No water vapour escapes from the container but heat
energy is exchanged between it and its surroundings.
Isolated system: A system that does not exchange both mass and energy with its surroundings.
Example hot water in a thermos flask or vacuum flask. The flask prevents exchange of both
mass (water vapour) and heat with its surroundings.

EXOTHERMIC AND ENDOTHERMIC REACTIONS

When a chemical reaction occurs, bonds in the reactants break, while new bonds form in the
product. The following example may help to explain this.

Hydrogen reacts with oxygen to form water, according to the following equation:
2H2 + O2 → 2H2O
In this reaction, the bond between the two hydrogen atoms in the H2 molecule will break, as
will the bond between the oxygen atoms in the O2 molecule. New bonds will form between the

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two hydrogen atoms and the single oxygen atom in the water molecule that is formed as the
product.
For bonds to break, energy must be absorbed. When new bonds form, energy is released.
In some reactions, the energy that must be absorbed to break the bonds in the reactants, is less
than the total energy that is released when new bonds are formed. This means that in the
overall reaction, energy is released as heat. This type of reaction is called an exothermic
reaction. Another way of describing an exothermic reaction is that it is one in which the energy
of the product is less than the energy of the reactants, because energy has been released
during the reaction. The enthalpy change for such a reaction is negative (-) since the reaction
has lost energy. Examples are neutralization and combustion reactions.

Definition: An exothermic reaction is a reaction that gives out heat energy to its surroundings.

In other reactions, the energy that must be absorbed to break the bonds in the reactants, is
more than the total energy that is released when new bonds are formed. This means that in the
overall reaction, energy must be absorbed from the surroundings. This type of reaction is
known as an endothermic reaction. Another way of describing an endothermic reaction is that
it is one in which the energy of the product is greater than the energy of the reactants, because
energy has been absorbed during the reaction. Such reaction has positive (+) value of enthalpy
change since energy has been absorbed. Photosynthesis and decomposition reactions are
examples of endothermic reaction.

Definition: An endothermic reaction is one which absorbs heat energy from its surroundings.

The diagram below shows the energy profile for both exothermic and endothermic reactions.

NB:

= Hproducts – Hreactants
ENTHALPY CHANGE

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Often than not when a chemical reaction takes place, it is accompanied by changes in the heat
content of the materials which are reacting. This heat content is the enthalpy, H. This heat
content or enthalpy is shown by the change in temperature of a reaction.
Definition: This is the amount of heat energy gained or lost during a chemical reaction
between molar quantities of reactants.
It is standard enthalpy change when measured under standard conditions. Its unit is kJ/mol. It is
calculated as the difference in heat energy between the products and reactants i.e.

= Hproducts – Hreactants

STANDARD ENTHALPY CHANGE OF REACTION ( )

Heat change or enthalpy of a reaction depends on the temperature, pressure, physical state of
the substances involved and the amount of substances involved in the reaction. For
comparison, energy changes of reactions are determined under standard conditions. Standard
enthalpy change of a reaction can therefore be defined as follows:

Definition: This is the amount of heat absorbed or given out when the molar quantities of
reactants as stated in the equation react together under standard conditions.

The standard conditions are:

 A temperature of 298K (25oC)
 Pressure of 1atm or 100kPa
 Concentration of 1.0 moldm-3
 Standard states of substances i.e. the most stable physical state of substances.

The standard enthalpy change of reaction is denoted by where indicates standard

conditions and r is the reaction.

STANDARD ENTHALPY CHANGE OF FORMATION ( )

Definition: This is the enthalpy change when one mole of a substance is formed from its
elements in their standard states under standard conditions.

Examples: H2(g) + ½O2(g) → H2O(l), = -286 kJ/mol

C(s) + O2(g) → CO2(g), = -393.5 kJ/mol

2C(s) + 3H2(g) + ½O2(g) → C2H5OH,
From the first example above, it means that 286kJ of energy is released when one mole of
liquid water is formed from 1 mole of hydrogen gas and half mole of oxygen gas under standard
conditions.

