CHAPTER 6: ENTHALPY CHANGES

Enthalpy Change of Reaction

 The enthalpy change of a reaction is the heat energy absorbed or evolved in a chemical reaction,
for the number of moles of reactants shown in the chemical equation.
 An example of a thermochemical equation is:
4NH3 (g) + 3O2 (g) → 2N2 (g) + 6H20 (l) ∆Hᶱ = -1260 kJ

a) ∆H = the enthalpy change of reaction

b) This shows that 1260 kJ of heat energy is evolved when 4 moles of NH3 react with 3 moles of O2
according to the equation.
c) The symbol ᶱ means that all reactants and products are at standard state conditions. Standard
state conditions are 101.3 kPa (1 atmosphere) and 298 K (25°C).
d) The negative sign (-) means that the reaction is exothermic (heat energy is given out). If a
positive sign (+) is used, the reaction is endothermic (heat energy is absorbed).

Exothermic or Endothermic Reaction?

Exothermic
 Chemical reactions that release energy to
the surroundings.
 The temperature of the surroundings
increases.
 Examples of exothermic reactions:
- Magnesium reacts with sulfuric acid
- The combustion of fuels
- The oxidation of carbohydrates in the
bodies of animals and plants
(respiration)
- The reaction of water with quicklime
(calcium oxide)
Endothermic
 Chemical reactions that absorb energy
from the surroundings.
 The temperature of the surroundings
decreases.
 Examples of endothermic reactions:
- Sodium hydrogencarbonate reacts
with aqueous solution of citric acid
- The decompositions of limestone by
heating (all thermal decomposition
reactions are endothermic)
- Photosynthesis
- Dissolving certain ammonium salts in
water

Enthalpy changes and enthalpy profile diagram

 Enthalpy is the total energy associated with the materials that react. We cannot measure
enthalpy, but we can measure an enthalpy change when heat energy is exchanged with the
surroundings.
 ∆H = Hproducts - Hreactants
Enthalpy Enthalpy of Enthalpy of
change products reactants

Enthalpy profile diagram

Exothermic reaction Endothermic reaction

The enthalpy profile diagram for the combustion The enthalpy profile diagram for the
of methane. decomposition of calcium carbonate
CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (l) CaCO3 (s) → CaO (s) + CO2 (g)
∆H = -890.3 kJ mol-1 ∆H = +572kJ mol-1

Standard enthalpy changes

To make any comparison of enthalpy changes a fair comparison, we must use the same conditions.
These are called standard conditions.

A variety of enthalpy changes

 Enthalpy change of formation

 Enthalpy change of combustion
 Enthalpy change of neutralization
 Enthalpy change of solution
 Enthalpy change of atomization
 Enthalpy change of hydration
1) Standard enthalpy change of reaction, ∆Hᶱr

The standard enthalpy change of reaction is the enthalpy change when the amounts of
reactants shown in the equation react to give products under standard conditions. The
reactants must be in their standard states.

 Enthalpy changes of reaction can be exothermic or endothermic.

 For example:
1
H2 (g) + 2 O2 (g) → H2O (l) ∆Hᶱr = -286 kJ mol-1

Show us the enthalpy change when one mole of water is formed from hydrogen and
Oxygen. In this case 286 kJ of energy are released.

2) Standard enthalpy change of formation, ∆Hᶱf

The standard enthalpy change of formation is the enthalpy change when one mole of a
compound is formed from its elements under standard conditions. The reactants and
products must be in their standard states.

 Enthalpy changes of reaction can be exothermic or endothermic.

 Enthalpy changes of formation are usually negative. However, some enthalpy changes of
formation are positive (eg. For the oxides of nitrogen).
 We write the formula of the compound in square brackets after ∆Hᶱf to help us when we do
calculations involving enthalpy changes
 For example:
1
Ag (s) + 2Cl2 (g) → AgCl (s) ∆Hᶱf = -127 kJ mol-1

3) Standard enthalpy change of combustion, ∆Hᶱc

The standard enthalpy change of combustion is the enthalpy change when one mole of a
substance is burnt in excess oxygen under standard conditions. The reactants and
products must be in their standard states.

