Introduction

Chemistry involves the study of reactions of the central to the nature of science. In this topic we
elen1ents of the periodic table . Conservation of exan1ine the relationship that exists between
energy is a fundamental principle of science. chemistry and energy. We will introduce the state
The use of models, en1pirical data, mathen1atics function enthalpy, investigate the applications of
and scientific terminology to explain the energy Hess's Law and gain a greater understanding of
changes associated with chemical reactions is the applications of bond enthalpies.

Understandings I) Applications and skills

, Heat is a form of energy.
, Calculation of the heat change when the
, Temperature is a measure of the average kinetic temperature of a pure substance is changed
energy of the particles. using q = mcD. T.
, Total energy is conserved in chemical , A calorimetry experiment for an enthalpy of
reactions. reaction should be covered and the results
, Chemical reactions that involve transfer of heat evaluated.
between the system and the surroundings are
described as endothermic or exothermic.
, The enthalpy change [D.H) for chemical
reactions is indicated in kJ mo1- 1 •
, D.H values are usually expressed under
standard conditions, known as D.He, including
standard states.

'l, Nature of science

, Fundamental principle - conservation of energy is a fundamental principle of science.
, Making careful observations - measurable energy transfers between systems and surroundings.

139
 ENERGETICS AND THERMOCHEMISTRY
(!) What is thermodynamics?
The uti liza ti on of energy is central to our lives.
Agricultural, in dustrial, and don1estic activities all
consume vast an1ot1nts of energy dai ly.
Thermodynamics is the study of ene rgy
and how it is interconverted. The first law of
thern1odynan1ics states that energy can be
converted from one forn1 to another and that
the total an1ount of energy fo r a given system
universe= system + surroundings
>----+------+- system
~ 1 ( contents
~::::: of flask)
.&. Figure 1 The un iverse is t he combination of t he
system and its surround ings
In an open system the transfer
of matter and energy is possible
across its boundary (eg matter
can be added to a beaker, and
energy can be transferred
through its sides). A closed
system allows no transfer of
matter, though energy may be
transferred across the boundary.
In an isolated system, matter
can neither enter nor exit, but
can only move around inside.
140
will ren1a in cons tan t. This law is often ca lled the
law of conservation of energy and states that
energy can be neither created nor des troyed; it
can only be converted between differen t forms .
This means tha t for a given systen1 we can
account fo r and qu antify all the en ergy changes.
This is one of the n1ost fundan1en tal principles
of scien ce.
Chemical potential energy, heat, and entropy
In a chen1ical reaction total energy is conserved. Chemical potential
energy is stored in the chemica l bonds of reactants and products, whi le
the temperature of the reacting m ixture is a function of the kinetic
energy of the a toms, ions, and 1no lecu les present.
Heat, q, is a form of energy that is transferred from a warn1er body to a
cooler body, as a resu lt of the tempera ture gradien t. Heat is son1etimes
referred to as thern1al energy. It can be transferred by the processes of
conduction, convection, and radia tion. Heat has the abi lity to do work.
When heat is transferred to an object, the result is an increase in the
average kinetic energy of its particles and therefore an increase in its
temp erature or a change in phase.
At abs olute zero, O I( (- 273. 15 °C), all motion of the particles
theoretically stops and the entropy S (see sub- topic 15.2) of a systen1
reaches its m in imum possible value . The absolute temperature (in
kelvin) is proportional to the average kinetic energy of the particles of
matter. As the temperature increases, the kinetic energy of the particles
.
increases.
Chemical energy
When exan1ining the energy changes involved in a chemical reaction,
we divide the universe into two parts: the sy stem in which the
chemical reaction is taking place, and its surroundings. You can
think of the systen1 as being all the reactants, products, and any
solvents . The surroundings include the app aratus that contains the
reaction, thern1on1eters or other n1east1ring devices, the labora tory, and
everything external to the reacting substances.
When a chen1ica l reaction takes place, the atoms of the reactan ts are
rearrange d to create new products. Chemical bonds in the rea cta nts
are broken and new chemica l bonds are made to form the products.
Energy is required to break the chen1ical b onds: b ond breaking is an
endothermic process. This energy is ter111ed the bond dis so ciation
energy a nd it can b e qua ntified for ea ch type of bond. Energy is
re leased when new chemica l bonds are made: bond making is an
exothermic p rocess . The transfer of energy between the surroundings
and the sys tem is an in1portant part of unders tanding the energy
changes in a reaction.
 5 . 1 MEASURING ENERGY CHANGES

Enthalpy and thermochemistry

A calorimeter is any apparatus
Enthalpy is an example of a state function . For a state function any
used to measure the amount
change in value is independent of the pathway between the initial and
of heat being exchanged
final n1easuren1ents. Other examples of state function include volume,
with the surroundings. In an
temperature and pressure.
exothermic reaction heat is
For example, taking the tempera ture of the water in a swimn1ing generated which is transferred
pool early in the morning (the initial value) and then again in the to the surroundings. In an
afternoon (final value), does no t tell the who le story of any tempera ture endothermic reaction heat
fluctuations that n1ay have occurred throughout the day. The calculation is consumed. In the school
is a simple one. However, it does not give any indication of the heating laboratory, experiments focus
and cooling which has occurred throughout the day. on the change in temperature
of the reaction solvent, which
!::::. T = T(fi·1n a I) - T(1111t1a
. . . I) in most cases is water.

Thermochemistry is the study of heat changes that occur during

chen1ical reactions. At cons tan t pressure, the change in enthalpy f::::.H
is defined as the heat transferred by a closed systen1 during a chemical
reaction. The term "change in en tha lpy" or "hea t of reaction" is
comn1only used when describing the thermodynamics of a reaction. The exothermic reaction
unit of en thalpy change !::::.His kJ. - - - - - - - - - - - - - - :.-T.....:- - - - - - - - - - - - - - - -

~ i--- - -'-- ----- l Ea --

cu reactants
Endothermic and exothermic reactions C
Cl)

A chemical reaction in which heat is transferred from the systen1

to the surroundings is defined as an exothermic reaction with a
--
C1l
C
Cl)

0
a..
products
negative f::::.H. In contrast, chemical reactions that absorb heat from
their surroundings are defined as endothermic reactions with a reaction pathway
positive f::::.H. A Figure 2 In an exothermic reaction t he
entha lpy of the products is lower than that
The calculations involved in investigating the energetics of the reaction
of the reactants. The products are described
between zinc and aqueous copper(II ) su lfate, Cu SO 4 are described
as being energetically more stable than the
later in the topic. Measured quantities of copper(II) sulfate solution
reactants. (We shall study t he activation
and zinc are rnixed in a calorirneter. The mixtlrre is stirred and the energy of a reaction in topic 6]
change in ten1perature measured using a thern1on1eter or data-logging
equipn1ent.
endothermic reaction
Zn(s) + CuS0 4 (aq) - Cu(s) + ZnS0 4 (aq)
The result of calcu lating !::::. T shows tha t this single rep lace111ent reaction ::::n products
00
....
involving the displacen1ent of the copper(II) ion by the n1etal zinc is an Cl)
C
Cl) Ea t
exothermic reaction (figure 2). -~ ~H
An1monium nitrate, NH 4 N0 3 is an important component of fer tilizers.
When the solid dissolves in water to forn1 aqueous an1n1oniun1 and
i 1--....l..-- -- _________________
reactants
I_______ _
nitrate ions, the reaction reqlrires hea t to proceed . This heat is absorbed reaction pathway
by the systen1 fron1 the surroundings, resulting in a decrease in the A Figure 3 In an endothermic reaction the
temperature of the surroundings as recorded by a thermometer. The enthalpy of the products is greater than that
apparatus containing the reaction feels cold to touch. This is an exan1ple of the reactants. The products are described
of an endo therrnic reaction ("figure 3) . as being energetically less stable than the
reactants

