TOPIC 5

ENERGETICS/THERMOCHEMISTRY

5.1
MEASURING
ENERGY CHANGES

By: Merinda Sautel

Alameda Int’l Jr/Sr High School
Lakewood, CO
msautel@jeffco.k12.co.us
 ESSENTIAL IDEA
The enthalpy changes from chemical
reactions can be calculated from their
effect on the temperature of their
surroundings.
NATURE OF SCIENCE (2.6)
Fundamental principal – conservation of energy is a
fundamental principle of science.
NATURE OF SCIENCE (3.1)
Making careful observations – measurable energy
transfers between systems and surroundings.
INTERNATIONAL-MINDEDNE
SS
The SI unit of temperature is the Kelvin
(K), but the Celsius scale (◦C), which has
the same incremental scaling, is
commonly used in most countries. The
exception if the USA which continues to
use the Fahrenheit scale (◦F) for all
non-scientific communication.
 THEORY OF KNOWLEDGE
What criteria do we use in judging
discrepancies between experimental
and theoretical values? Which ways
of knowing do we use when
assessing experimental limitations
and theoretical assumptions?
 UNDERSTANDING/KEY IDEA
5.1.A

Heat is a form of energy.

 ENERGY
• All chemical reactions are
accompanied by energy changes.
• Energy is a measure of the ability to
do work, that is to move an object
against an opposing force.
• Examples: heat, light, sound,
electricity and chemical energy
which is the energy released or
absorbed during chemical reactions.
 HEAT
• Heat is a form of energy which is
transferred as a result of a
difference in temperature and
produces an increase in disorder of
the behavior of particles.
• Heat increases the average kinetic
energy of the molecules in a
disordered fashion.
 Needed definitions
• Enthalpy
• Heat content of a substance (at constant
pressure)
• Enthalpy is also the internal energy stored
in the reactants.
• The absolute value for the enthalpy of
reactants and products cannot be known,
but the what can be measured is the
difference between the two.

• System – area of interest (Example:

beaker and its contents)
• Surroundings – everything else in the
universe
• An “open” system can exchange
matter and energy with the
surroundings.
• A “closed” system can only
exchange energy, not matter,
with the surroundings.
• The joule (J) is the SI unit for
energy and work.
 UNDERSTANDING/KEY IDEA
5.1.B

Temperature is a measure of
the average kinetic energy of
the particles.
 Temperature

• Def – measure of the average kinetic

energy of the particles
• Temperature increase depends upon:
• Mass of the object
• Amount of heat added
• Nature of the substance
• Different substances need different
amounts of heat to increase the temp
of a unit mass by 1K or 1ºC.
 UNDERSTANDING/KEY IDEA
5.1.C

Total energy is conserved in

chemical reactions.
 UNDERSTANDING/KEY IDEA
5.1.D

Chemical reactions that

involve transfer of heat
between the system and the
surroundings are described as
endothermic or exothermic.
EXOTHERMIC
REACTIONS
A reaction which results in a
transfer of energy from the
system to the surroundings.
• Heat is given off or produced.
• Products have less energy or heat
content than the reactants.
• ΔH is negative.
• The bonds in the products are stronger
than the bonds in the reactants.
 Exothermic reaction
Enthalpy diagram

reactants

enthalpy
H ΔH = negative

products

extent of reaction
ENDOTHERMIC
REACTIONS
• A reaction which results in a
transfer of energy from the
surroundings to the system.
• Heat is absorbed.
• Reactants have less energy than the
products.
• ΔH is positive.
• The bonds in the reactants are stronger
than those in the products.
Endothermic reaction
Enthalpy diagram

products

enthalpy
H ΔH = positive

reactants

extent of reaction
 UNDERSTANDING/KEY IDEA
5.1.E

The enthalpy change (ΔH) for

chemical reactions is
-1
indicated in kJ mol
 UNDERSTANDING/KEY IDEA
5.1.F

ΔH values are usually

expressed under standard
◦
conditions, given by ΔH ,
including the standard states.
 GUIDANCE
Standard state refers to the
normal, most pure stable state of
a substance measured at 100 kPa.
Temperature is not part of the
definition of standard state, but
298K is commonly given as the
temperature of interest.
 GUIDANCE

Be familiar with the enthalpy

◦
change of combustion (ΔHc )
and the enthalpy change of
◦
formation (ΔHf ).
 APPLICATION/SKILLS

Be able to calculate the heat

change when the temperature
of a pure substance is
changed using q = mcΔT.
 GUIDANCE
The specific heat capacity of
water is provided in the data
booklet in section 2.
 APPLICATION/SKILLS

Be able to evaluate
calorimetry experiments for
the enthalpy of a reaction.
 GUIDANCE

