8 Energetics Notes PDF
8 Energetics Notes PDF
8 Energetics Notes PDF
5 Chemical energetics
Enthalpy changes and entropy changes accompany chemical reactions. This topic
demonstrates why some reactions and processes are spontaneous and others are
not.
ENERGETICS
50
5 Chemical energetics
Enthalpy changes and entropy changes accompany chemical reactions. This topic demonstrates why
some reactions and processes are spontaneous and others are not.
Learning outcomes
Candidates should be able to:
5.1 Enthalpy change, ΔH a) explain that chemical reactions are accompanied by energy changes,
principally in the form of heat energy; the energy changes can be
exothermic (ΔH is negative) or endothermic (ΔH is positive)
b) explain and use the terms:
(i) enthalpy change of reaction and standard conditions, with
particular reference to: formation, combustion, hydration, solution,
neutralisation, atomisation
(ii) bond energy (ΔH positive, i.e. bond breaking)
(iii) lattice energy (ΔH negative, i.e. gaseous ions to solid lattice)
c) calculate enthalpy changes from appropriate experimental results,
including the use of the relationship
enthalpy change, ΔH = –mcΔT
d) explain, in qualitative terms, the effect of ionic charge and of ionic
radius on the numerical magnitude of a lattice energy
5.2 Hess’ Law, including a) apply Hess’ Law to construct simple energy cycles, and carry out
Born-Haber cycles calculations involving such cycles and relevant energy terms, with
particular reference to:
(i) determining enthalpy changes that cannot be found by direct
experiment, e.g. an enthalpy change of formation from enthalpy
changes of combustion
(ii) average bond energies
(iii) the formation of a simple ionic solid and of its aqueous solution
(iv) Born-Haber cycles (including ionisation energy and electron
affinity)
b) construct and interpret a reaction pathway diagram, in terms of the
enthalpy change of the reaction and of the activation energy
ENTHALPY CHANGES
Every chemical reaction involves the exchange of energy between (what we
call) the system and its surroundings. For example, when magnesium and
sulphuric acid react in a test-tube:
1. The system consists of the chemical bonds and other forces of attraction
and repulsion between the atoms of reactants and of the products formed.
2. The surroundings include:
a. The test tube.
b. The air around the test tube.
c. The thermometer dipped into the reacting mixture etc…
1
ENTHALPY CHANGES
The total heat (energy) content of any substance at constant pressure is called
its enthalpy. Because of how difficult it is to observe things at the atomic and sub-
atomic level, it is not possible to measure the total enthalpy of a substance.
A good analogy for this is trying to measure the volume of the Pacific Ocean. The
structure of the seabed is so diverse it is practically impossible to measure just
how much volume the Pacific Ocean has. However, you can easily measure
changes in the volume of the Ocean.
Similarly, we can easily measure the enthalpy change that accompanies
reactions. This is written as ∆H and pronounced ‘delta H.’ ∆H can either have a
positive or a negative value, depending on the nature of energy exchange in the
reaction.
2
ENTHALPY CHANGES
When energy flows from the system to the surroundings, the temperature of the
surroundings increases. This indicates that heat was given out as a result of the
reaction, and so the products of the reaction are at a lower energy level than the
reactants were. These types of reactions are called exothermic reactions.
The value for ∆H is negative for exothermic reactions.
When energy flows from the surroundings to the system, the temperature of the
surroundings decreases. This indicates that heat was taken in as a result of the
reaction, and so the products of the reaction are at a higher energy level than the
reactants were. These types of reactions are called endothermic reactions.
The value for ∆H is positive for endothermic reactions.
SKILL CHECK
Classify the following reactions as exothermic or endothermic:
1. Burning magnesium in excess oxygen.
ENTHALPY CHANGES
To summarise:
Enthalpy
Enthalpy
reactants Ea
Ea products
∆H ∆H
reactants
products
Enthalpy of reactants > products,∆H = —ve Enthalpy of reactants < products, ∆H = +ve
EXOTHERMIC: Heat given out ENDOTHERMIC: Heat absorbed
ENTHALPY CHANGES
We can draw enthalpy profile diagrams (also known as reaction
pathway diagrams) to show enthalpy changes, as shown on the previous
slide.
1. The enthalpy of the reactants and products is shown on the y-axis.
2. The x-axis shows the reaction pathway, with reactants on the left and
products on the right.
SKILL CHECK
Draw enthalpy profile diagrams for:
Notes There should be only one mole of product on the right side of the equation.
