AS Chemistry Unit1 Ch 2 Energetics

Topic 1.4

Energetics

1.

demonstrate an understanding of the term enthalpy change, H

2.

construct simple enthalpy level diagrams showing the enthalpy change

3.

recall the sign of H for exothermic and endothermic reactions,

eg illustrated by the use of exo- and endothermic reactions in hot and cold packs

4.

recall the definition of standard enthalpy changes of reaction, formation, combustion, neutralization and
atomization and use experimental data to calculate energy transferred in a reaction and hence the enthalpy
change of the reaction.
This will be limited to experiments where substances are mixed in an insulated container, and combustion
experiments

5.

recall Hesss Law and apply it to calculating enthalpy changes of reaction from data provided, selected from a
table of data or obtained from experiments and understand why standard data is necessary to carry out
calculations of this type

6.

evaluate the results obtained from experiments using the expression:

energy transferred in joules = mass x specific heat capacity x temperature change
and comment on sources of error and assumptions made in the experiments.
The following types of experiments should be performed:
i experiments in which substances are mixed in an insulated container and the temperature rise measured
ii simple enthalpy of combustion experiments using, eg a series of alcohols in a spirit burner
iii plan and carry out an experiment where the enthalpy change cannot be measured directly, eg the enthalpy
change for the decomposition of calcium carbonate using the enthalpy changes of reaction of calcium
carbonate and calcium oxide with hydrochloric acid

7.

demonstrate an understanding of the terms bond enthalpy and mean bond enthalpy, and use bond enthalpies in
Hess cycle calculations and recognize their limitations.
Understand that bond enthalpy data gives some indication about which bond will break first in a reaction, how
easy or difficult it is and therefore how rapidly a reaction will take place at room temperature

AS Chemistry Unit1 Ch 2 Energetics

2.1 Thermochemistry
Thermodynamics - study of the exchange of heat, energy and work between a system and its surroundings

System: the reaction mixture, containing reactants, products and solvents

Surroundings: everything outside the system

For example, in the reaction of HCl and NaOH

System: acid, alkali, salt and water
Surroundings: test tubes, air in the room, the entire rest of the universe
First Law of thermodynamics (or Law of conservation of energy) states that energy may be converted from one form
to another, but it is never created nor destroyed.

In a chemical reaction, the most usual form of energy exchanged is heat energy, which causes temperature
changes. The relationship between energy and temperature is calculated by
energy transferred in joules = mass x specific heat capacity x temperature change

2.2 Enthalpy change

The enthalpy of a substance, sometimes called its heat content, is an indication of the total energy content of the
substance at constant pressure that can be converted into heat.

The absolute enthalpy (H) value of a substance depends on

i. potential energy inherent in the electrical and nuclear interactions of the constituent particles (chemical energy),
ii. kinetic energy possessed by the atoms and sub-atomic particles (kinetic energy)
The absolute enthalpy value (H) of a substance cannot be found directly since it is still not possible to measure all the
interaction between the sub-atomic particles in an atom. Instead, we can measure the enthalpy change (H) of a
system through experiments.

In a chemical change. the enthalpy of the products is different from the enthalpy of the reactants

Enthalpy change, H, is the heat transferred at constant pressure by a chemical reaction. The units for H is kJ mol-1
Exothermic reaction

Endothermic reaction

A reaction in which heat is released

A reaction in which heat is absorbed from

to the surroundings

the surroundings

Enthalpy of products and

Hp < Hr

Hp>Hr

reactants

Enthalpy is converted into heat

Heat energy is converted into enthalpy

energy and released to the

(energy being stored in the products as

surroundings

chemical energy)

Negative (loss in enthalpy) H = -

Positive (gain in enthalpy) H = +

Rises (energy releases from reacting

Falls (the reacting chemicals absorb energy

Definition

Enthalpy change
H = Hp Hr
Temperature of surrounding

chemicals to the solution)

from the solution)

In terms of bond forming

Energy absorbed from surroundings

Energy absorbed from surroundings for

and breaking

for breaking bonds in the reactants is

breaking bonds in the reactants is greater

smaller than the energy released to

than the energy released to the surrounding

the surrounding during bond

during bond formation of products

Enthalpy level diagram

formation of products
Examples

(1) combustion

(1) cracking

(2) precipitation

(2) melting of solid

(3) displacement

(3) boiling and evaporation of liquid

(4) neutralization
2.3 Standard Enthalpy changes
Is there any difference between the enthalpy changes of the following two reactions?
CH4(g) + 1O2(g) CO(g) + 2H2O(l)

CH4(g) + 1O2(g) CO(g) + 2H2O(g)

