6.

1 Enthalpy Changes 2) Enthalpy change of a reaction, ∆H is the heat change(heat is absorbed or evolved)
when a chemical reaction takes place.
Exothermic and endothermic reactions 3) i. In exothermic reactions, the enthalpy change is always negative.(∆H < 0)
ii. In endothermic reactions, the enthalpy change is always positive.(∆H > 0)
1) Most chemical reactions are accompanied by energy changes. Some absorbs
energy while some releases it. Energetic stability of a system

2) An exothermic reaction is a reaction that releases energy to the surroundings. 1) Exothermic reactions are more energetically favourable than endothermic ones
Therefore the product contain less energy with respect to the reactants. The because a system with lower energy content is more stable.
energy is released as heat energy, so the surroundings warm up.
2) Thus, the more negative the ∆H value, the more stable the system is.
3) An endothermic reaction is a reaction that absorbs energy from the surroundings.
Therefore the products contain more energy with respect to the reactants. The 3) For example, oxygen,O2 is energetically more
energy is absorbed as heat energy, so the surroundings cool down. stable than ozone, O3. Their relative positions on
the energy level diagram are as follow:
4) An energy level diagram shows the relative energies of the products and
reactants. The higher its energy, the higher its position. 4) But ozone does not convert to oxygen
immediately in atmosphere, this is because ozone
is kinetically stable although it is energetically
unstable with respect to the products. The
activation energy is not sufficient for the reaction to take place.

