Learning outcomes

explain that some chemical reactions are

accompanied by energy changes, principally in the form of heat energy; the energy changes can be exothermic (H, negative) or endothermic explain and use the terms: (i) enthalpy change of reaction and standard conditions, with particular reference to: formation, combustion, hydration, solution, neutralisation, atomisation (ii) bond energy (H positive, i.e. bond breaking)

Learning outcomes
calculate enthalpy changes from appropriate experimental

results, including the use of the relationship enthalpy change = mcT

apply Hess Law to construct simple energy cycles, and carry

out calculations involving such cycles and relevant energy terms, with particular reference to: (i) determining enthalpy changes that cannot be found by direct experiment, e.g. an enthalpy change of formation from enthalpy changes of combustion (ii) average bond energies of the enthalpy change of the reaction and of the activation energy.

construct and interpret a reaction pathway diagram, in terms

Energy changes
lots of chemical reactions give out energy as

heat. Example: burning a fuel Splitting calcium carbonate into calcium oxide and carbon dioxide

Simple energy diagrams

Any chemical reaction will involve breaking some bonds and

making new ones.

Energy is needed to break bonds, and is given out when the

new bonds are formed

Enthalpy, H is an indication of a substances total energy

content and cannot be measured directly. However, enthalpy change, H, is measureable.

Enthalpy change, H
Energy transferred between a system and its surroundings

(constant pressure). unit: kJ mol

Depends on:

- temperature - physical states - pressures - concentration of solution

Enthalpy change, H
indicates the enthalpy change refers to a reaction carried out under standard conditions.

Standard conditions: pressure (1 atm, 100 kPa) temperature (298 K) each substance in its normal physical state at 100 kPa and 298 K.

Simple energy diagrams

For an exothermic change:
Notice that in an exothermic change, the products have a lower energy than the reactants. The energy that the system loses is given out as heat. The surroundings warm up.

Exothermic Reaction
A self-warming can of coffee.
The energy released heats the coffee

Simple energy diagrams

For an endothermic change:
This time the products have a higher energy than the reactants. The system absorbs this extra energy as heat from the surroundings.

Endothermic Reaction
Cold pack When chemicals in the cold pack react, they take in energy as heat and the pack gets cold.

A variety of enthalpy changes

Enthalpy changes can be described according to the

type of chemical reaction taking place. a) b) c) d) e) f) Enthalpy change of formation Enthalpy change of combustion Enthalpy change of neutralisation Enthalpy change of solution Enthalpy change of atomisation Enthalpy change of hydration

Standard enthalpy change of reaction

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

Standard enthalpy change of reaction

Standard enthalpy change of formation

Hof
The standard enthalpy change of formation is the enthalpy change when one mole of a compound is formed from its elements under standard conditions; both compound and elements are in standard states.

Standard enthalpy change of formation

Enthalpy changes of formation can be exothermic or endothermic. By definition, the standard enthalpy change of formation of any element in its standard state is zero.

Standard enthalpy change of combustion

Hoc The standard enthalpy change of combustion is the enthalpy change when one mole of an element or compound reacts completely with oxygen under standard conditions.

Other Standard Enthalpy Changes

Standard Enthalpy change of Hydration of an anhydrous salt

Enthalpy change when one mole of a hydrated salt is formed from one mole of the anhydrous salt under standard condition. Na2S2O3 (s) + 5 H2O (l) Na2S2O3.5 H2O (s) H = -55.0 kJmol-1

Standard Enthalpy change of Solution

Enthalpy change when one mole of a solute dissolves in a large volume of

solvent that addition of more solvent produces no further heat change under standard conditions

o o o

Hsol can be either positive or negative value If positive, compound is insolube in water If negative, compound is soluble in water

NaOH (s) + aq NaOH (aq)

Standard Enthalpy change of Neutralisation

Enthalpy change when one mole of water is formed when acid and alkali is neutralised in an aqueous solution under standard conditions. Hn is always negative.

HCl(aq) + NaOH(aq)

NaCl(aq) + H2O(l)

Hn = -57.1 kJmol-1

For any acid-alkali reaction the ionic equation is:

H (aq) + OH (aq) H2O (l) The other ions in solutions are spectator ions and take no part in the reaction.