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For basis of comparison, enthalpy changes are stated under standard conditions
(1) pressure: 1 atm
(2) temperature: 25oC, 298K
(3) substance involved must be in their normal physical states under standard conditions
eg: NaCl(s), H2(g), H2O(l), C(graphite)
(4) when solution is involved: concentration of solution: 1M
Standard enthalpy change of formation (Hof)

()

The standard enthalpy change of formation of a compound is the enthalpy change when 1 mole of the compound is
formed from its element in their standard states under standard conditions (at 25oC, 1 atm).
According to the definition, standard enthalpy change of formation of an element, e.g. oxygen, is the enthalpy change
associated with the following change, O2(g) O2(g). Actually, there is no change, the standard enthalpy change of
formation of an element is always zero.

AS Chemistry Unit1 Ch 2 Energetics

Example

Explain the meaning Hof [Na2CO3(s)] = -1130.7 kJ mol-1.

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Complete the table.

1.

Hof [CH4(g)] = -74.8 kJ mol-1

2.

Hof [H2O(l)] = -286 kJ mol-1

3. N2(g) N2(g)
4.

Hof [NO(g)] = +90 kJ mol-1

5.

Ho = 5 Hof [NO(g)] = + 450 kJ mol-1

6.

Hof [KMnO4(s)] = -813 kJ mol-1

7. C(graphite) + 2H2(g) + O2(g) CH3OH(l)

8. 2C(graphite) + 4H2(g) + O2(g) 2CH3OH(l)

= -239 kJ mol-1
Ho =
Hof [S8(s)] = 0 kJ mol-1

9.
10.

Hof [S8(g)] = + 103kJ mol-1

11.

Hof [S(g)] = + 279kJ mol-1

12. If Hof [H2O(l)] = -286 kJ mol-1, then Ho of 2H2O(l) 2H2(g) + O2(g) =

kJ mol-1

Standard enthalpy of combustion (Hoc) ()

The standard enthalpy change of combustion is the enthalpy change when 1 mole of a substance is completely burnt in
oxygen under standard conditions (at 25oC, 1 atm).
e.g. S(s) + O2(g) SO2(g)

Hoc [S(s)] = -297 kJmol-1

Example
1. Explain the meaning Hoc [C2H4(g)] = -1411 kJ mol-1.
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2. Which of the following represent the standard enthalpy change of combustion of graphite?
A. C(diamond) + O2(g) CO2(g)

[C(graphite)] = -393.5 kJmol-1

B. C(diamond) + O2(g) CO2(g)

[C(diamond)] = -393.5 kJmol-1

C. C(graphite) + O2(g) CO (g)

[C(graphite)] = -393.5 kJmol-1

D. C(graphite) + O2(g) CO(g)

[C(graphite)] = -393.5 kJmol-1

3. Given that the standard enthalpy change of combustion of ethanol, ethane and hydrogen are -1367.3 kJmol-1,
-1560kJmol-1 and 285.5kJmol-1 respectively. Write thermochemical equations to represent these data.
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AS Chemistry Unit1 Ch 2 Energetics

4. The molar enthalpy change of combustion of some alkanes is given below in kJ mol-1.
C3H8
2219

C4H10

C5H12

2877

C6H14

3509

4163

Another alkane was found to have an enthalpy change of combustion of -6125kJ mol-. The alkane is
A. C7H16

B. C8H18

C. C9H20

D. C10H22

Standard enthalpy of atomization Hoat (: energy must be absorbed to pull the atoms apart)
Standard enthalpy of atomization is the enthalpy change when 1 mole of gaseous atoms is formed from an element in
its standard state.
i. C(graphite) C(g)

Hoat [C(graphite)]= +715 kJmol-1

ii. H2(g) H(g)

Hoat [H2(g)]= +218 kJmol-1

1.

Hoat [O2(g)] = +249.2 kJ mol-1

2.

Hoat [Na(s)] = +108 kJ mol-1

3. Br2(l) Br(g)
Ho = 4 Hoat [H2(g)]= +856 kJmol

4.

5. The enthalpy change of atomization of iodine is the value of H for the process
A. I2(s) I2(g)

B. I2(s) 2I(g)

C. I2(g) 2I(g)

D. I2(s) I(g)

Standard enthalpy of neutralization Honeut ()

It is the heat change when an acid and a base react to form 1 mole of water under standard condition.
e.g. HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)

Honeut = -57.1 kJmol-1

H+(aq) + OH-(aq) H2O(l)

Honeut = -57.1 kJmol-1

CH3COOH(aq) + NaOH(aq) CH3COONa(aq) + H2O(l)

Honeut= -55.2 kJmol-1

Neutralization of a ___________ acid is found to be less exothermic than that of a ______________ acid because
energy is required to ___________ the molecules of ___________

acid first.