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NB:
 Every formation reaction must produce 1 mole of a substance. If it demands that
fractions are used on the reactants side in order to achieve this, so be it.
 The standard enthalpy change of formation of an element is zero. This is because no
heat change occurs when an element is formed from itself.
H2(g) → H2(g), =0
Cu(s) → Cu(s), =0
 Standard enthalpy change of formation values can be used to predict the thermal
stability of substances. The more negative the of a substance, the stable the
compound is.

Using the to determine the standard enthalpy change of reactions.

The standard enthalpy change of a reaction, , can be calculated using the following
expression:

Example 1:
Calculate the standard enthalpy change for the decomposition of ammonium nitrate into
dinitrogen oxide and water vapour using the following data.

NH4NO3(s)) = -365.56 kJ/mol, (N2O(g)) = +82.05 kJ/mol, (H2O(g)) = -241.82 kJ/mol]

Solution:
NH4NO3(s) → N2O(g) + 2H2O(g)

= +82.05 + (2× -241.82) = -401.59

= -365.56

= -401.59 – (-365.56) = - 36.03 kJ/mol

Example 2:
Calculate a value for the standard enthalpy change for the reaction:

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 3MnO2(s) + 4Al(s) → 2Al2O3(s) + 3Mn(s).

(MnO2(s))= -520 kJ/mol, (Al2O3(s)) = -1670 kJ/mol]

Solution:

= 2 × (-1670) = -3340

= 3 × (-520) = -1560

= -3340 – (-1560) = -1780 kJ/mol

Example 3:
Calculate the standard enthalpy change of formation of NH3(g) in the equation below given that
the enthalpy of reaction is – 905 kJ/mol and standard enthalpy change of formation in kJ/mol of
NO(g) and H2O(g) are +90.25 and -241.82.
4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)
Solution:
Let the standard enthalpy change of formation of NH3(g) be y

= (4(+90.25) + 6(-241.82)) – 4y = -905

4y = 905 - 1089.92 = -184.92
y = - 46.23 kJ/mol

STANDARD ENTHALPY CHANGE OF COMBUSTION, .

Definition: This is the enthalpy change when one mole of a substance is completely burnt in
excess oxygen under standard conditions.

Examples: C(s) + O2(g) → CO2(g), = -393.5 kJ/mol

CH4(g) + 2O2(g) → CO2(g) + 2H2O(l), = -890.3 kJ/mol

C2H5OH + 3O2(g) → 2CO2(g) + 3H2O(l), = -1368 kJ/mol

NB:

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The complete combustion of hydrocarbons, alcohols, glucose etc. gives carbon dioxide and
water as products.

Importance of the values

 They are used to determine the standard enthalpy change of formation of substances
from their oxidation products
 Used to determine the differences in energy content of allotropes
 Use in large – scale determination of calorific values or heating values of fuels.

Using to determine of substances

Example 1:
Calculate the standard enthalpy change of formation of propane (C3H8) from the following data.

C3H8 + 5O2 → 3CO2 + 4H2O, =-2220.1 kJ/mol

C + O2 → CO2, = -393.5 kJ/mol

H2 + ½ O2 → H2O, = -285.8 kJ/mol

Solution:
The formation reaction for C3H8 is 3C + 4H2 → C3H8. To be able to obtain this formation reaction
from the three combustion reactions above, we have to reverse one of the equations and
multiply through the others with suitable numbers. After this, we then add the three equations.
Any substance that appears on both sides of the equations with the same amount will cancel
out. For unequal amounts, cancel out the smaller amount from the bigger amount.
Hint: Reverse equation 1, multiply equation 2 by 3 and equation 3 by 4 then add all three
reactions. Note that whatever you do to the reaction must be done to the standard enthalpy
change value.
3CO2 + 4H2O → C3H8 + 5O2, +2220.1
3C + 3O2 → 3CO2, 3(-393.5)
4H2 + 2O2 → 4H2O 4(-285.8)
3C + 4H2 → C3H8 -103.6 kJ/mol

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The -103kJ is the is the standard enthalpy change of formation of one mole of propane (C 3H8)

Example 2:

Calculate the of carbon monoxide(CO) from the following reactions.

