6.

Energetics
Definition: Enthalpy change is the amount of heat energy taken in or given out during any
change in a system provided the pressure is constant, and that standard conditions are 100 kPa
and a specified temperature, usually 298 K
If an enthalpy change occurs then energy is
In an exothermic change energy is transferred from transferred between system and
the system (chemicals) to the surroundings. surroundings . The system is the
chemicals and the surroundings is
The products have less energy than the reactants. everything outside the chemicals.

In an endothermic change, energy is

Energy

Activation transferred from the surroundings to the

Energy: system (chemicals). They require an input of
EA heat energy e.g. thermal decomposition of
reactants calcium carbonate.
The products have more energy than the
reactants.
∆H
products
Activation
Energy:
Progress of Reaction EA
Energy

In an exothermic reaction the

∆H is negative reactants ∆H

Common oxidation exothermic processes are the In an endothermic reaction

combustion of fuels and the oxidation of the ∆H is positive
carbohydrates such as glucose in respiration.
Progress of Reaction

Standard enthalpy change of formation

The standard enthalpy change of formation of a compound is the Mg (s) + Cl2 (g)  MgCl2 (s)
enthalpy change when 1 mole of the compound is formed from 2Fe (s) + 1.5 O2 (g)  Fe2O3 (s)
its elements under standard conditions (298K and 100kpa), all
reactants and products being in their standard states The enthalpy of formation
Symbol fH of an element = 0 kJ mol-1

Standard enthalpy change of combustion

The standard enthalpy of combustion of a substance is defined as CH4 (g) + 2O2 (g) CO2 (g) + 2 H2O (l)
the enthalpy change that occurs when one mole of a substance is
combusted completely in oxygen under standard conditions. Incomplete combustion will lead to
(298K and 100kPa), all reactants and products being in their soot (carbon), carbon monoxide and
standard states water. It will be less exothermic than
complete combustion.
Symbol cH
When an enthalpy change is
Enthalpy changes are normally quoted at standard conditions.
measured at standard
Standard conditions are : conditions the symbol is
• 100 kPa pressure used
• 298 K (room temperature or 25oC) Eg H
• Solutions at 1mol dm-3
• all substances should have their normal state at 298K

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Definition: Enthalpy change of reaction is the enthalpy change when the number of moles of
reactants as specified in the balanced equation react together

Enthalpy change of neutralisation

The standard enthalpy change of neutralisation is the enthalpy change when solutions of an
acid and an alkali react together under standard conditions to produce 1 mole of water.

Enthalpy changes of neutralisation are always exothermic. For reactions involving strong
acids and alkalis, the values are similar, with values between -56 and -58 kJ mol-1

Enthalpy change of atomisation

The enthalpy of atomisation of an element is the enthalpy change when 1 mole of
gaseous atoms is formed from the element in its standard state
Na (s)  Na(g) [atH = +148 kJ mol-1]
½ O2 (g)  O (g) [atH = +249 kJ mol-1]

Hess’s Law
Hess’s law is a version of the first law
Hess’s law states that total enthalpy change for a reaction is of thermodynamics, which is that
independent of the route by which the chemical change takes place energy is always conserved.

2H (g) + 2Cl(g)
On an energy level diagram the directions of the arrows can
show the different routes a reaction can proceed by
a
In this example one route is arrow ‘a’
H2 + Cl2 b The second route is shown by arrows ΔH plus arrow ‘b’

ΔH So a = ΔH + b
2HCl (g) And rearranged
ΔH = a - b

ΔH
H+ (g) + Br - (g) H+ (aq) + Br - (aq) Interconnecting reactions can also be
shown diagrammatically.
a
d
In this example one route is arrow ‘a’ plus ΔH
The second route is shown by arrows ‘c’ plus arrow ‘d’
H (g) + Br (g) HBr (g)
c So a+ ΔH = c + d
And rearranged
ΔH = c + d - a

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 Often Hess’s law cycles are used to measure the enthalpy change for a reaction that cannot be measured
directly by experiments. Instead alternative reactions are carried out that can be measured experimentally.

