Chem@HC

Secondary 4 Chemistry Olympiad

Name: ______________________ Class: Sec 4_____ Date: ________

Thermochemistry
Enthalpy changes

Chemical reactions are typically accompanied by a change in energy, evolving or absorbing

heat. The heat transaction in a system at constant pressure is termed its enthalpy change,
denoted ΔH. Enthalpy changes are usually reported in J or kJ. A related term is the enthalpy
of reaction, denoted Δr H, which refers to the enthalpy change of a chemical reaction per
−1
mole of reaction. Enthalpies of reactions are typically reported in kJ mol .

If a reaction is accompanied by a positive enthalpy change (Δr H  0), it is endothermic.

This implies that the product has more energy than the reactants. When this occurs, the
reaction absorbs heat from the surroundings, decreasing the temperature of the
surroundings.

If a reaction is accompanied by a negative enthalpy change (Δr H  0), it is exothermic. This

implies that the product has less energy than the reactants. When this occurs, the reaction
releases heat into the surroundings, increasing the temperature of the surroundings.

If the energy level of the products is lower than that of the reactants, the products are
energetically more stable than the reactants and the reaction is energetically favoured.

Standard conditions and standard states

Standard conditions refer to a temperature of 298 K, a pressure of 1 bar and a concentration

−3
of 1mol dm for aqueous solutes. The standard state of a substance at a given temperature
is its normal, most stable physical state at 1 bar. We typically speak of standard states of
substances at 298 K.

Standard enthalpies

The enthalpies of reactions are affected by physical conditions such as temperature and
pressure. In scientific tables, reaction enthalpies are usually reported under standard
conditions. These are called standard enthalpies. The definitions of various standard
enthalpies are given below.

In general, the standard enthalpy of a reaction is the enthalpy change when molar
quantities of reactants as specified by the chemical equation react to form products under
standard conditions.
−1
4 Cl2 (g) + CH4 (g) → CCl4 (g) + 4 HCl(g) Δr H = −433kJ mol

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Standard enthalpy of formation

The enthalpy change when 1 mol of a substance is formed from its constituent elements in
their standard states under standard conditions
−1
C(s) + O2 (g) → CO2 (g) Δf H = −393.5 kJ mol

By definition, Δ f H = 0 for elements in their standard states.

Standard enthalpy of combustion

The enthalpy change when 1 mol of a substance is completely burnt in excess oxygen under
standard conditions
−1
CH4 (g) + 2 O2 (g) → CO2 (g) + H2O(l ) ΔcH = −866 kJ mol

Standard enthalpy of neutralisation

The heat evolved when 1 mol of water is formed in the neutralisation reaction between an
acid and a base under standard conditions
−1
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l ) Δneut H = −57.0kJ mol
+ −
Neutralisation is an exothermic reaction since it involves the attraction of H and OH ions to
form an O-H bond.
+ − −1
H (aq) + OH (aq) → H2O(l ) Δneut H = −57.0 kJ mol

The standard enthalpy of neutralisation is almost the same for all reactions between strong
−1
acids and bases (−57.0 kJ mol ). Strong acids and bases ionise completely in dilute
+
aqueous solutions, and the reaction between them is effectively that between aqueous H
−
and OH ions.

If the acid-base reaction involves a weak acid/base, the standard enthalpy of neutralisation
is slightly less exothermic, as weak acids/bases do not ionise completely in dilute aqueous
solution. During neutralisation, energy is absorbed to ionise the un-ionised weak acid/base,
releasing less energy in the neutralisation reaction.

Standard enthalpy of atomisation (for an element)

The energy required to form 1 mole of gaseous atoms from the element under standard
conditions
−1
Na(s) → Na(g) Δat H = +107 kJ mol
−1
1
2
Cl2 (g) → Cl(g) Δat H = +121kJ mol

Note that Δ at H = 0 for noble gases since they exist as free gaseous atoms under standard
conditions.

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Standard enthalpy of atomisation (for a compound)

The energy required to convert 1 mol of the compound into gaseous atoms under standard
conditions
−1
CH4 (g) → C(g) + 4 H(g) Δat H = +415.5 kJ mol

Since atomisation involves bond breaking, enthalpies of atomisation are always positive
(energy input is required to break the chemical bond).

