EN THA LP Y

CHAN GE S
A guide for A level students

KNOCKHARDY PUBLISHING
 ENTHALPY CHANGES
INTRODUCTION
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 ENTHALPY CHANGES
CONTENTS
• Thermodynamics
• Enthalpy changes
• Standard enthalpy values
• Standard enthalpy of formation
• Standard enthalpy of combustion
• Enthalpy of neutralisation
• Bond dissociation enthalpy
• Hess’s law
• Calculating enthalpy changes using bond enthalpies
• Calculating enthalpy changes using enthalpy of formation values
• Calculating enthalpy changes using enthalpy of combustion values
• Practical measurement
• Check list
 ENTHALPY CHANGES

Before you start it would be helpful to…

• be able to balance equations

• be confident with simple arithmetical operations
 THERMODYNAMICS
First Law Energy can be neither created nor destroyed but
It can be converted from one form to another

Energy
changes all chemical reactions are accompanied by some form of energy change
changes can be very obvious (e.g. coal burning) but can go unnoticed

Exothermic Energy is given out

Endothermic Energy is absorbed

Examples Exothermic combustion of fuels

respiration (oxidation of carbohydrates)

Endothermic photosynthesis
thermal decomposition of calcium carbonate
 THERMODYNAMICS - ENTHALPY CHANGES
Enthalpy a measure of the heat content of a substance at constant pressure
you cannot measure the actual enthalpy of a substance
you can measure an enthalpy CHANGE
written as the symbol ∆Η , “delta H ”

Enthalpy change (∆Η) = Enthalpy of products - Enthalpy of reactants

 THERMODYNAMICS - ENTHALPY CHANGES
Enthalpy a measure of the heat content of a substance at constant pressure
you cannot measure the actual enthalpy of a substance
you can measure an enthalpy CHANGE
written as the symbol ∆Η , “delta H ”

Enthalpy change (∆Η) = Enthalpy of products - Enthalpy of reactants

ENTHALPY

REACTION CO-ORDINATE

Enthalpy of reactants > products

∆Η = - ive
EXOTHERMIC Heat given out
 THERMODYNAMICS - ENTHALPY CHANGES
Enthalpy a measure of the heat content of a substance at constant pressure
you cannot measure the actual enthalpy of a substance
you can measure an enthalpy CHANGE
written as the symbol ∆Η , “delta H ”

Enthalpy change (∆Η) = Enthalpy of products - Enthalpy of reactants

ENTHALPY
ENTHALPY

REACTION CO-ORDINATE REACTION CO-ORDINATE

Enthalpy of reactants > products Enthalpy of reactants < products

∆Η = - ive ∆Η = + ive
EXOTHERMIC Heat given out ENDOTHERMIC Heat absorbed
 STANDARD ENTHALPY CHANGES
Why a
standard? enthalpy values vary according to the conditions
a substance under these conditions is said to be in its standard state ...

Pressure:- 100 kPa (1 atmosphere)

A stated temperature usually 298K (25°C)

• as a guide, just think of how a substance would be under normal lab conditions
• assign the correct subscript [(g), (l) or (s) ] to indicate which state it is in
• any solutions are of concentration 1 mol dm-3
• to tell if standard conditions are used we modify the symbol for ∆Η .

Enthalpy Change Standard Enthalpy Change

(at 298K)
 STANDARD ENTHALPY OF FORMATION
Definition The enthalpy change when ONE MOLE of a compound is formed in its
standard state from its elements in their standard states.

Symbol ∆Η°f

Values Usually, but not exclusively, exothermic

Example(s) C(graphite) + O2(g) ———> CO2(g)

H2(g) + ½O2(g) ———> H2O(l)

2C(graphite) + ½O2(g) + 3H2(g) ———> C2H5OH(l)

Notes Only ONE MOLE of product on the RHS of the equation

Elements In their standard states have zero enthalpy of formation.

Carbon is usually taken as the graphite allotrope.

 STANDARD ENTHALPY OF COMBUSTION
Definition The enthalpy change when ONE MOLE of a substance undergoes complete
combustion under standard conditions. All reactants and products are in
their standard states.

Symbol ∆Η°c

Values Always exothermic

Example(s) C(graphite) + O2(g) ———> CO2(g)

H2(g) + ½O2(g) ———> H2O(l)

C2H5OH(l) + 3O2(g) ———> 2CO2(g) + 3H2O(l)

Notes Always only ONE MOLE of what you are burning on the LHS of the equation
To aid balancing the equation, remember...
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.
 ENTHALPY OF NEUTRALISATION
Definition The enthalpy change when ONE MOLE of water is formed from
its ions in dilute solution.