H reaction This Hess’s law is used to work out the

CuSO4 (s) + 5H2O (l) CuSO4.5H2O (s) enthalpy change to form a hydrated salt
from an anhydrous salt.

-66.1 kJmol-1 + aq + aq +11kJmol-1

This cannot be done experimentally
because it is impossible to add the
CuSO4 (aq) exact amount of water and it is not easy
to measure the temperature change of
a solid.
H reaction + 11kJmol-1 = -66.1 kJmol-1
Instead both salts are dissolved in excess
H reaction = -66.1 - 11
water to form a solution of copper sulfate.
= -77.1 kJmol-1 The temperature changes can be measured
for these reactions.

H reaction This Hess’s law is used to work out the

CaCO3 (s) CaO (s) + CO2 (g) enthalpy change for the thermal
decomposition of calcium carbonate.
ΔH1 ΔH2
(+2HCl) (+2HCl)
This cannot be done experimentally
because it is impossible to add the heat
CaCl2 (aq) + H2O (l) + CO2 (g) required to decompose the solid and to
measure the temperature change of a
solid at the same time.
H reaction + ΔH2 = ΔH1

H reaction = ΔH1 - ΔH2 Instead both calcium carbonate and calcium

oxide are reacted with hydrochloric acid to
form a solution of calcium chloride. The
temperature changes can be measured for
these reactions.

Using Hess’s law to determine enthalpy changes from enthalpy changes of formation.

H reaction
Reactants Products
H reaction = Σ fH products - Σ fH reactants
Σ fH reactants Σ fH products

Elements in standard states

Example 1. Calculate the enthalpy change for this reaction

Al2O3 + 3 Mg  3 MgO + 2 Al H reaction
Remember Al2O3 (s) + 3 Mg (s) 3 MgO (s) + 2 Al (s)
H = ΣfH products – Σ fH reactants elements have
f H = 0 fH(Al2O3) 3 x fH (MgO)
H = 3 x fH (MgO) – fH (Al2O3)
H = (3 x –601.7) – –1675.7 fH(MgO)= -601.7 kJ mol-1 2Al (s) + 3 Mg (s) + 1.5O2 (g)
= -129.4 kJ mol-1 fH(Al2O3) = -1675.7 kJ mol-1

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 Example 2. Using the following data to calculate the enthalpy of combustion of propene
Hf C3H6(g) = +20 kJ mol-1 Hf CO2(g)= –394 kJ mol-1 Hf H2O(g)= –242 kJ mol-1
C3H6 + 4.5 O2  3CO2 + 3H2O
 cH
C3H6 (g) + 4.5 O2 (g) 3 CO2 (g) + 3 H2O (g)
cH = Σ fH products – Σ fH reactants
cH = [3 x fH (CO2) + 3 x fH (H2O)] - fH (C3H6) 3 x fH (CO2)
fH(C3H6) 3 x fH (H2O)
cH = [(3 x –394) + (3 x –242)] – 20
= -1928 kJ mol-1 3C (s) + 3 H2 (g) + 4.5 O2 (g)

Using Hess’s law to determine enthalpy changes from enthalpy changes of combustion.
H reaction
Reactants Products

H reaction = Σ cH reactants - Σ cH products Σ cH reactants

+O2 +O2
Σ cH products

Combustion Products

Example 3. Using the following combustion data to calculate the enthalpy of reaction
CO (g) + 2H2 (g)  CH3OH (g)
cH CO(g) = -283 kJ mol cH H2 (g)= –286 kJ mol-1 cH CH3OH(g)= –671 kJ mol-1
-1

H reaction
H reaction = Σ cH reactants - Σ cH products CO (g) + 2H2(g) CH3OH(g)
H = cH (CO) + 2 x cH (H2) - cH (CH3OH) +O2 +O2
cH(CO) + cH(CH3OH)
H = -283+ 2x –286 - -671 2x cH (H2)
CO2 (g) + 2 H2O (l)
= -184 kJ mol-1