 Enthalpy changes of combustion are always exothermic as heat is always evolved in the
combustion.
 For example:
C2H4 (g) + 3O2 (g) → 2CO2 (g) + 2H2O ∆Hᶱc = -1411 kJ mol-1

S (s) + O2 (g) → SO2 (g) ∆Hᶱc = -296.8 kJ mol-1

 The enthalpy change of combustion applies to the complete combustion of the carbon to CO2
not to CO.
Question

Classify each of the following reactions as ∆Hᶱr, ∆Hᶱf or ∆Hᶱc.

a) MgCO3 (s) → MgO (s) + CO2 (g)

b) C (graphite) + O2 (g) → CO2 (g)
c) HCl (g) + NH3 (g) → NH4Cl (s)
1
d) H2 (g) + O2 (g) → H2O (l)
2

4) Standard enthalpy change of neutralization, ∆Hᶱn

The standard enthalpy change of neutralization is the enthalpy change when one mole of
water is formed by the reaction of an acid with an alkali under standard conditions.

 An example of the enthalpy change of neutralization is the enthalpy change obtained in the
reaction between sodium hydroxide and hydrochloric acid.
NaOH (aq) + HCl (aq) → NaCl (aq) + H2O (l) ∆Hᶱn = -57.1 kJ mol-1

 For any acid-alkali reaction the ionic equation is:

H+ (aq) + OH- (aq) → H2O (l)

5) Standard enthalpy change of solution, ∆Hᶱsol

The standard enthalpy change of solution is the enthalpy change when one mole of solute
is dissolved in a solvent to form an infinitely dilute solution under standard solution.

 An example is the addition of a small amount of solid sodium hydroxide to a large amount of
water.
NaOH (s) + aq → NaOH (aq)

 We use known amounts of solute and solvent with the solvent in excess to make sure that all
the solute dissolves.
 Enthalpy changes of solution can be positive or negative.

6) Standard enthalpy change of atomization, ∆Hᶱat

The standard enthalpy change of atomization is the enthalpy change when one mole of
gaseous atoms is formed from its element under standard conditions.

 For example:
1 1
2
H2 (g) → H (g) ∆Hᶱat[2 H2 (g)] = +218 kJ mol-1
 All enthalpy changes of atomization of the noble gases such as helium and argon are zero. This is
because the elements are already in the form of separate gaseous atoms under standard state
conditions.

7) Standard enthalpy change of hydration of an anhydrous salt

The standard enthalpy change of hydration of an anhydrous salt is the enthalpy change
when one mole of a hydrated salt is formed from one mole of the anhydrous salt under
standard conditions.

 For example:
Na2S2O3 (s) + 5H2O (l) → Na2S2O3.5H2O (s) ∆Hᶱ = -55.0 kJ mol-1

 Enthalpy changes of hydration are always negative as heat energy is always evolved when the
‘bonds’ are formed.

Measuring enthalpy changes

 We can measure the enthalpy change of some reactions by a technique called calorimetry.
 The apparatus used is called a calorimeter. A simple calorimeter can be a polystyrene drinking
cup or a metal can.

 Calorimetry relies on the fact that it takes 4.18 J of energy to increase the temperature of 1 g of
water by 1°C.
 The energy required to raise the temperature of 1 g of a liquid by 1°C is called the specific heat
capacity, c of the liquid. So, the specific heat capacity of water is 4.18 J g-1 °C-1.
 The energy transferred as heat (the enthalpy change) is given by the relationship:

∆H = - mc∆T With solutions, we make the assumptions

that:
Where,
 1 cm3 of solution has a mass of 1 g
∆H = enthalpy change, in J
m = mass of water, in g  The solution has the same specific
c = specific heat capacity, in J g-1 °C-1 heat capacity as water
∆T = temperature change, in °C
 1) The enthalpy change of neutralization by experiment

Procedure:

1. Place 50 cm3 of 1.0 mol dm-3 hydrochloric acid in the cup and record its temperature.
2. Add 50 cm3 of 1.0 mol dm-3 sodium hydroxide (at the same temperature) to the acid in the
cup.
3. Stir the reaction mixture with the thermometer and record the highest temperature.