Measuring enthalpy changes

1) Enthalpy changes can be measured experimentally by measuring the

temperature change as a reaction proceeds. Two common examples are
measuring the enthalpy change of neutralisation and combustion.
An exothermic reaction An endothermic reaction
2) The formulae:
5) i. Examples of exothermic reactions are neutralisation, combustion, dissolving
anhydrous salts and the reaction between acids and metal carbonates. where m = mass of substance(or solution)/g
ii. Examples of endothermic reactions are atomisation, photosynthesis, Heat energy absorbed c = specific heat capacity of solution/J g⁻¹ °C⁻¹
= mc∆T where m = mass of solution/g
(c is normally assumed to be 4.18 J g⁻¹ °C⁻¹)
dissolving crystalline salts and thermal decomposition. or released c = specific heat capacity
∆T = change in temperature/°C
of solution
Enthalpy changes (c is normally taken
as 4.13 J g⁻¹ K⁻¹ )
heat energy absorbed or released ∆T = change in temperature
1) Enthalpy, H is an indication of the total energy of a substance and it cannot be ∆H = Unit = kJ mol⁻¹
measured directly. However, enthalpy change, ∆H is measurable. no. of moles of the limiting reagent
3) Assumptions made in this calculation:
- The density of all aqueous solution is 1 g cm⁻³. Thus, numerically, 1 cm³ = 1 g.
6.2 Standard Enthalpy Changes
- The solution has the same specific heat capacity as water(4.18 J g⁻¹ °C⁻¹).
The standard condition
4) An example - to calculate the enthalpy change of the reaction between sodium
hydroxide, NaOH(aq) and hydrochloric acid, HCl(aq). 1) To make comparison of enthalpy changes a fair comparison, same conditions
NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(l) must be used. These are called the standard conditions:
- A pressure of 100 kPa(approximately atmospheric pressure).
i. Pour 25 cm³ of NaOH into 25 cm³ of HCl - A temperature of 298 K or 25 °C.
in a polystyrene cup(polystyrene cup is used - Where solutions are involved, a concentration of 1.0 mol dm⁻³.
because it is a good heat insulator). Both solutions - Every substance involved must be in its normal physical state at 100 kPa
have concentrations of 1.0 mol dm⁻³. and 298 K. For example, water is in liquid, not ice or steam.
ii. Measure the initial and maximum temperature - If allotropes are involved, the allotrope which is more energetically stable is
reached. used. For example, for carbon, graphite is chosen over diamond because
iii. For example, the mean initial temperature of both graphite is energetically more stable than diamond.
solutions is 18.1 °C and the maximum temperature
reached is 24.8 °C. Then, ΔT = 6.7 °C. 2) Standard enthalpy changes can be represented by the symbol ΔH°. This
iv. Mass of both solutions is (25+25) x 1 = 50 g since density = mass/volume. refers that the reaction is carried out under standard conditions. For example:
v. Therefore heat released = 50 x 4.18 x 6.7 = 1400 J = 1.4 kJ
vi. Number of moles of water = 0.025 mol CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ; ΔH° = -890.3 kJ mol⁻¹
vii. Therefore ΔH = -(1.4/0.025) = -56 kJ mol⁻¹
Various enthalpy changes
5) Another example - to calculate the enthalpy change of the reaction of
combustion of ethanol, C2H5OH. 1) Enthalpy changes are described according to the type of reaction. Examples:
C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(g) - standard enthalpy change of reaction, ΔH°r (in general)
- standard enthalpy change of formation, ΔH°f
- standard enthalpy change of combustion, ΔH°c
i. In this experiment, a spirit burner is used to
- standard enthalpy change of neutralisation, ΔH°n
combust the flammable liquid ethanol. The heat
- standard enthalpy change of atomisation, ΔH°at
evolved is used to heat up the water, the maximum
temperature reached is then measured. - standard enthalpy change of solution, ΔH°sol
- standard enthalpy change of hydration, ΔH°hyd
ii. Mass of water = 250 g
Initial temperature of water = 19.5 °C
Standard enthalpy change of reaction, ΔH°r
Maximum temperature of water = 23.7 °C
Initial mass of ethanol = 41.36 g
1) Standard enthalpy change of reaction, ΔH°r is the enthalpy change when the amount
Final mass of ethanol = 41.18 g
iii. Therefore, ΔT = 4.2 °C and m = 250 g. of reactants shown in the equation react to give products under standard
iv. Heat released = 250 x 4.18 x 4.2 = 4389 J = 4.389 kJ condition. The reactants and products must be in their standard states.
v. Number of moles of ethanol burned = 0.18/46 = 0.0039 mol
vi. Therefore ΔH = -(4.389/0.0039) = -1100 kJ mol⁻¹ (2 s.f) 2H2(g) + O2(g) → 2H2O(l) ; ΔH°r = -576 kJ mol⁻¹
2) The equation shows that 576 kJ of energy is released when two moles of 3) The enthalpy change of neutralisation between strong acids and strong
hydrogen react with one mole of oxygen to give two moles of water. bases is a constant(-57.1 kJ mol⁻¹). This is because all strong acids and strong
bases dissociate completely in water to form aqueous ions.
3) This is a theoretical reaction, it does not happen in practice. The enthalpy
change can be found by applying Hess' law. 4) So, neutralisation between strong acids and strong bases involves the same
reaction, that is, H⁺ reacts with OH⁻ to form H2O. The other ions present are
Standard enthalpy change of formation, ΔH°f just simply spectator ions. They do not take part in the reaction. Hence, the
heat released is the same.
1) Standard enthalpy change of formation, ΔH°f is the enthalpy change when one mole
of a compound is formed from its elements under standard condition. 5) However, the enthalpy change of neutralisation between sulfuric acid and
The reactants and products must be in their standard states. sodium hydroxide is more exothermic(-66.8 kJ mol⁻¹) than expected. This is
because the enthalpy change of dilution of sufuric acid is significant. When
2Fe(s) + 1½O2(g) → Fe2O3(s) ; ΔH°f [ Fe2O3(s) ] = -824.5 kJ mol⁻¹ sulfuric acid is added to sodium hydroxide, the acid is diluted in the process and
heat is released.
2) By definition, the standard enthalpy change of formation of an element is zero.
6) The enthalpy change of neutralisation involving weak acids or weak bases
3) The standard enthalpy change of formation can be exothermic or endothermic. is less than 57.1 kJ mol⁻¹. For example:
CH3COOH(aq) + NaOH(aq) → CH3COONa(aq) + H2O(l) ;
Standard enthalpy change of combustion, ΔH°c ΔH°n = -56.1 kJ mol⁻¹
NaOH(aq) + HCN(aq) → NaCN(aq) + H2O(l) ; ΔH°n = -11.7 kJ mol⁻¹
1) Standard enthalpy change of combustion, ΔH°c is the enthalpy change when one mole
of a substance is burnt in excess oxygen under standard conditions. The 7) This is because weak acids and weak bases only partially dissociated in water.
reactants and products must be in their standard states. For example:
CH3COOH(aq) ⇌ CH3COO⁻(aq) + H⁺(aq) ; ΔH° = positive
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ; ΔH°c [ CH4(g) ] = -890.3 kJ mol⁻¹
8) On addition of strong base such as NaOH, the OH⁻ ions react with H⁺ from the
dissociation of CH3COOH. The removal of H⁺ ions causes the position of
2) The standard enthalpy change of combustion is always exothermic.
equilibrium to shift to the right and more CH3COOH molecules dissociate.
However the dissociation of CH3COOH is an endothermic process, hence,
Standard enthalpy change of neutralisation, ΔH°n
some energy is absorbed and the enthalpy change overall is less negative.
1) Standard enthalpy change of neutralisation, ΔH°n is the enthalpy change when one
9) The standard enthalpy change of neutralisation is always exothermic.
mole of water is formed by the reaction of an acid with an alkali under
standard conditions.
Standard enthalpy change of atomisation, ΔH°at
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l) ; ΔH°n = -57.1 kJ mol⁻¹
1) Standard enthalpy change of atomisation, ΔH°at is the enthalpy change when one mole
of gases atoms is formed from its element under standard conditions.
2) For any acid-alkali reaction, the ionic equation is:
½H2(g) → H(g) ; ΔH°at [ ½H2 ] = +218 kJ mol⁻¹
H⁺(aq) + OH⁻(aq) → H2O(l)
Na(s) → Na(g) ; ΔH°at [ Na ] = +107 kJ mol⁻¹
2) By definition, the standard enthalpy change of atomisation of the noble gases is
zero because all of them exist as monoatomic gases at standard conditions.
6.3 Hess' Law
3) The standard enthalpy change of atomisation of diatomic gases(example: O2, Hess' law and Hess' cycle
Cl2, N2 and F2) is equal to half the value of their bond energies.
1) Hess' law states that the total enthalpy change in a chemical reaction is
4) The standard enthalpy change of atomisation is always endothermic. independent of the route which the reaction takes place as long as the initial
and final conditions are the same.
Standard enthalpy change of solution, ΔH°sol
2) For example, the enthalpy change of reaction from A to C is the same whether
1) Standard enthalpy change of solution, ΔH°sol is the enthalpy change when one mole the reaction takes place in one stage(A to C) or two stages(A to B then to C).
of solute is dissolved in a solvent to form an infinitely dilute solution under
standard conditions.