Standard enthalpy of reaction Horxn

Standard enthalpy change of reaction (H

o
rxn)

is the energy transferred when the number of moles of reactants shown

in the equation react under standard condition..

e.g. 4NH3(g) + 3O2(g) 2N2(g) + 6H2O(l)

Horxn = -1260 kJmol-1

NH3(g) + 3/4O2(g) 1/2N2(g) +3/2H2O(l)

Horxn =

kJmol-1

2N2(g) + 6H2O(l) 4NH3(g) + 3O2(g)

Horxn =

kJmol-1

Class Practice
Write balanced equations for reactions that have the following enthalpy changes:
enthalpy of combustion of methane
enthalpy of formation of water
enthalpy of combustion of hydrogen
twice the enthalpy of formation of hydrogen sulfide
enthalpy of atomisation of chlorine
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AS Chemistry Unit1 Ch 2 Energetics

2.4 Hess Law
Not Hof of all compounds can be determined directly. This is because
(a) not all compounds can be synthesized directly from its constituent elements at standard state.

sucrose (C12H22O11) cannot be formed by direct combination of 12C(graphite), 11H2(g) and 5O2(g)

(b) formation of side products

4Na(s) + O2(g) 2Na2O(s), 2Na(s) + O2(g) Na2O2(s)

It is difficult to determine the enthalpy change of C(s) + O2(g) CO(g) since some carbon dioxide is always
formed in the reaction.

For the Hof of the compound which cannot be determined directly, Hesss Law can be used to determine its value.
Hesss Law
The total enthalpy change for a reaction is independent of the route taken for the reaction.
Example
Copper(II) sulfate exists as blue hydrated crystals and white anhydrous crystals. The enthalpy changes of solution for
these two substances may be represented by the following simplified equations:
CuSO4.5H2O(s) + aq CuSO4(aq)

H1 = +11.5 kJ mol1

blue
CuSO4(s) + aq CuSO4(aq)

H2 = 66.1 kJ mol1

white
(a) (i) Fill in the box and add labelled arrows to complete the Hess cycle to enable you to calculate Hreaction. (3)

(ii) Calculate a value for the enthalpy change Hreaction. (2)

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(b) Suggest why it is not possible to directly measure the enthalpy change for the conversion of the blue hydrated
copper(II) sulfate crystals into the white anhydrous crystals. (1)
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AS Chemistry Unit1 Ch 2 Energetics

Applying Hess's Law using enthalpy of formation data
Steps:
1. Write the balance equation interested at the top
2. Write no of mole of each constituent element of
the reactants and products at the bottom.
3. Complete the cycle by adding arrows, pointing
from the constituent elements to the reactants and
products.
4. Label the arrows with
H[reaction] =

Hfo[reactants]

Hfo[products]

Hof[chemical] appropriate no of mole

Example
1. Given that the standard enthalpy change of formation of SO2(g) and SO3(g) is -297kJ mol-1 -441kJ mol-1
respectively. Find the standard enthalpy change of contact process.

2. Find the standard enthalpy of reaction for Fe2O3(s) + 3CO (g) 2Fe(s) + 3CO2 at 25oC by drawing a Hess cycle.
Given: Hof [Fe2O3(s)] = -822.2kJ mol-1, Hof [CO(g)]= -110.5kJ mol-1 and

Hof [CO2(g)] = -393.5kJ mol-1

3. Hydrogen peroxide is a powerful oxidizing which decomposes slowly to form water and oxygen. Find the
standard enthalpy of this reaction. Given that Hof [H2O2(l)] = -187.8 kJ mol-1, Hof [H2O(l)]= -285.8 kJ mol-1.

AS Chemistry Unit1 Ch 2 Energetics

Applying Hess's Law using enthalpy of combustion data
Steps:
1. Write the balance equation interested at the top
2. Write the combustion products of the reactants and
products at the bottom.
3. Complete the cycle by adding arrows, pointing
from the reactants and products to their combustion
products.
4. Label the arrows with
H[reaction] = Hco[reactants]

Hco[products]

no of mole of oxygen needed for that combustion

Hoc[chemical] appropriate no of mole

1. Use the standard enthalpy changes of combustion, Hc, given in the table below to find the standard enthalpy
change of formation for ethanoic acid, CH3COOH, in kJ mol1.
Substance

Hc / kJ mol

C(s, graphite)

H2(g)

CH3COOH(l)

394

286

870

2. Calculate the enthalpy change of formation of ethanol in kJ mol1.

Substance

C(s, graphite)

