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6.1.1 Energetics of a Reaction

Exothermic & Endothermic Reactions
Heat Exchange in Reactions

• Chemical reactions occur so that elements can achieve a more stable energy state by gaining a
full outer shell of electrons
• This is done by chemical bonding (we have already seen ionic and covalent bonding) where
old bonds are broken, and new bonds are formed)
• This process involves the transfer of energy into and out of reaction mixtures
• The terms used to describe this are the system (what happens in the chemical reaction) and
the surroundings (anything other than the chemicals reacting)
• The energy within the system comes from the chemical bonds themselves which could be
considered as tiny stores of chemical energy
• In the majority of reactions, the energy transferred is in the form of heat energy, although
sometimes other types of energy are produced such as light or sound

Exothermic Reactions

• In exothermic reactions energy is transferred to the surroundings so the temperature of the

surroundings increases
• This energy is transferred from the chemical energy store of the chemical system to the
surroundings and so the energy of the system falls - this means that the energy change is
negative
• The overall transfer is from the system to the surroundings
• Combustion, oxidation, and neutralisation reactions are typical exothermic reactions
• Hand warmers used in the wintertime are based on the release of heat from an exothermic
reaction
• Self-heating cans of food and drinks such as coffee and hot chocolate also use exothermic
reactions in the bases of the containers

Diagram showing the transfer of heat energy outwards from an exothermic reaction
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Endothermic Reactions

• In endothermic reactions energy is taken in from the surroundings so the temperature of the
surroundings decreases
• This energy is transferred to the chemical energy store of the chemical system and so the energy
of the system increases - this means the energy change is positive
• The overall transfer is from the surroundings to the system
• These types of reactions are much less common than the exothermic reactions
• Electrolysis, thermal decomposition reactions and the first stages of photosynthesis are typical
endothermic reactions
• Sports injury treatments often use cold packs based on endothermic reactions to take heat away
from a recently injured area to prevent swelling

Diagram showing the transfer of heat energy from the surroundings into an endothermic reaction

Energy Level Diagrams

• Energy level diagrams (sometimes called reaction pathway diagrams or reaction profiles) are
graphical representations of the relative energies of the reactants and products in chemical
reactions
• The energy of the reactants and products are displayed on the y-axis and the reaction pathway (a
bit like time) is shown on the x-axis
• The difference in height between the energy of reactants and products represents the overall
energy change of a reaction.
o This is usually a sketch but can be drawn to scale if data is provided
• Arrows on the diagrams indicate whether the reaction is exothermic (overall reaction arrow is
downwards pointing, showing that the system has lost energy) or endothermic (overall reaction
arrow is upwards pointing, showing that the system has gained energy)
• The initial increase in energy represents the activation energy (Ea), which is the minimum
energy that colliding particles must have in order to react
• The greater the initial rise, the more energy that is required to get the reaction going e.g. more
heat needed
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Reaction profile of an exothermic reaction and an endothermic reaction

Exam Tip
To help you remember whether a chemical system is exothermic or endothermic, in Exothermic
reactions heat Exits the system and in Endothermic reactions heat Enters the system. Exothermic
reactions always give off heat and they feel hot, whereas endothermic reactions take heat in and they
feel cold.

You should be able to interpret (core) and draw/ label (supplement) energy level diagrams for both
exothermic and endothermic reactions.

This means including the reactants, products, overall change and activation energy if required.