Results and calculation:

Mass of solution =
Specific heat capacity =
Starting temperature = 21.3 °C
Final temperature = 27.8 °C
Temperature rise =

Heat energy released =

The number of moles of HCl and NaOH =

So __________ of energy was released by __________ of acid.

Therefore for one mole of acid (forming one mole of water) the energy released was =

2) The enthalpy change of solution by experiment

Procedure:

1. Weight an empty polystyrene cup.

2. Pour 100 cm3 of water into the cup and weigh the cup and water.
3. Record the steady temperature of the water with a thermometer reading to at least the
nearest 0.2 °C.
4. Add a few pellets of sodium hydroxide which have been stored under dry conditions.
5. Keep the mixture stirred continuously with a thermometer and record the temperature at
fixed intervals, every 20 seconds.
6. Keep recording the temperature for 5 minutes after the maximum temperature has been
reached.
7. Weight the cup and its contents to calculate the mass of sodium hydroxide which dissolved.

Results and calculations

Mass of polystyrene cup = 23.00 g

Mass of polystyrene cup + water = 123.45 g
Mass of water =
Mass of cup + water + sodium hydroxide = 124.95 g
Mass of sodium hydroxide that dissolved =
Initial temperature of water = 18.0 °C
Final temperature of water = 21.6 °C
Temperature rise =

From the result, __________ of sodium hydroxide dissolved in ___________ of water and
produced a temperature change of ____________.

Enthalpy change in J =

The enthalpy change for 1.0 mole of sodium hydroxide =

Questions

1. Calculate the energy transferred when 2. When 8 g of sodium chloride is

the temperature of 75 cm3 of water
rises from 23 °C to 54 °C.
dissolved in 40 cm3 of water the
temperature falls from 22 °C to 0.5 °C.
Calculate the energy absorbed by the
solution when sodium chloride
dissolves.

3. A student added 50 cm3 of sodium 4. 1.80 g of glucose was completely

hydroxide to 50 cm3 of hydrochloric
acid. Bothe solutions were at 18 °C to
start with. When the solutions were
mixed a reaction occurred. The
temperature rose to 33 °C. Calculate
the energy released in this reaction.
burnt in oxygen. The heat produced
was found to raise the temperature of
5.0 dm3 of water by 1.34 °C. Calculate
the enthalpy change of combustion of
glucose.
5. When 0.10 g of magnesium ribbon
was dissolved in an excess of dilute
hydrochloric acid, the temperature
rose by 4.3 °C. A separate experiment
showed that the same volume of acid
required 500 J to raise the
temperature by 1.0 °C.
a) Calculate the heat released in the
experiment.
b) Calculate the enthalpy change per
mol of magnesium.
6. Copper (II) sulfate is soluble in water.
A student dissolved 25.0 g of copper
(II) sulfate in 100 cm3 of water in a
polystyrene beaker stirring all the
time. The temperature of water fell
by 2.9 °C. Calculate the enthalpy
change of solution of copper (II)
sulfate.

7. 240 cm3 of ethane (C2H6) was burnt in a controlled way and found to raise the
temperature of 100 cm3 of water by 33.5 °C.
a) How many moles of ethane were burnt.
b) Calculate the heat change for the experiment.
c) Calculate the molar enthalpy change of combustion for ethane, as measured by
this experiment.
Hess’ Law
 Hess’ Law states that a reaction consists of a number of steps. The overall heat energy change is
equal to the sum of the heat energy changes for all the individual steps.

Hess’ 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’.

The enthalpy change is the same no matter which route is followed

Enthalpy change of reaction from enthalpy changes of formation

 The enthalpy change of any reaction can be found by calculation, from the enthalpy changes of
formation of all the substances in the chemical equation, using Hess’s Law.

