CHAPTER 6:

ENTHALPY CHANGES
 WHAT ARE ENTHALPY CHANGES?
Chemical reactions that transfer heat energy to the surroundings are described as exothermic. In an exothermic reaction,
the temperature of the surroundings increases.
For example, when magnesium reacts with sulfuric acid in a test-tube, the energy released is transferred to the
surroundings and the temperature of the reaction mixture in the tube increases.
The surroundings include:
Mg(s) + H2SO4 (aq) → MgSO4 (aq) + H2 (g)
(energy released) • the solvent (in this case water)
• the air around the test-tube
• the test-tube itself
• anything dipping into the test-
tube (e.g. a thermometer)

Other examples of exothermic reactions include:

• the combustion of fuels
• the oxidation of carbohydrates in the bodies of animals and plants
(respiration)
• the reaction of water with quicklime (calcium oxide)
The chemical reactions that absorb heat energy from the surroundings as endothermic. In an endothermic reaction,
the temperature of the surroundings decreases.

Other examples of endothermic reactions include:

• the decomposition of limestone by heating (all thermal decomposition
reactions are endothermic)
• photosynthesis (in which the energy is supplied by sunlight)
• dissolving certain ammonium salts in water.
NH4Cl(aq) + (Aq) → NH4+(aq) + Cl- (aq)
 ENTHALPY CHANGES AND ENTHALPY PROFILE DIAGRAMS
The energy exchange between a chemical reaction and its surroundings at constant pressure is called the enthalpy
change. Enthalpy is the total energy associated with the materials that react. The symbol for enthalpy is H.

The units of enthalpy change are

kilojoules per mole (kJ mol−1 ).

EXOTHERMIC. ENDOTHERMIC.

CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O(l) ΔH = −890.3 [Link]−1 CaCO3(s) → CaO(s) + CO2(g) ΔH = +572 kJ mol−1
STANDARD ENTHALPY CHANGES

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

• a pressure of 101 kPa (1.01 × 105 Pa, approximately normal atmospheric pressure)
• a temperature of 298 K (25 °C) (add 273 to the Celsius temperature to convert a temperature into kelvin)
• each substance involved in the reaction is in its normal physical state (solid, liquid or gas) at 101 kPa and 298 K.

CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O(l) = −890.3 kJ mol−1 shows us that when one mole of methane gas reacts with
two moles of oxygen gas to form one mole of carbon dioxide gas and two moles of water in the liquid state, the
standard enthalpy change is −890.3 kJ mol−1 .

The standard enthalpy change of reaction, is the enthalpy change when the amounts of reactants shown in the
stoichiometric equation react to give products under standard conditions. The reactants and products must be in
their standard states.
We can describe enthalpy changes according to the type of chemical reaction taking
place. For example:
• enthalpy change of formation
• enthalpy change of combustion
• enthalpy change of neutralization
Standard enthalpy change of formation, ΔH°f

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.

Standard enthalpy change of combustion, ΔH°c

the enthalpy change which occurs when one mole of the compound is burned completely in oxygen under standard
conditions, and with everything in its standard state.
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.
 MEASURING ENTHALPY CHANGES
We can measure the enthalpy change of some reactions by a technique called calorimetry. The apparatus used is called a
calorimeter.

When carrying out experiments in calorimeters, we use

known amounts of reactants and known volumes of
liquids. We also measure the temperature change of the
liquid in the calorimeter as the reaction occurs. The
thermometer should be accurate to 0.1 or 0.2 °C.
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 substance by 1 °C (1 K) 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 is given by the relationship: q = mcΔT where: q is the heat transferred, in J
and m is the mass of water, in g and c is the specific heat capacity, in J. g −1 °C −1 .ΔT is the temperature
change, in °C.
With solutions we make the assumptions that: Note: A rise in temperature is given a positive sign. So
• 1 cm3 of solution has a mass of 1 g the value of ΔH is negative for an exothermic reaction.
• the solution has the same specific heat capacity A fall in temperature is given a negative sign. So the
as water. value of ΔH is positive for an endothermic reaction.
QUESTIONS

Calculate the energy transferred when the temperature of 75 cm3 of water rises from 23 °C to 54 °C.

When 8 g of sodium chloride is dissolved in 40 cm3 of water, the temperature falls from 22 °C to
20.5 °C. Calculate the energy absorbed by the solution when sodium chloride dissolves.

A student added 50 cm3 of sodium hydroxide to 50 cm3 of hydrochloric acid. Both solutions were
at 18 °C to start with. When the solutions were mixed a reaction occurred. The temperature rose to
33°C. How much energy is released in this reaction?

A student added 10 g (0.25 mol) of sodium hydroxide to 40 cm3 of water to make a concentrated
solution. All the sodium hydroxide dissolved. The student measured the maximum temperature
rise. The student suggested that these results would give an accurate value for the standard
enthalpy change of solution. Give two reasons why the student is incorrect.
HESS’S LAW HESS’S LAW
The law of conservation of energy states that ‘energy cannot be created or destroyed’. This is also called the
first law of thermodynamics.

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’. The
states of the reactants and products must also be the same whichever route is followed.

We can use Hess’s law to calculate enthalpy changes that cannot be found by experiments using calorimetry.
For example, the enthalpy change of formation of propane cannot be found by direct experiment because
hydrogen does not react with carbon under standard conditions.

To calculate the enthalpy change of reaction using this type of enthalpy cycle, we use the following procedure:

The reaction enthalpy is calculated by subtracting the sum of enthalpies of all the reactants from that of the
products. Mathematically, ΔH = Sum of enthalpies of the product – sum of the enthalpies of the reactants.
 QUESTIONS

QUESTIONS

QUESTIONS
 BOND ENERGIES AND ENTHALPY CHANGES
Enthalpy changes are due to the breaking and forming of bonds. Breaking bonds requires energy. The energy is
needed to overcome the attractive forces joining the atoms together. Energy is released when new bonds are formed.
Bond breaking is endothermic and bond forming is exothermic.

BOND ENERGY
The amount of energy needed to break a specific covalent bond is called the bond dissociation energy. We sometimes
call this the exact bond energy or bond enthalpy.
 calculate a value for the standard enthalpy change
QUESTION

QUESTION calculate a value for the standard enthalpy change

QUESTION calculate a value for the standard enthalpy change