H2(g)

C2H5OH(l)

Hc/ kJ mol1

394

286

1370

3. Hex-1-ene can be converted to hexane in the following reaction.C6H12(l) + H2(g) C6H14(l)

(i) What catalyst is used in this reaction? .................................................................
(ii) Find the enthalpy change of this reaction Hreaction from the following data of enthalpy changes of combustion.
Substance

Hc / kJ mol

Hex-1-ene, C6H12

Hydrogen, H2

Hexane, C6H14

4003

286

4163

AS Chemistry Unit1 Ch 2 Energetics

Class Practice/HW
1. Calculate the heat of formation of ethene given that its heat of combustion is -1305 kJ mol-1, the heat of formation
of CO2 is -393.4 kJ mol-1 and the heat of formation of water is -285.5 kJ mol-1.
2. Given that 2CO(g) + 2NO(g) 2CO2(g) + N2(g)

[-52.8kJ mol-1]

H= -746.8kJ mol-1

Calculate the standard enthalpy change of formation of nitrogen monoxide if

Hof [CO(g)]= -111kJ mol-1 and

Hof [CO2(g)] = -394kJ mol-1

[90.4kJ mol-1]

3. Calculate the standard enthalpy change of formation of ethane. Draw a Hesss Law cycle as part of your answer.
[-84kJ mol-1]

Substance

C(s, graphite)

H2(g)

Ethane(g)

Hc/ kJ mol1

393

286

1560

4. Given the following enthalpies:

Hof [MgCO3(s)]= -1113kJ mol-1
Hof [CO2(s)] = -394kJ mol-1
Hof [MgO(s)]= -602kJ mol-1
Calculate the enthalpy for the thermal decomposition of magnesium carbonate. [+117kJ mol-1]
5. The standard enthalpy change of formation of CO2(g) is 394 kJ mol1 and that of H2O(l) is 286 kJ mol1.
Draw a Hess cycle to calculate Hof [C5H12(g)] if Hc [pentane(g)] = 3509 kJ mol1.

[-177kJ mol-1]

6. Methylhydrazine (CH3NHNH2) and dinitrogen tetraoxide (N2O4) are fuels of Apolo 11 which landed the first man
on moon on 1969. They are expected to react very exothermically according to the following reaction:
CH3NHNH2(l) + N2O4(l) CO2(g) + H2O(l) + N2(g)
(a) Balance the equation.
(b) The standard enthalpy changes of formation are:
The standard enthalpy changes of combustion are:

CH3NHNH2(l) = +53kJ mol-1

N2O4(l) = -20kJ mol-1

C(s, graphite) = -393 kJ mol-1

H2(g) = -286 kJ mol-1

Calculate the enthalpy change for the reaction between CH3NHNH2(l) and N2O4(l).

[-5116kJ mol-1]

2.5 Experimental Determination of enthalpy changes

Simple calorimetric method is used to determine enthalpy change of reaction and enthalpy change of neutralization.

Basic steps of simple calorimetric methods:

(1) Mixing known mass of reactants in an insulated container called calorimeter**
(2) measure the initial temperature and final temperature
(3) calculate the heat energy transferred in joules = mass specific heat capacity temperature change
**Example of calorimeter is a coffee-cup calorimeter, which is two expanded polystyrene cup, one inside
the other, with a lid. It is an excellent insulator of heat and also has low specific heat capacity.
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AS Chemistry Unit1 Ch 2 Energetics

Example
In an experiment performed to measure the enthalpy change for the reaction Cu2+ (aq) + Zn (s) Cu (s) + Zn2+ (aq)
3g of zinc powder (an excess) was added to 30.0 cm3 of copper(II) sulfate solution of concentration 1.00 mol dm3.
The temperature rise of the mixture was 47.6 K.
Assuming that the heat capacity of the solution is 4.2 J K1 g1, the enthalpy change for the reaction is given by
A H = - (30 4.2 47.6)

B H = - (33 4.2 47.6)

0.03

C H = - (30 4.2 47.6) 0.03

Jun 2011

D H = - (33 4.2 47.6) 0.03

Unit 1 Question 18c (Design experiment to measure the enthalpy change of the reaction)

CuSO4.5H2O(s) + aq
(i)

0.03

CuSO4(aq)

H1 = +11.5 kJ mol1

Describe briefly the experimental procedure that you would use to obtain the data necessary to calculate H1,
given a known mass of hydrated copper(II) sulfate crystals, CuSO4.5H2O(s).