Example 4. Using the following combustion data to calculate the enthalpy of formation of propene
3C (s) + 3H2 (g)  C3H6 (g)
cH C (s) = -393kJ mol-1 cH H2 (g)= –286 kJ mol-1 cH C3H6(g)= –-2058 kJ mol-1

f H
H = Σ cH reactants - Σ cH products
3C (s) + 3H2 (g) C3H6 (g)
fH = 3 x cH (C) + 3 x cH (H2 ) - cH (C3H6)
3 x cH (C) + cH(C3H6)
fH = 3x -393+ 3x –286 - -2058 3 x cH (H2 )

= +21 kJ mol-1
3 CO2 (g) + 3 H2O (l)

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Measuring the enthalpy change for a reaction experimentally
Calorimetric method This equation will only give the
energy for the actual quantities
used. Normally this value is
For a reaction in solution we use the following equation converted into the energy
energy change = mass of solution x heat capacity x temperature change change per mole of one of the
Q (J) = m (g) x cp (J g-1K-1) x T ( K) reactants. (The enthalpy
change of reaction, Hr)

Practical
Calorimetric method dont memorize but understand
One type of experiment is one in which substances are This could be a solid dissolving or reacting
mixed in an insulated container and the temperature rise in a solution or it could be two solutions
measured. reacting together

General method
 washes the equipment (cup and pipettes etc) with the solutions to be used
 dry the cup after washing
 put polystyrene cup in a beaker for insulation and support
 Measure out desired volumes of solutions with volumetric pipettes and transfer to
insulated cup
 clamp thermometer into place making sure the thermometer bulb is immersed in solution
 measure the initial temperatures of the solution or both solutions if 2 are used. Do this
every minute for 2-3 minutes
 At minute 3 transfer second reagent to cup. If a solid reagent is used then add the
solution to the cup first and then add the solid weighed out on a balance.
 If using a solid reagent then use ‘before and after’ weighing method
 stirs mixture (ensures that all of the solution is at the same temperature)
 Record temperature every minute after addition for several minutes

If the reaction is slow then the exact temperature rise can be

difficult to obtain as cooling occurs simultaneously with the
reaction

To counteract this we take readings at regular time intervals

and extrapolate the temperature curve/line back to the time
the reactants were added together.

We also take the temperature of the reactants for a few

minutes before they are added together to get a better
average temperature. If the two reactants are solutions then
the temperature of both solutions need to be measured
before addition and an average temperature is used.

Errors in this method Read question

carefully. It may be
• energy transfer from surroundings (usually loss) necessary to describe:
• approximation in specific heat capacity of solution. The method assumes all • Method
solutions have the heat capacity of water. • Drawing of graph
• neglecting the specific heat capacity of the calorimeter- we ignore any with extrapolation
energy absorbed by the apparatus. • Description of the
• reaction or dissolving may be incomplete or slow. calculation
• Density of solution is taken to be the same as water.

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Calculating the enthalpy change of reaction, Hr from experimental data
The heat capacity of water is
General method 4.18 J g-1K-1. In any reaction
where the reactants are
1. Using q= m x cp x T calculate energy change for quantities used dissolved in water we assume
that the heat capacity is the
2. Work out the moles of the reactants used same as pure water.

3. Divide q by the number of moles of the reactant not in excess to give H Also assume that the solutions
have the density of water,
4. Add a sign and unit (divide by a thousand to convert Jmol-1 to kJmol-1
which is 1g cm-3. Eg 25cm3 will
weigh 25 g

Example 5. Calculate the enthalpy change of reaction for the reaction where 25cm3 of 0.2 M
copper sulfate was reacted with 0.01mol (excess of zinc). The temperature increased 7oC .

Step 1: Calculate the energy change for the amount of reactants in the calorimeter.
Q = m x cp x T Note the mass is the mass of the copper sulfate
Q = 25 x 4.18 x 7 solution only. Do not include mass of zinc powder.
Q = 731.5 J

Step 2 : calculate the number of moles of the reactant not in excess.

moles of CuSO4 = conc x vol If you are not told what is in excess, then you need to
= 0.2 x 25/1000 work out the moles of both reactants and work out
= 0.005 mol using the balanced equation which one is in excess.