141
 ENERGETICS AND THERMOCHEMISTRY

(I Calculating enthalpy changes in aqueous solutions

We stated earlier that the change in enthalpy 6.H
is defined as the heat transferred by a closed
systen1 during a che111ical reaction. To calculate
6.H for a reaction we therefore need to find the
heat change. When calculating the heat change of
a pure substance such as water, we need to have
an understanding of the physical quantity, the
specific heat capacity, c.
The units for specific heat capacity are kJ kg- 1 K- 1 •
The specific heat capacity of water is 4.18 kJ kg- 1
K- 1 and this can be found in section 2 of the
Data booklet.
The specific heat capacity of a pure substance is
defined as the an1ount of heat needed to raise
the temperature of 1 g of the substance by 1 °C
or 1 I<. For example, the specific heat capacity of
copper is 0.385 J g- 1 l(- 1 while that of ethanol is
2 .44 J g I I< 1 • The lower the specific heat capacity
of a given substance, the higher the tcn1pcraturc
rise achieved for the san1e a1nount of heat
transferred to the sample.
Specific heat capacity is an intensive property
that docs not vary in n1agnitudc with the size of
the systen1 being described. For example, a 10 cn1 3
san1plc of copper has the san1c specific heat
capacity as a 1 tonne block.
Specific heat capacity is used to calculate the heat
q o[ a systen1 using the relationship:
q = mc6.T
where m is mass in kg and 6. Tis the change in
tern pera tu re.

Worked examples: calculating enthalpy changes

Example 1 Example 2
When a 1.15 g sample of anhydrous lithium chloride, Li Cl 180.0 J of heat is transferred to a 100.0 g sample of
was added to 25.0 g of water in a coffee-cup calorimeter, iron, resulting in a temperature rise from 22.0 °Cto
a temperature rise of 3.80 K was recorded. Calculate the 26.0 °C. Calculate the specific heat capacity of iron.
enthalpy change of solution for 1 mol of lithium chloride.
Solution
Solution ~T= (299 - 295) K=4K.
q = mc~T Make c the subject of the equation and solve:
= 0.025 kg X 4.18 kJ kg- 1 K- 1 X 3.80 K q
c = --
m~T
= 0.397 kJ
0.180kJ
Convert to energy gained for 1 mol of Li Cl. 0.100gx4K
0.397kJ I 1.15g LiCI x 42.394 g/mol = 14.6 kJ/mol LiCI = 0.450 kJ K- 1
~H = - q = - 14.6 kJ mol 1
.

n - - - thermometer
Coffee-cup calorimeters
Performing reactions in a polystyrene coffee cup to measure the enthalpy
change is a convenient experimental procedure. The methodology introduces ;---glass stirrer
t---'1,-
systematic errors that can be analysed and the effect of their directionality - cork stopper

assessed.
Systematic errors are a consequence of the experimental procedure. Their
effect on empirical data is constant and always in the same direction. With the
two polystyrene cups nested
coffee-cup calorimeter, the measured change in enthalpy for a reaction will together containing reactants
always be lower than the actual value, as heat will be transferred between the - in solution
contents and the surroundings in every experiment. A Figure 4 Acoffee-cup calorimeter

142
 5.1 MEASURING ENERGY CHANGES

9 Investigation to find the molar enthalpy change for a reaction

Earlier we looked at the exo ther111ic n1etal
displacen1ent reaction between zinc and copper(!!)
sulfa te:
Zn(s) + CuS0 4 (aq) - Cu(s) + ZnS0 4 (aq)
The following n1ethod is used to calculate the
molar enthalpy change for this reaction from
the equation:
q = mc6.T
Experimental method to determine D..T
I Using an electronic balance, accurately
measure the n1ass of 2 5 cm 3 of 1.0 n1ol dn1 3
CuS0 4 solution. Subtract the mass of the
cylinder from the n1ass of the cylinder +
solution foll owing the transfer of the solution
to the coffee-cup calorimeter.
2 Using a thermometer or a temperature probe and
related software, record the temperature of the
solution every 30 seconds for up to 3 minutes, or
until a constant ten1perature is achieved.
3 At 3 m inutes, introduce powdered zinc
(between 1.3 g and 1.4 g, previously we ighed)
and con1n1cncc stirring .
4 Continue to take temperature readings for up
to 5 n1inutcs after the n1aximun1 temperature
has been reached.
5 Produce a ten1perature versus tin1e graph to
determine the change in temperature .
Assumptions and errors
A nun1ber of assun1ptions arc n1adc when using
this method:
• The heat released fron1 the reaction is
completely transferred to the water.
• The coffee cup acts as an insulator aga inst
• The specific heat capacity of an aqueous
solution is the san1e as that of water.
Loss of heat fron1 the systen1 to the surroundings
is the n1ain source of error in this experiment and
one that is difficult to quantify. The change in
tcn1pcraturc 6. T calculated fron1 a graph w ill include
a systematic or directional error. This loss of heat
n1cans that the n1aximun1 temperature recorded
w ill be lower than the actua l va lue, ma ki ng the
calculated value of q lower than the actual value.
The effect of errors in the procedure on the result of
subsequent calculations is in1portant in considering
in1proven1ents in experin1ental procedures.
An accepted method of calculating the n1aximum
temperature to compensate for systematic
errors in data is to look at the cooling section
of the curve after the reaction is complete, and
extrapolate this back to the point of introduction
of the zinc, as shown in figure 5 . A more accurate
value for 6. T can then be determined.
Calculation of molar enthalpy change
Mass of copper(ll) sulfate solution/g 28.8
Mass of zinc/g 1.37
Change in temperature T(final) - T(initial)l°C 39.0
... Table 1 Sample results
Taking the resu lts in table l we can calculate the
n1olar enthalpy change as follows:
q = mc6.T
= 0 .02 88 kg X 4 .18 kJ kg- 1 1<:- 1 X 39.0 I(
= 4 .69 kJ
w

heat loss to the surroundings . However, the ~

-
~

:J
(0
t::. T
coffee cup also has a heat capacity and heat ~

<1>
c..
is transferred to it from the water. It would
be difficult to quantify the heat capacity of a -
E
<1>

polystyrene cup, so it is assumed to be zero.

