Topic 8 SLOP Booklet

Energetics I

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We now know that the principle of the conservation of energy states that energy is never created or
destroyed but only changed in it’s store, however for a long time scientists had only a vague idea of what
“energy” was, which given that energy changes are a characteristic feature of all chemical reactions
means for a long time we didn’t have a full understanding of the energetics of chemical processes.

Without “energy” there would be no life, no warmth, no movement. It enables us to do work and its study is
a fundamental part of chemistry. In this topic we will look at the use of specific terminology to chemical
energetics, understand how we can measure enthalpy changes in chemical reactions and then at a
microscopic level understanding the interactions that occur to calculate bond enthalpies.

Enthalpy Changes: The Fundamentals and Review

In a chemical reaction, the atoms of the reactants are separated and rearranged to form the
products. There is always an energy change in a chemical reaction. Most reactions release
energy to the surroundings, and this chemical energy is transferred to thermal energy. However,
some reactions are the opposite and take in thermal energy from the surroundings.

You cannot have negative energy in Science. Recall that the principle of the conservation of
energy states that energy is never created or destroyed but only changed in it’s store.

Energy that is converted from chemical energy stores to thermal energy stores is not “lost”, it is
transferred to the surroundings, even if the new products have less energy than the reactants.

As Chemists we are typically focussed on the chemical and thermal energy changes happening
within the reaction mixture. For this reason (and many more), Scientists therefore use the term
ENTHALPY rather than energy. (A physicist will happily talk for ages about Enthalpy!)

The table below refers to some key definitions that we will use throughout the course of this unit.

Key Term Definition

Enthalpy, H The systems internal energy plus product of it’s pressure and volume.
The total enthalpy, H, of a system cannot be measured directly.

System The material/reaction mixture being studied

Surroundings Everything around the system

Enthalpy Change, ∆H Total energy change between the system and surrounding measured at
a constant pressure.
Open System A system which can exchange energy and matter with the surroundings

Closed System A system which can exchange energy but not matter with the
surroundings.

Figure 1- Visual Explanation of System and Surroundings

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 1. In the following scenarios; identify the system and surroundings.
(a) Solution of 1-chloropropane, KOH in a beaker in a lab.
(b) Vaporised Crude Oil in a fractionating column.
(c) Melting ice in a cup.
(d) Greenhouse containing photosynthesising plants.
2. Identify what type of systems the following environments are: open or closed.
(a) Ocean
(b) Bottled Water
(c) Greenhouse
(d) Conical Flask in a Titration
(e) Aquarium
(f) Boiling Pot with a lid on it.
3. Explain your answer to question 2(a).
4. Explain your answer to question 2(f).
5. When an alcohol is heated under reflux is this an example of an open or closed system?
6. Critique the statement “The reactants lost energy”. How could the statement be changed
to make it more specific?

Exothermic and Endothermic Reactions

As detailed earlier, enthalpy changes are characteristic of all chemical processes, but not all
enthalpy changes are the same. The enthalpy changes within chemical processes are typically
seen as temperature changes, due to the movement of energy: exothermic or endothermic.

Exothermic Reactions Endothermic Reactions

The enthalpy of the reacting system decreases. The enthalpy of the reacting system increases.

Enthalpy Change, ∆H, is negative Enthalpy Change, ∆H, is positive

Energy is transferred from the reacting system to the Energy is transferred to the reacting system from
surroundings. the surroundings
The change in reaction enthalpy can be detailed in a diagram called an enthalpy level diagram. It is important to
note the following in enthalpy level diagrams.
• They do not have a “curved line” between reactant and products.
• They have an arrow showing the direction of the enthalpy change.
• Values for ΔH should be given, including the correct sign.
• Formulae for the reactants and products, including state symbols, should be given when a reaction is
provided.

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7. State whether the following reactions are an example of an exothermic or endothermic
reaction.
(a) A candle burning.
(b) Dynamite being detonated to blast rocks.
(c) A leaf photosynthesising.
(d) Coal Burning.
(e) Evaporating Water.
(f) Respiration in Mitochondria
(g) Freezing Water
(h) Thermal decomposition of Calcium Carbonate.
8. Identify whether the following reactions are exothermic or endothermic based on the value
for ∆H for the reaction.
a) CH4(g) + 2O2(g) → CO2 + 2H2O ∆H = -890kJ mol-1
b) CH4(g) + Cl•(g) → ClCH3 + H• ∆H = +20.5kJ mol-1
c) 2HgO(s) → 2Hg + O2 ∆H = +181.67kJ mol-1
d) PCl3(g) + Cl2(g) → PCl5(g) ∆H = -92.5kJ mol-1
e) N2O4(g) → 2NO2 ∆H = +54.4kJ mol-1
f) C(s) + O2(g) → CO2 ∆H = -393.5kJ mol-1
9. Construct an enthalpy level diagram for the reaction in Q8d.
10. Construct an enthalpy level diagram for the reaction in Q8e.
11. Critique the statement “The reactants lost energy” with regards to the reaction in 8a. How
could the statement be changed to make it more specific?
12. Consider this reaction: 2H2(g) + O2(g) → 2H2O(l) | ∆H = -576kJ mol-1
(a) Is the above reaction endothermic of exothermic?
(b) Which have the greater enthalpy, the reactants or products?
(c) Given the information detailed above, what is the ∆H value for the following process:
2H2O(l) → 2H2(g) + O2(g)
(d) Given the information detailed above, what is the ∆H value for the following process: :
H2(g) + ½O2(g) → H2O(l)

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 Standard Enthalpy Changes
Standard Conditions
To compare energy changes, it is important to state the conditions under which a reaction is
performed. Enthalpy changes vary with changes in temperature, pressure, and concentration. For
this reason, standard enthalpy changes in data tables refer to the following standard conditions.

• Pressure of 100kPa.
• Temperature of 298K (25°C)
• Substances in their standard state at the above temperature and pressure.
• Any solutions have a concentration of 1 mol dm-3.

Convert the following temperatures from °C to K or vice versa.

298K 373K 1087K 47K

25°C -273°C 385°C 78°C

243K 293K 57K

256°C -73°C -185°C 250°C

Standard States
The standard state of a chemical is the state the chemical is found in at standard temperature
and pressure.

What is the standard state of Oxygen at 298K? Gas

What is the standard state of HCl at 298K? Aqueous
What is the standard state of Gold at 298K? Solid

13. For each of the chemical substances listed below; state their symbol formulae and their
standard state. [Tm = melting temperature | Tb = Boiling temperature]
(a) Carbon Monoxide
(b) Water
(c) Nitrogen
(d) Iodine
(e) Bromine
(f) Sulfuric Acid
(g) Butane [Tm = 135K | Tb = 273K]
(h) Calcium Carbonate
(i) Carbon(graphite)
(j) Magnesium Oxide
(k) Fluorine
(l) Ammonia
(m) Ethanol [Tm = 156K | Tb = 352K]
(n) Butanoic Acid [Tm = 269K | Tb = 439K]
(o) Copper

NOTE: Elements with different allotropes, and compounds that exist in differing forms, the most
stable form at 298K and 1atm is chosen as the standard, so for Carbon, data used relates to the
allotrope of carbon rather than diamond.

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 Standard Enthalpy Changes – Reaction and Formation

Standard Enthalpy Change of Reaction.

Any enthalpy change measured under standard conditions is described as the standard enthalpy
change

The standard enthalpy change of a reaction, ∆rHϴ, is the enthalpy change when a reaction occurs
in the molar quantities as shown in the chemical equation, under standard conditions.

Examples
C(s) + 2H2(g) → CH4(g) 𝜃
∆𝑟 𝐻298 = −75𝑘𝐽 𝑚𝑜𝑙 −1
2H2(g) + O2(g) → 2H2O(l) 𝜃
∆𝑟 𝐻298 = −576𝑘𝐽 𝑚𝑜𝑙 −1

Standard Enthalpy Change of Formation

The Standard Enthalpy Change of Formation, ∆fHϴ, is the enthalpy change when one mole of a
compound is formed from its elements in their standard states, under standard conditions.