Standard enthalpy of hydration

The heat evolved when 1 mol of free gaseous ions is dissolved in an infinite volume of water
under standard conditions
+ + −1
Na (g) → Na (aq) ΔhydH = −405 kJ mol

Enthalpies of hydration are always negative, as heat is evolved in forming ion-dipole

interactions between the ions and the polar water molecules. Therefore, the hydration of ions
is an energetically favoured process.

Mathematically, the magnitude of ΔhydH of an ion is proportional to its charge density (q/r).
Higher charge density would mean stronger ion-dipole interactions leading to an increase in
the magnitude of ΔhydH .

Standard enthalpy of solution

The enthalpy change when 1 mol of solute is completely dissolved in an infinite volume of
solvent under standard conditions
2+ 2− −1
CuSO4 (s) → Cu (aq) + SO4 (aq) ΔsolH = −73.2 kJ mol

Bond energies/lattice energy

The bond dissociation energy is the energy required to homolytically break 1 mol of a
particular covalent bond in a specific molecule in the gaseous state. A stronger bond will
require more energy to cause bond dissociation. As such, the bond dissociation energy is a
measure of the strength of covalent bonds. The stronger the covalent bond, the greater the
bond dissociation energy.

Note: Bond dissociation energies of the same type of bond in different molecules may differ.
For example, the bond dissociation energy of a C-H bond in CH4 and C2H4 are different.

The bond energy is the average energy required to homolytically break 1 mol of a covalent
bond in the gaseous state. It is an averaged value of bond dissociation energies across a
large range of molecules containing that bond. It is typically denoted E(bond), like E (C=O)
for instance.

In thermochemical calculations, it can be convenient to use this formula:

Δr H =  E (bonds broken) −  E (bonds formed)

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If Δ r H is positive, bonding in the reactants is stronger than in the products. Hence, energy
must be absorbed from the surroundings to break the bonds in the reactants for the reaction
to proceed (endothermic process). Conversely, if Δ r H is negative, bonding in the reactants
is weaker than in the products. Hence, energy will be released to the surroundings
(exothermic process).

The lattice energy of an ionic compound, EL, is the heat evolved when 1 mol of the solid
compound is formed from its constituent gaseous ions.
+ − −1
Na (g) + Cl (g) → NaCl(s) EL = −742 kJ mol

Lattice energy is always negative as heat is evolved during the formation of ionic bonds. To
put it in another way, energy input is required to overcome the electrostatic forces of
attraction between the ions in an ionic compound.

Ionisation energy/electron affinity

Ionisation energy

The first ionisation energy, I1, of an element is the energy required to remove 1 mol of
electrons from 1 mol of gaseous atoms to form 1 mol of singly charged gaseous cations.
Subsequent ionisation energies, In, are similarly defined.

Electron affinity

The first electron affinity, A1, of an element is the enthalpy change when 1 mol of electrons is
added to 1 mol of gaseous atoms to form 1 mol of singly charged gaseous anions.
Subsequent electron affinities, An , are similarly defined.

The first electron affinity is usually negative due to the attraction between the incoming
electron and the atom. The second and subsequent electron affinities are always positive
because energy is required to overcome the electrostatic repulsion between the incoming
electron and the anion.
− − −1
O(g) + e → O (g) A1 = −141kJ mol
− − 2− −1
O (g) + e → O (g) A2 = +844 kJ mol

Calorimetry

Calorimetry is the measurement of heat transactions during a chemical reaction or physical

process. Reaction enthalpies can be determined by measuring the heat absorbed or
released during the reaction. This can be done by the following equation:

q
Δr H = − ,
n
where q is the heat transaction and n is the amount of limiting reactant.

However, to use the above equation, we need to first determine the value of q . This can be
done by allowing the heat released (or absorbed) by a process to heat up (or cool down) a
solution. The heat transaction of the process, q , can then be calculated as:

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 q = mcΔT ,

where m is the mass of the solution, c the specific heat capacity of the solution, and ΔT the
temperature change of the solution.

Note that ΔT is a signed quantity; that is, ΔT  0 if there is an increase in temperature, and
ΔT  0 if there is a decrease in temperature. The computation of q must account for the sign;
otherwise, the value of Δr H will have the wrong sign.