• The maxin1u1n temperature reached is an
0 2 4 6 8 10
accurate representation of the heat evolved time/min
during the reaction. _. Figure 5 Determination of the change in temperature
in calorimetry experiments

143
 ENERGETICS AND THERMOCHEMISTRY
amou11t of CuSO 4 = 1.37 g x - - -1- - -
65.38 g n101-1
= 0.0210 n1ol
4 ·69 kJ
molar enthalpy change=
0.0210 n10 1
= 223 kJ mo1- 1
In theory of knowledge there
are eight specific ways of
knowing. These are: language,
sense perception, emotion,
reasoning, imagination,
faith, intuition, and
memory. Scientists perform
experiments and process
the raw data to enable us
to draw conclusions. We
compare experimental and
theoretical values. What
criteria do we use when
making these comparisons?
Are our judgments subjective
or objective? When analysing
and appraising experimental
limitations and making
theoretical assumptions,
which of the ways of knowing
are we utilizing?
The standard enthalpy change of
e
a reaction ~H 298 is determined
at temperature 25 °C/298 Kand
pressure 100 kPa with all species
in their standard state. Standard
conditions are denoted by the
symbol e .
Study tip
Section 12 in the Data booklet
gives the standard enthalpy of
formation for a large number
of common compounds. In
examinations, questions will
provide any other values not
included in the Data booklet.
144
Th.e shape of th.e graph and the change in
temperature fron1 a lower to a higher value lead
to the conclusion that the reaction is exothermic:
fiH = -223 kJ mol 1
Temperature scales
The SI unit of temperature is the kelvin [K). Note that a change in temperature ~T
calculated from experimental data in Celsius will be identical to the value of ~T
calculated in kelvin.
Throughout the world, the majority of countries use the Celsius scale for the
everyday description of temperature. As the Celsius and kelvin scales are linked,
you will often see both scales being used in an 18 question. The USA uses a
mixture of metric and imperial units of measurement. For example, the Fahrenheit
scale of temperature is used in the USA.
OF
100
80
60
40
20
0
-20
~
A Figure 6 We use SI units in science, but a mixture of imperial and metric s~stems of
measurement is used in different countries
9 Enthalpy change of formation
Th.e change in. enthalpy durin.g a reaction can. be determin.ed using th.e
following equation:
fiHereaction = L(fiH~products) - L (D.H~rcactants)
fiHre is the standard enthalpy change of formation of a substance.
Tl1is is tl1e energy change upon the formatio11 of 1 n1ol of a substa11cc
fron1 its constituent elen1enls in their standard state. We can use
existing c11thalpy of forn1ation data to calculate the c11tl1alpy of
reaction. The value and sign of the calculated enthalpy of forn1ation
inforn1s us about the c11ergctics of tl1c rcactio11.
For example, the standard enthalpy change of formation for methane is:
fiH~ = -74.9 kJ mo1- 1
It is important to note that the clcn1c11ts carbo11 and hydrogen arc
represented in their standard slates. Equations for tiH; must represent
tl1c forn1ation of 1 mol of a substance. In son1c cases, sucl1 as tl1c
 5.1 MEASURING ENERGY CHANGES

forn1ation of phe11ol shown below, this results i11 ~ n1ol of diaton1ic

oxygen 0 2 appearing on the reactant side: Quick question
Write equations to describe
1
f).H ~ = -165.0 kJ n1ol the standard enthalpy change
of formation for the following
compounds and state the
Enthalpy change of combustion enthalpy value by referring to
The standard enthalpy change of combustion f).H: is the heat the Data booklet.
evolved upon the complete combustion of 1 mol of substance.
a) propane
The enthalpies of combustion found in section 13 of the Data booklet b) chloromethane
are values derived under standard conditions. Butane, one of the gases
classified as liquefied petroleum gas (LPG) is highly flan1n1able: c) ethanol
d) benzoic acid
e) carbon monoxide
!).H e= -2878 kJ mol- 1 f) methylamine
C

Tl1is thermochemical equation can also be written witl1 tl1e

enthalpy of combustion value included in the equation. The negative Compound ~H~/kJ mo1-1
enthalpy change indicates an exotl1ern1ic reactio11 so tl1e value would
CGHG[I) +49.0
be included on the product side:
C0 2 [g) - 393.5
H2 0[1) - 285.8
A Table 2 Standard enthalpy changes
Working method of formation.
Benzene, C6 H6 is highly flammable, producing a sooty flame:
2C 6 H 6 (l) + 150 2
(g) - 12C0 2 (g) + 6H 0(l)
2

f).H6 reaction = L(!).Ht products) - L(f).H~reactants)

= [ 12 X ( - 3 9 3 .5 ) +6 X ( - 2 8 5 .8) - 2 X ( +4 9. 0) - 15 X O] kJ
= (- 4 7 2 2 - 1714. 8 - 9 8. 0) kJ

= -6535 kJ

9 Investigation to find the enthalpy change of combustion

The entl1alpy cl1ange of con1bustion of con1n1on
alcohols can be detern1ined in the laboratory.
Fron1 a homologous series of alcohols, patterns
in enthalpy change of combustion values can be
determined and subseque11tly analysed.
Experimental method
The following procedure utilizes equipn1ent
available in a standard school laboratory. Five
spirit burners are required, each co11tai11ing one
of the alcohols methanol, ethanol, propan-1-ol,
buta11-l-ol a11d pentan-1-ol.
2 Accurately detern1ine the mass of 30 cn1 3 of
water contained in a 250 cm 3 beaker.
3 Place the beaker or metal calorimeter on a
tripod with the spirit burner beneath.
4 Using either a temperature probe or a
thermometer, detern1i11e and record tl1e initial
temperature of the water.
5 A spirit burner is lit under tl1e calorimeter and
the alcohol is burnt to heat the water. The
period over which it burns can be n1onitored
in one of two different ways:

1 Detern1ine the initial mass of the spirit burners a) allow each alcohol to burn until a
using an electronic balance. temperature change of 30 °C is achieved

