6.

1 ENTHALPY CHANGES

 The total chemical energy inside a substance is called the enthalpy (or heat content)
 When chemical reactions take place, changes in chemical energy take place and therefore the enthalpy
changes
 An enthalpy change is represented by the symbol ΔH (Δ= change; H = enthalpy)
 An enthalpy change can be positive or negative

Exothermic reactions

 A reaction is exothermic when the products have less energy than the reactants
 Heat energy is given off by the reaction to the surroundings
o The temperature of the environment increases - this can be measured on a thermometer
o The temperature of the system decreases
 There is an enthalpy decrease during the reaction so ΔH is negative
 Exothermic reactions are thermodynamically possible (because the enthalpy of the reactants
is higher than that of the products)
 However, the rate may be too slow to observe any appreciable reaction
o In this case the reaction is kinetically controlled
o This means the reaction could have a high activation energy which is preventing the reaction
from taking place.

Endothermic reactions

 A reaction is endothermic when the products have more energy than the reactants
 Heat energy is absorbed by the reaction from the surroundings
o The temperature of the environment decreases - this can be measured with a thermometer
o The temperature of the system increases
 There is an enthalpy increase during the reaction so ΔH is positive

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Exam Tip

It is important to specify the physical states of each species in an equation when dealing with enthalpy changes as any
changes in state can cause very large changes of enthalpy. For example: Na+Cl- (s) → Na+ (aq) + Cl- (aq)

ΔH = +4 kJ mol-1 Na+Cl- (g) → Na+ (g) + Cl- (g) ΔH = + 500 kJ mol-1Also, remember that the system is the molecules that
are reacting (ie. the reaction itself) and the surroundings is everything else (eg. the flask the reaction is taking place in).

6.2 ENERGY LEVEL DIAGRAMS

 An energy level diagram is a diagram that shows the energies of the reactants, the transition state(s)
and the products of the reaction with time
 The transition state is a stage during the reaction at which chemical bonds are partially broken and
formed
 The transition state is very unstable – it cannot be isolated and is higher in energy than the reactants
and products
 The activation energy (Ea) is the energy needed to reach the transition state
 We can define the activation energy as ‘the minimum amount of energy needed for reactant molecules
to have a successful collision and start the reaction’

Exothermic reaction

 In an exothermic reaction, the reactants are higher in energy than the products

 The reactants are therefore closer in energy to the transition state

 This means that exothermic reactions have a lower activation energy compared to endothermic reactions

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Endothermic reaction
 In an endothermic reaction, the reactants are lower in energy than the products
 The reactants are therefore further away in energy to the transition state
 This means that endothermic reactions have a higher activation energy compared to exothermic
reactions

Worked example: Drawing energy level diagrams of the combustion of methane

Answer
 Step 1: The chemical equation for the complete combustion of methane is:
CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (l)

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 Step 2: Combustion reactions are always exothermic (ΔH is negative) so the reactants should be
drawn higher in energy than the products

 Step 3: Draw the curve in the energy level diagram clearly showing the transition state

 Step 4: Draw arrows to show the Ea and ΔH including their values

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Worked example: Determining the activation energy

Answer

The Ea is the energy difference from the energy level of the reactants to the top of the ‘hump’

Ea (forward reaction) = (+70 kJ mol-1) + (+ 20 kJ mol-1 ) = +90 kJ mol-1

As the question is asking for the reverse reaction the Ea is the energy difference from the energy level of the
products to the ‘hump’

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Ea (reverse reaction) = +20 kJ mol-1

Exam Tip

The activation energy is the energy difference from reactants to transition state. The enthalpy change of the reaction is
the energy difference from reactants to products. Remember to label the axis of the energy level diagrams!

