Energetics (Hess’s Law)

D.Hines Chemistry Unit I

Hess’s law

German Hess developed the thermochemical application of the law of conservation of energy known as Hess’s law.
Hess’ law states the total enthalpy change for a chemical reaction does not depend on the route by which the reaction
proceeds but only on the nature of the reactants and products. This means that the heat change in a reaction is the
same whether the reaction takes place in once stage or through intermediate stages.

Consider the example above, the enthalpy change of the reaction A to B is the same whether the reaction proceeds in
one stage A → B or in three stages A → X→ Y → B. The enthalpy cycle (Hess cycle) is represented above.

Calculating the enthalpy change (∆H) in a reaction

Calorimeters are able measure the enthalpies of combustion and neutralization, some enthalpies cannot be measured
directly. For example in the formation of methane, carbon will not react with hydrogen under standard conditions in a
calorimeter. The standard enthalpy of formation of methane cannot be measured directly, but it can be calculated
indirectly by applying Hess’s law or using bond energies.

Deducing enthalpy change of reaction using ∆Hfɵ values

Hess’s law can be used to determine the enthalpy of formation for substance E.g, methane indirectly from other known
standard enthalpy changes such as enthalpy of combustion. This is done by constructing an energy cycle diagram. The
enthalpy of combustion can be found by using the enthalpy of formation.

 First write the balanced equation for the information given

∆Hr
C(s) + 2H2(g) CH4(g)
 Use the given data to complete an energy cycle, the elements or compounds should be drawn at the bottom as
shown.

∆Hr
C(s) + 2H2(g) CH4(g)

∆H2
∆H1
∆H3

CO2(g) + 2H2O

 Apply Hess’s law

Clockwise arrows = anticlockwise arrows
∆Hr + ∆H3 = ∆H1 + ∆H2
 Calculate the enthalpy change using the equation formulated

∆HϴC(CH4(g)) = -890 kJ/mol

∆HϴC(H2(g)) = -286 kJ/mol

∆HϴC(C(s)) = -394 kJ/mol

∆Hϴr = (-394) + 2(-286) – (-890)

= -76 kJ/mol

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Deducing enthalpy changes of reaction using ∆Hfɵ

Using Hess’s law ∆H [reaction] + ∆Hf [reactants] = ∆Hf [products]

Therefore ∆H [reaction] = ∆Hf [products] - ∆Hf [reactants]

Example 2

Calculate ∆Hr for the reaction: SO2(g) + 2H2S(g) → 3S(s) + 2H2O(l)

∆Hf values: SO2(g) = -296.8 kJ/mol, H2S(g) = -20.6 kJ/mol, H2O(l) = -285.8 kJ/mol

Example 3

Calculate ∆HϴC of ethene given the following data:

∆Hϴf (C2H4) = 52 kJ/mol, ∆Hϴf (CO2) = - 394 kJ/mol, ∆Hϴf (H2O) = -286 kJ/mol

Deducing enthalpy changes of reaction using ∆HCɵ

Example 4

Calculate the ∆Hrɵ for the reaction: 3C(graphite) + 4H2(g) → C3H8(g)

∆HCɵ values: C(graphite) = -393.5 kJ/mol, H2(g) = -285.5 kJ/mol, C3H8(g) = -2219.2 kJ/mol

Example 5

Calculate the ∆H for the hydrogenation of ethene given the following data:

∆HϴC (C2H4) = - 1411 kJ/mol, ∆HϴC (H2) = - 286 kJ/mol, ∆HϴC (C2H6) = - 1560 kJ/mol

Enthalpy changes in solution

When an ionic solid dissolve in water two processes occur. Firstly the ions in the solid become separated from each
other that is the reverse of lattice energy. This process is endothermic since bonds are broken. Secondly the separated
ions become surrounded by water molecules, this process is called hydration or solvation and this process is exothermic
since bonds are formed between water molecules and the ions.

Standard enthalpy of hydration (∆Hɵhyd)

The standard enthalpy of hydration is the enthalpy change when one mole of gaseous ions is completely hydrated in
water to infinite dilution under standard conditions

Na+(g) + Cl-(g) →Na+(aq) + Cl+(aq)

The enthalpy of hydration of sodium chloride is the sum of the enthalpy of hydration of the cation and anion.

Na+(g) → Na+(aq) ∆Hɵhyd = -406 kJ/mol

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Cl-(g) → Cl+(aq) ∆Hɵhyd = -377 kJ/mol

The enthalpy of hydration of NaCl is -783 kJ/mol

Standard enthalpy of solution ((∆Hɵsoln)

Standard enthalpy of solution is the enthalpy change when 1 mole of solute dissolves in a solvent to form an infinitely
dilute solution under standard conditions.