145
 ENERGETICS AND THERMOCHEMISTRY
Quick question
Write equations to describe the
standard enthalpy change of
combustion for the following
compounds, and state the
enthalpy value by referring to
section 134 of the Data booklet.
a) octane, C8 H18
b) chloroethane, C2H5 CI [hint:
a corrosive strong acid is
one of the products)
c) cyclohexanol, C6 H1 2 D
d) methanoic acid, CH 2 D2
e) glucose, C6 H12 06
As in all investigations, first
determine the dependent and
independent variables and the
variables that will be controlled.
Data loggers can be used to
record temperature changes
accurately and the associated
software to perform data
analysis and graphing. The
use of data-logging equipment
demonstrates the practical
application of technology in the
laboratory.
Energetics experiments
provide a useful set of
raw data and involve
experimental procedures
that can be evaluated for
random and systematic errors
[ topic 11). The identification
of the systematic errors
and examination of their
directionality is an essential
aspect of the analysis of
experimental results.
146
b) allow each alcohol to burn for a p eriod of 2 m in.u tes .
6 After th is tin1e period, extingu ish each spirit burn er by rep lacing th e
cap, re- w eigh ea ch one an d record the ch ange in n1ass of the alcohol.
Calculation of enthalpy of combustion
Alcohol .6.m of alcohol/g .6.T/°C Mass ofwater/g
methanol 0.348 30.0 31.2
• Table 3 Sample results
q = mcf::l T
= 0.0312 kg x 4.1 8 kJ kg- 1 1<.- 1 x 30.0 I(
= 3 .91 kJ
0. 34 8 g
an1ou n t of CH 3 0 H = - - - - --1 = 0.0 109 mol
32.05 g n 1 0 1
molar energy cha11ge = 3 ·91 kJ
0.0 109 mo.1
= 35 9 kJ mol- 1
fl H = - 3 59 kJ 0101 1
Assumptions
• Heat loss to the environmen t is negligib le (i n rea lity, it is
significant bu t cannot be quantifie d ) .
• All the alcohols are pure and u n d ergo complete combu stion.
Obesity and the energy content of food
The world increase in obesity
Obesity, eating disorders, and unhealthy diet are serious health issues facing many
cultures throughout the world, as many societies become more affluent and food is
readily available. Obesity is generally defined as an excessive accumulation of fat
I
that can lead to health problems. The body mass index (BMI) is found by taking a
person's mass [in kilograms) and dividing it by the square of their height [in metres).
An adult with a BMI above 25 is considered overweight while one with a BMI
greater than 30 is obese. The World Health Organization [WHO) has been
monitoring the effect of changes in diet on different nations for decades. Their
research has found the following:
• In 2013 the occurrence of obesity worldwide was more than double the level
in 1980.
• In 2008 over 1.4 billion adults worldwide were overweight, with approximately
200 000 000 men and 300 000 000 women being classified as obese.
• 65 % of the world's population reside in countries where more people die from
obesity-related causes than from being underweight.
• More than 40 000 000 children under the age of 5 years were overweight in 2010.
• Obesity is a preventable disease.
 5.1 MEASURING ENERGY CHANGES

In China, the rapid increase in affluence and the globalization of the economy
has seen an unprecedented expansion in the fast-food industry and of nutritional
choices. With these has come a significant increase in the number of children
who are overweight and obese. Type 2 diabetes is normally associated with
adults, but the rise in the prevalence of the disease amongst children in China
and in other countries is seen as a significant threat to the wellbeing of future
generations.

Food labelling and determination of energy content

Governments throughout the world have a responsibility to their citizens to
provide leadership, education, and guidance in health and nutrition. Linked
to the globalization of economies and free-trade agreements has been the
standardization of labelling of food products to include an analysis of the contents
including energy content.

To determine their energy content, foods were traditionally placed in a calorimeter

surrounded with water and completely burnt, causing the water to rise in
temperature. This temperature change was then used to calculate the energy
content ( sometimes referred to as "calorific value") of the food. Today the
preferred method of calculation is using the Atwater system. This system relies on
average energy values for proteins, carbohydrates, fats, and alcohol being applied
to foods of a known composition. The National Data Laboratory (NOL) in the USA
holds information on the energy content of over 6000 foods.

•
fu?ctl,00~~
ack ,o
one-sixth of a P
Fat
Calories Sugar
150 0.4g 9.2g
8 0/0 <1 13 01
/ I0

of your guid Ii

.&. Figure? Nutritional information displayed on food packaging

147
 ENERGETICS AND THERMOCHEMISTRY

5.2 Hess's law

Understandings
~ 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.
(I Applications and skills
~ Application of Hess's law to calculate enthalpy
changes.
~ Calculation of D.H reactions using D.Hr0 data.
~ Determination of the enthalpy change of a
reaction that is the sum of multiple reactions
with known enthalpy changes.

0 Nature of science
~ Hypotheses - based on the conservation of energy and atomic theory, scientists can test the hypothesis
that if the same products are formed from the same initial reactants then the energy change should be
the same regardless of the number of steps.

'e) Testing hypotheses

In TOK, a primary focus is on
questions about knowledge
which are open ended
with multiple perspectives
and expressed without
using subject-specifi c
language. Hess's law can be
considered an applicat ion
of the law of conservation
of energy. Wh at are the
challenges in applying
general prin ciples of a law
to something as specific as
Hess's law?
148
Experimental evidence enables scien tists to prove or disprove a
hypothesis . Based on the principles of conservation of energy and
atomic theory, scientists are able to test experimentally the hypothesis
that when products are forn1e d from the san1e set of reactants, the
ch ange in enthalpy should be identical regardless of the rou te taken
and the number of chen1ical reactions involved . Quantitative data
can be analyse d an d use d as evidence for this hypothesis.
Overall and net reactions
If you have travelled to New York, Tokyo, London, Hong I(ong, Paris,
Beijing, Berlin, or Seou l, you wi ll have experienced the subways that
criss-cross these enorn1ous cities and transport n1illions of p e ople every
day. In any transport ne twork there is n1ore than one way to trave l
b etween point A an d B. For the adventuro u s traveller, h alf the fu n is
often working out which is the fas tes t route.
The san1e idea can be true in the field of chemistry. A chen1ical equation
usually shows the net reaction - it is a summary of a number of different
reactions, which when added together result in an overall reaction.
Hess's law is an application of the conservation of energy law:
Regardless of the route by which a chemical reaction proceeds, the erzthalpy change will
always be the same providing the initial and final states of the system are the same.
Figure 2 shows that summing all the equations, taking into account the
direction and magnitu de of each, results in an overall equation. Hess's
law can then be applied to find the enthalpy change for the reaction.
 5 . 2 HESS ' S LAW

B
A Figure 2 Hess's law

A Figure 1 You can take many alternative routes on the Paris Metro

9 Worked example : calculating enthalphy change

Usi11g Hess's law, a11d the fo llowi11g information, reversing the chen1ical equation we n1ust
calculate the enthalpy change 6.H4 for the reaction: change tl1c sig11 of the c11thalpy valu e:

C + 2H2 + 2 0 2 -1
CH 30H 6.H4 ( 4) CO 2 + 2H 2 0 - CH 3 0H + 12l 0 2
l 6.H 1 = +676 .k J
CH3 0H + 1 0 2 CO 2 + 2H 0
2 -
2
• Because oxygen is found in all three
flH 1 = -676 kJ ( l)
cquatio11s, the next point of focus
C + 02- CO 2 6.H2 = -394 kJ (2) should be hydrogen. We require 2 mo t of
l1ydrogcn as a reactant. Therefore, equation
H2 +; 02 - H 20 6.H3 = -242 kJ (3) 3 can be used in the direction as written but
witl1 double the number of n1olcs. This mca11s
IB, May, 2006 that the enthalpy value n1ust be doubled:

Solution
• Look at the overall equation 4 for the entha lp y • Now we ca11 add the three cquatio11s togctl1cr,
of forn1ation of n1ctl1a11ol. eli111inating those species co111mon to both
sides a11d sumn1i11g the enthalpy values as
• Fron1 equations 1-3, the rcacta11t carbo11 and
shown in table l .
the product methanol shou ld be the main
focus of your n1ethodology. Reactants Products Enthalpy
• For carbon, we require a reaction that uses c +~ ---+ ~ ~ H2= - 394kJ
1 mol of carbon as a reactant. Carbon is a
~ + ~ o ---+ CH 3 0H + 1~ ~H 1 = +6?6kJ
reactant in equatio n 2, so this equation can be
used as w ritten: 1 ~H3 =-484kJ
2H2 +~ 2 02 ---+ 2~
C +02- CO 2 flH 2 = - 394 kJ
C+ 2H 2 ---+ CH 3 0H ~H4 = - 202 kJ
• Fo r 1nethanol we need Lo use equation 1, 1
+ 2 02
but we 11ccd to reverse tl1c cquatio11 so tl1at
methanol is a product not a reactant. When A Table 1

149
 ENERGETICS AND THERMOCHEMISTRY

The con1bination of these reactions can also

be represented diagran1matica ll y as shown in
figure 3.
You will notice that the enthalpy cycle diagram
shows the combustion of methanol equation
reversed, in the same way it was during the
sumn1ation of equations method.
CO 2 + 2H 2 D
A Figure 3 Enthalpy cycle for the formation of methanol

The energetics of recycling

With the world population exceeding 7 billion people,
and increasing international concern over the world's
resources, recycling of materials has become mainstream
in many countries. Recycling developed from a desire to
use raw materials more efficiently, to reduce energy use
in the production of goods, to protect the environment
from excessive pollution, and to utilize waste materials
and thereby reduce landfill waste disposal. However,
economic and other pressures to recycle can lead
to potentially harmful impacts on the environment.
For example, electronic ore-waste is an escalating
problem throughout the world. This waste contains
heavy metals such as lead and cadmium, highly toxic
phosphor dust, and other hazardous substances. Guiyu in
China has become a centre fore-waste disposal and the
rapid expansion of recycling processes in villages around
Guiyu has resulted in heavy metal contamination of the
groundwater and soil, and air pollution from the burning of
plastics within the waste.
Despite good intentions, the end result of recycling can
be extremely negative. What is more, the efficiency
of recycling processes in energy terms varies widely.
Many countries and environmental organizations are
investigating how we can address the long-term
effects of recycling programmes on the environment
and communities.

••

A Figure 4 Technology waste recycling in Guiyu, China

150
 5 . 2 HESS ' S LAW

9 Worked example
De tern1ine the en tha lpy of fo rn1a ti on of e thane, In sun11na ry:
C2H 6 u sing tl1e enth alpy of con1bustion data i11
• Tl1e equatio11 for th e con1bustion of carbon
secti on 13 of the Data booklet.
is do u bled.

Solution • The eq u a tion for the comb ustion of

hydrogen is tripled.
• Wri te a ba lanced chen1ical equ a tion for the
formatio11 of 1 n1ol of etl1ane: • The equa tion for the combus ti on of ethane
e
flH 1 is r evers ed.
2C (s) + 3H 2 (g) C2 H 6 (g)
2C(s) + 3H 2 (g) - C2H 6 (g)
• Wri te equ a ti ons for the combu stion o f carbon,
l1ydrogen, an d eth an e a11d de termin e th eir ~ HCe= 84 kJ
en tha lpy va lues fro n1 the Data booklet: Figure 5 shows how the enthalpy of formation
1 .. ..C (s) + 0 2 (g) - C0 2 (g) can be fo u nd u sing an enthalpy cycle diagran1.

~ .HCe = - 393 .5 kJ
~Hf
2 .... H 2 (g) + 21 0 2 (g) - H 2 0 (1) 2C(s] + 3Hz(g]
~HCe = - 2 86 kJ
3 .... C2 H 6 (g) + 7 0 2 (g) - 2 C0 2 (g) + 3H2 0 (l)
2 3 ?
~ .Hee = - 156 1 kJ - Oz - Oz
202 2 2
• Multiply or revers e the sign o f tl1e en th alpy
change for each equa ti on accordingly.
2(-394] 3( - 286) + 1561
• Now con1bine the equ ations to forn1 the ne t
enthalpy of forma tion equation for ethane :
l .. .. (x2): 2C(s) +~ - '2-G.QJg)
2COz(g] + 3Hz0(1]
~ H Ce = - 7 87 kJ • Figure S Alternative met hod: ent halpy cyc le t o find t he

2 .. .. ( x 3): 3H 2 (g) + ~ - ~ ) enthalpy of formation of et hane

~ HCe = -858 kJ

3 ... . (reversed ): 2C 0 2 (g) +~ (l) - ~ g)

+N )
~HCe = + 156 1 kJ

Study tips
You may find the summation of equations method easier when working out the
direction of the equations and the mole coefficients. During examinations you
may be asked to use the summation of equations method and/ or construct an
enthalpy cycle.
Often candidates make simple arithmetical errors when calculating the enthalpy
of reaction . It is advisable to clearly show you r full working rather than simp ly
recording the f inal answer. This gives the examiner the opportunity to assign part
marks where appl icable.

151
 ENERGETICS AND THERMOCHEMISTRY

5.3 Bond enthalpy

Understandings
~ Bond forming releases energy and bond
9 Applications and skills
~ Calculation of the enthalpy changes from
breaking requires energy.
known bond enthalpy values and comparison
~ Average bond enthalpy is the energy needed of these with experimentally measured values.
to break 1 mol of a bond in a gaseous molecule
~ Sketching and evaluation of potential energy
averaged over similar compounds.
profiles in determining whether reactants or
products are more stable and if the reaction is
exothermic or endothermic.
~ Discussion of the bond strength in ozone
relative to oxygen in its importance to the
atmosphere.

(l; Nature of science

~ Models and theories - measured energy changes can be explained based on the model of bonds broken
and bonds formed. Since these explanations are based on a model, agreement with empirical data depends
on the sophistication of the model and data obtained can be used to modify theories where appropriate.

(l; Modelling energy changes

Scientific mo dels are develop e d to explain
certa in processes tha t cann ot be observed
dire ctly. Based on a the ore tical u n derstan ding
of the processes, such mode ls can p rodu ce
evide n ce in supp ort of the theories, or can
info rm n1odi fica tions to the theories. Energy
ch a nge s in re actions can be u n ders tood u sing
n1od els of bond b rea ki ng an d bond 111aki ng. The
degree of a greement b e twe e n these mo dels an d
the e n1pirica l da ta ob ta ine d in the labo ra tory is
dep endent on the validity of the n1odel an d th e
accu ra cy o f the da ta .