You should state the apparatus that you would use and any measurements that you would make.
You are not required to calculate the amounts of substances or to explain how you would use the data obtained. (4)
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(ii)

List three possible errors which do not relate to the quality of the apparatus or chemicals used or possible
mistakes in carrying out the procedure. (3)

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Graphical method for obtaining T

To be more accurate, instead of just measuring the initial and final temperature, we can measure the temperature
of the reactants along time.

A graph is then plotted and extrapolated () to determine a more accurate value of T.

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AS Chemistry Unit1 Ch 2 Energetics

Two possible forms of graph you encountered: heat of reaction / heat of neutralization + experiment steps
(1) Enthalpy change of reaction (eg.metal displacement;
CO32- + H+)

Take Zn and CuSO4(aq) as an example.

Known volume and molarity of CuSO4 is added to a

polystyrene cup.

The temperature of CuSO4(aq) was measured every

minute for 3 minutes.

After exactly 3.5 minutes, solid zinc was added and

the mixture was stirred.

The temperature of the mixture was then taken every

minute for another 8 minutes. Extrapolates the two
lines formed.

Measure the difference between these two lines

at the time when zinc is added.

(2) For neutralization titration,

Measure the temperature of alkali in the conical flask.

Add acid from burette with 2cm3 each time, stirring

and measuring the temperature after each addition.

Continue to add alkali for a few times after reaching

the maximum temperature. (end point)

Extrapolates the line of rising temperature and falling

temperature until they intersect. This is the maximum
temperature reached in the neutralization reaction.

The point at which the two extrapolated lines meet

corresponds to the volume of titre required for
neutralization.

Read off this volume from the graph.

Possible source of errors of calorimetric methods

(1) There was heat loss to the surroundings
(2) The specific heat capacities of the expanded polystyrene cup and the thermometer were not taken into account
(3) The specific heat capacity of the reaction mixture was not the same as that of water.
(4) The density of the reaction mixture was not the same as that of water.
(5) The experiment was not done under standard conditions.
Error (3)and Error (4) are not suitable for enthalpy change of combustion since water is used as the medium for
absorbing heat directly. So its density is really 1g/cm3 and c = 4.18J/g/K.
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AS Chemistry Unit1 Ch 2 Energetics

Jan 2011

Unit 1 Question 19 ( Determination of enthalpy change of combustion)

The enthalpy change of combustion of ethanol was determined using the apparatus shown below. In the experiment,
the temperature increase of the water in the beaker is measured when a known mass of the ethanol is burned.
(a) The results of the experiment are summarised in the table below.
Mass of water in the beaker

250.00 g

Mass of spirit burner + contents (initial)

63.21 g

Mass of spirit burner + contents (final)

62.47 g

Temperature of water (initial)

21.0 C

Temperature of water (final)

31.5 C

(i) Calculate the heat energy produced by the combustion of the alcohol using the equation
heat energy produced (J) = mass of water 4.18 temperature change (1)

(ii) Calculate the number of moles of ethanol burned in this experiment (the formula of ethanol is C2H5OH). (3)

(iii) Use the equation below to calculate the enthalpy change of combustion of ethanol in kJ mol1. Give the value an
appropriate sign. (2)

(b) The data book value for the enthalpy change of combustion of ethanol is 1370 kJ mol1.
(i) Calculate the percentage error in the value calculated in (a)(iii) in comparison with the data book value. (1)

(ii) List three ways in which the design of the experiment causes the results to be so different from the data book
value. (You should be specific but detailed explanations are not required.) (3)
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AS Chemistry Unit1 Ch 2 Energetics

Jan 2012 Unit 3 Question 3 ( Determination of enthalpy change of reaction)
Magnesium carbonate reacts with dilute nitric acid :

MgCO3(s) + 2HNO3(aq) Mg(NO3)2(aq) + CO2(g) + H2O(l)

The enthalpy change for this reaction can be determined as follows:

Procedure
1. Weigh 3.50 g of finely powdered magnesium carbonate.
2. Transfer 50.0 cm3 of 2.00 mol dm3 nitric acid into a polystyrene cup and record the temperature of the acid.
3. Add the magnesium carbonate to the nitric acid.
4. Stir the mixture and record the maximum temperature reached.
Results
Temperature of nitric acid before addition of magnesium carbonate

21.0 oC

Final temperature of solution

29.7 oC

(a) Explain why the magnesium carbonate used in this experiment should be finely powdered rather than in lumps. (1)
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(b) (i) Calculate the number of moles of magnesium carbonate in 3.50 g. (1)

(ii) The volume of dilute nitric acid used contained 0.100 mol of HNO3. Suggest why this amount is suitable.(1)
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(c) (i) Calculate the heat energy transferred, in joules, in this reaction between magnesium carbonate and nitric acid.

