2020_Student’s copy Energetics Core_Jteo

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Topic 5: Energetics Core

Exothermic and endothermic reactions
Heat is a form of energy.
Temperature is a measure of the average kinetic energy of particles.
Total energy is conserved in chemical reactions.
Chemical reactions that involve transfer of heat between the system and the surroundings are
described as endothermic or exothermic.
Exothermic Endothermic
surrounding gives out heat to absorb heat from surrounding
surrounding
temperature of increases decreases
solution
Sign negative positive
energy profile
diagram

Products are more stable due to

lower enthalpy.
stability product more stable reactant more stable

bond amount of energy absorbed amount of energy absorbed during bond

making/breaking during bond breaking < amount of breaking > amount of energy released
energy released during bond during bond making
making
Examples combustion thermal decomposition
neutralization photosynthesis
gas liquid  solid solid  liquid  gas

Q 1) Classify the following processes as exothermic or endothermic:

evaporation, crystallization, making magnesium oxide from magnesium and air, making copper oxide
from copper carbonate
Exothermic Endothermic

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Inthinking 5.1 Q4

Two factors that affects the feasibility of a reaction:

Exothermic reactions are more spontaneous as lower enthalpy (more stable)
1. Energetic factor : the more negative the ∆H, the more likely the reaction is feasible
2. Kinetic factors : the lower the activation energy, Ea. the reaction is more feasible.

Standard enthalpy change of reaction (ΔHө)

The standard conditions are: 100 kPa , 298 K
The reactants and products must be in the physical states that are normal for these conditions
Standard enthalpy change is ∆Hϴ and Unit is kJ mol-1

Calorimetry
Calorimetry method - measures temperature change experimentally by using a calorimeter.

Calculation involving calorimetry ( Data Booklet Section 1)

Specific heat capacity of a substance (c) is the energy (J) required to raise the temperature of 1 g of
substance by 1 K ( or 1 0 C)
Or the energy (kJ) required to raise the temperature of 1 kg of substance by 1 K ( or 1 degree C)

Unit for c for water = 4.18 J g-1K-1 or 4.18 kJ kg-1 K-1

The energy required to change the temperature of a substance (q) ∆H (enthalpy change)
q = m x c x ∆T
m = mass of substance that absorbs/release heat can be -ve or +ve and is
c = Specific Heat Capacity fixed but q(heat
∆T = change in temperature change) does not have a
sign and can change
Calorimetry involving solid

2) Aluminium c = 0.90 J g-1 K-1

Find the amount of energy required to raise the temperature of 10 g of Al by 5 º C

3) How much heat energy is required to increase the temperature of 10 g of nickel (specific
heat capacity 440 Jkg-1K-1) from 50oC to 70oC?

4) Copper has a specific heat capacity of 400 Jkg -1K-1. If a 50 g cylinder of copper
absorbs 800 J of energy, by how much will its temperature rise?

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T Pg 191 Q 1 a, b
B
Calorimetry that involves a chemical reaction in an aqueous solution

When 50.0 cm3 of hydrochloric acid solution was added to 50.0 cm 3 of sodium hydroxide
solution in a beaker, heat is given out. This heat is absorbed by the solution and cause the
temperature of the solution to increase.

Total volume = 100 cm3

Mass of 100 cm3 of water = 100g

Assumptions
1. Reaction occurs rapidly so that all heat evolved is used to raise temperature of solution. (means
that all molecules react together at the same time which doesn’t happen)
2. No heat is lost to surrounding
3. Calorimeter does not absorb the heat.
4. Density of water (1g/cm3) is the same as density of solution
5. Specific heat capacity (c) of water is equal to specific heat capacity of solution

5) 50.0 cm3 of 1.00 moldm-3 hydrochloric acid solution was added to 50.0 cm 3 of 1.00
moldm-3 sodium hydroxide solution in a polystyrene beaker. The initial temperature
of both solutions was 16.7oC. After stirring and accounting for heat loss the highest
temperature reached was 23.5oC. Calculate the enthalpy change for this reaction.