Elements in their standard states have zero enthalpy of formation
Carbon is usually taken as the graphite allotrope
11
Symbol ∆HOc
Notes There should only one mole of what is being combusted on the left side of the equation.
To aid balancing the equation, remember that you get one carbon dioxide molecule for
every carbon atom in the original and one water molecule for every two hydrogen
atoms. When you have done this, go back and balance the oxygen.
12
Definition The enthalpy change when an acid and a base react to form one mole of
water under standard conditions.
Symbol ∆HOneutralisation
Values Exothermic
Notes A value of -57kJmol-1 is obtained when strong acids react with strong
alkalis.
13
SKILL CHECK
Classify the following reactions as standard enthalpy changes of
formation, combustion or neutralisation:
1. MgCO3 (s) MgO (s) + CO2 (g)
14
dissolved in water - so water isThe enthalpy change of a reaction usually appears as heat, which means that there is
the natural choice to measure a variety of
a temperature change. If the products have less enthalpy than the reactants, there is
an enthalpy decrease during the reaction water (∆H is negative) and an equivalent amount
enthalpy changes. of heat energy must be given out by the reaction; the reaction is said to be
exothermic. The heat given out is passed to the surroundings – that is, the ‘bomb’
calorimeter
The enthalpy change of reaction causes
environment thethetemperature
around reaction – where itof canthe water to
be measured. change:
Most chemical
reactions are exothermic, but there are some in which the enthalpy increases (∆H is oxygen under pressure
and the reaction is then said to be endothermic. These reactions take in
Endothermic reactions take positive), in energy, temperature of water falls.
heat from the surroundings because the enthalpy of the products is more than the
exothermic reactions, ∆H is heated wire crucible containing
enthalpy of the reactants. to ignite sample fuel under test
Exothermic reactions give energy
negative. The temperature of the It is notout, temperature
surprising that most chemical of water
reactionsrises.
are exothermic. In everyday life, stirrer
surroundings increases and the
the changes we observe are usually those in which the potential energy decreases
potential energy of the system (that
and the kinetic energy increases in heated
outer the form of heat. If we push a book to the side
is, the reacting chemicals) decreases.
of a desk, we expect to see it fall water
frombath
the desk to the floor (its potential energy
endothermic reactions, ∆H is
therefore 15
decreases). We would be very surprised if it suddenly rose back up again
positive. The temperature of the
surroundings decreases and the (its potential energy would increase). Both processes are possible in theory, as they
Experiment doThe
potential energy of the system (the
reacting chemicals) increases.
not break the Law of Conservation of Energy.
direction of a chemical change is determined by the relative energy levels
To measure
of the reactants and products. If the enthalpy ∆Hof 1the
c
reactants is higher than that
of the products (exothermic, ∆H negative), the reaction is thermodynamically
A simple
possible. It might not, however, takeapparatus
place because the rate is too slow; it is then
05_075.8
Figure Cam/Chem
shows AS&A2
said to be kinetically controlled. These akinetic
simplefactors
apparatus aretoconsidered
measure the
in enthalpy
Topic 8).change of combustion
forBarking
a fuel Dog
suchArt
as methanol. A known volume of water is placed in a copper
Measuring temperature calorimeter and its changes
temperature andis measured. The calorimeter is clamped so that its
base is just a few centimetres above a spirit burner, which contains the fuel. The
calculating ∆H spirit burner is weighed, placed under the calorimeter and lit. The water in the
The enthalpy change of a reaction, ∆H, If we measure the heat given out or taken in during a reaction, we can find this
calorimeter is stirred with the thermometer. When the temperature has risen about
is the change in enthalpy accompanying enthalpy change. The simplest way of measuring it is to use the energy to heat (or
10 °C, the flame is put out, the temperature is noted and the spirit burner re-weighed.
reactants into products.
SIMPLE CALORIMETERS
the complete conversion of one mole of cool) some water or a solution. We need to make the following measurements:
We also need to know the amount of energy needed to raise the temperature of
thermometer
water by one degree. This is known as the specific heat capacity of water and is
given the symbol c. It has the value 4.18 J g−1 K−1. (Note that we can measure the
temperature change using a thermometer marked in degrees Celsius, because a
change in temperature is the same on either the Celsius or the kelvin scale.)