Step 3 : calculate the enthalpy change per mole which is often called the enthalpy change of reaction
H = Q/ no of moles
= 731.5/0.005
= 146300 J mol-1
Remember in these
= 146 kJ mol-1 to 3 sf
questions: sign,
Finally add in the sign to represent the energy change: if temp increases unit, 3 sig figs.
the reaction is exothermic and is given a minus sign e.g. –146 kJ mol-1

Example 6. 25cm3 of 2M HCl was neutralised by 25cm3 of 2M NaOH. The temperature increased 13.5oC
Calculate the enthalpy change per mole of HCl?

Step 1: Calculate the energy change for the amount of reactants in the calorimeter.
Q = m x cp x T Note the mass equals the mass of acid + the
Q = 50 x 4.18 x13.5 mass of alkali, as they are both solutions.
Q = 2821.5 J

Step 2 : calculate the number of moles of the HCl.

moles of HCl = conc x vol

= 2 x 25/1000
= 0. 05 mol
Step 3 : calculate H, the enthalpy change per mole which might be called the enthalpy change of neutralisation
Hr = Q/ no of moles
= 2821.5/0.05
= 56430 J mol-1
Remember in these
Exothermic and so is given a minus sign questions: sign,
= -56.4 kJ mol-1 to 3 sf
unit, 3 sig figs.

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 Measuring Enthalpies of combustion using calorimetry

Enthalpies of combustion can be calculated by using calorimetry. Generally the fuel is burnt and the flame
is used to heat up water in a metal cup

Example 7. Calculate the enthalpy change of combustion for the reaction where 0.65g of propan-1-ol was
completely combusted and used to heat up 150g of water from 20.1 to 45.5oC

Step 1: Calculate the energy change used to heat up the water in the metal cup.

Q = m x cp x T
Note the mass is the mass of water in the
Q = 150 x 4.18 x 25.4 calorimeter and not the alcohol
Q = 15925.8 J

Step 2 : calculate the number of moles of alcohol combusted.

moles of propan-1-ol = mass/ Mr

= 0.65 / 60
= 0.01083 mol

Step 3 : calculate the enthalpy change per mole which is called cH (the enthalpy change of combustion)
H = Q/ no of moles
= 15925.8/0.01083
= 1470073 J mol-1
Remember in these
= 1470 kJ mol-1 to 3 sf
questions: sign,
Finally add in the sign to represent the energy change: if temp increases unit, 3 sig figs.
the reaction is exothermic and is given a minus sign eg –1470 kJ mol-1

Errors in this method

• Energy losses from calorimeter

• Incomplete combustion of fuel
• Incomplete transfer of energy
• Evaporation of fuel after weighing
• Heat capacity of calorimeter not included
• Measurements not carried out under standard conditions as
H2O is gas, not liquid, in this experiment

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 Mean Bond enthalpies
These values are positive because
Definition: The mean bond enthalpy is the enthalpy needed to
energy is required to break a bond.
break the covalent bond into gaseous atoms, averaged over
different molecules
The definition only applies when the
substances start and end in the
We use values of mean bond enthalpies because every single
gaseous state.
bond in a compound has a slightly different bond energy. E.g. In
CH4 there are 4 C-H bonds. Breaking each one will require a
different amount of energy. However, we use an average value for
the C-H bond for all hydrocarbons.

The value for the bond enthalpy for the C-H bond in methane matches this reaction ¼ CH4 (g)  C (g) + H (g)

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

Gaseous atoms
Gaseous atoms
Energy
Energy

Energy

Energy
breaking Activation In an exothermic reaction Energy
breaking Activation making
bonds Energy Energy the sum of the bonds in Energy
bonds products bonds
reactants making
bonds
the reactant molecules
H will be less than the sum H
products reactants
of the bonds in the
product molecules
Progress of reaction
Progress of reaction
Reaction profile for an Reaction profile for an
EXOTHERMIC reaction ENDOTHERMIC reaction

In general (if all substances are gases)

H =  bond enthalpies broken -  bond enthalpies made

H reaction
Reactants Products

Σbond energies Σbond energies

broken in reactants made in products

Gaseous atoms of
elements

H values calculated using this method will be less accuate

than using formation or combustion data because the mean
bond energies are not exact