Examples
Mg(s) + ½O2(g) → MgO(s) 𝜃
∆𝑓 𝐻298 = −602𝑘𝐽 𝑚𝑜𝑙 −1
H2(g) + ½O2(g) → H2O(l) 𝜃
∆𝑓 𝐻298 = −286𝑘𝐽 𝑚𝑜𝑙 −1
One important thing to note about this definition, is that the standard enthalpy changes for an
element is 0kJ mol-1, as there is no enthalpy change involved when an element is formed from
itself.
Cu(s) → Cu(s) 𝜃
∆𝑓 𝐻298 = 0𝑘𝐽 𝑚𝑜𝑙 −1
H2(g) → H2(g) 𝜃
∆𝑓 𝐻298 = 0𝑘𝐽 𝑚𝑜𝑙 −1
NOTE: The ∆fH , equations are an example of where the use of non-integers is acceptable.
ϴ

Remember ALL EQUATIONS MUST BE BALANCED, it’s just that the standard enthalpy of formation
must involve the formation of 1 mole of a compound.

14. Write equations to show the standard enthalpy change of reaction for the following
compounds. You must include state symbols otherwise the answers are incorrect! If the
standard state is not given, you need to work out what it is.
(a) CH4
(b) NH3
(c) C4H10(l)
(d) Al2O3
(e) C6H12O6(l)
15. Write equation to signify the standard enthalpy change of formation for the following
reactions. You must include state symbols otherwise the answers are incorrect! If the
standard state is not given, you need to work out what it is.
(a) MgCl2
(b) C2H5OH(l)
(c) NH3
(d) CH3Br(l)
(e) Na2O
(f) C4H10(l)
(g) Al2O3
(h) Pb(NO3)2(s)

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 Standard Enthalpy Changes – Combustion and Neutralisation
Standard Enthalpy of Combustion
Standard Enthalpy Change of Combustion, ∆cHϴ, is the enthalpy change when one mole of a
substance is completely burnt in oxygen, under standard conditions.

Theoretically, the substance should be burned under standard conditions – however in practice
this isn’t possible, so we burn the substance in the normal way and make adjustments.

Examples
CH4(g) + 2O2(g) → CO2(g) + H2O(l) ∆𝑐 𝐻𝜃 = −890𝑘𝐽 𝑚𝑜𝑙 −1
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C2H6(g) + O2(g) → 2CO2(g) + 3H2O(l) ∆𝑐 𝐻𝜃 = −1561𝑘𝐽 𝑚𝑜𝑙 −1
2
H2(g) + ½O2(g) → H2O(l) ∆𝑐 𝐻𝜃 = −286𝑘𝐽 𝑚𝑜𝑙 −1
C(s) + O2(g) → CO2(g) ∆𝑐 𝐻𝜃 = −394𝑘𝐽 𝑚𝑜𝑙 −1
NOTE: When any carbon containing compound undergoes oxidation it should form CO2(g) not CO(g).

Standard Enthalpy of Neutralisation

Standard Enthalpy Change of Neutralisation, ∆neutHϴ, can be measured from the energy given out
when acids react with alkalis in aqueous solution to form a salt and one mole of water.

Examples
NaOH(aq) + HCl(aq) → NaCl + H2O(l) 𝜃
∆𝑛 𝐻298 = −51𝑘𝐽 𝑚𝑜𝑙 −1
NaOH(aq) + ½H2SO4(aq) → ½Na2SO4 + H2O(l) 𝜃
∆𝑛 𝐻298 = −51𝑘𝐽 𝑚𝑜𝑙 −1

16. Write equations to show the standard enthalpy change of combustion for the following
compounds.
(a) C3H6(g)
(b) C4H10(g)
(c) Be(s)
(d) C2H5OH(l)
(e) C6H14(l)
(f) S(s)
(g) CHALLENGE: Na(s)
17. Write equations to show the standard enthalpy change of neutralisation for the following
reactions.
(a) HNO3(aq) + KOH(aq)
(b) H2SO4(aq) + NaOH(aq)
(c) HCl(aq) + Ba(OH)2(aq)
(d) H2SO4(aq) + Sr(OH)2(aq)
18. The equations for three reactions are as follows:-
reaction 1 C(s) + O2(g) → CO2(g) ∆rHθ= −394 kJ mol−1
reaction 2 CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ∆rHθ = −890 kJ mol−1
reaction 3 2H2(g) + O2(g) → 2H2O(l) ∆rHθ = −572 kJ mol−1
(a) Give two reasons why all three reactions are classified as examples of combustion.
(b) What type of reaction are all three reactions based on their enthalpy change?
(c) Only reaction 1 represents a standard enthalpy change of formation. Give reasons why
reactions 2 and 3 do not.
(d) Draw an enthalpy level diagram for reaction 3.
(e) Which physical property should be kept constant when measuring an enthalpy
change?
(f) A reaction occurs under standard conditions.

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19. Compound X consists of carbon, hydrogen, and oxygen only. The mass spectrum of
Compound X has a molecular ion peak at 44m/z, and a significant peak at 29m/z.
(a) A 1.76g sample was completely burned in oxygen. It produced 3.52g of carbon dioxide
and 1.44g of water. Use combustion analysis to determine the empirical formula of
Compound X
(b) Determine the molecular formula of Compound X.
(c) Draw the displayed formula for Compound X.
(d) State the homologous series Compound X is a member of.
(e) State the starting chemical, reagent, and conditions to synthesis Compound X.
(f) State the standard enthalpy of formation for Compound X.
(g) State the standard enthalpy of combustion for Compound X.
(h) Would you expect the enthalpy change for the combustion of compound X to be
exothermic or endothermic?

20. A scientist had an unknown hydrocarbon.

(a) 0.104g of a hydrocarbon gave 42.0cm3 of vapour measured at 101000Pa and 150oC.
The relative molecular mass of the hydrocarbon is 58.0g mol-1. Calculate the molecular
formula of the hydrocarbon.
(b) State the standard enthalpy of formation for the hydrocarbon.
(c) State the formula of two fragment ions that would be produced in the mass spectrum of
the hydrocarbon.
(d) State the name of the alkene with an equal chain length
(e) Explain why this hydrocarbon would be a better fuel than the alkene mentioned in (d).
(f) Determine the standard enthalpy of combustion for the alkene mentioned in (d).

21. BOX THIS QUESTION:- The reaction of Potassium Carbonate with Sulfuric Acid is performed
at 15oC, 101kPa. 2.20g of CO2 is formed in this reaction. [R = 8.31 J K-1 mol-1]
(a) Write the balanced equation for this reaction including state symbols.
(b) Does the standard enthalpy of neutralisation for this reaction differ from the reaction
written in part (a)?
(b) Write an ionic equation for this neutralisation process.
(c) Calculate the number of mol of CO2 formed in this reaction.
(d) Calculate the volume, in m3, of CO2 formed in this reaction at the stated conditions.
(e) Calculate the concentration of the Potassium Carbonate solution if 50cm3 of it is used.
(f) The sulfuric acid is in excess, 200cm3 of 2mol dm-3 sulfuric acid is supplied, how many
moles are remaining at the end of the reaction?

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 Measuring Enthalpy Changes
The energy given out or taken in during many chemical reactions can be measured through
temperature changes and this makes it possible to calculate enthalpy changes during a reaction
process.

Calorimetry involves the practical determination of enthalpy changes

usually involves heating (or cooling) of known amounts of water and
allows us to calculate the Standard Enthalpy Change of Combustion,
Formation or Neutralisation for an Experiment. Fundamentally:

• When water or an object increases in temperature; the reaction

must be exothermic.
• When water or an object decreases in temperature; the reaction
must be endothermic.