The specific heat of capacity, c , of a substance is the heat required to raise the
−1 −1
temperature of one unit mass of the substance by one unit. It is typically reported in J K g .

The heat capacity, C , of a system is the heat required to raise the temperature of the
−1
system by one unit. It is typically reported in J K .

Question 1:

Gummibar was first manufactured by the German company Haribo in 1922. It is produced by
pouring a liquid mixture containing sucrose (C12H22O11) into a mould which is then cooled to
form the sweet. The balanced equation for the combustion of sucrose is given below:

C12H22O11(l ) + 12 O2 (g) → 12 CO2 (g) + 11H2O(l )

To determine the energy content of Gummibar, food scientists carried out the combustion
3
process in a bomb calorimeter. In one experiment, 20 cm of liquid Gummibar was burnt and
the maximum temperature rise in the water was recorded to be 55 K. The volume of water
3
present in the bomb calorimeter was 1.5 dm . Calculate the standard enthalpy of combustion
of Gummibar.

You may assume that:

−3
• Gummibar is only made up of sucrose, which has a density of 1.55 g cm ;
• only 80% of the heat from the combustion was absorbed by the water; and
−1 −1
• the specific heat capacity of water is 4.18 J K g .

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Hess’ Law

Hess’ Law states that reaction enthalpies are determined only by the initial and final
states and are independent of the reaction pathway taken.

A B

D E

Hence, for the diagram above, Δr H1 = Δr H2 + Δr H3 = Δr H4 + Δr H5 + Δr H6 .

By using Hess’ Law, one can deduce a few relationships between different standard
enthalpies. The equations are as follows (convince yourself of them!)

Δr H =  mΔc H (reactants) −  mΔc H (products)

Δr H =  mΔf H (products) −  mΔf H (reactants)
ΔsolH = −EL +  ΔhydH (all ions)

(the m’s denote the stoichiometric coefficients of the species in the given reaction).

Question 2:

Calculate the standard enthalpy of formation of propane, C3H8 (g) , given the following data:

-1
Substance Δ c H /kJ mol

Graphite, C(s) −394

Hydrogen, H2 (g) −286
Propane, C3H8 (g) −2220

Question 3:

Calculate the standard enthalpy change of combustion of propane, C3H8 (g) , given the
following data:

-1
Chemical species Δ f H /kJ mol
C3H8 (g) −104
CO2 (g) −394
H2O(l ) −286

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Question 4:

Sulfur hexafluoride is used as a gaseous dielectric medium in the electrical industry. It can
be made by reacting sulfur tetrafluoride with fluorine.
−1
SF4 (g) + F2 (g) → SF6 (g) Δr H = −434 kJ mol

By considering the bonds broken and formed during the reaction, calculate E(S ⎯F). State
−1
any assumptions you have made. You are told that E(F⎯F)= 158 kJ mol .

Born-Haber Cycles

This is an application of Hess’ Law used primarily for determining lattice energies. Lattice
energies cannot be determined directly and hence a more “roundabout” method must be
used. The Born-Haber cycle considers all the various reactions that have to occur in order
for the elements to form a solid ionic product or as a solution containing the ionic compound.

Example
By means of drawing a Born-Haber cycle, calculate the lattice energy of calcium oxide using
the information given below.

I1(Ca), A1(O),
Δat H (Ca) Δat H (O2 ) Δf H (CaO)
I2 (Ca) A2 (O)
Enthalpy +177 +590 +249 −141 −636
−1
change/kJ mol +1100 +790

Δf H (CaO) = Δat H (Ca) + Δat H (O2 ) + I1(Ca) + I2 (Ca) + A1(O) + A2 (O) + EL (CaO)
−636 = +177 + 249 + (590 + 1100) + ( −141 + 790) + EL (CaO)
−1
EL (CaO) = −3401kJ mol

Figure 1. Born-Haber cycle used to compute the lattice energy of calcium oxide.

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Question 5:

By means of drawing a Born-Haber cycle, calculate the standard enthalpy of solution of

sodium chloride using the information given below.

Δat H (Na) I1(Na) Δat H (Cl2 ) A1(Cl )

−1
Enthalpy change/kJ mol +108 +494 +121 −364
+ −
Δf H (NaCl ) ΔhydH (Na ) ΔhydH (Cl )
−1
Enthalpy change/kJ mol −411 −406 −306

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