NaCl(s) + water → NaCl(aq)

The relationship between the enthalpy of solution, the lattice enthalpy and the enthalpy of hydration is shown in the
energy cycle below.

Therefore ∆Hɵsoln = - ∆Hɵlatt + ∆Hɵhyd

∆Hɵsoln (NaCl(s) = -(787 kJ/mol) + (-783 kJ/mol)

= + 4 kJ/mol

Energy cycle for the enthalpy of solution of NaCl

The enthalpy of solution can either be exothermic (enthalpy of hydration- always negative) or endothermic (reverse
lattice energy – always positive) depending on which of the process is larger. On dissolving solid sodium chloride, the
energy required to break the lattice is more than the energy given off when the ions are hydrated thus the overall
reaction is endothermic.

Born-Haber Cycles

Max Born and Fritz Haber extended Hess’s energy cycle to find enthalpy changes for ionic compounds. The energy cycle
showing the formation of an ionic compound from its elements in a series of steps is called Born-Haber cycle.

Other enthalpy changes

In order to calculate lattice energy, we need to use ionisation energies, enthalpy change of formation, enthalpy of
atomisation and electron affinity.

Electron affinity (∆Hϴea1): The first electron affinity is the enthalpy change when 1 mole of electrons are added to a mole
of gaseous atoms to form one mole of gaseous ions X-.

Examples Cl(g) + e- → Cl-(g) ∆Hϴea1 = -348 kJ/mol

S(g) + e- → S- ∆Hϴea1 = -200 kJ/mol

As with ionisation energies, successive electron affinities are used to form anions with multiple charges:

O(g) + e- → O-(g) ∆Hϴea1 = -141 kJ/mol

O-(g) + e- → O2- ∆Hϴea2 = +798 kJ/mol

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It is important to remember the correct signs (+ or -) when you carry out enthalpy change calculations to find lattice
energy.

∆Hϴea1 is generally negative but ∆Hϴea2 is always positive, because the incoming electron is added to the negatively
charged ion. The repulsive forces have to be overcome, so energy has to be absorbed.

Hess’s law states the enthalpy change for a reaction is independent on the pathway.

We can construct an enthalpy cycle and use Hess’s law to determine the lattice energy of an ionic solid.

Ions in gaseous Ionic solid

state

Elements in their
standard states

∆Hϴ1 consists of several steps:

Atomise metal → atomise non-metal → ionise metal atoms (ionisation energy) → ionise non-metal atoms (electron
affinity)

General Born-Haber cycle diagram

Born – Haber cycle for sodium chloride

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∆Hϴf(NaCl) = ∆Hϴat(Na(s)) + ∆Hϴi1st(Na) + ∆Hϴat(Cl2(g)) + ∆Hϴe1st(Cl(g)) + ∆Hϴlatt(NaCl)

Therefore the lattice energy is:

∆Hϴlatt(NaCl) = ∆Hϴf(NaCl) – [∆Hϴat(Na(s)) + ∆Hϴi1st(Na) + ∆Hϴat(Cl2(g)) + ∆Hϴe1st(Cl(g))]

= -411 – [107 + 502 + 121 + (-355)]

= -786 kJ/mol

The Born-Haber cycle for magnesium oxide

Magnesium forms an ion with a +2 charge. The oxide ion has a charge of 2. So when constructing a Born-Haber cycle for
magnesium oxide we have to take into account.

 The first and the second ionisation energies of magnesium and

 The first and second electron affinities of oxygen

Construct the Born-Haber cycle for MgO

Born-Haber cycles for AlCl3, Na2O and Al2O3

Aluminum chloride, AlCl3 has an Al3+ ion and 3Cl- ions. So in the calculation:

 ∆Hɵat [Cl] and ∆Hɵea1 [Cl] must be multiplied by 3

 The energy required to form Al3+(g) from Al (g) is ∆Hɵi1 + ∆Hɵi2 + ∆Hɵi3

Sodium oxide, Na2O has 2 Na+ ions and 1 O2- ion. So in the calculation:

 ∆Hɵat [Na] and ∆Hɵi [Na] must be multiplied by 2

 The energy required to form O2-(g) from O (g) is ∆Hɵea1 + ∆Hɵea2

Aluminium oxide, Al2O3 has a 2 Al3+ ions and 3 O2- ions. So in the calculation:

 ∆Hɵat [Al] must be multiplied by 2 and ∆Hɵat [O2] must be multiplied by 3.