The calculation for the energy required to change the temperature of

a substance is linked through the following equation you would have
Figure 2 - Spirit Burner - Enthalpy of
come across in your Physics GCSE. Combustion
𝑸
𝑸 = 𝒎𝒄∆𝑻 ∆𝑯 = −
Where: 𝒏
Symbol Unit
Q Heat Energy J
m Mass g
c Specific Heat Capacity J K-1 g-1
∆T Change in Temperature K

∆H Enthalpy Change kJ mol-1

n Number of moles mol

Worked Example 1 – Enthalpy of Combustion Partial Example 1 – Enthalpy of Combustion

On complete combustion, 0.18g of hexane raised On complete combustion, 1.650g of ethanol raised
the temperature of 100g water from 22°C to 47°C. the temperature of 300g water from 17.4°C to
Calculate its enthalpy of combustion. 21.6°C. Calculate its enthalpy of combustion.
Mass of Water (not the fuel!) = 100g Mass of Water (not the fuel!) = _______ g
Specific Heat Capacity = 4.18J K-1 g-1 Specific Heat Capacity = 4.18J K-1 g-1
∆T = 25K ∆T = ______K
𝑸 = 𝒎𝒄∆𝑻 𝑸 = 𝒎𝒄∆𝑻
Q = 100 x 4.18 x 25 Q = _____ x 4.18 x ______
Q = +10,450J Q = +_________J
Q = +10,450J/1000 = +10.45KJ Q = +10,450J/1000 = +10.45KJ
I prefer converting to kJ here when handling the energy.
Enthalpy change is measured in kJ mol-1 so additional Enthalpy change is measured in kJ mol-1 so additional
calculations needed! calculations needed!
𝒎 𝟎. 𝟏𝟖 𝒎 _______
𝒏= = = 𝟎. 𝟎𝟎𝟐𝟏𝒎𝒐𝒍𝒔 𝒏= = = _____________𝒎𝒐𝒍𝒔
𝑴𝒓 𝟖𝟔. 𝟎 𝑴𝒓 _______
𝒒 +𝟏𝟎. 𝟒𝟓 𝒒 ___________
∆𝑯 = − = − ∆𝑯 = − = −
𝒏 𝟎. 𝟎𝟎𝟐𝟏 𝒏 ___________
∆H = -5000 kJ mol-1 ∆H = -___________ kJ mol-1
This is the enthalpy change for this reaction This is the enthalpy change for this reaction
process, ALL enthalpy changes have a sign. process, ALL enthalpy changes have a sign.

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 Calorimetry – Enthalpy of Combustion Problems
22. When 1.60g of ethanol are burned, enough heat is produced to heat 200g of water from
22.0oC to 67oC. Calculate the enthalpy of combustion of ethanol. The specific heat
capacity of water = 4.18J K-1 g-1.
23. Complete Q1 on the Chemsheet Overleaf
24. Complete Q2 on the Chemsheet Overleaf
25. Complete Q3 on the Chemsheet Overleaf
26. An experiment was conducted to determine the enthalpy of combustion of liquid
methanol. The energy obtained from burning 2.12g of methanol was used to heat 150g of
water. The temperature of the water rose from 298K to 362K. The specific heat capacity of
water = 4.18J K-1 g-1.
(a) Define the term standard enthalpy of combustion.
(b) Write the equation for the standard enthalpy of combustion of methanol.
(c) Use the above data to calculate a value for the enthalpy of combustion of one mole of
liquid methanol.
(d) Classify the reaction for the combustion of methanol.
27. CHALLENGE: A vessel and it’s contents of total heat capacity 120J K-1 were heated using a
methane burner. Calculate the maximum theoretical temperature rise when 0.10g of
methane was completed burned. The standard enthalpy of combustion of methane is -
890kJ mol-1.

Standard Enthalpy of Neutralisation

We can apply our understanding of the definition for ∆neutHϴ to find the Standard Enthalpy Change
of Neutralisation as many reactions involving acids and alkalis are in solution.

Worked Example 2 – Enthalpy of Neutralisation Partial Example 2 – Enthalpy of Neutralisation

25.0cm3 of 2.00 mol dm-3 HCl was added to 25.0cm3 of 250cm3 of 0.400 mol dm-3 HCl was added to 250cm3 of
2.00 mol dm-3 NaOH in an insulated beaker. The initial 0.400 mol dm-3 NaOH in an insulated beaker. The initial
temperature of both solutions was 20.0°C. The highest temperature of both solutions was 17.05°C. The
temperature reached by the solution was 33.0°C. highest temperature reached by the solution was
Calculate the Standard Enthalpy of Neutralisation. 19.97°C. Calculate the Standard Enthalpy of
Neutralisation.
NaOH + HCl → NaCl + H2O NaOH + HCl → NaCl + H2O
Volume of TOTAL Solution = 25+25 = 50cm3 Volume of TOTAL Solution = _____+_____ = ____cm3
(DensityH2O is 1g per cm )
3 = 50g (DensityH2O is 1g per cm3) = _____g
Specific Heat Capacity = 4.18J K-1 g-1 Specific Heat Capacity = 4.18J K-1 g-1
∆T = 13K ∆T = _____K
𝑸 = 𝒎𝒄∆𝑻 𝑸 = 𝒎𝒄∆𝑻
Q = 50 x 4.18 x 13 Q = _____ x ______ x _______
Q = +2,717J Q = __________J
Q = +2,717J/1000 = +2.717KJ Q = __________J/1000 = +_________KJ
I prefer converting to kJ here when handling the energy. I prefer converting to kJ here when handling the energy.
Molar Ratio is 1:1:1:1. Remember n = c x v Molar Ratio is 1:1:1:1. Remember n = c x v
Moles of HCl reacting: (2 x 25)/1000 = 0.05 mol Moles of HCl reacting: (________)/1000 = _______ mol
Moles of NaOH reacting: (2 x 25)/1000 = 0.05 mol Moles of NaOH reacting: (________)/1000 = _______ mol
Moles of water produced = 0.05 mol Moles of water produced = _______ mol
𝒒 +𝟐. 𝟕𝟏𝟕 𝒒 __________
∆𝑯 = − = − ∆𝑯 = − = −
𝒏 𝟎. 𝟎𝟓 𝒏 __________

∆H = -54.34 kJ mol-1 ∆H = -________________ kJ mol-1

This is the enthalpy change for this reaction process, This is the enthalpy change for this reaction process,
ALL enthalpy changes have a sign. ALL enthalpy changes have a sign.

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 Calorimetry – Enthalpy of Neutralisation Problems
28. A student added 50.0cm3 of hydrochloric acid to 50.0cm3 of sodium hydroxide solution in a
polystyrene cup. The temperature rose by 6.5oC from the initial temperature of each
solution. The initial concentration of each solution was 1.00 mol dm-3.
(a) Write an ionic equation for the reaction occurring.
(b) Calculate the standard enthalpy of neutralisation for the reaction.
29. Complete Q4 on the Chemsheet on the previous page
30. Complete Q5 on the Chemsheet on the previous page
31. Complete Q6 on the Chemsheet on the previous page

Standard Enthalpy of Reaction – Reagent in Excess

As we know from our work in Topic 5, reactions do not always occur in the molar quantities stated
by the stoichiometric ratio in the chemical reaction. Sometimes reagents are in excess and we
need to first determine which reactant is the limiting reagent and therefore determine how this
dictates the standard enthalpy of reaction.

Worked Example 3 – Enthalpy of Reaction Partial Example 3 – Enthalpy of Reaction

25 cm3 of 1.00 mol dm-3 copper sulphate solution was
put in a calorimeter and 6.0 g of zinc powder added.
The temperature of the solution rose by 50.6C.
Calculate the enthalpy of reaction. The specific heat
capacity of water = 4.18J K-1 g-1.
25 cm3 of 0.20 mol dm-3 copper sulphate solution was
put in a calorimeter and 0.4 g of Iron powder added.
The temperature of the solution rose by 8.5C.
Calculate the enthalpy of reaction. The specific heat
capacity of water = 4.18J K-1 g-1.