HCl and NaOH react exactly. HCl + NaOH  NaCl + H2O

TB Q5a, Q5bi
Inthinking 5.1 Q1

Calorimetry that involving the dissolution of a solid

6) When 8.00 g of ammonium nitrate was completely dissolved in 100 cm 3 of water,

the temperature fell from 19.0oC to 14.5oC.
Calculate the enthalpy of solution of ammonium nitrate. (Mr of NH 4NO3 = 80.06)
( Assume 8g of ammonium nitrate is does not absorb heat.)

Mr of NH4NO3 = 80.06

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T Pg 196 Q6a, b, c
B
Extrapolation of graph

Extrapolation of graph backwards – assume reaction occurs instantaneously.

(highest temperature achieved before heat loss to surrounding)

Actual graph shows heat released is lost to surrounding simultaneously as the reaction progresses.

Assumptions:
Reaction occurs rapidly such that all heat produced is used to raise temperature of water or solution.
The rate of heat loss to environment is constant.

Q7) 50.0 cm3 of 0.200 moldm-3copper(II) sulfate solution was placed in a polystyrene cup.
After two minutes, 1.20 g of powdered zinc was added. The temperature was taken every 30
seconds and the following graph was obtained.

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Calculate the enthalpy change for the reaction taking place. (Assume zinc does not absorb
heat.)
Zn + Cu2+  Zn2+ + Cu

Inthinking 5.1 Q2

Calorimetry involving the combustion of a liquid fuel

Q8) C2H5OH(l) + 3O2(g) à 2CO2(g) + 3H2O(l)

When 0.690 g (0.015 mol) of ethanol was burned, it produced a temperature rise of 13.2 K in
250 g of water. Calculate ∆H for the reaction.

TB pg 191 Q2a, 3 and 4

Inthinking 5.1 Q3

Systematic errors and improvement involving aqueous solutions

Assumption not true How it affects reading or result improvement

1. Reaction does not
occur rapidly
2. Heat is lost to
surrounding
3. Heat is lost to
calorimeter
temperature is lower than expected
Temperature is always lower than
actual
Temperature is always lower than
actual
extrapolate the graph to obtain
max temp rise
Improve insulation to minimise
heat loss- be specific
Take into account of heat
capacity of calorimeter in
calculation

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4. Density of water is less
than density of solution
5. Shc of water not equal
to shc of solution
Heat change is less than expected.
Heat change is less than expected if
shc of water < shc of solution and
vice versa
Use the density of solution to
determine mass of solution
Use the shc of solution to in
calculation.

Systematic errors and improvements for combustion of fuel

Assumption not true How it affects reading or improvement
result
1. Heat is lost to Temperature is always lower Improve insulation to minimise heat loss-
surrounding than actual be specific
2. Heat is lost to Temperature is always lower Take into account of heat capacity of
calorimeter than actual calorimeter in calculation

Other errors during combustion of a liquid fuel

a) Incomplete combustion
b) Evaporation of water and alcohol during combustion.

Hess’s law
The enthalpy change for a reaction that is carried out in a series of steps is equal to the sum of the
enthalpy changes for the individual steps.

Hess law is useful because some enthalpy change cannot be measured directly.

Applying Hess’s Law to find enthalpy change :

Use heat of formation

Use heat of combustion
Born Haber cycle (HL)
Heat of solution (HL)
Entropy change (HL)
Gibbs free energy change (HL)

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Two methods to calculate enthalpy change when a few related enthalpy changes are given.

Algebraic method:

9) Calculate DH for the combustion of methane, CH4:

CH4 + 2O2à CO2 + 2H2O

    Reaction DHØ  

C + 2H2à CH4 (1) -74.80 kJ

C + O2à CO2 (2) -393.50 kJ

H2 + ½ O2à H2O (3) -285.83 kJ

10) Iron and chlorine react directly to form iron(III) chloride, not iron(II) chloride, so that
it is not possible to directly measure the enthalpy change for the following reaction:

Fe(s) + Cl2(g) à FeCl2(s)

The enthalpy changes for the formation of iron(III) chloride from the reaction of
chlorine with iron and with iron(II) chloride are given below.