NaCl(s) + aq → NaCl(aq) ; ΔH°sol = +6.0 kJ mol⁻¹

NaOH(s) + aq → NaOH(aq) ; ΔH°sol = -44.5 kJ mol⁻¹ 3) This is because the enthalpy change of a chemical reaction depends only on the
difference between enthalpy of the products and the reactants. It does not
2) An infinitely dilute solution is one which does not produce any further enthalpy depend on how the reaction took place.
change when more solvent is added.

3) The standard enthalpy change of solution can be exothermic or endothermic.

Standard enthalpy change of hydration, ΔH°hyd

1) Standard enthalpy change of hydration, ΔH°hyd is the enthalpy change when one mole
of gases ions dissolves in water to form hydrated ions of infinite dilution under
standard conditions.
4) Hess' law is useful to calculate enthalpy changes that cannot be measured
directly from experiments(theoretical reactions that will not occur under
Ca²⁺(g) + aq → Ca²⁺(aq) ; ΔH°hyd = -1650 kJ mol⁻¹
standard conditions).
2) Water is a polar molecule, this means that it has a negative end and a positive
5) Steps to construct a Hess' cycle:
end. The negative end of the water molecule will be attracted to the cations
i. Write down the equation for the enthalpy change that you are asked to find
while the positive end of the water molecule will be attracted to the anions.
and write ΔH on top of the arrow.
ii. Use the information that you have been given to complete a cycle.
3) The attraction set up is called the ion-dipole forces.
iii. Find the direct route and indirect route. The routes should not go against any
arrows. (Equations may be reversed when necessary, but do not forget to
4) The standard enthalpy change of hydration is always exothermic.
reverse the sign as well.)
iv. Apply Hess' law and form an equation to solve for ΔH.
6) Examples:

An endothermic reaction An exothermic reaction

Bond energy

1) Bond energy, E is the energy needed to break one mole of covalent bonds between
two atoms in the gaseous state.

Br-Br(g) → 2Br(g) ; E(Br-Br) = +193 kJ mol⁻¹

2) Bond energy is often called bond enthalpy or bond dissociation energy.

Average bond energy

1) Bond energy is often affected by the presence of other atoms in the molecule.
6.4 Bond Energy For example, the O-H bond in water has a different bond energy value than the
O-H bond in ethanol. Even in the same molecule, for example, CH4, the energy
Bond breaking and bond forming needed to break all the C-H bonds are not identical.

1) i. Breaking bonds needs energy, energy is absorbed from the surroundings. 2) Therefore, bond energies are taken from a number of bonds of the same type
Therefore, bond breaking is an endothermic process. from different environment and average out to get the average bond energy.
ii. Forming bonds releases energy to the surroundings. Therefore, bond forming The values are not always accurate.
is an exothermic process.

2) i. If the energy needed to break bonds is less than the energy released when
new bonds are formed, then the reaction will be exothermic
ii. If the energy needed to break bonds is more than the energy released when
new bonds are formed, then the reaction will be endothermic.

3) In most chemical reactions, bonds have to be broken first and then reformed
into a new compound.
Hess' law involving average bond energy

1) Average bond energies can also be used to estimate enthalpy changes of

reactions involving covalent molecules

2) Example:

3) If the given reactants or products are not in the gaseous state, enthalpy
change of vaporisation or enthalpy change of fusion must be considered
because the non-gaseous compounds needed to be converted to the gaseous
state. Changing from other states to the gaseous state needs to absorb extra
energy.