CuSO4 + Zn → ZnSO4 + Cu CuSO4 + Fe → FeSO4 + Cu

Mass = 25cm3 = 25g Mass = _____cm3 = _____g

Only use the mass of the solution. Only use the mass of the solution.
Specific Heat Capacity = 4.18J K-1 g-1 Specific Heat Capacity = 4.18J K-1 g-1
∆T = 50.6K ∆T = ________K
𝑸 = 𝒎𝒄∆𝑻 𝑸 = 𝒎𝒄∆𝑻
Q = 25 x 4.18 x 50.6 Q = ____ x ____ x ____
Q = +5,288J Q = +__________J
Q = +5,288J/1000 = +5.288KJ Q = +__________J/1000 = +_________KJ
CuSO4 + Zn → ZnSO4 + Cu CuSO4 + Fe → FeSO4 + Cu

Mol CuSO4 = c x v = (1x25)/1000 = 0.025 Mol CuSO4 = c x v =

Mol Zn = mass ÷ Mr = 6.0/65.4 = 0.0917 XS Mol Fe = mass ÷ Mr =
The Zinc is in excess, so mols of CuSO4 will be used in
determining the enthalpy change of the reaction as
the ration is 1:1:1:1

𝒒 +𝟓. 𝟐𝟖𝟖 _____ +___________

∆𝑯 = − = − ∆𝑯 = − = −
𝒏 𝟎. 𝟎𝟐𝟓 _____ ___________
∆H = -212 kJ mol-1 ∆H = -_____________ kJ mol-1
This is the enthalpy change for this reaction process, This is the enthalpy change for this reaction process,
ALL enthalpy changes have a sign. ALL enthalpy changes have a sign.

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Calorimetry – Enthalpy of Reaction Problems
32. A student reacted 0.25 mol dm-3 of 50cm3 Copper Sulphate solution was placed in a
calorimeter with 4.0g of Magnesium powder. The temperature of the solution rose by
64.5oC. Calculate the enthalpy of the reaction. The specific heat capacity of water = 4.18J
K-1 g-1.
33. Complete Q7 on the Page 11
34. Complete Q8 on the Page 11
35. Complete Q9 on the Page 11
36. CHALLENGE: A sample of cobalt, A, with a mass of 5.00 g, is initially at 25.0 °C. When this
sample gains 6.70J of heat, the temperature rises to 27.9 °C. Another sample of cobalt, B,
with a mass of 6.50 g, is initially at 25.0 °C. If sample B gains 5.00 J of heat, what is the final
temperature of sample B. (Hint: think about the specific heat of both samples.

Measuring Enthalpy Changes and Sources of Error

In all of the differing calorimetry experiments detailed in this section, the calculation is based on a
number of assumptions, the most important one being that all the energy from the
fuel/flame/reaction is transferred to heat the water. In reality, we know this isn’t true, with the
energy transfer being affected by draughts, incomplete combustion or energy being transferred
to a container rather than the water.

Potential sources of error include:-

• Some of the heat energy produced

in burning is transferred to the air
and not the water.
• Some of the fuel may not burn
completely to form carbon dioxide
and water.
• Some of the heat energy is
produced is transferred to the
container/polystyrene cup and not
the water.
• Conditions are not standard.
• Heat capacity of the calorimeter is
not included.
• Experiment takes time, so not all of
Figure 3 - Bomb Calorimeter
the heat
energy
transferred from the water to surrounding is compensated for.

To improve the accuracy of data from enthalpy of combustion

reaction we can use a bomb calorimeter, which is specifically
designed to ensure that the sample burns completed, and energy
losses are minimised.

To improve the accuracy of data from enthalpy of

neutralisation/reaction reactions we can use an insulated plasti
c/polystyrene cup, polystyrene has a negligible heat capacity and is
an excellent insulator.
Figure 4 - Insulated Polystyrene Cup

12
 Measuring Enthalpy Changes – Mixed Practice
37. This question pertain to the enthalpy of neutralisation reactions.
(a) Define the term enthalpy change of neutralization. [2]
The enthalpy change of the neutralization reaction between hydrochloric acid, HCl(aq), and sodium
hydroxide, NaOH(aq), can be determined by the following procedure.
• 50.0 cm3 of 2.00 mol dm−3 hydrochloric acid is transferred to a polystyrene cup and its temperature
recorded
• 50.0 cm3 of 2.00 mol dm−3 sodium hydroxide solution is placed in another polystyrene cup and its
temperature recorded
• The two solutions are mixed, with stirring, and the maximum temperature is recorded
Results:
Initial temperature of both the HCl(aq) and NaOH(aq) 19.0 °C
Maximum temperature reached after mixing 32.5 °C

Assumption:
• The specific heat capacity of all aqueous solutions is 4.18 J g−1 °C−1
• The density of all aqueous solutions is 1.00 g cm−3
(b) Calculate the heat energy released (in joules) on mixing the hydrochloric acid and the sodium
hydroxide solutions. Use the expression: energy released (J) = mass of solution × 4.18 ×
temperature change [2]
(c) Calculate the number of moles of hydrochloric acid used in the experiment. [1]
(d) Give the ionic equation, including state symbols, for the reaction between hydrochloric acid
and sodium hydroxide solution. [1]
(e) Use your answers to (b), (c) and (d) to calculate the enthalpy change of neutralisation for the
above reaction. Include a sign and units in your answer. [3]
(f) Explain why the enthalpy change of neutralization for the reaction between dilute nitric acid,
HNO3(aq), and potassium hydroxide solution, KOH(aq), is predicted to be the same as the
enthalpy change of neutralization for the reaction carried out in part (b)-(e). [1]

38. The diagram shows apparatus that can be used, with appropriate
safety precautions, to find the enthalpy change of combustion,
ΔcH, of a liquid fuel.

The fuels used in an investigation are

• two alkanes – pentane and octane
• two alcohols – methanol and ethanol
The lid should be removed from the spirit burner just before igniting the
fuel, and replaced after the flame is extinguished.

These are the results of the experiment using pentane.

Mass of water in glass beaker 150.0g
Initial Temperature of Water 18.6oC
Final Temperature of Water 54.8oC
Initial Mass of Burner, Lid and Pentane 152.25g
Final Mass of Burner, Lid and Pentane 151.38g

(a) Calculate the heat energy, in kJ, transferred to the water. Give your answer to 3 sig figs. [3]
(b) State the reason why using the lid increases the accuracy of this experiment. [1]
(c) In the experiment using octane, a black solid formed on the underside of the glass beaker. Write an
equation for the combustion of octane that shows the formation of this black solid. State symbols are
not required. [2]
(d) In the experiment using methanol, the heat energy transferred to the water was 8960J, and the mass
of methanol burned was 0.717g. Calculate the enthalpy change of combustion of methanol, in kJ
mol−1, using these data, giving your answer to an appropriate number of significant figures. [3]
(e) In the experiment involving ethanol, a value of −747kJ mol−1 was calculated for ΔcH. Justify how, if at
all, using a copper can in place of the glass beaker would affect the calculated value of ΔcH. [2]

13
 (f) Data book values for the enthalpy changes of combustion, in kJmol−1, of the compounds in the
investigation are
Organic Compound Enthalpy of Combustion (kJ mol-1)
Pentane -3509
Octane -5512
Methanol -715
Ethanol -1371
Give two reasons why the combustion of 1 mol of each of the alcohols releases less energy than the
combustion of 1 mol of each of the alkanes. [2]

39. Propanone, C3H6O, is a member of the homologous series the ketones. Propanone can be
used as a fuel.
(a) State the structural formula for propanone.
(b) State the name of the alcohol which can be oxidised to form propanone.
(c) State the reagents and conditions needed for the reaction detailed in (b).
(d) Write an equation for the complete combustion of propanone, C3H6O, to form carbon
dioxide and water.