Use these to calculate the enthalpy change for the reaction of iron with chlorine to
form iron(II) chloride.

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TB Pg 202 Q 7,8,9

Cycle method :

11) Reaction DHө

C + 2H2à CH4 -74.80 kJ (1)

C + O2à CO2 -393.50 kJ (2)
H2 + ½ O2à H2O -285.83 kJ (3)

Find ∆H of the following reaction

CH4 + 2O2à CO2 + 2H2O

TB Page 202 , Q7a– cycle method

Inthinking 5.2 Q4,5

Heat of combustion

Symbo Name, definition & example Calculation

l
Standard enthalpy change of ∆Hө = ∑∆Hөc(reactants) - ∑∆Hөc(products)
combustion
ΔHcө is the enthalpy change when 1 mole of a ( Data Booklet, Section 13)
compound burns completely in oxygen
under standard conditions.

Example: complete combustion of

methane (CH4) in excess oxygen

CH4(g) + 2O2(g)  CO2(g) + 2H2O(l)

Heat of combustion
12) Write balanced equations with state symbols for the combustion of
(a)liquid octane (C8H18),
(b) liquid ethanol (C2H5OH).

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Using Heat of combustions of reactants and products to calculate enthalpy change

∆ Hө = ∑∆Hөc(reactants) - ∑∆Hөc(products)

13) 4C(s) + 5H2(g) à C4H10(g)

Butane Carbon Hydrogen

∆HѲc (kJmol-1) -2876 -393 -286

Calculate the enthalpy of formation of butane.

14) The enthalpies of combustion of ethene, ethane and hydrogen are -1390 kJmol -1,
-1550 kJmol-1 and -286 kJmol-1respectively.

Use these data to calculate the enthalpy of hydrogenation of ethene (the reaction of
ethene with hydrogen to form ethane).

C2H4 + H2  C2H6
∆H Ѳ
c (kJmol ) -1390
-1
-286 -1550

TB Pg 203Q10

Heat of formation
Symbol Name, definition & example Calculation
Standard enthalpy change of formation Δ H = ΣH f(products) - Σ H f(reactants)
ΔHfө is the enthalpy change when 1 mole of a
compound is formed from its elements (Data Booklet, Section 12)
under standard conditions.

Example: Formation of sodium chloride (NaCl)

from its elements

Na(s) + ½Cl2(g)  NaCl(s)

Note that the enthalpy of formation of any

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element in its standard state is zero by

definition.

15) Write balanced equations with state symbols for the formation of
(i) gaseous ethane (C2H6),
(ii) solid aluminium oxide (Al2O3).

16) The standard enthalpy change of formation for hydrogen chloride is the enthalpy
change for:

TB Pg 206Q11b11d

Use heat of formation of reactants and products to calculate enthalpy change:

∆Hө = ∑∆Hөf(products) - ∑∆Hөf(reactants)

17) NH4NO3(s) à N2O(g) + 2H2O(l)

The standard enthalpies of formation of the compounds involved are:

NH4NO3(s) -366 kJmol-1; N2O(g) +82 kJmol-1; H2O(l) -285 kJmol-1
 
Hence calculate the standard enthalpy change of decomposition of ammonium
nitrate.

∆Hө = ∑∆Hөf(products) - ∑∆Hөf(reactants)

18) Hydrazine (N2H4) reacts with oxygen to form nitrogen and steam.

i)Write a balanced chemical equation to represent the reaction of hydrazine with

oxygen to form nitrogen and steam.
N2H4 + O2  N2 + 2H2O

(ii) Calculate the enthalpy change for the above reaction given the following values.
Standard enthalpies of formation of hydrazine and steam are given as +50.6

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kJmol-1 and -241.8 kJmol-1 respectively.