Be familiar with reactions

occurring in aqueous solutions
and combustion reactions.
 GUIDANCE
Students can assume the specific
heat and density of aqueous
solutions are equal to those of
water, but be aware of this
limitation.
 GUIDANCE
Heat losses to the environment
and the heat capacity of the
calorimeter in experiments should
be considered, but the use of a
bomb calorimeter is not required.
 THERMOCHEMICAL
EQUATION EXAMPLES
Combustion of Methane
CH4(g) + 2O2(g) CO2(g) + 2H2O(l) ΔH = -890 kJ mol-1

Photosynthesis
6CO2(g) + 6H2O(l) C6H12O6(aq) + 6O2(g) ΔH = +2802.5 kJ mol-1

Thermite Reaction
2Al(s) + Fe2O3(s) Al2O3(s) + 2Fe(s) ΔH = -841 kJ mol-1
• You must give the “state”
symbols such as (s), (g), (l), (aq)
in thermochemical equations
because energy changes
depend upon the state of the
reactants and the products.
• Standard enthalpy change of reaction
ΔHº
• This is the heat or enthalpy change of a
reaction when carried out at standard
conditions.
• Temperature = 298K or 25ºC
• Pressure = 101.3 kPa (1atm)
• Solution concentration = 1mol dm-3 (1M)
• All substances are in their standard states
(how they are found in nature)
• The actual amount of heat absorbed
or produced in a chemical reaction
depends upon several factors:
• Nature of the reactants and products
• The amount or concentration of the
reactants. (The greater the amount that
reacts, the greater the heat change.)
• The states of the reactants and
products. Changing states involves an
enthalpy change so this will affect the
total heat change.
• The temperature of the reaction.
• All combustion reactions are
exothermic processes.
• All neutralization reactions are
exothermic processes.
• Apply the relationship between
temperature change, enthalpy
change and be able to classify
the reaction as endothermic or
exothermic.
• This will be determined by
calorimetry.
 Specific Heat Capacity

• The following relationship allows

the heat change in a material to be
calculated from the temperature
change.
q = mcΔT
heat = mass x specific heat x ΔT
• Specific heat capacity (c) is the
heat needed to increase the
temperature of a unit mass
(usually 1g) by 1K or 1ºC.
• Specific heat of water
c = 4.18 J K-1g-1
• Be able to deduce from an
enthalpy level diagram, the
relative stabilities of reactants
and products and the sign of the
enthalpy change for the
reaction.
• There is a natural direction for
change.
• The direction of change is in the
direction of lower stored energy.
• We generally expect a reaction to
occur if ΔH is negative (exothermic),
but some endothermic reactions do
occur. These occur when the
entropy (S) of the system is large.
 Enthalpy Diagram for Hydrogen
Peroxide (H2O2)
H2(g) + O2(g)

ΔH1
H2O2(l)
ΔH3

ΔH2
Enthalpy

H2O(l) + 1/2 O2(g)

In this diagram, hydrogen peroxide in the middle is stable

compared to H2 and O2, but unstable compared to the
decomposition of water and oxygen on the bottom line.
• The heat produced when one
mole of a substance is burned in
excess oxygen is called the
enthalpy of combustion.
• ΔHc is exothermic and always
negative.
• Calculate the heat energy
change when the temperature
of a pure substance is changed.
 How to calculate heat
changes from temp changes.
• When heat released by an exothermic
reaction is absorbed by water, the
temperature of the water increases.
• The heat produced by the reaction can
be calculated if it is assumed that all
the heat is absorbed by the water.
heat change of rxn = -heat change of water
= - mH2O x cH2O x ΔTH2O
As the water has gained the heat produced by the reaction, the heat change of
the reaction is negative when the temperature of the water increases.
 Example Problem 1

• Calculate the enthalpy of

combustion of ethanol from the
following data. Assume all heat
from the reaction is absorbed by
the water. Compare your value
with the IB Data booklet value and
suggest reasons for any
differences.
• Mass of water in Cu Calorimeter = 200.00g
• Temperature increase in water = 13.00ºC
• Mass of ethanol burned = 0.45g
heat change of rxn = - mH2O x cH2O x ΔTH2O

= -(200.00g)(4.18Jg-1ºC-1)(13.00ºC)
= -10868 J
The heat calculated above is the heat gained by the water which is
also the heat lost by the combustion of the ethanol.

Since ΔHc is per mole of substance combusted, you have to find

moles of ethanol burned and divide the heat it lost by the moles.