6.3 STANDARD ENTHALPY CHANGES

Enthalpy Changes at Standard Conditions

 To fairly compare the changes in enthalpy between reactions, all reactions should be carried out under
standard conditions
 These standard conditions are:
o A pressure of 101 kPa
o A temperature of 298 K (25 oC)
o Each substance involved in the reaction is in its normal physical state (solid, gas or liquid)
 To show that a reaction has been carried out under standard conditions, the symbol Ꝋ is used
o ΔHꝊ = the standard enthalpy change
 These are a number of key definitions for common language relating to enthalpy change that all
chemists need to know

Enthalpy definitions table

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Worked example: Calculating the enthalpy change of reaction of water

Answer

Since two moles of water molecules are formed in the question above, the energy released is simply:

ΔHrꝊ = 2 mol x (-286 kJ mol-1)

= -572 kJ mol-1

Worked example: Calculating the enthalpy change of formation

Answer

Since two moles of Fe2O3 (s) are formed the total change in enthalpy for the reaction above is:

ΔHfꝊ = 2 x ( -824.2 kJ mol-1)

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= - 1648 kJ

Worked example: Calculating enthalpy changes

Answer

Answer 1: ΔHrꝊ

Answer 2: ΔHrꝊ as one mole of CO2 is formed from its elements in standard state and ΔHcꝊ as one mole of
carbon is burnt in oxygen

Answer 3: ΔHneutꝊ as one mole of water is formed from the reaction of an acid and alkali

Exam Tip

The ΔHfꝊ of an element in its standard state is zero. For example, ΔHfꝊ of O2(g) is 0 kJ mol-1

6.4 ENTHALPY AND BOND ENERGIES

 During a reaction, enthalpy changes take place because bonds are being broken and formed
 Energy (in the form of heat) is needed to overcome attractive forces between atoms
 Bond breaking is therefore endothermic
 Energy is released from the reaction to the surroundings (in the form of heat) when new bonds are
formed
 Bond forming is therefore exothermic

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  If more energy is required to break bonds than energy is released when new bonds are formed, the
reaction is endothermic
 If more energy is released when new bonds are formed than energy is required to break bonds, the
reaction is exothermic
 In reality, only some bonds in the reactants are broken and then new ones are formed

Enthalpy Calculations

Exact bond energy

 The amount of energy required to break one mole of a specific covalent bond in the gas phase is
called the bond dissociation energy
 Bond dissociation energy (E) is also known as exact bond energy or bond enthalpy
 The type of bond broken is put in brackets after E
o Eg. EE(H-H) is the bond energy of a mole of single bonds between two hydrogen atoms

Average bond energy

 Bond energies are affected by other atoms in the molecule (the environment)
 Therefore, an average of a number of the same type of bond but in different environments is
calculated
 This bond energy is known as the average bond energy
 Since bond energies cannot be determined directly, enthalpy cycles are used to calculate the average

bond energy

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Calculating enthalpy change from bond energies

 Bond energies are used to find the ΔHrꝋ of a reaction when this cannot be done experimentally

 Eg. the Haber Process

Worked example: Calculating the enthalpy change in the Haber process

Answer

 Step 1: The chemical equation for the Haber process is:

N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

 Step 2: Set out the calculation as a balance sheet as shown below:

 Step 3: Calculate the standard enthalpy of reaction

ΔHrꝋ = enthalpy change for bonds broken + enthalpy change for bonds formed

= (+2253 kJ mol-1) + (-2346 kJ mol-1)

= -93 kJ mol-1
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Worked example: Calculating the average bond enthalpy

Answer

 Step 1: The enthalpy of combustion is the enthalpy change when one mole of a substance reacts in
excess oxygen to produce water and carbon dioxide

The chemical reaction should be therefore simplified such that only one mole of ethyne reacts in excess
oxygen:

H-C=C-H + 2 ½ O=O → H-O-H + 2O=C=O

 Step 2: Set out the calculation as a balance sheet as shown below:

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ΔHrꝋ = enthalpy change for bonds broken + enthalpy change for bonds formed

= (+2912 kJ mol-1) + (- 4142 kJ mol-1)

= -1230 kJ mol-1

Measuring enthalpy changes

 Calorimetry is a technique used to measure changes in enthalpy of chemical reactions

 A calorimeter can be made up of a polystyrene drinking cup, a vacuum flask or metal can

A polystyrene cup can act as a calorimeter to find enthalpy changes in a chemical reaction

 The energy needed to increase the temperature of 1 g of a substance by 1 oC is called the specific
heat capacity (c) of the liquid
 The specific heat capacity of water is 4.18 J g-1 oC-1
 The energy transferred as heat can be calculated by:

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Worked example: Specific heat capacity calculations