∆Hө = ∑∆Hөf(products) - ∑∆Hөf(reactants)

19) Given the standard enthalpy of formation data:

What is the enthalpy change for the reaction below?
2NaHCO3(s) à Na2CO3(s) + CO2(g) + H2O(l)

20) Write balanced equations for the following reactions and use standard enthalpy of
formation data to calculate the standard enthalpy change associated with each:

(a) Zinc and chlorine reacting to form zinc chloride.

(b) Hydrogen sulfide and sulfur dioxide reacting to form sulfur and water.
(c) Lead(II) nitrate decomposing to lead(II) oxide, nitrogen dioxide and oxygen.

TB Pg 206Q12-14
Inthinking 5.2 Q1-3

Bond enthalpies (Data booklet , Section 11)

It is the energy required to break 1 mole of a particular type of bond in gaseous molecules under
standard conditions (298 K and 100 kPa).

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X – Y (g)  X (g) + Y (g) ∆H = + (endothermic) – bond breaking is endothermic

X (g) + Y (g)  X – Y (g) ∆H = - (exothermic) – bond forming is exothermic

Averages for each type of bond.

These values have been obtained by considering a number of similar compounds. In practice the
energy of a particular bond will vary slightly in different compounds, as it will be affected by
neighbouring atoms.)

Compare calculated bond enthalpy with experimentally measured values

Average bond enthalpies are only valid for gases.
Bond enthalpies may be inaccurate because they do not take into account intermolecular forces.
Enthalpy change of reaction = ∆Hө = ∑ BE(reactants) - ∑ (BE(products)

21) For which of the following equations is the value of ∆H equivalent to the bond
enthalpy for the carbon-oxygen bond in carbon monoxide?

22) Calculating enthalpy change of reactions using bond enthalpies.

Calculate the enthalpy change of hydrogenation of ethene.

23) Calculate the enthalpy change of combustion of hydrazine.

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24) The bond enthalpy of the bond between nitrogen and oxygen in nitrogen dioxide is
305 kJmol-1. If those of the bonds in the oxygen molecule and the nitrogen
molecule are 496 kJmol-1 and 944 kJmol-1 respectively, what will be the enthalpy
change for the reaction?

N2(g) + 2O2(g) à 2NO2(g)

25) Given that the bond enthalpy of the carbon-oxygen bonds in carbon monoxide and
carbon dioxide are 1073 kJmol-1 and 743 kJmol-1 respectively, and that of the bond
in the oxygen molecule is 496 kJmol-1, calculate the enthalpy change for the
combustion of one mole of carbon monoxide.
CO + ½ O2  CO2

26) Given that the enthalpy change for the reaction

N2(g) + 3Cl2(g) à 2NCl3(g)
is +688 kJmol-1, calculate the bond enthalpy of the N – Cl bond, given that the bond
enthalpies in the nitrogen molecule and the chlorine molecule are 944 kJmol -1 and
242 kJmol-1 respectively.

TB Q 15-18
Inthinking 5.3 Q1-4

Compare bond strength of Oxygen and Ozone

Compare bond strength in ozone relative to oxygen in its importance to the atmosphere.
In O2, O-O is double bond, shorter bond length (bond order is 2). Stronger.
In O3, O-O is intermediate between single and double bond, longer bond length. (Bond order is 1.5). so
has weaker bond.

O2 à 2O
To break O-O bond in O2, λ is shorter à higher energy absorbed

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O3 à O + O2 , λ is longer à lower energy is absorbed.

O-O in O2 is stronger than O-O in O3

O2 O3
Bond order 2 1.5
Bond strength stronger weaker
Bond length shorter longer
Energy required to break bond Shorter wavelength Longer wavelength

Importance of ozone in atmosphere

Ozone in atmosphere is important in protecting the surface of earth from allowing too much UV
radiation to reach the earth.
Excessive exposure of UV radiation can cause skin cancer.

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