In a laboratory experiment, 1.45g of propanone were burned completely in oxygen. The heat
from this combustion was used to raise the temperature of 100g of water from 293.1K to 351.2K

(e) Calculate the number of moles of propanone in the 1.45g

(f) Calculate the heat energy required to raise the temperature of 100g of water the
stated temperature above. The specific heat capacity of water = 4.18 J K-1 g-1.
(g) Hence, calculate a value, in kJ mol-1, for the enthalpy of combustion of propanone.

In a similar experiment, the enthalpy of combustion of butanone, C4H8O, was found to be -1290 kJ
mol-1. A data book value for the same reaction is ∆cHϴ = -2430kJ mol-1.

(h) Suggest one reason why the experimental value is very different from the data book
value.
(i) This data book value of ∆cHϴ for butanone, refers to the formation of carbon dioxide gas
and water in the gaseous state. How would this value differ if it referred to the formation
of water in the liquid state? Explain your answer.

40. Organic Compound D contains the elements carbon, hydrogen, oxygen and nitrogen only.
A sample of D was
burned completely in
the apparatus shown.
Solid X absorbed the
water formed in the
combustion. Solid Y
absorbed the carbon
dioxide.
(a) The masses of solids
X and Y increased during the experiment. Explain the effect, if any, on the changes in
mass of X and Y if the oxygen gas was not dry.
(b) On combustion in dry oxygen, 3.36g of D produced 0.72g of water and 5.28g of carbon
dioxide. This sample of D also contained 0.56g of nitrogen.
Use these data to calculate the empirical formula of compound D.
(c) On the mass spectrum of compound D, the molecular ion is at 168m/z. State the
molecular formula of compound D.

14
 Hess’s Law
The First Law of Thermodynamics says energy can be neither created nor destroyed but it can be
converted from one form to another.

Hess’s Law states that the total enthalpy change of a reaction, depends only on the initial and final
states of the reactants and products, and is independent of the route taken.

This is particularly helpful for reactions where you cannot directly find out the enthalpy change of
the reaction by doing an experiment.

As detailed in the above reaction process, the enthalpy changes for route 1 is exactly the same
as the enthalpy change for route 2 provided the reactants and products remain the same. This
links to the first law of thermodynamics, that energy cannot be created or destroyed.

In reality, we don’t show the reaction process at the bottom as a singular curved arrow. It would
be shown as two separate reaction processes, one detailing the enthalpy of formation of SO2(g)
and H2S(g) and another to show the enthalpy of formation of H2O(l).

Hess’s Law can be used to calculate standard enthalpies of formation, combustions and reaction
from differing particularly scenarios which can will be detailed in the examples shown below.

15
Hess’s Law – Example 1 – Enthalpies of Formation
Edexcel Textbook: Page 239 - 240
For a detailed explanation see Mr. Adenekan’s Video uploaded to the Google Classroom.

ΔfHθ values give the enthalpy change going from the elements to form the compound

Standard Enthalpies of Formation

ΔfHθ [SO2(g)] = -297 kJmol-1 | ΔfHθ[H2S(g)] = -20.2 kJmol-1 |ΔfHθ[H2O(l)] = -286kJmol-1

We can use the enthalpy of formation data to work out the unknown ∆H2 and ∆H3 to allow us to
calculate the ∆H1 the unknown.

∆H2 – Enthalpy of Formation of SO2(g) and 2H2S(g)

To work out the enthalpy for ∆H2 we need to do the following: -

Enthalpy of Formation of SO2(g) = -297 kJ mol-1
Enthalpy of Formation of 2H2S(g) = 2 x -20.2 kJ mol-1 = -40.4 kJ mol-1
The reason this is 2x is due to needing to form
2 moles of 2H2S(g)
Total Enthalpy Change = -297 + 40.4 = -337.4 kJ mol-1

∆H3 – Enthalpy of Formation of 2H2O(l)

To work out the enthalpy for ∆H3 we need to do the following: -

Enthalpy of Formation of 2H2O(l) = 2 x -286 kJ mol-1 = -572 kJ mol-1
Enthalpy of Formation of 3S(s) = 0 kJ mol-1
The Enthalpy of Formation for S(s) is 0kJ mol-1 as no change in enthalpy change is needed to
form S(s) from it’s element as it is an element!!
Total Enthalpy Change = -572 kJ mol-1

∆H1 – Enthalpy of Reaction of SO2(g) and H2S(g)

To work out the enthalpy for ∆H1 we need to do the following: -

We cannot go directly across from the reactants to products, however we can use the
alternative route, which is the reverse of the ∆H2 arrow and along the ∆H3 arrow.

Whenever you go AGAINST an arrow, you need to place a negative sign in front of that ∆H.

∆H1 = ∆H3-∆H2 -234.6kJ mol-1 is the direct enthalpy value for the
∆H1 = -572 – (-337.4) standard enthalpy of reaction of SO2(g) + H2S(g) to form
3S(s) + 2H2O(l)
= -234.6 kJ mol-1

16
Hess’s Law Task 1a – Drawing Enthalpy Cycles.
For the following questions you are simply drawing the enthalpy cycles for the differing equations
which are shown using the elements, in their standard states, that would form the differing
compounds.

NOTE: View the Worked Example Video posted by Mr. Adenekan on the Google Classroom if
unsure.

41. CH4(g) + 2Cl2(g) → CH2Cl2(g) + 2HCl(g)

42. N2H4(l) + O2(g) → N2(g) + 2H2O(l)
43. Fe2O3(s) + 3CO(g) → 2Fe(s) + 3CO2(g)
44. PCl5(s) → PCl3(g) + Cl2(g)
45. C4H10(g) + 6.5O2(g) → 4CO2(g) + 5H2O(l)
46. Fe(s) + H2O(g) → H2(g) + Fe3O4(s) – Is this equation balanced?
47. NO(g) + O2(g) → NO2(g) – Is this equation balanced?

Hess’s Law Task 1b – Calculating Enthalpy Values.

Use the values in the tables shown below to calculate the standard enthalpy of reaction for each
of the above equations.

41b CH4(g) CH2Cl2(g) 2HCl(g)

ΔfHθ [kJ mol-1] -74.8 -124.1 -92.3

42b N2H4(g) H2O(l)

ΔfHθ [kJ mol-1] -74.8 −285.8

43b Fe2O3(s) CO(g) CO2(g)

ΔfHθ [kJ mol-1] −824.2 −110.5 −393.5

44b PCl5(s) PCl3(g)

ΔfHθ [kJ mol-1] −443.5 −319.7

For this reaction below you are calculating the standard enthalpy of combustion.

45b C4H10(g) CO2(g) H2O(l)

ΔfHθ [kJ mol-1] −824.2 −110.5 −285.8

46b H2O(g) Fe3O4(s)

ΔfHθ [kJ mol-1] −241.8 −1118.4

47b NO(g) NO2(g)

ΔfHθ [kJ mol-1] +90.2 +33.2
NOTE: Chemsheets Hess’s Law Sheet 1

48. Complete Question 2 on the next page

49. Complete Question 3 on the next page
50. Complete Question 5 on the next page

17
Hess’s Law – Example 2 – Calculating/Using Enthalpies of Combustion
Edexcel Textbook: Page 241
For a detailed explanation see Mr. Adenekan’s Video uploaded to the Google Classroom.

Enthalpy Changes of Combustion are also useful for calculating enthalpy changes you can’t find
directly, as many of these ΔHθc have been calculated before.