To find moles, divide mass by molar mass:

0.45g / 46.08 g mol-1 = .0098mol

ΔHc = -10868J / .0098mol = -1112883 J/mol = -1112.883 kJ/mol

Using sig figs, the answer is limited by the mass = -1100 kJ/mol
• The IB Data booklet value is -1367 kJ/mol.
• What are some reasons for the difference
in values?
• Not all the heat produced by the combustion is
transferred to the water.
• Some is needed to heat the Cu calorimeter and some has
passed to the surroundings.
• The combustion of ethanol is unlikely to be
complete due to the limited oxygen available.
Heat of Combustion
Set up
 Example Problem 2
• When 0.824 g of ethanol was burned,
it produced a temperature rise of
15.7 K in 275g of water.
• a. Draw the calorimetry set up.
• b. Write the ΔHc reaction.
• c. Calculate the ΔH for the reaction.
• d. The Data Book value is -1367 kJ/mol.
Include three reasons for the
discrepancy.
• It is important to record qualitative as
well as quantitative data.
• When asked to evaluate experiments
and suggest improvements, avoid
giving trivial answers such as
incorrect measurements.
• Incomplete combustion can be
reduced by burning the fuel in oxygen
and heat loss can be reduced by
insulating the apparatus.
• Design suitable experimental
procedures for measuring the
heat energy change of
reactions.
 ΔH of reactions in
solution
• The enthalpy changes of reaction in
solution can be calculated by carrying
out the reaction in an insulated system
such as a polystyrene cup or Styrofoam
calorimeter.
• The heat released or absorbed by the
reaction can be measured by the change
in temp of the water.
• The largest source of error in this type of
experiment is heat loss to the
environment.
• To compensate for the heat lost by
the water in exothermic reactions
to the surroundings as the reaction
proceeds, a plot of temperature vs
time can be drawn.
• We want the highest temperature
that would have been reached had
the reaction been instantaneous.
• If we graph the temp vs time, we
can extrapolate back to determine
the highest temperature.
 Compensating for Heat Loss
T0 = initial temp of reactants
T1 = highest temp actually reached
T2 = temp that would have been reached if
no heat were lost to the surroundings

extrapolation at same rate of cooling

T2

T1
∆T ∆T for rxn = T2-T0
Temp
(K or ⁰C)
T0
point where reactants are mixed

time (s)
• Calculate the enthalpy change for
a reaction using experimental
data on temperature changes,
quantities of reactants and mass
of water.
 Example problem 3

• 50.0 cm3 of 1.00 mol/dm3 hydrochloric

acid was added to 50.0 cm3 of 1.00
mol/dm3 sodium hydroxide solution in a
polystyrene beaker. The initial
temperature of both solutions was 16.7
ºC. After stirring and accounting for the
heat loss, the highest temperature
reached was 23.5ºC. Calculate the
enthalpy change for the reaction.
• Step 1 – write the equation
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)

• Step 2 – calculate molar quantities

Anytime you are given a volume and a molarity,
multiply them together (watch your units) to get
moles. Convert cm3 to dm3 first.
50.0cm3 x 1dm3/1000cm3 = 0.0500 dm3
Then multiply the volume by the molarity.
0.0500dm3 x 1.00 mol/dm3 = 0.0500 mol
• Step 3 – calculate the heat evolved
• Assumptions:
• The solution has the same density as water which
is 1.00 g/cm3.
• The solution has the same specific heat as water
which is 4.18 J/gK.
• Total volume of solution
50.0 cm3 + 50.0 cm3 = 100.0 cm3
• Using the density of water, calculate the mass of the
solution
100.0 cm3 x 1.00 g/cm3 = 100.0 g
• Temperature change
23.5ºC – 16.7ºC = 6.8ºC = 6.8 K
• The heat evolved from the reaction = mcΔT.
q = (100.g)(4.18 J/gK)(6.8 K) = 2840 J = -28.4kJ
• The ΔH is per mole so
ΔH = -28.4kJ/.0500mol = -56.8 kJ/mol
• Evaluate the results of
experiments to determine
enthalpy changes.
 Example Problem to evaluate
the results of an experiment.
• The experiment involves the neutralization of
sodium hydroxide with sulfuric acid to form
water and sodium sulfate.
• Assumptions:
• The NaOH and H2SO4 are 1M (1mol dm-3).
• The total volume is kept constant at 120 cm 3
with varying volumes of NaOH and H2SO4.
• No heat is lost from the system.
• All heat is transferred to the water.
• Assume 120cm3 of solution contains 120cm3
of water.
• Your task is to evaluate the following when
the temperature changes are measured
when different volumes of NaOH and H2SO4
are mixed:
• Determine the volumes of the solutions which
produce the largest increase in temperature.
• Calculate the heat produced by the reaction when
the maximum temperature was produced.
• Calculate the heat produced for one mole of NaOH.
• Calculate the %error and suggest a reason for the
discrepancy between the experimental and
literature values.
• The literature value at standard conditions is
-57.5 kJ/mol-1.
 35
34
33
32
Temp ºC 31
30
29
28
27
26
25 □