Bond Breaking & Bond Forming

EXTENDED

Chemical bonds in reactions

• Whether a reaction is endothermic or exothermic depends on the difference between the energy
needed to break existing bonds and the energy released when the new bonds are formed
• Bond breaking is always an endothermic process as energy needs to be taken in from the
surroundings to break the chemical bonds
• Bond making is always an exothermic process as energy is transferred to the surroundings as
the new bond is formed

Overall exothermic reactions

• If more energy is released than is absorbed, then the reaction is exothermic

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• More energy is released when new bonds are formed than energy required to break the bonds in
the reactants
• The change in energy is negative since the products have less energy than the reactants
• Therefore, an exothermic reaction has a negative ΔH value

Making new chemical bonds releases energy which radiates outwards from the reaction to the
surroundings in the form of heat

Overall endothermic reactions

• If more energy is absorbed to break bonds than is released to form new bonds, this reaction
is endothermic overall
• The change in energy is positive since the products have more energy than the reactants
• The symbol ΔH (delta H) is used to show the change in heat energy. H is the symbol for
enthalpy, which is a measure of the total heat of reaction of a chemical reaction
• Therefore, an endothermic reaction has a positive ΔH value, which is shown on the energy
level diagrams and in calculations
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Breaking chemical bonds requires energy which is taken in from the surroundings in the form of
heat

Bond making and breaking in energy level diagrams

Diagram of energy level diagrams showing bond making and breaking

Exothermic reactions:

• During an exothermic reaction, more energy is energy is given out when new bonds are made
than the energy taken in to break bonds
• This means that the energy of the products will be lower than the energy of the reactants, so the
change in enthalpy (ΔH) is negative
• This is represented on the energy-level diagram above with the energy of the products being
lower than that of the reactants
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Endothermic reactions:

• During an endothermic reaction, more energy is taken in to break bonds than the energy given
out to make bonds
• This means that the energy of the products will be higher than the energy of the reactants, so the
change in enthalpy (ΔH) is positive
• This is represented on the energy-level diagram above with the energy of the products being
higher than that of the reactants

Calculating the Energy of a Reaction

EXTENDED

Energy of reaction calculations

• Each chemical bond has a specific bond energy associated with it

• This is the amount of energy required to break the bond or the amount of energy given out
when the bond is formed
• This energy can be used to calculate how much heat would be released or absorbed in a reaction
• To do this it is necessary to know the bonds present in both the reactants and products

Method

• Write a balanced equation if none is present already

• Optional - draw the displayed formula in order to identify the type and number of bonds more
easily
• Add together all the bond energies for all the bonds in the reactants – this is the ‘energy in’
• Add together the bond energies for all the bonds in the products – this is the ‘energy out’
• Calculate the energy change: Energy change = energy in - energy out

Equation

Energy change = Energy taken in - Energy given out

Worked Example
Hydrogen and chlorine react to form hydrogen chloride gas:

H2 + Cl2 ⟶ 2HCl

The table below shows the bond energies. Calculate the energy change for the reaction and deduce
whether it is exothermic or endothermic:
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Answer:

Worked Example
Hydrogen bromide decomposes to form hydrogen and bromine:

2HBr ⟶ H2 + Br2

The table below shows the bond energies. Calculate the energy change for the reaction and deduce
whether it is exothermic or endothermic:
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Answer:

Exam Tip
For bond enthalpy questions, it is helpful to write down a displayed formula equation for the
reaction before identifying the type and number of bonds, to avoid making mistakes. The reaction
thus becomes: H-H + Cl-Cl → H-Cl + H-Cl
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6.1.2 Energy Transfer

Fuel, Combustion, Hydrogen

Energy from fuels

• A fuel is a substance which releases energy when burned

• When the fuel is a hydrocarbon then water and carbon dioxide are produced in complete
combustion reactions
• Propane for example undergoes complete combustion according to the following equation:

C3H8 + 5O2 → 3CO2 + 4H2O ΔH = -2219 kJ/mol

• The efficiency of a fuel refers to how much energy is released per unit amount - this can be per
gram or per mole
• We can measure the efficiency of fuels by calorimetry
• A known mass of the fuel is combusted and used to heat up a known mass of water to calculate
its heat of combustion
• Different fuels heat the water by different amounts and they can be analysed and compared in
this way
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Calorimetry experiment – combustion

Diagram showing the calorimetry experiment for combustion

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Method:

• Using a measuring cylinder, place 100 cm3 of water into a copper can
• Measure and record the initial temperature of the water
• Fill the spirit burner with test substance and measure and record its mass, with the lid on the
burner to prevent evaporation
• Place the burner under the copper can and light the wick
• Stir the water constantly with the thermometer and continue heating until a predetermined
temperature rise is achieved (usually a rise of 10-20oC is easily attainable in a reasonable time)
• Put the lid back over the spirit burner to extinguish the flame
• Measure and record the highest temperature of the water - this is likely to be within the minute
after the flame is extinguished
• Measure the mass of the spirit burner with the lid on again, in order to be able to calculate the
mass of fuel that has reacted

Calculation:

• Temperature change of water = final temperature - initial temperature

o The temperature change will be the same regardless of if the measurements were made
in K or oC
• Mass of fuel used (g) = initial mass of burner - final mass of burner
• Number of moles burned (moles) = mass of fuel used ÷ molecular mass of fuel
• Amount of energy (J)= change in temperature x mass of water x specific heat capacity
• Amount of energy per mole (J/mol) = total amount of energy ÷ moles burned
o Amount of energy per mole is often required in kJ/mol, so be prepared to convert the
units.

Hydrogen as a fuel

• Hydrogen is used in rocket engines and in fuel cells to power some cars
• Hydrogen has some unique advantages and disadvantages regarding its use as a fuel:
o Advantages:
▪ It releases more energy per kilogram than any other fuel (except for nuclear
fuels)
▪ It does not pollute as it only produces water on combustion, no other product is
formed
o Disadvantages:
▪ Expensive to produce and requires energy for the production process
▪ Difficult and dangerous to store and move around (usually stored as liquid
hydrogen in highly pressurised containers) as it is so flammable it easily
explodes when stored under pressure

Radioactive isotopes as fuels

• Uranium-235 undergoes decay and gives off heat energy which nuclear power stations harness
• The heat it produces is used to heat water to steam, which in turn is used to power turbines to
generate electricity
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• Nuclear fuel energy is clean as it does not produce pollutants such as CO2 or oxides of nitrogen
or sulfur
• But nuclear power plants are expensive to build and maintain as well as being potentially
dangerous in the event of an accident as radioactive materials may be released
• Radioactive waste still needs to be safely stored so that it does not contaminate the local
ecosystems

The nuclear fission of a large nucleus of uranium-235 into smaller daughter nuclei

Fuel Cells
The hydrogen fuel cell

• A fuel cell is an electrochemical cell in which a fuel donates electrons at one electrode and
oxygen gains electrons at the other electrode
• This keeps the hydrogen and oxygen separate, reducing the hazards associated with combustion
of hydrogen
• The only product is water
• These cells are becoming more common in the automotive industry to replace petrol or diesel
engines
• H2 and O2 are pumped through two porous electrodes where the half-reactions occur
• The following reaction occurs at the anode:

2H2 → 4H+ + 4e-

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• At the cathode the following reaction takes place:

4H+ + O2 + 4e- → 2H2O

• The overall reaction is:

2H2 + O2 → 2H2O

• The electrons move around the external circuit from the cathode to the anode
• This movement of electrons is used to drive an electric motor

Diagram showing the movement of hydrogen, oxygen and electrons in a Hydrogen-Oxygen fuel
cell
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Advantages and disadvantages of fuel cells

• Advantages
o They do not produce any pollution
o They produce more energy per kilogram than either petrol or diesel
o No power is lost on transmission as there are far fewer moving parts than in an internal
combustion engine
o Fuel cells are quiet and lightweight compared to combustion engines
• Disadvantages
o Materials used in producing fuel cells are expensive
o High-pressure tanks are needed to store the oxygen and hydrogen in sufficient amounts
o Fuel cells are affected by low temperatures, becoming less efficient
o Hydrogen is expensive to produce and store