- ΔcHθ values give the enthalpy change going from the elements/compounds to form the
combustion products.
- Combustion is complete
- Combustion Products are the most stable oxidised compounds of the element being combusted
e.g. SO2 not SO3.
Standard Enthalpies of Combustion
ΔcHθ [C(s)] = -394 kJmol-1 | ΔcHθ[H2(g)] = -286 kJmol-1 |ΔcHθ[C2H5OH(l)] = -367kJmol-1

We can use the enthalpy of formation data to work out the unknown ∆H2 and ∆H3 to allow us to
calculate the ∆H1 the unknown.
∆H2 – Enthalpy of Combustion of 2C(s) and 3H2(g)

To work out the enthalpy for ∆H2 we need to do the following: -

Enthalpy of Combustion of 2C(s) = 2 x -394 kJ mol-1 = -788 kJ mol-1
Enthalpy of Formation of 3H2(g) = 3 x -286 kJ mol-1 = -858 kJ mol-1

Total Enthalpy Change = -788 + -858 = -1646 kJ mol-1

∆H3 – Enthalpy of Combustion of C2H5OH(l)

To work out the enthalpy for ∆H3 we need to do the following: -

Enthalpy of Combustion of = -1367 kJ mol-1 = -1367 kJ mol-1
C2H5OH(l)
Total Enthalpy Change = -1367 kJ mol-1

∆H1 – Enthalpy of Reaction of 2C(s) + 3H2(g) + ½O2(g)

To work out the enthalpy for ∆H1 we need to do the following: -

We cannot go directly across from the reactants to products, however we can use the
alternative route, which is the along the ∆H2 arrow and the reverse the ∆H3 arrow.

Whenever you go AGAINST an arrow, you need to place a negative sign in front of that ∆H.

∆H1 = ∆H2-∆H3 -279 kJ mol-1 is the direct enthalpy value for the standard
∆H1 = -1646 – (-1367) enthalpy of formation of 2C(s) + 3H2(g) + ½O2(g) to form
C2H5OH(l)
= -279 kJ mol-1

18
Hess’s Law Task 2a – Drawing Enthalpy Cycles - Combustion
For the following questions you are simply drawing the enthalpy cycles for the differing equations
which are shown using the elements, in their standard states, that would form the differing
compounds.

NOTE: View the Worked Example Video posted by Mr. Adenekan on the Google Classroom if
unsure.

51. 3C(s) + 4H2(g) → C3H8(g)

52. 2C(s) + 3H2(g) → C2H6(g)
53. C6H6(l) + 3H2(g) → C6H12(l)
54. C6H12O6(s) + 6O2(g) → 6CO2(g) + 6H2O(l) – which elements would the respective
compounds be formed from?
55. 4NH3(g) + 7O2(g) → 4NO2(g) + 6H2O(g)
56. C6H14(l) + 9.5O2(g) → 6CO2(g) + 7H2O(l)

Hess’s Law Task 1b – Calculating Enthalpy Values.

Use the values in the tables shown below to calculate the missing standard enthalpy in each of
the above equations.

51b C(s) H2(g) C3H8(g)

ΔcHθ [kJ mol-1] -394 -286 -92.3

52b C(s) H2(g) C2H6(g)

ΔcHθ [kJ mol-1] -394 -286 -1559.7

53b C6H6(l) H2(g) C6H12(l)

ΔcHθ [kJ mol-1] −3267 -286 −3920

54b ΔcHθ C6H12O6(s) ΔfHθ CO2(g) ΔfHθ H2O(l)

ΔcHθ [kJ mol-1] −2800.8 -394 −286

55b NH3(g) NO2(g) H2O(g)

ΔfHθ [kJ mol-1] −45.9 +33.1 −242

56b C6H14(l) CO2(g) H2O(l)

ΔfHθ [kJ mol-1] −203 -394 −286

NOTE: Chemsheets Hess’s Law Sheet 2

57. Complete Question 3 on the next page

58. Complete Question 4 on the next page
59. Complete Question 5 on the next page
60. Complete Question 6 on the next page.

19
 Hess’s Law Mixed Practice

61. This question is about the oxidation of ammonia.

Nitric acid is made from ammonia. One of the stages in nitric acid production involves the
oxidation of ammonia to produce nitrogen oxide, NO. In this process, a mixture of
ammonia and oxygen is passed over a platinum-rhodium catalyst. One manufacturer uses
a pressure of 5 atm and a temperature of 850°C.
4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g) | ΔfHθ -904.8 kJ mol-1
(a) State the systematic name off nitrogen oxide, NO.
(b) Using oxidation numbers, explain why the above reaction is a redox reaction.
(c) Use the above equation and the enthalpy changes of formation of nitrogen oxide and
water, to calculate the enthalpy change of formation of ammonia in kJ mol-1.

NO(g) H2O (g)

ΔfHθ [kJmol-1] +90.4 -241.8
(d) Calculate the atom economy by mass for the formation of NO in this reaction. Give
your answer to an appropriate number of significant figures.

62. Sodium hydrogencarbonate decomposes on heating to form sodium carbonate. It is

difficult to measure the enthalpy change of this reaction directly.
2NaHCO3(s) → Na2CO3(s) + CO2(g) H2O(l)
One method of determining this enthalpy change is to react known amounts of sodium
hydrogencarbonate and sodium carbonate, separately, with excess dilute hydrochloric
acid.
(a) 0.010 mol of solid sodium hydrogencarbonate was added to 25 cm3 of dilute
hydrochloric acid. A temperature rise of 11°C was measured using a thermometer
graduated at 1°C intervals.
Calculate the heat energy produced by this reaction using the equation:
Energy transferred in joules = mass × 4.18 × change in temperature
(b) Calculate the standard enthalpy change for the reaction when one mole of sodium
hydrogencarbonate reacts with hydrochloric acid your answer should be given to three
significant figures.
(c) The standard enthalpy change for the reaction between sodium carbonate and dilute
hydrochloric acid is found by a similar method to be ΔrHθ = −321.6 kJ mol−1

Complete the Hess energy

cycle below by adding the
missing arrow and entities. Use
it to calculate the standard
enthalpy change for the
decomposition of two moles
of sodium
hydrogencarbonate as in the
equation below.

Remember to show your reasoning clearly.

(d) The uncertainty for each thermometer reading is ± 0.5 °C. Calculate the percentage
error in the temperature rise of 11 °C.
(e) Sodium hydrogencarbonate is used in cooking. Suggest what it is used for and how it
works.

20
 63. The reaction of calcium oxide with hydrochloric acid is an exothermic reaction.

CaO(s) + 2HCl(aq) → CaCl2(aq) + H2O(l)

In an experiment to investigate this reaction, the following procedure was carried out.

1. 50.0 cm3 of hydrochloric acid, concentration 2.0 mol dm−3 (an excess), was pipetted into
a polystyrene cup and the initial temperature measured using a thermometer with 0.5°C
graduations.

2. 1.46 g of calcium oxide powder was weighed out and added to the acid. The mixture
was stirred and the maximum temperature measured.

Maximum Temperature (°C) 35.0

Initial Temperature (°C) 19.5

(a) Calculate the enthalpy change, in joules, for the quantities in this experiment.
Assume that the specific heat capacity of the solution is 4.18 J g−1 C−1. Use the expression:
energy transferred in joules = 50.0 × specific heat capacity × temperature change
(b) Using your answer from (a), calculate the molar enthalpy change for the reaction between
calcium oxide and hydrochloric acid. Include a sign and units in your answer.
(c) The standard molar enthalpy change for the reaction between calcium oxide and
hydrochloric acid is −196.8 kJ mol−1.
Suggest three reasons why the calculated value in part (b) is different from this value.
(d) Using the standard enthalpy change of −196.8 kJ mol−1, calculate the minimum mass of
calcium oxide that would be needed to raise the temperature of 250 cm3 of hydrochloric
acid (an excess) by 25.0°C.

(e) The reaction of calcium carbonate with hydrochloric acid has the following standard molar
enthalpy change: ΔrHθ = −18.8 kJ mol−1.
This value can be used, with the
enthalpy change for the reaction of
calcium oxide with hydrochloric acid, to
determine the enthalpy change for the
thermal decomposition of calcium
carbonate. This cannot be measured
directly.
Complete the Hess energy cycle below
by adding the missing arrows and entities.