(ii) Calculate the enthalpy change, H, for the reaction of one mole of magnesium carbonate with nitric acid. Your
answer should be in units of kJ mol1, expressed to three significant figures, and include a sign. (2)

(d) (i) The nitric acid for this experiment could be measured using either a pipette or a measuring cylinder. Give one
practical advantage of using each piece of apparatus. (2)
Pipette ..................................................................................................................................................................................
Measuring cylinder ..............................................................................................................................................................
(ii) The total error in measuring the mass of the magnesium carbonate was 0.01 g.
Calculate the percentage error in the weighing. (1)

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AS Chemistry Unit1 Ch 2 Energetics

(e) State and explain the effect, if any, on the calculated enthalpy change, H, if
(i) a copper calorimeter were used instead of the polystyrene cup. (2)
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(ii) 3.50 g of damp magnesium carbonate were used. (2)
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*(f) The experiment was repeated with a change in the procedure. The temperature of the dilute nitric acid was
measured every minute for three minutes. After exactly three and a half minutes, the magnesium carbonate was added
and the mixture was stirred. The temperature of the mixture was then taken every minute for another six minutes.
A graph of the temperature readings against time using this procedure is shown below.

*(i) Use this graph to calculate the maximum temperature change. Show your working on the graph. (2)
Maximum temperature change = ............................................................................o C
*(ii) Why does this method give a more accurate result than the original procedure? (1)
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AS Chemistry Unit1 Ch 2 Energetics

June 2011

Unit 3

Question 3 ( Graphical determination of enthalpy change of neutralization)

A titration was carried out in order to investigate the neutralization reaction between NaOH and HCl.
Procedure : 1. Using a pipette, transfer 50.0 cm3 of sodium hydroxide solution, concentration 1.00 mol dm3, to a
polystyrene cup. Allow to stand for a few minutes.
2. Record the temperature of the solution.
3. From a burette, add 5.00 cm3 of dilute hydrochloric acid to the solution in the cup.
4. Stir the mixture with the thermometer and record the temperature.
5. Add successive 5.00 cm3 portions of hydrochloric acid, stirring the mixture and recording the
temperature after each addition.
6. Continue adding hydrochloric acid until a total of 50.00 cm3 of the acid has been added.
Results
Volume of HCl added / cm3

0.00

5.00

10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00

50.00

Temperature / C

22.2

23.7

25.1

26.0

26.6

28.0

29.5

29.2

28.4

27.6

26.8

A graph of the temperature (y-axis) against the volume of hydrochloric acid added (x-axis) enables the maximum
temperature rise and the volume of acid required for neutralization to be determined.
From this information it is possible to calculate (a) the concentration of the hydrochloric acid

(b) the enthalpy

change for the reaction.

(a) (i) Plot a graph of temperature against volume of acid added on the axes below. Draw two straight lines on your
graph and extrapolate the lines until they intersect.

15

AS Chemistry Unit1 Ch 2 Energetics

(ii) Use the extrapolated lines on your graph to read off the maximum temperature reached in the neutralization. (2)
Maximum temperature ................................................oC
(iii) The point at which the two extrapolated lines meet corresponds to the volume of hydrochloric acid required for
neutralization. Read off this volume from your graph. (1)
Volume of hydrochloric acid ...................................................cm3
(iv) Calculate the number of moles of sodium hydroxide in 50.0 cm3 of a 1.00 mol dm3 solution. (1)

(v) HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)

Use this equation and your answers to (iii) and (iv) to calculate the molarity of the hydrochloric acid (2)

(b) (i) Use your graph and answer to (a)(ii) to calculate the maximum temperature change, T, for the reaction. (1)
T = ................................................ C

(ii) Use your value for the temperature rise, T, to calculate the heat energy produced when 50.0 cm3 of sodium
hydroxide is exactly neutralized by the volume of hydrochloric acid you obtained in (a)(iii).
Use the expression energy = total mass of solution specific heat capacity of solution temperature rise
[Assume the specific heat capacity of the solution to be 4.2 J g1 C1 and the density of the solution to be 1.0 g cm3]
(2)

(iii) Use your answers to (a)(iv) and (b)(ii) to calculate the enthalpy change, in kJ mol1, for this reaction.
Give your answer to two significant figures and include a sign. (3)H = ................................................. kJ mol1

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AS Chemistry Unit1 Ch 2 Energetics

Jan 2010

Unit 3 Question 3d ( Determination of enthalpy change of neutralization)

The standard enthalpy change for the reaction of calcium hydroxide with hydrochloric acid was found by reacting
0.0100 mol of solid calcium hydroxide with 50.0 cm3 of a 1.00 mol dm3 solution of hydrochloric acid (an excess), in
a polystyrene cup. The temperature rose from 21.2 C to 26.7 C.
(i)