C + O2 → CO2, = -393.5 kJ/mol

CO + ½ O2 → CO2, = -283 kJ/mol

Solution:
The formation reaction for CO is C + ½O2 → CO. To obtain this reaction from the above
reactions, just reverse the second equation and add the two equations cancelling out anything
that appears on both sides of equations with the same amount. Do same to the enthalpy
values.
C + O2 → CO2, -393.5
CO2 → CO + ½O2, +283
C + ½O2 → CO - 110.5 kJ/mol
Therefore 110.5 kJ of energy given in the formation of one mole of carbon monoxide.

EXPERIMENTAL DETERMINATION OF HEAT OF COMBUSTION OF SOLID COMPOUNDS USING

BOMB CALORIMETER

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 A known mass of the sample is placed in the sample dish in the calorimeter
The calorimeter is filled with excess oxygen gas and immersed into known mass of water
Take the initial temperature of the water before combustion
The sample is then ignited electrically
Measure the temperature of water after combustion
The heat produced by the combustion reaction can be calculated using the temperature
difference of the known mass of water as follows:
Heat evolved Q = - (Qwater + Qcalorimeter)

Q = - (mc +C )

Where m = mass of water, c = specific heat capacity of water, = change in temperature, C =

heat capacity of the calorimeter.

= - Q/moles of sample
Example:
1.435g of naphthalene (C10H8) was burnt in a bomb calorimeter. The temperature of water rose
from 20.17oC to 25.85oC. If the mass of the water was 2000g and heat capacity of bomb
calorimeter 1.80 J/K, calculate the enthalpy change of combustion of naphthalene.
[C =12, H = 1, specific heat capacity of water is 4.18 J/gK]
Solution:

Heat evolved, Q = - (mc +C )

= - (2000 × 4.18 × (25.85-20.17) + 1.80 × (25.85-20.17))

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 = - 4750.33 J
= - 4.75033 kJ
Moles of naphthalene = 1.435/128 = 0.0122 mol

= - Q/moles of naphthalene
= - 4.75033/0.0122
= - 424.1 kJ/mol

EXPERIMENTAL DETERMINATION OF HEAT OF COMBUSTION OF LIQUID e.g. ETHANOL

The mass of water in the metal container should be known before the burning of
ethanol
The mass of ethanol before and after the burning should be determined in order to
know the mass of ethanol burnt.
Temperature of water before and after the burning should be determined in order to
know the mass of water heated.

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For example, if mass of ethanol before and after experiment is 4 and 2.5g respectively and mass
of water is 500g. Also if initial and final temperature of water is 26 and 45.5 oC respectively, then
heat of combustion of ethanol can be calculated as follows:
Assuming heat absorbed by container is negligible,

Heat evolved, Q = -mc

= - (500× 4.18 × (45.5-26))
= - 40,775 J = 40.755 kJ
Moles of ethanol (C2H5OH) = 4 – 2.5/ 46 = 0.0326 mol

Therefore, (ethanol) = - 40.755/0.0326 = -1250 kJ/mol

STANDARD ENTHALPY CHANGE OF NEUTRALIZATION,

Definition: This is the enthalpy change when one mole of an acid(H +) reacts with one mole of
an alkali(OH-) to produce one mole of water under standard conditions.
Examples: HNO3(aq) + NaOH(aq) → NaNO3(aq) + H2O(aq), = -57.3 kJ/mol

HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(aq), = -57.5 kJ/mol

Enthalpy change of neutralization is always negative because heat energy is given out when an
acid reacts with an alkali. For reactions involving a strong acid and a strong base, the value is
approximately constant but the value reduces slightly if the reaction involves a weak acid or a
weak alkali.
NB:
 Enthalpy change of neutralization of strong acid and strong base is approximately
constant and is equal to -57.3 kJ/mol. This is because both strong acid and strong base
fully ionize in solution to produce H+ and OH- respectively. The net ionic equation for
such reaction and for that matter every neutralization reaction is H +(aq) + OH-(aq) → H2O(l)
 For neutralization reactions involving weak acid or weak alkali, part of the enthalpy
change of neutralization value is used in the dissociation of the weak acid or base since
this acid or base dissociates partially. Therefore, the enthalpy change of neutralization is
less than – 57.3 kJ/mol. For example, neutralization reaction between ethanoic acid and
sodium hydroxide gives a value of -56.1 kJ/mol.