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Example 8. Use the following mean bond enthalpy data to calculate the Bond Mean enthalpy
enthalpy of combustion of propene
(kJ mol-1)
H H
O C=C 612
H C C C + 4.5 O O 3 O C O + 3
H H C-C 348
H H
H
O=O 496
H =  bond enthalpies broken -  bond enthalpies made
= [E(C=C) + E(C-C) + 6 x E(C-H) + 4.5 x E(O=O)] – [ 6 xE(C=O) + 6 E(O-H)] O=C 743

= [ 612 + 348 + (6 x 412) + (4.5 x 496) ] – [ (6 x 743) + (6 X 463)] O-H 463

= - 1572 kJmol-1 C-H 412

Example 9. Use the following mean bond enthalpy data to calculate the enthalpy of formation of NH3
½ N2 + 1.5 H2  NH3 (note the balancing is to agree with the definition of heat of formation (i.e. one mole of product)

E(N≡N) = 944 kJ mol-1 E(H-H) = 436 kJ mol-1 E(N-H) = 388 kJ mol-1

H =  bond enthalpies broken -  bond enthalpies made

= [0.5 x E(N≡N) + 1.5 x E(H-H)] – [ 3 xE(N-H)]

= [ (0.5 x 944) + (1.5 x 436) ] – [ 3 x 388)]
= - 38 kJmol-1

A more complicated example that may occur

This is a more complicated
Working out fH of a compound using bond energies and other data example of the type in example 9

elements  fH
Compound in
standard state The H’s can be
combinations of
H to turn elements H to turn
compound into different data
into gaseous atoms
gaseous atoms
Gaseous atoms

Can be bond energies

E(Cl-Cl) Cl2  2Cl  bond energies of
Or atomisation energies (if compound + (H to turn to
the substance is not diatomic gas if compound is not
gaseous)
C(s)  C(g)

Example 10
Calculate ΔfH for propane, C3H8(g), given the following data. Bond C–C C–H H–H
C(s)  C(g) ΔH = 715 kJ mol-1
kJ mol-1 348 412 436
3C (s) + 4H2 (g)  C3H8(g),

Σ H to turn elements - Σ H to turn compound

 fH =
into gaseous atoms into gaseous atoms

fH = (3xHat [C] + 4 x E[H-H] ) – (2 x E[C-C]+ 8 x E[C-H] )

= (3x715 + 4 x 436 ) – (2 x 348+ 8 x 412 )
=-103 kJ mol-1

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 Enthalpies of combustion in a homologous series

When comparing the heats of combustion for successive members of a homologous series such as
alkanes or alcohols there is a constant rise in the size of the heats of combustion as the number of
carbon atoms increases

H H O 1 C-C, 5C-H 1C-O 1O-H and 3 O=O

H C C O H + 3 O O 2 O C O + 3
H H
bonds are broken
H H 4 C=O and 6 O-H bonds are made
ethanol ΔHc = -1365 kJ mol-1

H H H 2C-C, 7C-H 1C-O 1O-H and 4.5 O=O

O bonds are broken
H C C C O H + 4.5 O O 3 O C O + 4
H H 6 C=O and 8 O-H bonds are made
H H H
ΔHc = -2016 kJ mol-1
Propan-1-ol

H H H H
3C-C, 9C-H 1C-O 1O-H and 6 O=O
H C C C C O H + 6 O
4 bonds are broken
O O O C O+ 5 H H
H H H H
8 C=O and 10 O-H bonds are made
Butan-1-ol
ΔHc = -2677 kJ mol-1

As one goes up the homologous series there is a constant amount and type of extra bonds being broken and
made e.g. 1C-C, 2C-H and 1.5 O=O extra bonds broken and 2 C=O and 2 O-H extra bonds made, so the
enthalpy of combustion increases by a constant amount

calculated If the results are worked out experimentally

using a calorimeter the experimental results
combustion kJ mol-1
Enthalpy of

will be much lower than the calculated ones

because there will be significant heat loss.
There will also be incomplete combustion
experimental which will lead to less energy being
released.

Mr of alcohol

Remember that calculated values of enthalpy of combustions will

be more accurate if calculated from enthalpy of formation data than
if calculated from average bond enthalpies. This is because
average bond enthalpy values are averaged values of the bond
enthalpies from various compounds.

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