Bond enthalpy
The breaking of the hydrogen n1olecu le in to individua l hydrogen a to1ns
requires energy. The bond enthalpy of a bond (the H- H bond in this
example) is defined as the energy required to break 1 n1o l of bonds in
gaseous covalent n1olecules under standard con ditions.
Bond breaking is an endo thern1ic process and has a positive entha lpy
value, fo r exan1ple:
H 2 (g) -t 2H(g) 6He = + 436 kJ n101- 1
Bond enthalpy is also referred to as bond dissociation enthalpy,
and selected va lues are p rovided in section 11 of the Data booklet
and in table 1. These are average values and are therefo re only an

152
 5 . 3 BOND ENTHALPY

approximation. They are derived from experimental data involving

Bond Average bond
the breaking of the same bond found in a wide variety of compounds. enthalpy/kJ mo1- 1
For example, the C- H bond enthalpy will vary through the alkane
series as the chemical environn1ent of the individual bonds changes. H- H 436
If a n1olecule of methane underwent a series of steps in which one 144
0- 0
hydrogen aton1 was ren1oved at a time, the bond dissociation enthalpy
would be different each time, as the chen1ical environment changes 0=0 498
upon the removal of successive hydrogen aton1s. Additionally, the bond 463
0- H
enthalpy for n1olecules in the gaseous state does not take account of the
intern1olecular forces that exist. These limitations are not considered to C- H 414
be significant and the average bond enthalpy is an accepted value to use
c-c 346
for enthalpy of reaction calculations.
C=C 614
Bond length C C 839
Consider the molecules hydrogen fluoride H- F, hydrogen chloride
c-o 358
H- Cl, hydrogen bron1ide H- Br, and hydrogen iodide H- 1. In topic 3 we
discussed how as you n1ove down group 17 the aton1ic radius increases C=O 804
with increasing a ton1ic nl1mber, Z. The consequence of this is tha t bond 615
C=N
length increases, and bond strength decreases, in the hydrogen halides as
you move down group 17 (table 2). C N 890
N- N 158
Bond H- F H- CI H- Br H- 1
N=N 470
Bond length/pm 92 128 141 160
N N 945
A Table 2 Bond lengths of the h1:Jdrogen halides
Cl- Cl 242
Bond strength Br- Br 193
The bond enthalpy re'f1ects the strength of the covalen t bond . As we 151
1- 1
move fron1 single to double to triple bonds the nun1ber of electrons in
the bond increases resulting in an increase in electrostatic forces and a A Table 1 Average bond enthalpies
shortening of the bond length. This trend can be seen in the carbon- at 298 K
carbon bond of the hon1o logous series of a lkanes, alkenes, and alkynes.

Bond polarity
The polarity of a bond can be described by the difference in
electronegativity of the bonded a toms (tables 3 and 4).

Atom Electronegativity Bond .6. ( Electronegativity) Bond enthalpy/

kJ mo1- 1
H 2.2
F 4.0 H- F 1.8 567

Cl 3.2 H- CI 1.0 431

8-
Br 3.0 H- Br 0.8 366
o+
A Table 3 Electronegativitld values A Table 4 Bond polarit1:J and bond enthalp1:J at 298 K
H F
Fluorine has the highest electronegativity value of any elen1ent.
The polarity of the H- F bond results in a partial charge on each
a tom . The bond is said to have ionic character. The partial charges
attract one another, increasing the strength of the bond (figure 1). A Figure 1 The polar H- F bond

153
 ENERGETICS AND THERMOCHEMISTRY

I) Worked example: using bond enthalpies to

find the enthalpy change of reaction
Using the da ta from section 11 o f the Data booklet find the en tha lpy
cha11gc for th e clcctrop h ilic a ddition of l1ydrogcn b rom ide to e tl1cn c to
form bro n1oethane .
C 2 H 4 (g) + HBr (g) -t C 2 H 5 Br (g)
6. He = I:(BE bonds brok en) - L(B E bonds forme d )

6.H = [4BE C-H + BEC=C + BER-Br ] - [5BEC-H + BEC-C + BEC-Br]

6

6.H6 = [(4 X 41 4) + 6 14 + 366] - [(5 X 4 14) + 34 6 + 2 85]

1
6. H6 = 2 636 - 2701 = - 6 5 kJ 0 1 0 1-

The bond entha lpy calcula ted w ill va ry significan tl y fro n1 the ca lcu lation
u sing 6. He r eaction= I:6. H 16 (pro ducts) - I: 6. Ht (rcacta11ts)
(-1 0 5.7 kJ) beca u se bond en tha lpies are average values. Ad diti ona ll y,
when liqu ids arc involved in the reaction, bond enthalpy calculations
do not take in to accou n.t the in termolecu lar forces w ith in the liqui ds .

Study tips
A frequent error made by candid ates is to confuse the different equations for the
calculation of a change in enthalpy. For bond enthalpy, think in terms of bond
breaking and formation:
6.He = L[BE bonds broken) - L[BE bonds formed)

For enthalpy of form ation , think in terms of products and reactants:

6.H6 reaction = L[ 6.H~products) - L( 6.H~reactants)

Bond enthalpy values and enthalpies

of combustion
Gasoline or petrol is p roduced by the fractiona l distil lation of petroleum and
used to power various n1odes of transport. The automotive industry has
witnessed significant changes in its markets as the den1and for automobiles in
developed eco11omies is being overtake11 by tl1at of tl1e developing eco11omies.
The e11tl1alpy of combustio11 of octane, C8 H 18 can be calculated usi11g
bond entha lpy va lues fron1 section 11 of the Data booklet:

25
C 8 H 18 (g) + 2
0 2 (g) -t 8C0 2 (g) + 9H 2 0(g)

6.Hce = L(BE bonds b roken) - L(BE bonds for rned)

25
= (18BEC-H + 7BEC-C + BEO=O) - (16BEC=O + 18BEO_H)
2
2
= (18( 414) + 7(34 6) + ; (4 98)) - (16(804 ) + 18( 4 63))
= 16 099 - 21 198 = -5099 kJ mo1- 1

154
 5 . 3 BOND ENTHALPY

In comparison, the experimentally determined value for the enthalp y

change of con1b ustion i6. Hce fo r octane (section 13 o f the Data booklet) is Ouick questions
- 54 70 kJ mo1- 1 • 1 In the chlor-alkali industry
The reason fo r the difference is that when calcu lating the enthalpy chlorine gas is combined
change u sing b ond enthalpy values, it is assumed that the reaction with hydrogen gas
takes p lace in the gaseous state, with no inte rmolecular fo rces involved . to produce hydrogen
However, the experimentally derived enthalpy of con1bustion involves chloride:
octane and water in their standar d states, namely liquid . Additionally, Cl 2 [g) + H2 [g)-+ 2HCl[g)
as mentioned a b ove, all bond dissociation enthalpy values are a ve raged
across a wid e range of rela ted compou nds so they. represent only. an If the enthalpy change for
a p proximation of the true value . his reaction is - 185 kJ,
calculate the bond enthalpy
for the H- CI bond.
Ozone 2 Methane and chlorine react
O zone, 0 3 is bo th create d an d d es troye d in the strat osp heric layer of to produce chloromethane
Earth's atn1osphere . U ltrav io le t (UV ) rays fron1 the sun a r e absorbed and hydrogen chloride.
b y oxygen, 0 2 , sp litting the n1o le cu le in to single oxygen aton1s.
These oxygen ato1ns can then con1bine w i th oxygen 1n olecl1les to a) Write the balanced
fo rn1 ozone : chemical equation for
this reaction.
UV . . b) Using bond enthalpy
02 (g) - 0 (g) +0 (g)
values from the Data
0 2 (g) + O' (g) - 0 3 (g) booklet, determine
O zone is very effective at absorbing harn1fu l long- and sh o rt-wavelength the enthalpy change
UV radia tion. This absorp tion breaks d own the oz one n1olecule to reform for this reaction .
1no lecu lar oxygen and a single oxygen a to1n . Withou t the presence c) Deduce whether this
of ozone in the stratosp here, life on Earth wou ld change forever, a s reaction is exothermic
harmfu l UV radia tion would damage cells in bo th p lan ts and an in1a ls. or endothermic.
The bond dissociation enthalpy of an oxygen molecu le is 498 kJ mol- 1. In d) Which are more
comparison, the energy reql1ired to break an oxygen-oxygen bond w ith in energetically stable,
an ozone n1olecu le is 3 64 kJ n101- 1. The consequ ence of this is that an the reactants or the
ozone molecule is decomp osed by UV rays 111ore readily than an oxygen products?
molecu le. The ozone photolysis reaction d escribed above is an endotherm ic
reaction w ith the requ ired energy coming fron1 the UV radiation. The
p otential energy p rofile for this reaction is shown in fig u re 2 .
Exan1 ina tion o f th is energy profi le revea ls tha t the oxygen n1o lecu le and
oxygen a tom have a grea ter com bine d energy tha n the rea ctant ozone
mo lecu le . The products of this reactio n are said to be less stab le, as they
exist at a higher energy.