If we represent the heat change as q, we have the following equation:
lid
q = mc∆T
copper rather than pure water, it is the mass of
If we are dealing with aqueous solutions
polystyrene cup calorimeter
water in the solution that should be included as the ‘m’ in this equation. Since the
solutions are often quite dilute, and since the volume and heat capacity of a dilute
solution are about the same as thosewater
of the water it contains, we normally use the
following equation:
solution
q = 4.18 × v × ∆T, where v = volume of the solution in cm3
spirit burner
Figure 5.3 A basic calorimeter, used for Figure 5.3 shows a simple apparatus that can be used measure the heat change. The
simple heat experiments expanded polystyrene cup has a lid to keep heat losses to a minimum.
16
99
105
05_08 Cam/Chem AS&A2
05_03 Cam/Chem AS&A2
Barking Dog Art
Barking Dog Art
181333_05_AS_Chem_BP_097-117.indd 99 15/10/14 10:43 AM
181333_05_AS_Chem_BP_097-117.indd 105 15/
q = m x c x ∆T
If we are dealing with aqueous solutions rather than pure water, it is the mass of
water in the solution that should be included as the ‘m’ in this equation. Since the
solutions are often quite dilute, and since the volume and heat capacity of a
dilute solution are about the same as those of the water it contains, we normally
use the volume of the solution rather than its mass to give this equation:
q = volume x c x ∆T
18
19
1 mole 1 mole
20
21
(b) Comment on why this experimental value is lower than the data
booklet value.
24
26
28
SKILL CHECK
75cm3 of 2.0 moldm−3 ethanoic acid, CH3CO2H, were placed in a
plastic cup. The temperature was 18.2°C. To this were added 75cm3 of
2.0 moldm−3 ammonium hydroxide, NH4OH, whose temperature was
18.6 °C. After mixing, the highest temperature was 31.0 °C.
29
SKILL CHECK
A burner containing hexanol, C6H13OH, had a mass of 325.68g. It was
lit and placed under a copper calorimeter containing 250 cm3 of
water. The temperature of the water rose from 19.2°C to 31.6°C.
Afterwards the burner’s mass was 324.37 g.
Calculate:
30
Hess’s law En
Conserving energy fro
HESS’ LAW
The Law of Conservation of Energy states that ‘energy for
There are very few reactionscannot
whosebeenthalpy
created or destroyed’.
change Thismeasured
can be is called the First Law We c
of Thermodynamics. the t
directly by measuring the change in temperature in a calorimeter. We can
This law also applies to chemical reactions. The total
find enthalpy changes for other reactions
energy indirectly.and
of the chemicals To their
do this we make must
surroundings
use of Hess’ Law. remain constant. In 1840 Germain Hess applied the Law of
Conservation of Energy to enthalpy changes.
Hess’ law is an application of the first law of thermodynamics, which in its
simplest form is the law of conservation of energy. Since energy cannot
Hess’s law states that ‘the total enthalpy change in a
be destroyed or created the energy change
chemical in is
reaction a independent
chemical process
of the route by which
Figur
should be the same as long as the
thechemical reaction
initial and takes place
final states are as
thelong as the initial and
same. chan
final conditions are the same’.
step)
31 We u
Enthalpy cycles and p
We can illustrate Hess’s law by drawing enthalpy cycles react
(Hess cycles). In Figure 6.7, the reactants A and B combine find
directly to form C. This is the direct route. Whe
Two indirect routes are also shown. One other way
of changing A + B to C is to convert A + B into different di
substances F + G (intermediates), which then combine to
So Δ
form
HESS’C. LAW
T
Hess’ law states that ‘the total type
F+G
enthalpy change in a chemical ■ w
irect route 1 d
ind
■
reaction is independent of the ■ d
route by which the chemical A+B C co
reaction takes place as long as direct route ■ ap
o
the initial and final conditions are
ind If the
the same’. i rect route 2
mult
X Y+Z
reme
of an
Figure 6.7 ∆H(direct)
The enthalpy change is1)the
= ∆H(indirect same no matter
= ∆H(indirect 2) which
route is followed.
32 W
Hess’s law tells us that the enthalpy change of reaction
1
for the direct route is the same as for the indirect route. It
does not matter how many steps there are in the indirect
CEDAR COLLEGE route. We can still use Hess’s law. ENERGETICS
We can use Hess’s law to calculate enthalpy
changes that cannot be found by experiments using
67
HESS’ LAW
Some enthalpy changes are easy to measure experimentally, e.g.:
33
HESS’ LAW
This can be shown by making a Hess cycle as shown below:
∆H1
A B
∆H2 ∆H3
C
34
HESS’ LAW
1. Write out balanced equations for all energy changes mentioned in question.
5. Balance each box to ensure the number of atoms in each box is the same.
6. The box with which your cycle begins is the start box and the one where the
cycle ends is the stop box.