Standard Enthalpy change of Atomisation The enthalpy change of atomisation is the enthalpy change when one mole of gaseous atoms is formed from its element under standard conditions. H2 (g) H(g) Hat = +218 kJmol-1

Measuring Enthalpy Changes

A polystyrene cup can act as a calorimeter for finding some enthalpy changes

The energy transferred as heat (the enthalpy change) is given by the relationship:

q = mcT

MEASURING ENTHALPY CHANGES

Example
25cm3 of 2.0M HCl was added to 25cm3 of 2.0M NaOH in an insulated beaker. The initial temperature of both solutions was 20C. The highest temperature reached by the solution was 33C. Calculate the Molar Enthalpy of Neutralisation. [The specific heat capacity (c) of water is 4.18 J K -1 g -1]

NaOH + HCl > NaCl + H2O

Temperature rise (DT) = 13C Volume of resulting solution= 25 + 25 = 50cm3 Equivalent mass of water = 50g (density is 1 g per cm3)

Heat absorbed by the water (Q)

= m x c x DT
= 50 x 4.18 x 13 = 2717 J

MEASURING ENTHALPY CHANGES

NaOH + HCl > NaCl + H2O

Moles of HCl reacting Moles of NaOH reacting

Moles of water produced

Enthalpy change per mol (DH)

= = = = =

2 x 25/1000 0.05 mol 2 x 25/1000 0.05 mol 0.05 mol

= heat energy / moles of water = 2717 / 0.05

= 54340 J mol -1
= - 54.34 kJ mol -1

MEASURING ENTHALPY CHANGES

Example calculation When 0.18g of hexane underwent complete combustion, it raised the temperature of 100g (0.1kg) water from 22C to 47C. Calculate its enthalpy of combustion.

Heat absorbed by the water (Q) = m C DT = 100 x 4.18 x 25 = 10450 J

Moles of hexane burned

= mass / Mr = 0.18 / 86 = 0.00209

Enthalpy change

DH

= heat energy / moles = 10450/ 0.00209 = 5000000 J mol -1 = - 5000 kJ mol -1

MEASURING ENTHALPY CHANGES

Learning Check
1. 50 cm3 of HCl(aq) added to 50 cm3 of NaOH (aq), concentration 1 mol dm-3, temperature rise 6.2 C.

2. Calculate the enthalpy change of combustion for propanol

HESSS LAW
Energy cycles Consider the reaction: Reactants A Product B

Example:

Hesss Law says that the total enthalpy change for a chemical reaction is independent of the route by which the reaction takes place. If we take the example above then the enthalpy change of route 1 would equal the total of the enthalpy changes for route 2:

Enthalpy Change of Reaction From Enthalpy Changes Of Formation An energy cycle for calculating standard enthalpies of reaction from standard enthalpies of formation

Enthalpy Change of Reaction From Enthalpy Changes Of Formation

Enthalpy Change of Reaction From Enthalpy Changes Of Formation

Learning Check

Enthalpy Change of Formation From Enthalpy Changes Of Combustion

An energy cycle for calculating standard enthalpies of formation from standard enthalpies of combustion: H1 = H2 - H3

Enthalpy Change of Formation From Enthalpy Changes Of Combustion

Calculate the enthalpy change of formation of propane, C3H8 at 298 K given the following standard enthalpies of combustion. Propane, Hoc [C3H8 (g)] = -2220 kJ mol -1 Carbon, Hoc [C (graphite)] = -393 kJ mol -1 Hydrogen Hoc [H2 (g)] = -286 kJ mol -1

Enthalpy Change of Formation From Enthalpy Changes Of Combustion

Solution:

Calculating the enthalpy change of hydration of an anhydrous salt

An enthalpy cycle to calculate the enthalpy change of hydration of an anhydrous salt.

Calculating the enthalpy change of hydration of an anhydrous salt

Enthalpy change of hydration of anhydrous sodium thiosulfate

Bond Energies and Enthalpy Changes

Bond breaking and Bond making

Energy is needed to break bonds, and is given out when the new bonds are formed. In a chemical reaction: Energy is needed to break bonds < energy released when new bonds are formed (Exothermic)

Energy is needed to break bonds > energy released when new bonds are formed (Endothermic)

Bond Energies and Enthalpy Changes

Bond Energy
- The amount of energy needed to break a specific covalent bond is called the bond dissociation energy (also called bond energy or bond enthalpy).
Example: 2H2 (g) + O2 (g) 2H2O (g)

Bond Energies and Enthalpy Changes

When H and O react, more energy is released in making four new O-H bonds in the two H2O molecules than in breaking the bonds in two H2 molecules and one O2 molecule. So, the overall reaction is exothermic

Bond Energies and Enthalpy Changes

Average Bond Energy
-The average bond energy of the C H bond in methane can be found using the enthalpy changes of atomisation of carbon and hydrogen and the enthalpy change of combustion or formation of methane.

- The average C H bond energy can be found by dividing the value of H on the diagram by 4.

Calculating enthalpy changes using bond energies

Use mean bond enthalpies to estimate the enthalpy of formation of hydrazine, N2H4 . Ans: Write out the equation for the reaction (show all the atoms and bonds).