:::n
...
00
Cl)
C
Cl) ---- ---t-.,_p-ro- d-uc-ts- Oz + O
--
C1l
C
Cl)
Ea
0
a..
03
l !H
reactants

reaction pathway
.&. Figure 2 Endothermic energy profil e for ozone phot olysis

155
 ENERGETICS AND THERMOCHEMISTRY

Depletion of the ozone layer

Since the early 1980s scientists have been monitoring ozone depletion globally,
particularly the giant holes in the ozone layer which have appeared above the
Arctic and Antarctic polar icecaps (figure 3).

A Figure 3 ERS-2 satellite map of Antarctic ozone hole in 2010

Chlorofluorocarbons (CFCs) are a type of hydrocarbon conta ining carbon,

hydrogen, and halogen atoms. The compounds themselves are considered to be
non-toxic and have a low level of both flammab ility and reactivity. First used in
industry in the late 1920s, a CFC called Freon gas became an industry standard
refrigerant in domestic refrigerators throughout the world. Over the following
decades the use of CFCs in commercial air conditioning and the automobile
industry, as an aerosol propellant, and as a solvent saw the demand for this class
of compounds increase rapidly.
Scientific research in 19?3 discovered that while CFCs remained harmless
close to the Earth 's surface, when exposed to UV radiation in the stratosphere
these compounds underwent chemical reactions resulting in the release
of chlorine . The chlorine released then had a catalytic effect on the
destruction of ozone in this layer of the atmosphere. As the chlorine is not
directly consumed in the reaction, small amounts of CFCs were found to be
responsible for the destruction of large quantities of ozone.

Cl(g) + 0 3 (g)-+ CID' (g) + 0 2 (g)

CIO'(g) + 0 (g) -+ Cl(g) + 20
3 2
(g)

Science has made many advances that have improved people's daily lives and
extended life expectancy and quality. As a consequence the world's population
is increasing. The use of CFCs has had a massive economic (positive) and
environmental (negative) impact on the world. Whether the blame for the
environmental consequences lies with multinational companies who utilize
technology or the scientists who invent it is the focus of many discussions.

156
 OUESTIONS

Questions
I Consider the specific heat capacity of the 5 Use da ta fron1 section 12 of the Data booklet to
fo llowi11g metals (table 4 ). calcu late tl1c enthalp y change of rcactio11 fo r
each o f these chen1ica l reactions:
Metal Specific heat capacity/J kg- 1 K- 1
Cu 385
a) C 2 H4 {g) + H 2 (g) - C 2 H 6 (g)

Ag 234 b) CH4 (g) + H 2 0(g) - CO (g) + 3H2 (g)

Au 130
Pt 134 6 a) Defi11c the tcrn1 standard enthalpy change of
A Tabl e 4 formation, !:::,,H~. [2]
Which n1etal will show the greatest b) (i) Use the inforn1ation in table 5 to
ten1perature increase if 50 J of heat is supplied calculate th.e enthalpy change for the
to a 0.00 1 kg san1ple of each n1etal at the same complete con1bustion of but- 1-ene
initial temperature? according to th.e fo llowing equation..
A. Cu C Au C 4 H8 (g) + 60 2 (g) - 4C0 2 (g) + 4H 2 0 (g)
B. Ag D. Pt [l ]
IB, May 2007
Compound C4HB[g) C02 [g) H2 0[g)
~ H ~/kJ mo1- 1 +1 - 394 - 42
[3]
2 When 40 joules of heat are added to a sample of • Table 5
solid H 2 0 at - 16.0 °C the temperature increases to
- 8.0 °C. What is the n1ass of the solid H 2 0 sample? (ii ) Deduce, giving a reason, whether
tl1c reactants or the p roducts arc
Specific heat capacity of H 2 0 (s) = 2.0 Jg I I< 1
more stable. [2]
A. 2.5 g C. 10 g
(iii) Pre dict, giving a reason, how the
B . 5.0 g D. 160 g [l] en tha lpy change for the con1p le te
IB, Nov 2007 combustion of but- 2 -c11c would
compare w ith that of bu t- 1-ene
based 011 ave rage bond cntl1alpics. [l ]
3 The temperature of a 2.0 g san1ple of alum in iun1 IB, May 2007
i11crcascs fron1 2 5 °C to 3 0 °C. How ma11 y j oulcs
of heat energy were added? {Specific heat
capacity of aluminiun1 = 0.90 Jg I I( 1.) 7 The !:::,,He values for tl1c forn1a tion of two oxides
A. 0.36 C. 9 .0 of n itrogen are given be low.
1 1
B. 2 .3 D. 11 [ l] N 2 (g) + 0 2 (g) - N0 2 (g) !:::,,He = - 57 kJ n1ol
2
IB, May 2003 N 2 (g) + 20 2 (g) - N 2 0 4 (g) !:::,,He = +9 kJ mo1- 1

Use these va lues to calcula te !:::,, H e for the

4 What is tl1c energy cl1angc (i11 kJ) when tl1c fo llowing r cactio11 (in kJ ):
temperature of 20 g of water increases by 10 °C? 2N0 2 (g) - N2 0 4 (g)
A. 20 X 10 X 4 .18 a) 105 c) + 66
B. 20 283 X 4. 18
X b) - 48 d) + 123
20 X 10 X 4.18
C. IB , November 2007
1000
2 0 X 283 X 4 .18
D. [l ]
100 0
IB, November 2003
 ENERGETICS AND THERMOCHEMISTRY