 Step 1: q = m x c x ΔT

m (of water) = 500 g

c (of water) = 4.18 J g-1 K-1

ΔT (of water) = 68 oC - 25 oC

= 43 oC

= 43 K

The change in temperature in oC is equal to the change in temperature in K

 Step 2: q = 500 x 4.18 x 43

= 89 870 J

 Step 3: This is only 30% of the total energy released by methane

Total energy x 0.3 = 89 870 J

Total energy = 299 567 J

 Step 4: This is released by 2.50 g of methane

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 = 119 827 J

= 120 kJ

Exam Tip

When new bonds are formed the amount of energy released is equal to the amount of energy absorbed
when the same bonds are broken.
For example:
O2 (g) → 2O (g) E (O=O) = +498 kJ mol-1 2O (g) → O2 (g) E (O=O) + -498 kJ mol-1 Aqueous
solutions of acid, alkalis and salts are assumed to be largely water so you can just use
the m and c values of water when calculating the energy transferred. To then calculate any changes in
enthalpy per mole of a reactant or product the following relationship can be used:

When there is a rise in temperature, the value for ΔH becomes negative suggesting that the reaction is
exothermic and when the temperature falls, the value for ΔH becomes positive suggesting that the
reaction is endothermic. Also, remember that the ΔT is the same in oC and K!
6.5 HESS’S LAW
Hess Cycles

 Hess’s Law states that:

"The total enthalpy change in a chemical reaction is independent of the route by which the
chemical reaction takes place as long as the initial and final conditions are the same."

 This means that whether the reaction takes place in one or two steps, the total enthalpy change of the
reaction will still be the same

The diagram above illustrates Hess’ Law: the enthalpy change of the direct route, going from reactants (A+B) to
product (C) is equal to the enthalpy change of the indirect routes

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  Hess’ Law is used to calculate enthalpy changes which can’t be found experimentally
using calorimetry, eg:

3C (s) + 4H2 (g) → C3H8(g)

 ΔHf (propane) can’t be found experimentally as hydrogen and carbon don’t react under standard
conditions

Calculating ΔHr from ΔHf using Hess’s Law energy cycles

 The products can be directly formed from the elements = ΔH2

OR

 The products can be indirectly formed from the elements = ΔH1 + ΔHr

The enthalpy change from elements to products (direct route) is equal to the enthalpy change of elements
forming reactants and then products (indirect route)

Equation

ΔH2 = ΔH1 + ΔHr

Therefore,

ΔHr = ΔH2 – ΔH1

Worked example: Calculating the enthalpy change of reaction

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 Step 1: Write the balanced equation at the top

 Step 2: Draw the cycle with the elements at the bottom

 Step 3: Draw in all arrows, making sure they go in the correct directions. Write the standard
enthalpy of formations

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  Step 4: Apply Hess’s Law

Calculating ΔHf from ΔHc using Hess’s Law energy cycles

 The combustion products can be formed directly from elements to combustion products = ΔH1

OR

 The combustion products can be formed indirectly from elements to compound to combustion products
= ΔHf+ ΔH2

The enthalpy change going from elements to products (direct route) is equal to the enthalpy change of
elements forming reactants and then products (indirect route)

 Equation

ΔH1 = ΔHf + ΔH2

Therefore,

ΔHf = ΔH1 – ΔH2

Worked example: Calculating the enthalpy change of formation of ethane

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 Step 1: Write the equation for enthalpy change of formation at the top and add oxygen on both
sides

 Step 2: Draw the cycle with the combustion products at the bottom

 Step 3: Draw all arrows in the correct direction

 Step 4: Apply Hess’s Law

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Calculating average bond energies using Hess's cycles

 Bond energies cannot be found directly so enthalpy cycles are used to find the average bond energy
 This can be done using enthalpy changes of atomisation and combustion or formation
 The enthalpy change of atomisation (ΔHatꝋ ) is the enthalpy change when one mole of
gaseous atoms is formed from its elements under standard conditions.
o Eg. ΔHatꝋ [H2] relates to the equation:

½ H2(g) → H(g)

Worked example: Calculating average C-H bond energy

 Step 1: Write down the equation for the dissociation of methane at the top

 Step 2: Write down the elements at the bottom

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  Step 3: Draw all arrows in the correct direction

 Step 4: Apply Hess’s Law

 Step 5: Since there are 4 C-H bonds in methane:

Exam Tip
Remember to take into account the number of moles of each reactant and product. For example, there
are two moles of NaHCO3(s) so the ΔHf value is multiplied by 2.

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