Calculate the energy, in joules, transferred in the reaction. Use the expression

Energy transferred = mass specific heat capacity temperature change

[Assume density of solution = 1.0 g cm3, specific heat capacity of solution = 4.18 J g1C 1]

(1)

(ii)

Calculate the standard enthalpy change, H, for the reaction. Include a sign and units in your answer. (2)

(iii)

Calculate the percentage error in the temperature change caused by an uncertainty of 0.1C in each
thermometer reading. (1)

(iv)

The experiment was repeated using 50.0 cm3 of a 1.00 mol dm3 solution of nitric acid instead of the
hydrochloric acid. Explain why the temperature change was the same in both experiments. (1)

..............................................................................................................................................................................................
..............................................................................................................................................................................................
..............................................................................................................................................................................................
(v)

The experiment was repeated again using 25 cm3 of 2.00 mol dm3 hydrochloric acid. Predict the temperature
change in this experiment. (1)

..............................................................................................................................................................................................
..............................................................................................................................................................................................
..............................................................................................................................................................................................
(vi)

Which of the experiments in (iv) and (v) gave the least error in the temperature change? Justify your answer.
(1)

..............................................................................................................................................................................................
..............................................................................................................................................................................................
..............................................................................................................................................................................................
17

AS Chemistry Unit1 Ch 2 Energetics

2.6 Bond enthalpy
Bond enthalpy of a particular bond in a specific compound is the energy required to break one mole of this covalent
bond in gaseous state.
H2(g) 2H(g)

H = +436kJ mol-1

HCl(g) H(g) + Cl(g)

E(H H) = +436kJ mol-1

H = + 432 kJ mol-1

E(H Cl) = +432kJ mol-1

Example
Explain and write equation: bond enthalpy of chlorine is +242kJ mol-1
..............................................................................................................................................................................................
..............................................................................................................................................................................................
Example
Find the C H bond enthalpy in methane if CH4(g) C(g) + 4H(g)

H = 1663.5kJ mol-1

This process involves the breaking of four C H bond. So the C H bond enthalpy in methane is 1663.4 / 4 =
+415kJ mol-1. Symbol: E( C H) = +415kJ mol-1
Mean bond enthalpy

The same type of bond in different compound can have slightly different bond enthalpies depending on the
environment of the bond within a particular molecule.

For example:
(1) Consider CH4 and CH3Cl. The Cl atom in CH3Cl affects the environment of the C H bonds. Thus, C H bonds
have different strengths and different bond enthalpies value in different compound.
(2) The C H bond enthalpy in methane will be slightly different from the value of the C H bond in ethanol.
The mean bond enthalpy of a particular kind of bond is the average value of the bond enthalpy for that bond in a wide
range of different compounds.
Example
1. If the mean C - H bond enthalpy is +x, which of the

2. Which equation represents the reaction for which the

following represents a process with an enthalpy

enthalpy change, H, is the mean bond enthalpy of

change of +4x?

the CH bond?

A C(g) + 4H(g) CH4(g)

A CH4(g) C(g) + H(g)

B CH4(g) C(g) + 4H(g)

B CH4(g) C(s) + 2H2(g)

C CH4(g) C(s, graphite) + 2H2(g)

D C(s, graphite) + 2H2(g) CH4(g)

C CH4(g) C(g) + 4H(g)

D CH4(g) C(g) + 2H2(g)

3. For which of the following reactions is the enthalpy

4. The enthalpy change for the reaction

change equal to the bond enthalpy of HI?

CH4(g) C(g) + 4H(g)

A HI(g) H2(g) + I2(s)

is +1648 kJ mol1. Hence the mean bond enthalpy for the

B HI(g) H2(g) + I2(g)

CH bond is

C HI(g) H(g) + I(g)

A +329.6 kJ mol1

C +1648 kJ mol1

D HI(g) H+(g) + I(g)

B +412.0 kJ mol1

D +6592 kJ mol1
18

5. This question is about some standard enthalpy changes, H

A enthalpy of reaction

B enthalpy of combustion

(a) Which enthalpy change is represented by p?

CH4 (g) CH3(g) + H(g)

H = p

C mean bond enthalpy

D bond enthalpy

(b) Which enthalpy change is represented by q?

CH4(g) C(g) + 4H(g)

H = 4q

Bond enthalpies can be used in the calculation in Hess Cycle.