Values Exothermic

Equation H+(aq) + OH¯(aq) ———> H2O(l)

Notes A value of -57kJ mol-1 is obtained when

strong acids react with strong alkalis.

See later slides for practical details of measurement

 BOND DISSOCIATION ENTHALPY
Definition Energy required to break ONE MOLE of gaseous bonds to form gaseous atoms.

Values Endothermic - Energy must be put in to break any chemical bond

Examples Cl2(g) ———> 2Cl(g) O-H(g) ———> O(g) + H(g)

Notes • strength of bonds also depends on environment; MEAN values quoted

• making bonds is exothermic as it is the opposite of breaking a bond
• for diatomic gases, bond enthalpy = 2 x enthalpy of atomisation
• smaller bond enthalpy = weaker bond = easier to break
 BOND DISSOCIATION ENTHALPY
Definition Energy required to break ONE MOLE of gaseous bonds to form gaseous atoms.

Values Endothermic - Energy must be put in to break any chemical bond

Examples Cl2(g) ———> 2Cl(g) O-H(g) ———> O(g) + H(g)

Notes • strength of bonds also depends on environment; MEAN values quoted

• making bonds is exothermic as it is the opposite of breaking a bond
• for diatomic gases, bond enthalpy = 2 x enthalpy of atomisation
• smaller bond enthalpy = weaker bond = easier to break

Mean Values H-H 436 H-F 562 N-N 163

C-C 346 H-Cl 431 N=N 409
Average (mean) C=C 611 H-Br 366 N≡N 944
values are quoted C≡C 837 H-I 299 P-P 172
because the actual
C-O 360 H-N 388 F-F 158
value depends on
the environment of C=O 743 H-O 463 Cl-Cl 242
the bond i.e. where C-H 413 H-S 338 Br-Br 193
it is in the molecule C-N 305 H-Si 318 I-I 151
C-F 484 P-H 322 S-S 264
C-Cl 338 O-O 146 Si-Si 176

UNITS = kJ mol-1
 HESS’S LAW
“The enthalpy change is independent of the path taken”

How The enthalpy change going from

A to B can be found by adding the
values of the enthalpy changes for
the reactions A to X, X to Y and Y to B.

∆Η r = ∆Η 1 + ∆Η 2 + ∆Η 3
 HESS’S LAW
“The enthalpy change is independent of the path taken”

How The enthalpy change going from

A to B can be found by adding the
values of the enthalpy changes for
the reactions A to X, X to Y and Y to B.

∆Η r = ∆Η 1 + ∆Η 2 + ∆Η 3

If you go in the opposite direction of an arrow, you subtract the value of

the enthalpy change.

e.g. ∆Η 2 = - ∆Η 1 + ∆Η r - ∆Η 3

The values of ∆Η 1 and ∆Η 3 have been subtracted because the route

involves going in the opposite direction to their definition.
 HESS’S LAW
“The enthalpy change is independent of the path taken”

Use applying Hess’s Law enables one to calculate enthalpy changes from
other data, such as...

changes which cannot be measured directly e.g. Lattice Enthalpy

enthalpy change of reaction from bond enthalpy

enthalpy change of reaction from ∆Η°c

enthalpy change of formation from ∆Η°f

 Enthalpy of reaction from bond enthalpies
Theory Imagine that, during a reaction, all the bonds of reacting species are broken
and the individual atoms join up again but in the form of products. The
overall energy change will depend on the difference between the energy
required to break the bonds and that released as bonds are made.

energy released making bonds > energy used to break bonds ... EXOTHERMIC
energy used to break bonds > energy released making bonds ... ENDOTHERMIC

Step 1 Energy is put in to break bonds to form separate, gaseous atoms

Step 2 The gaseous atoms then combine to form bonds and energy is released
its value will be equal and opposite to that of breaking the bonds

Applying Hess’s Law ∆Η r = Step 1 + Step 2

 Enthalpy of reaction from bond enthalpies
Alternative view
Step 1 Energy is put in to break bonds ATOMS
to form separate, gaseous atoms.
SUM OFTHE BOND
Step 2 Gaseous atoms then combine ENTHALPIES OF SUM OFTHE
to form bonds and energy is THE REACTANTS BOND
released; its value will be equal ENTHALPIES OF
and opposite to that of breaking THE PRODUCTS
REACTANTS
the bonds
∆Η
∆Η r = Step 1 - Step 2

Because, in Step 2 the route involves PRODUCTS

going in the OPPOSITE DIRECTION
to the defined change of bond enthalpy,
it’s value is subtracted.