∆H2 = ∆H1 + ∆Hr

Direct route Indirect route

So, ∆Hr = ∆H2 - ∆H1

An enthalpy cycle for calculating an enthalpy change of reaction. The dashed line shows the indirect
(two step) route.
Example:
1. Calculate the standard enthalpy change
for the reaction:
2NaHCO3 (s) → Na2CO3 (s) + CO2 (g) + H2O (l)
The relevant enthalpy changes of formation
are:
∆Hᶱf [NaHCO3 (s)] = -950.8 kJ mol-1
∆Hᶱf [ Na2CO3 (s)] = -1130.7 kJ mol-1
∆Hᶱf [CO2 (g)] = -393.5 kJ mol-1
∆Hᶱf [H20 (l)] = -285.8 kJ mol-1
Using Hess’s Law:
∆H2 = ∆H1 + ∆Hr
3. The enthalpy changes of formation of
aluminium oxide and copper (II) oxide are
-1676 and -155 kJ mol-1 respectively.
What is the enthalpy change of the
reaction?
2Al (s) + 3CuO (s) → Al2O3 (s) + 3Cu (s)
2. SnO2 + 2CO → Sn + 2CO2
Calculate the enthalpy change of the above
reaction from the following enthalpy changes
of formation:
∆Hᶱf [SnO2] = -581 kJ mol-1
∆Hᶱf [CO] = -111 kJ mol-1
∆Hᶱf [ CO2] = -394 kJ mol-1
4. Calculate the enthalpy changes of the
following reactions. Use the enthalpy
changes of formation at the end of the
question. Assume that all substances are
under standard state conditions.
(a) Fe3O4 + 2C → 3Fe + 2CO2
(b) 3MnO2 + 4Al → 3Mn + 2Al2O3
(c) 2H2O2 → 2H2O + O2
(d) 2Cu(NO3)2 → 4NO2 + 2CuO +O2
(e) TiCl4 + 2H2O → TiO2 + 4HCl
(f) 2NH3 + 3CuO → 3Cu + N2 + 3H2O
Enthalpy changes of formation, in kJ mol-1
Fe3O4 = -1117
MnO2 = -521
H2O2 = -188
Cu(NO3)2 = -307
CuO = -155
TiO2 = -912
NH3 = -46
CO2 = -394
Al2O3 = -1669
H2O = -286
NO2 = +34
TiCl4 = -750
HCl = -92
Enthalpy change of formation from enthalpy changes of combustion

 We use the enthalpy changes of combustion of the reactants and products to calculate the
enthalpy change of formation.

∆H1 → ∆Hf + ∆H2

Direct route Indirect route

So, ∆Hf = ∆H1 - ∆H2

An enthalpy cycle for calculating an enthalpy change of formation from enthalpy changes of
combustion. The dashed line shows the two-step route.

Example:

1. Calculate the standard enthalpy change 2. Calculate the enthalpy change of

of formation of ethane, C2H6. formation of methanoic acid. HCOOH
The relevant enthalpy changes of from the following enthalpy changes of
combustion are: formation:

C (graphite) + O2 (g) → CO2 (g) ∆Hᶱc [H2] = -286 kJ mol-1

∆Hᶱc [C(graphite)] = -393.5 kJ mol-1 ∆Hᶱc [C] = -394 kJ mol-1
∆Hᶱc [HCOOH] = -263 kJ mol-1
1
H2 (g) + 2O2 (g) → H2O (l)
∆Hᶱc [H2(g)] = -285.8 kJ mol-1

1
C2H6 (g) + 32O2 (g) → 2CO2 (g) + 3H2O (l)
∆Hᶱc [C2H6(g)] = -1559.7 kJ mol-1
 3. The enthalpy changes of combustion of 4. Draw an enthalpy cycle to calculate the
ethyne (C2H2), hydrogen (H2) and ethane enthalpy change of formation of ethanol,
(C2H6) are: C2H5OH, using enthalpy changes of
combustion. Calculate a value for ∆Hᶱf
Substance ∆Hᶱc/ kJ mol-1 [C2H5OH (l)] using the following data:
Ethyne -1300 ∆Hᶱc [C (graphite)] = -393.5 kJ mol-1
Hydrogen -285 ∆Hᶱc [H2 (g)] = -285.8 kJ mol-1
Ethane -1560 ∆Hᶱc [C2H5OH (l)] = -1367.3 kJ mol-1

What is the enthalpy change of the

reaction:z
C2H2 + 2H2 → C2H6

Bond energies and enthalpy changes

Bond breaking and bond making

 Enthalpy changes are due to the breaking and forming of bonds.