Given that E (C H) = 413 kJ mol-1, E (C O) = 358 kJ mol-1, E (H O) = 463 kJ mol-1.
Hoat [C(graphite)]= +716.7 kJmol-1

Hoat [H2(g)]= +218 kJmol-1

Hoat [O2(g)] = +249.2 kJ mol-1

Find the enthalpy change of formation of methanol by drawing a Hess Cycle.

[-222 kJ mol1-]

Use of bond enthalpy

(1) Compare the strength of different bonds. It indicates the covalent bond strength. Bonds with small bond enthalpies
are weak and break first. In contrast, strong bonds have high bond enthalpies. Triple bond has a high enthalpy.
E(H H)= +436kJ mol-1 , E(Cl Cl) = +242kJ mol-1. Thus Cl Cl bond is a weaker bond and will break first in the
reaction.
(2) Indicate how fast a reaction might be. Low bond enthalpies indicate that a reaction will take place quickly.
(3) Estimate the enthalpy change in chemical reactions involving covalent molecules.
Example
Calculate the standard enthalpy change of combustion of ethanol according to the data given.
(1) The standard enthalpy change of formation of CO2(g) is 394 kJ mol1 and that of H2O(l) is 286 kJ mol1.
Draw a Hess cycle to calculate Hoc [C2H5OH(l)] if Hf [C2H5OH(l)] = 278kJ mol1.

19

(2) 0.388g of ethanol is burnt in a spirit burner. 100cm3 of water is used to absorb the heat released. The
temperature change of the water is + 24.6oC.

(3) E (C-C) = 347 kJ mol1., E(C-H) = 413 kJ mol1., E(C-O) = 336 kJ mol1., E (C=O) = 805 kJ mol1.,
E (H-O) = 464 kJ mol1., E (O=O) = 498 kJ mol1.

Summary
Enthalpy change of a reaction can be determined by
(1) Using standard enthalpy change data and calculate through Hess Cycle
(2) Doing experiment ( Energy transfer = mcT)
(3) Using mean bond enthalpies (

Value of (2.experiment value) different from (1.value in data booklet):

Mainly due to experimental error such as
a) heat loss to the surroundings
b) specific heat capacity of apparatus not considered
c) experiment not done under standard conditions

Value of (3. by mean bond enthalpies) different form (2. experiment value) :
a) Mean bond enthalpies values are used for calculation. It is only an average value from wide range of compounds.
There are variations in the strength of one particular bond in different molecules.
b) Bond enthalpies values only apply to substances in the gaseous state. Not all the reactants or products of the
reaction are in the gaseous state.

20

HW
1. Calculate the heat of formation of ethene given that its heat of combustion is -1305 kJ mol-1, the heat of formation
of CO2 is -393.4 kJ mol-1 and the heat of formation of water is -285.5 kJ mol-1.
2. Given that 2CO(g) + 2NO(g) 2CO2(g) + N2(g)

[-52.8kJ mol-1]

H= -746.8kJ mol-1

Calculate the standard enthalpy change of formation of nitrogen monoxide if

Hof [CO(g)]= -111kJ mol-1 and

Hof [CO2(g)] = -394kJ mol-1

[90.4kJ mol-1]

3. Calculate the standard enthalpy change of formation of ethane. Draw a Hesss Law cycle as part of your answer.
[-84kJ mol-1]

Substance

Hc / kJ mol

C(s, graphite)

H2(g)

Ethane(g)

393

286

1560

4. Given the following enthalpies:

Hof [MgCO3(g)]= -1113kJ mol-1
Hof [CO2(g)] = -394kJ mol-1
Hof [MgO(g)]= -602kJ mol-1
Calculate the enthalpy for the thermal decomposition of magnesium carbonate. [+117kJ mol -1]
5. The standard enthalpy change of formation of CO2(g) is 394 kJ mol1 and that of H2O(l) is 286 kJ mol1.
Draw a Hess cycle to calculate Hof [C5H12(g)] if Hc [pentane(g)] = 3509 kJ mol1.

[-177kJ mol-1]

6. Methylhydrazine (CH3NHNH2) and dinitrogen tetraoxide (N2O4) are fuels of Apolo 11 which landed the first man
on moon on 1969. They are expected to react very exothermically according to the following reaction:
CH3NHNH2(l) + N2O4(l) CO2(g) + H2O(l) + N2(g)
(a) Balance the equation.
(b) The standard enthalpy changes of formation are:
The standard enthalpy changes of combustion are:

CH3NHNH2(l) = +53kJ mol-1

N2O4(l) = -20kJ mol-1

C(s, graphite) = -393 kJ mol-1

H2(g) = -286 kJ mol-1

Calculate the enthalpy change for the reaction between CH3NHNH2(l) and N2O4(l).

[-5116kJ mol-1]

21