0 20 40 60 80 100 120
volume of NaOH cm3
• The highest increase in temp is produced at
80 cm3 of NaOH which means that there is
120-80 = 40 cm3 of H2SO4.
• The maximum temp where the lines cross on
the graph was 33.5ºC.
q = -mcΔT
= -(120.0g)(4.18J/gºC)(33.5ºC-25.0ºC)
= -4264J
• To calculate the heat produced per mole:
80.0cm3 x 1dm3/1000cm3 x 1mol/dm3 = .0800mol
ΔH = -4264J/.0800mol = -53300Jmol-1 = -53.3kJmol-1
• Percent Error
%error = (-57.5--53.3)/-57.5 x 100% = 7%
• There are uncertainties in temp, vol and
concentration measurements and it is assumed
all heat is transferred to the water and no heat
is lost from the system.
Another fine example
• 50.0 cm3 of 0.200 mol dm-3
copper II sulfate was placed in a
polystyrene cup. After 2 min,
1.20 g of powdered zinc was
added. The temperature was
taken every 30 seconds and the
following graph was obtained.
Calculate the enthalpy change
for the reaction taking place.
 Temp Change for the Reaction of
Copper II Sulfate and Zinc
T0 = initial temp of reactants = 17⁰C
T1 = highest temp actually reached = 26.5 ⁰C
T2 = temp that would have been reached if
no heat were lost to the surroundings = 27.4 ⁰C
extrapolation at same rate of cooling
T2

T1
∆T ∆T for rxn = T2-T0
Temp
(⁰C)
T0
point where zinc was added

time (min)
• From the graph, we are able to extrapolate back
and determine that T2 would have been 27.4⁰C.
• That gives us a ∆T of
27.4⁰C - 17.0⁰C = 10.4⁰C
• Next we should recognize that we are mixing
two given amounts which gives us a limiting
reactant problem.
CuSO4(aq) + Zn(s) Cu(s) + ZnSO4(aq)
1.20 g Zn x mol/65.4g = 0.0183mol Zn given

50.0cm3 x 1dm3/1000cm3 x 0.200mol/dm3 = 0.0100mol CuSO4 given

0.0183mol Zn x 1/1 = 0.0183mol CuSO4 needed

0.0100mol CuSO4 x 1/1 = 0.0100mol Zn needed

We need 0.0183 mol CuSO4 and are only given 0.0100 mol so CuSO4 is
the limiting reactant.
• We know that the reaction will stop
after the 0.0100 mol of CuSO4 is
used up so the heat evolved is per
0.0100 mol of CuSO4.
• q = mc∆T
= (50.0 cm3 x 1.00 g/cm3)(4.18J/g⁰C)(10.4⁰C)
= 2170 J = 2.17 kJ
• ∆H = -2.17kJ / 0.0100 mol = -217 kJ mol-1
 Comments on problem
• Why was there a wait time at the beginning?
• The highest temp was reached 5 min after the
zinc had been added. What exactly was
happening at this point?
• Copper II sulfate solution is blue. Zinc sulfate
solution is colorless. Zinc is a silver – grey
metal and copper is a reddish brown metal.
State what you would think you would observe
as the reaction proceeds.
• What are three assumptions you have made in
arriving at your answer?
• The literature value is -218 kJ/mol. Comment
on the validity of your assumptions you stated.
Final comments on
calculating ∆H
• There are 4 types of problems
that you should be familiar with.
• Combustion calorimetry
• Neutralization rxns
• Extrapolation for heat loss
• Finding answers from a graph
when 2 solutions are mixed and
volumes are kept constant.
• Make sure you always record
qualitative as well as
quantitative results.
• Be sure to state the
assumptions you are making
which are often that no heat is
lost from the system, all heat is
transferred to the water and
that the mass of the solution is
assumed to be water so you are
using the specific heat of water
in your calculations.
 Citations
International Baccalaureate Organization. Chemistry Guide,
First assessment 2016. Updated 2015.
Brown, Catrin, and Mike Ford. Higher Level Chemistry. 2nd
ed. N.p.: Pearson Baccalaureate, 2014. Print.
ISBN 978 1 447 95975 5
eBook 978 1 447 95976 2

Most of the information found in this power point comes

directly from this textbook.

The power point has been made to directly complement the

Higher Level Chemistry textbook by Brown and Ford and is
used for direct instructional purposes only.