Importance of the values

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 1. They are used to differentiate between strong acid and weak ones
2. They are used to determine the basicity (number of replaceable H+ ions) of an acid if the
relative molecular mass is known. For example, a dibasic acid like H2SO4 when it reacts
with an alkali will give an enthalpy change of 2×(-57.3kJ/mol) to indicate that two (2)
moles of water have been formed i.e.
H2SO4(aq) + 2KOH(aq) → K2SO4(aq) + 2H2O(aq), = -114.6 kJ/mol

EXPERIMENTAL DETERMINATION OF ENTHALPY CHANGE OF NEUTRALIZATION

The set -up is shown below:

Equal volumes and concentration of both acid and base are used. Example 1mol/dm 3,
25cm3 HCl and NaOH.
Their initial temperatures are recorded before mixing
The solutions are mixed in the calorimeter and stirred until maximum temperature is
attained.
The heat evolved and enthalpy of neutralization can be calculated as follows:
Heat evolved, Q = - (Qwater + Qcalorimeter)

Q = - (mc +C )

= - Q/moles of water
Assumptions:
 Density of the solution or mixture is the same as that of water
 Specific heat capacity of the solution or mixture is the same as that of water

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  The system is isolated.

Example 1:
100cm3 of 0.5mol/dm3 HCl is mixed with 100cm3 of 0.5mol/dm3 NaOH in a well lagged beaker
having a heat capacity of 335 J/K. The initial temperature of the HCl and NaOH solutions is
22.5oC and the final temperature of the mixture is 24.9oC. Determine the enthalpy change of
neutralization. [ density of water = 1g/cm3, specific heat capacity of water = 4.18 J/gK]
Solution:
HCl + NaOH → NaCl + H2O
V(mixture) = 100 + 100 = 200cm3 = v(water)
m(water) = 200g since density of water is 1g/cm3
Heat evolved, Q = - (Qwater + Qcalorimeter)

Q = - (mc +C )
= - (200 × 4.18 (24.9-22.5) + 335(24.9-22.5))
= - 2810.4 J = - 2.8104 kJ
n(HCl) = cv = 0.5 × 0.1 = 0.05 mol
n(HCl) = n(H2O) = 0.05 mol since mole ratio between HCl and water is 1:1

= - Q/moles of water
= -2.8104/0.05 = - 56.2 kJ/mol

Example 2:
400cm3 of 0.60mol/dm3 HNO3 is mixed with 400cm3 of 0.3mol/dm3 Ba(OH)2 in a calorimeter
having a heat capacity of 387 J/K. The initial temperature of both solutions is 18.88 oC. What is
the final temperature of the solution if the heat of neutralization is -56.2 kJ/mol?
Solution:
2HNO3 + Ba(OH)2 → Ba(NO3)2 + 2H2O
n(HNO3) = cv = 0.60× 0.4 = 0.24mol
n(HNO3) = n(water) = 0.24 mol since mole ratio between the acid and water is 2:2.

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V(mixture) = v(water) = 400 + 400 = 800 cm3
Therefore, mass of water, m(water) = 800g since density of water is 1g/cm 3

= - Q/moles of water
-56.2 = -Q/0.24
Q = 13.488 kJ = 13488 J
Let the final temperature be T. Therefore

Q = mc +C
Q = 800×4.18(T - 18.88) + 387(T - 18.88)
13488 = 3344T - 63134.72 + 387T - 7306.56
T = 22.5oC

STANDARD ENTHALPY CHANGE OF SOLUTION, , AND HYDRATION,

Definition: Standard enthalpy change of solution
This is the enthalpy change when 1 mole of an ionic substance dissolves in water to give a
solution of infinite dilution under standard conditions.

Examples: NaCl(s) + aq → NaCl(aq), = +5 kJ/mol

KI(s) + aq → KI(aq), = +31 kJ/mol

Na2CO3(s) + aq → Na2CO3(aq), = -23 kJ/mol

An infinite dilute solution is one whe re there is a sufficiently large excess of water that adding
any more water doesn’t cause any further heat to be absorbed or released. Enthalpy of
solution can be positive or negative i.e. some ionic substances dissolve endothermically (e.g.
K2SO4, NaCl) while others dissolve exothermically (e.g. NaOH, MgCl2).
When an ionic compound dissolves in a water, two enthalpy changes are involved.
1. The ions must be separated from the ionic lattice in their gaseous form. The energy
required is the lattice dissociation enthalpy. This enthalpy change is always positive. E.g.
NaCl(s) → Na+(g) + Cl-(g), = +776 kJ/mol.