 In a chemical reaction:
 - If the energy needed to break bonds is less than the energy released when new bonds are
formed, the reaction will release energy and is exothermic.
- If the energy needed to break bonds is more than the energy released when new bonds are
formed, the reaction will absorb energy and is endothermic.

Calculating the enthalpy change of hydration of an anhydrous salt

 Hydrated salts such as hydrated copper (II) sulfate, CuSO4.5H2O, contain water molecules
surrounding their ions.
 We use the standard enthalpy changes of solution to complete the enthalpy cycle.

Example:

The enthalpy cycle for calculating the enthalpy of hydration of anhydrous sodium thiosulfate is shown
below:

Using Hess’s Law:

Bond breaking and bond making

 Energy level diagram sowing bond breaking and bond forming for the combustion of methane
(exothermic) and energy level diagram showing bond breaking and bond forming for the
decomposition of hydrogen bromide (endothermic).

Bond energy

 The amount of energy needed to break a specific covalent bond is called bond energy or bond
enthalpy. The symbol is E.
 For example: E (C-H) refers to the bond energy of a mole of single bonds between carbon and
hydrogen atoms.
Br2 (g) → 2Br (g) E (Br-Br) = +193 kJ mol-1
O=O (g) → 2O (g) E (O=O) = +498 kJ mol-1
 When new bonds are formed the amount of energy released is the same as the amount of
energy absorbed when the same type of bond is broken.
2O (g) → O2 (g) E (O=O) = -498 kJ mol-1

Average bond energy

 We cannot usually find the value of bond energies directly so we have to use the enthalpy cycle.
 The average bond energy of the C-H bond in methane can be found using the enthalpy changes
of atomization of carbon and hydrogen and the enthalpy change of combustion or formation of
methane.

Calculate the bond energy of the C-H bond.

Calculating enthalpy changes using bond energies

 We can use bond enthalpies to calculate the enthalpy change of a reaction that we cannot
measure directly. For example, the reaction for the Haber process.
N2 (g) + 3H2 (g) ⇌ 2NH3 (g)
 The relevant bond energies are:
E (N≡N) = 945 kJ mol-1
E (H-H) = 436 kJ mol-1
E (N-H) = 391 kJ mol-1

From the enthalpy cycle:

∆Hr = ∆H1 + ∆H2

Questions

1. Use the average bond enthalpies that follow 2. Calculate the standard enthalpy
to calculate a value for the enthalpy change change of combustion of methane
for the reaction: using the following bond energies:
H2 + I2 → 2HI
E (C-H) = +412 kJ mol-1
E (H-H) = +436 kJ mol-1 E (O-O) = +496 kJ mol-1
E (I-I) = +151 kJ mol-1 E (C=O) = +805 kJ mol-1
E (H-I) = +299 kJ mol-1 E (O-H) = +463 kJ mol-1

3. The equation for the combustion of ethanol is: 4. The equation for the complete
C2H5OH (l) + 3O2 → 2CO2 (g) + 3H2O (l) combustion of propanone is:
CH3COCH3 (l) + 4O2 (g) → 3CO2 (g) +
Use the following bond energies (in kJ mol-1) 3H2O (l)
to calculate a value for the standard enthalpy
change of this reaction: Use the following bond energies (in kJ
E (C-C) = +347 mol-1) to calculate a value for the
E (C-H) = +410 standard enthalpy change of this
E (C-O) = +336 reaction:
E (O=O) = +496 E (C-C) = +347
E (C=O) = +805 E (C-H) = +413
E (O-H) = +465 E (O=O) = +496
E (C=O) = +805
E (O-H) = +465
5. Some average standard bond enthalpies are 6. Calculate the enthalpy change for
listed below: the reaction:
C2H4 + HBr → C2H5Br

Calculate the enthalpy change for the

reaction:
CH3CH=CH2 + H2 → CH3CH2CH3