(f) Use the cycle, and the standard enthalpy

change for the reaction of calcium oxide
and hydrochloric acid (−196.8 kJ mol−1), to
determine the standard enthalpy change for
the decomposition of calcium carbonate.

(g) Complete and label the enthalpy level

diagram below, for the series of reactions in
(e). Your diagram does not have to be to
scale.

21
 Bond Enthalpies
Edexcel Textbook 1: Page 242 - 245
At the simplest level of understanding, a chemical bond is a strong attraction between atoms or
ions. However just to ensure we can recall our definitions!

64. Define a covalent bond.

65. Define an ionic bond.
66. Define a metallic bond.

There should be a term that crops up in each of the above definitions. Electrostatic. When you
break a bond, you have to perform work in order to overcome these attractions. To break a bond,
you need to separate the atoms or ions.

Chemical reactions involve bond breaking followed by bond making. This means the enthalpy
change of a reaction is the energy difference between these bond making and bond breaking
processes.

Bond Breaking Bond Making

Endothermic Process. Exothermic Process
Energy must be supplied to break bonds Energy must be released when a bond is
between atoms or ions formed.
Key Term Definition
Bond Enthalpy

Mean Bond Enthalpy

67. Why are bond enthalpy values always positive?

68. Write an equation to represent the mean bond enthalpy of HCl(g)
69. Why do chemists prefer to use mean bond enthalpies when performing bond enthalpy
calculations?

Bond Average Bond Enthalpy (kJ mol-1) Bond Length (nm)

C-C +347 0.154
C=C +612 0.134
C≡C +838 0.120
C-H +412 0.108
O-H +464 0.096
C-O +358 0.143
C=O +745 0.116

70. Explain the general pattern shown between average bond enthalpy and bond length?
71. Suggest a reason why the bond lengths for the C-H and O-H bonds are so short.
72. Explain why the bonds which contain a double or triple bond have a higher bond enthalpy
than those with single bonds.
73. Draw a dot and cross diagram for Lithium Fluoride.
74. What type of compound is Lithium Fluoride classified as?
75. Why is there no bond enthalpy values for Li-F bond in Lithium Fluoride?
76. Would you expect Sodium Fluoride to have a higher or lower melting point than Lithium
Fluoride, explain your answer.

22
 Using Bond Enthalpies
The most important application of bond energies is their use in estimating the enthalpy changes in
a chemical reaction involving molecular substances with covalent bonds. It is very important to
note they don’t apply to ionic compound.

Exothermic Reactions Endothermic Reactions

The enthalpy of the reacting system decreases. The enthalpy of the reacting system increases.

Enthalpy Change, ∆H, is negative Enthalpy Change, ∆H, is positive

In general, if all the substances are gases then the following applies.

∆𝑯 = ∑ 𝑩𝒐𝒏𝒅 𝑩𝒓𝒐𝒌𝒆𝒏 − ∑ 𝑩𝒐𝒏𝒅𝒔 𝑭𝒐𝒓𝒎𝒆𝒅

∑ = The sum of.

For a detailed video see the examples posted on the Google Classroom by Mr. Adenekan

This example only works if the reactants and products are in the gaseous phase.

Worked Example 4
Use your knowledge of bond enthalpies to find out the enthalpy of reaction for the reaction of
nitrogen with hydrogen to form ammonia.
Bond Enthalpies.
N≡N = +945 kJ mol-1 | H-H = +436 kJ mol-1 | N-H = +391 kJ mol-1
N2(g) + 3H2(g) → 2NH3(g)
Bond Broken
1 x N≡N bond =1 x +945 kJ mol-1 =945 kJ mol-1
3 x H-H bond =3 x +436 kJ mol-1 =1308 kJ mol-1
TOTAL Bonds Broken
= 945 + 1308 =2253 kJ mol-1
Bonds Formed
6 x N-H bond =6 x +391 kJ mol-1 =2346 kJ mol-1
TOTAL Bonds Formed
=2346 kJ mol-1
Enthalpy Change

∆𝑯 = ∑ 𝑩𝒐𝒏𝒅 𝑩𝒓𝒐𝒌𝒆𝒏 − ∑ 𝑩𝒐𝒏𝒅𝒔 𝑭𝒐𝒓𝒎𝒆𝒅

∆H = 2253 - 2346 = -93 kJ mol-1
NOTE
As you are calculating an enthalpy change there must always be a sign, even though all bond
enthalpies are positive values.

23
Using Bond Enthalpies Task 1.
Use the following bond enthalpies to help calculate the ∆H for the differing reaction. You may
assume that all species are in the gaseous state.

Bond H-H C-H C-C C=C C-O O-H C=O

Mean Bond 436 412 348 612 360 463 743
Enthalpy in
kJ mol-1
Bond H-Cl H-Br O=O C=O N-H N=O
Mean Bond 432 366 496 743 391 628
Enthalpy in
kJ mol-1

77. Calculate the enthalpy change for the following reaction:

CH3CH = CH2(g) + H2(g) → CH3CH2CH3(g)
78. Calculate the standard enthalpy change for the following reaction:
CH4(g) + 2O2(g) → 2CO2(g) + 2H2O(l)
79. The following reaction details the reaction between propene and Bromine gas.
CH2CHCH3(g) + HBr(g) →
(a) State the molecular formula of the gaseous halogenoalkane formed.
(b) Calculate the standard enthalpy change for the reaction.
(c) Draw the mechanism for the above reaction.
(d) State the name of the major organic product.
(e) Use Markovnikov’s rule to explain why this is the major product of the reaction.
(f) State the name of the isomer of the organic product that would be the minor product
of this reaction.
80. Calculate the standard enthalpy change for the cracking of butane.
C4H10(g) → C2H6(g) + C2H4(g)
81. Explain why cracking needs to occur in industry?
82. This question is about the thermal decomposition of ammonia. This reaction is catalysed by
platinum and is represented by the equation:
2NH3(g) → N2(g) + 3H2(g) | ∆H = +92 kJ mol-1
The table shows the bond enthalpies for the N≡N and H–H bonds.
Bond Bond Enthalpy (kJ mol-1)
N≡N +944
H-H +436

Use this data, together with the standard enthalpy change of reaction, for the
decomposition of ammonia, to calculate a value, in kJ mol−1, for the mean bond enthalpy
of the N–H bond in ammonia.
83. Ammonia is used in the manufacture of nitric acid.
The equation for one step in this manufacturing process is:
4NH3(g) + 5O2(g) ⇋ 4NO(g) + 6H2O(g) = −900 kJ mol−1

Use the bond enthalpy data from the table above to prove the enthalpy of this reaction is
in fact approximately -900kJ mol-1.

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 Using Bond Enthalpies – Non gaseous method
As detailed earlier, the method which applies the difference in bond enthalpies broken and
formed only works when all the reactants are in the gaseous phase.
How can we calculate the bond enthalpies if the reactants are not in the gaseous phase?
For a detailed video see the examples posted on the Google Classroom by Mr. Adenekan
Worked Example 5
Ethanol burns completely in excess oxygen.
Bond Enthalpies.
C-C = +347 kJ mol-1 | C-H = +413 kJ mol-1 | C-O = +358 kJ mol-1
O-H = +464 kJ mol-1 | O=O = +498 kJ mol-1 | C=O = +805 kJ mol-1
C2H5OH(l) + 3O2(g) → 2CO2 + 3H2O(l)

We need to set up a Hess’s cycle as follows and use the technique used in Hess’s Law to
calculate the enthalpy of combustion of ethanol.
Note the atoms are not diatomic in the case of hydrogen and oxygen as gaseous atoms.
Bond Broken
1 x C-C bond =1 x +347 kJ mol-1 =347 kJ mol-1
5 x C-H bond =5 x +413 kJ mol-1 =2065 kJ mol-1
1 x C-O bond =1 x +358 kJ mol -1 =358 kJ mol-1
1 x O-H bond =1 x +464 kJ mol-1 =464 kJ mol-1
3 x O=O bond =3 x +498 kJ mol-1 =1494 kJ mol-1
TOTAL Bonds Broken
= 347 + 2065 + 358 + 464 + 1494 =4728 kJ mol-1
Bonds Formed
4 x C=O bond =4 x +805 kJ mol-1 =3220 kJ mol-1
6 x O-H bond =6 x +464 kJ mol-1 =2784 kJ mol-1
TOTAL Bonds Formed
= 3220 + 2784 =6004 kJ mol-1
Enthalpy Change
∆𝑯𝟏 = ∆𝑯𝟐 − ∆𝑯𝟑
∆H = 4728 - 6004 = -1276 kJ mol-1
NOTE
As you are calculating an enthalpy change there must always be a sign, even though all bond
enthalpies are positive values.