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 2. The separate gaseous ions interact with the water molecules. The heat given out as the
ions are solvated or hydrated is called the hydration enthalpy. This enthalpy change is
always negative.
Na+(g) + Cl-(g) → Na+(aq) + Cl-(aq), = -771 kJ/mol.

Definition: Standard hydration enthalpy

This is the enthalpy change when one mole of gaseous ions forms one mole of hydrated ions
under standard conditions.

The enthalpy of solution is the sum of the two enthalpy changes i.e.

NaCl(s) → Na+(g) + Cl-(g), = +776 kJ/mol

Na+(g) + Cl-(g) → Na+(aq) + Cl-(aq), = -771 kJ/mol

NaCl(s) → NaCl(aq), = +5 kJ/mol

In the experimental determination of the enthalpy of solution, the following steps are used.
o Measure a given volume of water into a container (calorimeter) and note the initial
temperature.
o Add a weighed mass of solute into the water in the container
o Stir well until the solute dissolves
o Record the final temperature of the solution after sometime.

The calculations involved is as follows:

Quantity of heat, Q = mc +C

= Q/ moles of the solute

Example:
10g of NH4Cl were dissolved in 100cm3 of water in a calorimeter of heat capacity 50 J/K. If the
temperature of the solution fell by 5oC, calculate the enthalpy of solution.
[Density of water= 1 g/cm3, specific heat capacity of water=4.18 J/gK]

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Solution:
Mass of water = 100g
Mass of solution = 10 + 100 = 110g

Q = mc +C
Q = (110 × 4.18(-5)) + 50(-5)
= -(2299 + 250) = -2549 J = 2.549 kJ
Moles of NH4Cl = m/M = 10 /53.5 = 0.187mol

= Q/ moles of the solute

= - 2.549/0.187
= - 13.63 kJ/mol

HESS’S LAW OF CONSTANT HEAT SUMMATION

It states that the total enthalpy change of a reaction is independent of the route taken
provided initial and final conditions are the same.
For example, a reactant 'A' changes to a product 'B' in one step and the heat change during this
process is H. If the reaction is carried out in two steps where 'A' first changes to 'C' an
intermediate stage and then 'C' changes to 'B' in the following step then let the heat change
during the formation of 'A' to 'C' be H1 and that from 'C' to 'B' be H2.
From Hess's law the heat change for the reaction is given as:

This means that the amount of heat evolved or absorbed in a chemical reaction depends only
upon the energy of initial reactants and the final products. The heat change is independent of
the path or the manner in which the change has taken place.

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The formation of carbon dioxide from carbon and oxygen can be illustrated as follows. Carbon
can be converted into carbon dioxide in two ways. Firstly, solid carbon combines with sufficient
amount of oxygen to form CO2. The same reaction when carried in presence of lesser amount of
oxygen gives carbon monoxide which then gets converted to CO2 in step two in the presence of
oxygen.

Thus, the enthalpy change for the formation of CO2(g) is 393.5 kJ/mol
From the above, one can conclude that thermochemical equations can be added, subtracted or
multiplied like algebraic equations to obtain the desired equation.

APPLICATIONS OF HESS’S LAW

Hess's law has been useful in determining the heat changes of reactions, which cannot be
measured directly with calorimeter.
Example:
Determine the standard enthalpy change of formation of carbon disulphide(CS 2) given that
enthalpy of formation of CO2 and SO2 are -393.13 and -296.53 kJ/mol respectively and that the
enthalpy of combustion of CS2 is -1103.4 kJ/mol.

Solution:
C + O2 → CO2 - 393.13
S + O2 → SO2 - 296.53
CS2 + 3O2 → CO2 + 2SO2 -1103.4
The required enthalpy of formation of CS2 equation is C + 2S → CS2.

To obtain the required equation from the three equations above, maintain the first one,
multiply the second equation by 2 and reverse the last equation and add all of them.