 The energy required to form Al3+ (g) from Al (g) is ∆Hɵi1 + ∆Hɵi2 + ∆Hɵi3
 The energy required to form O2- (g) is ∆Hɵea1 + ∆Hɵea2

Exercises
1. What is the standard enthalpy change for the formation of liquid benzene given the following
Substance Standard heat of combustion/ (kJ/mol)
H2(g) -286
C(s) -394
C6H6(l) -3350
2. Discuss the factors that affect the size of the lattice energy of a substance
3. The enthalpy changes for two reactions are given below.
2Fe + 11⁄2 O2 → Fe2O3 ∆Hϴ = -822 kJ/mol
C + ½ O2 → CO ∆Hϴ = -110 kJ/mol
Calculate the enthalpy change for the following reaction:
Fe2O3 + 3C → 2Fe + 3CO
4. (a) State Hess’s law
(b) Use the data below to draw the Born-Haber cycle for the formation of solid potassium chloride
(c) Calculate the enthalpy change of formation of potassium chloride.
Enthalpy change of atomization of potassium = +90 kJ/mol
Enthalpy change of atomization of chlorine = -121 kJ/mol
First ionization of potassium = +418 kJ/mol
Electron affinity of chlorine = -364 kJ/mol
Lattice energy of potassium chloride = +701 kJ/mol
5. Draw the Born-Haber cycle for the formation of solid Magnesium oxide
6. Explain the following observations as fully as you can:
a. The enthalpy change for the neutralization of 1 mole of hydrochloric acid is -57 kJ/mol while that for the
neutralization of sulphuric acid is -114 kJ/mol
b. The enthalpy change of solution of lithium chloride is negative while that of potassium chloride is positive.
7. Given the following data: ∆Hf(CH4) = -74.8 kJmol-1, ∆Hf(CH3Cl) = -134.5 kJmol-1, ∆Hf(HCl) = -92.3 kJmol-1;
Calculate H for the reaction CH4(g) + Cl2(g)  CH3Cl(g) + HCl(g)

8. Given the data:

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 4NH3(g) + 3O2(g)  2N2(g) + 6H2O(l), ∆H = -1530kJmol-1

H2(g) + 1/2O2(g)  H2O(l), ∆H = -288 kJmol-1

Calculate the enthalpy of formation of ammonia.

9. Given the following data:

CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) ∆H = -890 kJmol-1

CO(g) + 1/2O2(g)  CO2(g) ∆H = -284 kJmol-1

C(s) + O2(g)  CO2(g) ∆H = -393 kJmol-1

H2(g) + 1/2O2(g)  H2O(l) ∆H = -286 kJmol-1

Calculate:

a) The enthalpy of formation of methane

b) The enthalpy of formation of carbon monoxide
c) The enthalpy change when methane is burned in limited oxygen to form carbon monoxide and water.

10. June 2007 #1 [15 marks]

(a) Hess’s Law states that the total energy change in a reaction is independent of the route from reactants to
products if the initial and final conditions of temperature and pressure are identical.

Given the following data:

Mg(s) + 2H+(aq)  Mg2+(aq) + H2(g) ΔH = - 511.1 kJ

MgO(s) + 2H+(aq)  Mg2+(aq) + H2O(g) ΔH = - 151.1 kJ

2H2(g) + O2(g)  2H2O(g) ΔH = - 483.6 kJ

Use Hess’s Law to calculate the enthalpy change for the following reaction:

2Mg(s) + O2(g)  2MgO(s) (3 marks)

(b) A student carries out an experiment to determine the enthalpy change of the

reaction between magnesium and hydrochloric acid. She measures the steady

temperature of 100 cm3 of hydrochloric acid in a polystyrene cup. She then places

a 10 cm long piece of magnesium, of mass 0.5971 g, in the acid and records the

temperature every 30 seconds for 4 minutes, while stirring at regular intervals.

(i) Explain the reason for stirring the mixture at regular intervals. (1 mark)

(ii) Given that the initial and final temperatures are 280C and 570C respectively,

sketch a typical graph for the results of the experiment to illustrate how the

student arrived at the temperature change, ΔT, for the experiment. (2 marks)

(iii) Give the main source of error for the experiment. (2 marks)

(iv) Calculate the enthalpy change, in kJ mol-1, of Mg for the reaction at

constant pressure, given

ΔT = 29.00C

C = 4.20 Jg-1 0C-1

The density of dilute HCl is 1.0 g cm-1 (3 marks)

(c) (i) Use the results of your calculation in (b)(iv) above to state whether the

reaction is endothermic or exothermic. (1 mark)

(ii) Draw a clearly labelled energy profile diagram for the reaction between

magnesium and hydrochloric acid. Include on your diagram the enthalpy

change for the reaction.

(4 marks)

Total 15 marks