Enthalpy values calculated using bond enthalpies, or even enthalpy cycles may be different from values
that we’ll determine experimentally (same again).
There are two main reasons for this:-
1. The value of ∆H calculated may not be a standard value. In certain reactions solids or liquids are
produced, however bond enthalpies always refer to bonds being broken in the gaseous state.
2. Bond Enthalpies given are average from several different compounds. This means that their useful for
a general reference, but it means the results aren’t 100% precise. However it allows calculations
when there is little specific data for the compound.

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Using Bond Enthalpies Task 2.
Bond H-H C-H C-C C=C C-O O-H C=O
Mean Bond 436 412 348 612 360 463 743
Enthalpy in
kJ mol-1
Bond H-Cl H-Br O=O C=O N-H N=O ∆Hvap
Mean Bond 432 366 496 743 391 628 Glucose
Enthalpy in 117.51
kJ mol-1

84. Determine the enthalpy change of the following reaction using the enthalpy data in the
table above.
CH3CH=CH2 + 4.5O2 → 3CO2 + 3H2O
85. This question is about 2-methylpropan-2-ol.
(a) Draw the fully displayed formula of 2-methylpropan-2-ol.
(b) The mass spectrum of 2-methylpropan-2-ol is shown below, the relative molecular mass
of 2-methylpropan-2-ol is 74.
Explain which of the following
student answers is the correct
explanation for why there is no
molecular ion peaks in the mass
spectrum of 2-methylpropan-2-ol.
(c) Write the formula for a species
that could be responsible for the
peak at m/z = 59.
(d) The equation for the complete
combustion of 2-methylpropan-2-
ol is
C4H10(l) + 6O2(g) → 4CO2(g) + 5H2O(l)
Using the bond enthalpies shown in the table, calculate a value for the enthalpy
change, in kJ mol-1, for the complete combustion of 2-methylpropan-2-ol.
(e) 2-methylpropan-2-ol burns in air with a smoky flame. Explain how burning with a smoky
flame affects the values of the experimentally determined enthalpy change of
combustion.
(f) A Data Book value for enthalpy of combustion of 2-methylpropan-2-ol is -2643.8 kJ mol-1.
Give the main reason for the difference between this value and your answer to part (d).

NOTE: Chemsheets Hess’ Law 3

86. Complete Q2 on the Chemsheet on the next page.

87. Complete Q3 on the Chemsheet on the next page.
88. Complete Q4 on the Chemsheet on the next page.
89. Complete Q5 on the Chemsheet on the next page.
90. Complete Q6 on the Chemsheet on the next page.
91. Determine the enthalpy change of the following reaction using
the enthalpy data in the table above. The structure of glucose
is given to the side.
C6H12O6(s) + 6O2(g) → 6CO2(g) + 6H2O(l)

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 Mixed Energetics Practice

92. The table below contains data which are needed to answer the questions.

Name hydrazine Ethane

Formula of Compound N2H4 C 2 H6
Boiling Temperature/K 387 184

Formula and state of compound C2H6(g) CO2(g) H2O(l)

Standard enthalpy of formation (at -85 -394 -286
298K)/ kJ mol-1.

(a) Suggest why hydrazine has a much higher boiling temperature than ethane. [2]
When liquid hydrazine burns in oxygen, it forms nitrogen and water. The standard enthalpy
change for this reaction when one mole of hydrazine forms water in the liquid state is -624
kJ mol-1.
(b) Write a balanced equation for the combustion of hydrazine in oxygen. [1]
(c) Calculate the standard enthalpy of formation of liquid hydrazine. [3]
(d) Write an equation for the complete combustion of ethane. [2]
(e) Use appropriate standard enthalpies of formation to calculate the standard enthalpy of
combustion of ethane. [2]
(f) Suggest one reason why hydrazine is a more suitable fuel than ethane for rocket fuel. [1]

93. Propane is a saturated hydrocarbon with molecular formula C3H8.

(a) Explain the meaning of the term saturated and hydrocarbon. [2]
(b) Propane is sold in small cylinders for use as a fuel in camping stoves. The enthalpy
change of combustion of propane can be measured by experiment using one of these
cylinders.
(c)
A known mass of propane is burned to heat a container of water, and the temperature
rise of the water is measured.
The results of the experiment are shown below.

Mass of propane burned 0.33g

Temperature of water at start 18°0C
Final temperature of water 45°1C
Mass of water in container 100g

(d) How would the mass of propane which was burned be measured? [1]
(e) Calculate the energy transferred in the experiment, using the results above and the
following expression.
(f) Energy transferred (J) = mass × specific heat capacity × temperature change
The specific heat capacity of water is 4.18 J g−1 °C−1. [1]
(g) Calculate the enthalpy change of combustion of propane, ΔHc, in kJ mol−1. Give your
answer to three significant figures and include a sign. [3]
(h) The results of this experiment are inaccurate due to heat loss. Suggest one other source
of error, other than the measurements errors and limitations of the equipment. [1]

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 (i) Another way of calculating the
enthalpy change of combustion
for propane is to use mean bond
enthalpy data.
Complete the equations in the
Hess cycle below. The enthalpy
change of +6490 kJ mol−1 is the
total energy required to break the
bonds in propane and in oxygen.
[1]

(j) Use the data in the table to calculate the enthalpy change, Z, in kJ mol-1. [1]

Bond Mean Bond Enthalpy (kJ mol-1)

C=O 805
H-O 464

(k) Use the cycle in (i), and your answer to (j), to calculate the enthalpy change, ∆Hx, in kJ
mol-1, for the combustion of propane. [1]
(l) The data book value for the standard enthalpy change of combustion, ∆Hx, for
propane is −2219.2 kJ mol−1. This value is more exothermic than that calculated using
mean bond enthalpy data. Give one reason for this.

94. Methane reacts with steam to produce carbon monoxide and hydrogen. The equation for
this process is given adjacent: CH4(g) + H2O(g) → CO(g) + 3H2(g)
The table below shows the standard enthalpy changes of formation.

Bond Mean Bond Enthalpy (kJ mol-1)

CH4 -75.0
H2 O -242
CO -110

(a) Define the term enthalpy of formation. [2]

(b) In ∆fHθ, what are the conditions indicated by the symbol θ? [1]
(c) Write the equation, including state symbols, that represents the standard enthalpy change
of formation of carbon monoxide. [2]
(d) Using the ∆fHθ, values in the table above, calculate the enthalpy change for the reaction
of methane with steam. [3]
(e) Draw a labelled enthalpy level diagram for the reaction of methane with steam including
your answer to (d). [3]
(f) State one important manufacturing process in which hydrogen is used. [1]

95. The equations for the combination of gaseous atoms of carbon and hydrogen to form
methane, CH4, and ethane, C2H6, are shown below.
C(g) + 4H(g) → CH4(g) ∆H = -1652 kJ mol-1
2C(g) + 6H(g) → C2H6(g) ∆H = -2825 kJ mol-1
Use the data to calculate:
(a) The bond enthalpy of a C-H bond. [1]
(b) The bond enthalpy of a C-C bond. [2]

28