C + O2 → CO2 - 393.13
2S + 2O2 → 2SO2 2(- 296.53)

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CO2 + 2SO2 → CS2 + 3O2 +1103.4
C + 2S → CS2 +117.2 kJ/mol

BORN-HABER CYCLE
A Born – Haber cycle is an energy diagram which shows the relationship between the lattice
energy of an ionic compound with the ionization energy, electron affinity, sublimation energy,
formation and bond dissociation energies of its constituent elements.
The direct route is always the formation process and it enthalpy change whiles the indirect
route is made up of the remaining processes and their enthalpy changes. By applying Hess’s
law, the direct route should be equal to the sum of the enthalpy changes for the indirect route
i.e.

The diagram below show the Born – Haber cycle for the formation of NaCl(s)

With the exception of the lattice energy, all the other energy terms are determined
experimentally and their values have been provided. Thus to find the lattice enthalpy of the
sodium chloride, we equate the formation enthalpy to the sum of the other enthalpies as
indicated by the arrows.

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 -411 = +107 + (+502) + (+121) + (-355) +

= - 786 kJ/mol

The Born – Haber cycle for formation of calcium oxide is shown below. Notice that in this case,
calcium would have to undergo 1st and 2nd ionizations whiles the oxygen would also have 1st and
2nd electron affinity in order to obtain +2 and -2 charge respectively.

BOND ENERGIES (ENTHALPIES)

The strength of a covalent bond is defined by the amount of energy required to break it. A
quantitative measure of the stability of a molecule is the bond dissociation energy. The bond
dissociation enthalpy is the energy needed to break one mole of a covalent bond to give
separate atoms in the gaseous state. For example, the bond dissociation energy of a simple
diatomic molecule like H – Cl bond is +432kJ/mol.
For a more complicated molecule like CH4 which has 4 C – H bonds, the bond dissociation
energy is not the energy needed to break just any one of the C – H bonds. This is because the
bond dissociation energy of the individual C – H bonds are not the same since the environment
around the molecule changes whenever one of the C – H bonds is broken.

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In the methane case, you can work out how much energy is needed to break a mole of methane
gas into gaseous carbon and hydrogen atoms. That comes to +1662 kJ and involves breaking 4
moles of C-H bonds. The average bond energy is therefore +1662/4 kJ, which is +415.5 kJ per
mole of bonds.

Bond energy can therefore be defined as the average energy required to break a covalent
bond in one mole of a covalent compound into its isolated gaseous atoms.
NB:
The bond energy of a diatomic molecule is the same as its bond dissociation energy. For such
species, the bond dissociation energy is double the value of the standard energy of atomization.

CALCULATIONS INVOLVING BOND ENERGIES

The enthalpy change of a reaction can be determined using the bond energies of the
substances involved in the reaction. The following relation is used.

Example 1:
Use bond energies to calculate the enthalpy change of the reaction between chlorine and
ethane to given chloroethane and hydrogen chloride: C2H6 + Cl2 → C2H5Cl + HCl

bond enthalpy (kJ mol-1)

C-H +413

Cl-Cl +243

C-Cl +346

H-Cl +432

C-C +347
Solution:
To be able to know all the various bonds in each of the molecules, it is important to expand
each of the molecules in the reaction as shown below:

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On the reactants side, 1C – C and 6C – H bonds are broken in the ethane and 1Cl – Cl in
chlorine. On the products side, 1C – C, 1C – Cl and 5C – H bonds are formed in chloroethane
and 1H – Cl in hydrogen chloride. Therefore,

= 1(347) + 6(413) + 1(243) = 3068 kJ/mol

= 1(347) + 1(346) + 5(413) + 1(432) = 3190 kJ/mol

= 3068 – 3190 = - 122 kJ/mol

Example 2:
Using bond enthalpies, calculate the enthalpy change for the combustion reaction between
methane and oxygen to form carbon dioxide and water: CH4 + 2O2 → CO2 + 2H2O.

bond enthalpy (kJ mol-1)

C-H +413

O=O +498

C=O +805

O-H +464

Solution:
From the balanced equation, the expanded structure of the reaction is as shown below:

On the reactants side, 4C – H and 2 O = O bonds are broken.

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On the products side, 2C = O and 4 O – H bonds are formed.