8 The standard enthalpy change of three Reaction II

con1bustion reactions is given below in kJ .
S0 2 (g) + ; 0 2 (g) ~ S0 3 (g) 6~ = - 92 kJ
2C 2H 6 (g) + 70 2 (g) -t 4C0 2 (g) + 6H 2 0 (l)
6He = - 3120 a) State the name of the term 6He. State,
with a reason, w hcthcr reaction I would be
2H 2(g) + 0 2(g) - t 2H 2 0(1) 6He = - 572
accompanied by a decrease or increase in
C2H 4(g) + 30 2 (g) - t 2C0 2 (g) + 2H 2 0(1) tcn1pcraturc. [3]
6He= 1411 b) At room te1nperature su lfur trioxide, S0 3, is
Based on the above inforn1ation, calculate a solid. Deduce, with a reason, whether the
the standard change in enthalpy, 6He, for the 6He value would be more negative or less
following reaction. negative if S0 3 (s) instead of S0 3 (g) were
formed in reaction II. [2]
C2H6(g) -t C2H4(g) + H2(g) [4]
c) Deduce the 6He value of this rcactio11: [l]
IB, November 2009
S(s) + l; 0 2 (g) -t S0 3 (g)

9 Approximate values of the average bond IB, November 2005

enthalpies, in kJ n101- 1, of three substances arc
shown in tab le 6.
12 But-1-ene gas burns in oxygen to produce
H- H 430 carbo11 dioxide and water vapour according to
the fol lowing equation .
F- F 155
C4H8 + 60 2- t 4C0 2 + 4H 20
H- F 565
a) Use the data in table 7 to calculate the value
• Table 6 of 6H"' for the combustion of but-1-ene. [3]
What is the enthalpy change, in kJ, for this Bond c-c C=C C- H 0= 0 C=O 0- H
rcactio11?
Average 348 612 412 496 743 463
2HF -t H2 + F2 bond
enthalpy/
A. +545 B. +20 C. 20 D. 545
kJ mo1- 1
IB, May 2006
• Table 7
b) State and explain whether the reaction
10 The reaction between ethene and hydrogen gas above is endothermic or exothermic. [ l]
is exothermic. IB, May 2006
a) Write an equation for this reaction. [l]
b) Deduce the relative stabilities and
13 Given the following data:
energies of the reactants and products. [2]
c) Explain, by referring to the bonds in C(s) + 2F 2 (g) -t CF4 (g); 6H 1 = - 680 kJ n101-1
the molecules, why the reaction is F2 (g) -t 2F(g); 6H 2 = + 158 kJ n101-1
exothcrn1ic. [2]
C (s) -t C (g); 6 H3 = +71 5 kJ n1 o 1 1
IB, November 2007
calculate the average bo11d cntl1alpy (in kJ n1ol- 1)
for the C- F bond.
11 Two reactions occurring in the manufacture
IB, November 2003
of sulfuric acid are shown below:
Reaction I
 OUESTIONS

14 Methanol is n1ade in large quantities as it c) The Data booklet value for the enthalpy of
is used in the production of polymers and con1bustion of methanol is - 726 kJ n1ol 1 •
i11 fuels. Suggest why this value differs from the
The enthalpy of con1bustion of n1ethanol can values calculated in parts a) and b).
be determined theoretically or cxpcrin1c11tally. (i) Part a) [l]
(ii) Part b) [l]
IB, May 2011
a) Usi11g tl1c i11formatio11 fron1 section 11
of the Data booklet, determine the
15 One important property of a rocket fuel mixture
theoretical e11thalpy of con1bustion
is the large volun1e of gaseous products formed
of n1ethanol. [3]
which provide thrust. Hydrazine, N2H 4, is
b) The enthalpy of combustion of methanol often used as a rocket fuel. The combustion of
can also be determined experimentally in hydrazine is represented by the equation below.
a school laboratory. A burner containing
methanol was weighed and used to heat N 2H 4(g) + 0 2(g) - N 2(g) + 2H 20{g)
water in a test tube as illustrated in 6.HC"" = - 585 kJ mo1-1
figure 4.
a) Hydrazine reacts with fluorine Lo produce
thermometer nitrogen and hydrogen fluoride, all in the
gaseous state. State an equation for the
\t rcactio11. [2]
11 b) Draw the Lewis structures for hydrazine
I=
and nitrogen. [2]
test tube with water
c) Use the average bond enthalpies given in
stand scctio11 11 of the Data booklet to detcrn1inc
shield the enthalpy change for the reaction in
~
part a) above. [3]
d) Based on your answers to parts a) and c),
burner
~ " suggest whether a mixture of hydrazine
c-
_/'

1)/

and fluorine is a better rocket fuel than a

mixture of hydrazine and oxygen. [2]
.&. Figure 4
IB, May 2010
Tl1c data shown in table 8 were collected.

Initial mass of burner and methanol/g 80.557
Final mass of burner and methanol/g 80.034
Mass of water in test tube/g 20.000
Initial temperature of water/°C 21.5
Final temperature of waterf C 26.4
.&. Table 8
i) Calculate the amount, in mol, of
methanol burned.
ii) Calculate the heat absorbed, in kJ,
by the water.
iii) Determine the enthalpy change,
in kJ mol 1, for the co1nbustion
of 1 n1olc of n1ethanol.
16 Two stude11ts were asked to use i11forn1ation
fro1n the Data booklet to calculate a value for the
e11thalpy of hydrogcnatio11 of cthcnc to forn1
ethane.
C2H4(g) + H2(g) - C2H6(g)
Jol111 used the average bond enthalpies fron1
section 11. Maril used the values of enthalpies
of combustion from sectio11 12.
a) Calculate the value for the enthalpy of
[2] hydrogenation of ethene obtained using
the average bond enthalpies given in
[3] section 11. [2]
b) Marit arranged the values sl1c found in
section 12 into an energy cycle (figure 5).
[2]
ENERGETICS AND THERMOCHEMISTRY

t:i.ff' (hydrogenation]
CzH4[g] + Hz(g] C2H6(g)
...I ...I
0 0
N E E \:\)1. / \.
0
M
-,
.:.::.
"'
0 -, :i1, o\
..-<IN .:.::.
....... lD
'f)~
.......
'S1" 00 s<o\)
....... N / '},
I I

2COz(g] + 3Hz0(1]
• Figure 5

Calculate the value for the enthalpy

of hydrogenation of ethene fro1n the
energy cycle. [1J
c) Suggest one reason why John's answer
is slightly less accurate than Marit's
answer. [ l]
d) John then decided to determine the
enthalpy of hydrogenation of cyclohexene
to produce cyclohexane.
C6H IO (l) + H2(g) ~ C6Hl2(l)

(i) Use the average bond enthalpies to

deduce a value for the enthalpy of
hydrogenation of cyclohexene. [l)
(ii) The percentage difference between
these two n1ethods (average
bond enthalpies and enthalpies
of con1bustion) is greater for
cyclohexene than it was for ethene.
John's hypothesis was that it would
be the same. Determine why the
use of average bond enthalpies is
less accurate for the cyclohexene
equation shown above, than it
was for ethene. Deduce what extra
inforn1ation is needed to provide a
more accurate answer. [2)
IB, May 2009