Note: The enthalpies given are per mole therefore as the number of moles change,
the energies have to be multiplied by the same number.
35
SUMMARY CYCLES
Box A Box B
∆H FOR FORMATION REACTIONS
reactants products
Start box: C End box: B
∆H cts C ➜ A + A ➜B = C ➜ B
du
f re pro
∆H
ac f
tan elements
ts
Box C: Elements
Box A Box B
FOR COMBUSTION REACTIONS ∆H
reactants products
Start box: A End box: C
A ➜ B + B ➜C = A ➜ C ∆H cts
du
cr
ea pro
∆H
cta c
nts elements
EXAMPLE 1
Consider the following two reactions:
We can use Hess’s Law to find the value of the incomplete combustion of
carbon to form CO.
37
EXAMPLE 1
Box A Box B
∆H1 = – 394 kJ mol–1
C CO2
–1
mol
∆H kJ
3 83
–2
CO =
2
∆H
Box C
∆H3 = ?
38
EXAMPLE 2
Calculate the standard enthalpy of formation of methane from the following data:
39
EXAMPLE 2
Step 2: enter the reactants Box A Box B
∆H1 = ?
(in Box A) and products (in C(s) + 2H2(g) CH4(g)
Box B) of Step 1 into the 2x
∆H ∆H 0
Hess cycle °
c (C °c (H 89
)=
—3 2)
=2 ) =—
93 (— H4
28 C
6) ° c(
Step 3: enter the combustion ∆H
products of the Box A and CO2 + 2 H2O
Box B into Box C
Box C : Combustion products
A ➜B + B ➜ C = A ➜ C
Step 4: work out ∆H1 from
∆H1 + ∆H°c(CH4) = ∆H°c(C) + 2 x ∆H°c(H2)
∆H1 = ∆H2 + ∆H3
∆H1 + (—890) = (—393) + 2(—286)
∆H1 = ?
40
SKILL CHECK
Calculate the standard enthalpy change for the following reaction, given
that the standard enthalpies of formation of water, nitrogen dioxide and
nitric acid are —286, +33 and —173 kJ mol—1 respectively. The value for
oxygen is ZERO as it is an element (—252 kJ mol—1)
41
SKILL CHECK
Calculate the standard enthalpy change of combustion of ethane from the
following data:
42
SKILL CHECK
Calculate the enthalpy change for the reaction:
43
BOND ENTHALPY
Bond Enthalpy is the energy required to break one mole of a particular
type of bond in gaseous molecules under standard conditions.
Bond enthalpy values are all positive, showing that bond enthalpies are
endothermic (breaking bonds takes in energy).
The values found in the data booklet are average values for each type of
bond. The same bond may have very slightly different bond enthalpies in
different compounds.
The O—H bond has a slightly different enthalpy value in each compound.
44
BOND ENTHALPY
When a particular bond is broken, energy is taken in (endothermic):
Note: The amount of energy needed to break or form the same type of
bond is the same.
45
÷ EXAMPLE
=÷ ÷
Calculate the enthalpy change of reaction when 1 mole of methane, CH4 ,
÷
=÷
burns completely to form carbon dioxide and water.
÷
t O H
=÷
A
- -
÷
1
t H
=÷
O A
H
-
C
-
-
-
H + +
÷
1
I t -
O -
H H CA H
=÷
-
-
H I1
=÷
H -
C
H
-
H
4 x C—H bonds 2 x O=O bonds 2t x C=O
- -
H
O bonds 4A
x O—H bonds I
H
1
H
t breakO bonds A Product bonds H -
C H -
O -
H A
1
I
H
2 x O=O 2 x +498 = +996 4 x O—H 4 x —464 = —1856
H -
CI H
-
EXAMPLE
Bond breaking
+2648 kJ
Bond forming
—3466kJ
CH4(g) + 2O2(g)
∆H CO2(g) + H2O(l)
48
49
SKILL CHECK
The equation for the combustion of ethanol is:
A. Rewrite this equation to show all the bonds in the reactants and products.
B. Use bond energies (in kJ mol–1) to calculate a value for the standard
enthalpy change of this reaction.
50