= 4(413) + 2(498) = 2648 kJ/mol

= 2(805) + 4(464) = 3466 kJ/mol

= 2648 – 3466 = - 818 kJ/mol

USES OF BOND ENERGIES

 Used to compare bond strengths
 Used to understand the mechanism of chemical reactions
 Used to understand the structure and bonding of covalent compounds
 Used to calculate the enthalpy change of reactions.

End of topic summary questions

1. Explain each of the following:
a) Heat of neutralization
b) An exothermic reaction
c) A closed system
d) Enthalpy of combustion
2. a) What is enthalpy change of a reaction?
b) State the type of enthalpy change involved in each of the following processes:
i) C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(l)
ii) NaOH(s) + H2O(l) → NaOH(aq)
iii) HCl + NaOH → NaCl + H2O
c) Consider the enthalpy change of formation values given below:

Compound
CH4 -75.0
CO2 -393.5
H 2O -286.0
Calculate the for the reaction:
CH4 + 2O2 → CO2 + 2H2O
3. a) Define each of the following terms:
i) enthalpy of combustion

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 ii) enthalpy of neutralization
b) Write a balanced equation to illustrate each of the terms in a) above.
c) Explain the following observations: The heat of neutralization of a strong acid by a
strong base is approximately constant.
4. Consider the following equations and their enthalpy changes and use the information to
answer the questions that follow:
a) The enthalpy of combustion of ethanol (C2H5OH) is – 1420 kJ/mol.
b) The enthalpy of formation of water is – 286 kJ/mol
c) The enthalpy of formation of carbon (IV) oxide is – 393.5 kJ/mol.
i) Use thermochemical equations to represent each of the above statements.
ii) Calculate the enthalpy of formation of ethanol.
5. a) State whether each of the following reactions is exothermic or endothermic
i) Na(s) and H2O(l)
ii) NH4Cl(s) and H2O(l)
b) Draw and label the energy diagram for the reaction in a) i) above indicating
i) activation energy
ii) activated complex
iii) enthalpy change of the reaction
c) Consider the reactions represented by the following equations:
i) H2(g) + ½O2(g) → H2O(l),
ii) H2(g) + ½O2(g) → H2O(g),
Calculate the for the reaction: H20(l) → H2O(g)
6. a) Define standard enthalpy change of neutralization.
b) Describe briefly how enthalpy change of neutralization of HCl and NaOH can be
determined.
c) In a separate experiment to determine the heat of neutralization of strong acid and a
base, 25cm3 of 1.0 mol/dm3 HCl exactly neutralized 25cm3 of 1.0 mol/dm3 NaOH. The
following data was obtained during the reaction:
Temperature, T1 of the acid = 26.5oC
Temperature, T2 of the base = 26.8oC
Temperature, T4 of the mixture = 33.3oC
i) Determine the average temperature, T3 of the acid – base solution.
ii) Determine the change in temperature T during the reaction.
iii) Determine the mass, m of the reaction mixture.
[ 1cm3 of the mixture weighs 1g]
d) From the information given in c) above, calculate
i) heat evolved during the reaction.
ii) heat of neutralization, Hn of the reaction.
[specific heat capacity of water, c = 4.2 Jg-1oC-1]

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 e) i) What is the sign of Hn in d) ii) above
ii) Name the apparatus used in determining the heat of neutralization.
7. a) State Hess’s law of constant heat summation.
b) What is standard enthalpy of formation?
c) Write a balanced chemical equation for the standard enthalpy of formation of
methane.
d) Use the following data to calculate a value for the enthalpy of formation of methane:
C + O2 → CO2, H = - 394 kJ/mol
H2 + ½O2 → H2O, H = - 242 kJ/mol
CH4 + 2O2 → CO2 + 2H2O, H = -802 kJ/mol
8. a) Define the term bond dissociation energy.
b) Use the bond dissociation energies given below to calculate the H for the reaction:
CH3C(CH3)=CH2 + HCl → CH3C(CH3)ClCH3

Bond C–C C=C H – Cl C – Cl C–H

Bond energy 347 610 341 339 414

9. Draw an energy cycle for the formation of MgO form its elements, relating clearly the
various enthalpy changes to the reactions.

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