∆Η = Σ bond enthalpies – Σ bond enthalpies

of reactants of products
 Enthalpy of reaction from bond enthalpies
Calculate the enthalpy change for the hydrogenation of ethene
 Enthalpy of reaction from bond enthalpies
Calculate the enthalpy change for the hydrogenation of ethene

∆Η 2 1 x C=C bond @ 611 = 611 kJ

4 x C-H bonds @ 413 = 1652 kJ
1 x H-H bond @ 436 = 436 kJ
Total energy to break bonds of reactants = 2699 kJ
 Enthalpy of reaction from bond enthalpies
Calculate the enthalpy change for the hydrogenation of ethene

∆Η 2 1 x C=C bond @ 611 = 611 kJ

4 x C-H bonds @ 413 = 1652 kJ
1 x H-H bond @ 436 = 436 kJ
Total energy to break bonds of reactants = 2699 kJ

∆Η 3 1 x C-C bond @ 346 = 346 kJ

6 x C-H bonds @ 413 = 2478 kJ
Total energy to break bonds of products = 2824 kJ

Applying Hess’s Law ∆Η 1 = ∆Η 2 – ∆Η 3 = (2699 – 2824) = – 125 kJ

 Enthalpy of reaction from enthalpies of formation

If you formed the products from their elements you should need the same amounts
of every substance as if you formed the reactants from their elements.

Enthalpy of formation tends to be an exothermic process

 Enthalpy of reaction from enthalpies of formation

Step 1 Energy is released as reactants ELEMENTS

are formed from their elements.
SUM OFTHE
Step 2 Energy is released as products ENTHALPIES OF
are formed from their elements. FORMATION OF SUM OFTHE
THE REACTANTS ENTHALPIES
OF
∆Η r = - Step 1 + Step 2 REACTANTS
FORMATION
OF THE
PRODUCTS
or Step 2 - Step 1
∆Η
In Step 1 the route involves going in the
OPPOSITE DIRECTION to the defined
PRODUCTS
enthalpy change, it’s value is subtracted.

∆Η = Σ ∆Η f of products – Σ ∆Η f of reactants
 Enthalpy of reaction from enthalpies of formation

Sample calculation
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

2H2O(l) + 4NO2(g) + O2(g) ———> 4HNO3(l)

∆Η = Σ ∆Η f of products – Σ ∆Η f of reactants

By applying Hess’s Law ... The Standard Enthalpy of Reaction ∆Η°r will be...

PRODUCTS REACTANTS
[ 4 x ∆Η f of HNO3 ] minus [ (2 x ∆Η f of H2O) + (4 x ∆Η f of NO2) + (1 x ∆Η f of O2) ]

∆Η°r = 4 x (-173) - 2 x (-286) + 4 x (+33) + 0

ANSWER = - 252 kJ
 Enthalpy of reaction from enthalpies of combustion

If you burned all the products you should get the same amounts of oxidation products
such a CO2 and H2O as if you burned the reactants.

Enthalpy of combustion is an exothermic process

 Enthalpy of reaction from enthalpies of combustion

Step 1 Energy is released as reactants REACTANTS

undergo combustion.
∆Η
Step 2 Energy is released as products
SUM OFTHE
undergo combustion.
ENTHALPIES OF
PRODUCTS COMBUSTION
∆Η r = Step 1 - Step 2 OF THE
SUM OFTHE REACTANTS
ENTHALPIES OF
COMBUSTION OF
THE PRODUCTS
Because, in Step 2 the route involves going
in the OPPOSITE DIRECTION to the OXIDATION
defined change of Enthalpy of Combustion, PRODUCTS
it’s value is subtracted.

∆Η = Σ ∆Η c of reactants – Σ ∆Η c of products
 Enthalpy of reaction from enthalpies of combustion

Sample calculation
Calculate the standard enthalpy of formation of methane; the standard enthalpies of
combustion of carbon, hydrogen and methane are -394, -286 and -890 kJ mol-1 .

C(graphite) + 2H2(g) ———> CH4(g)

∆Η = Σ ∆Η c of reactants – Σ ∆Η c of products

By applying Hess’s Law ... The Standard Enthalpy of Reaction ∆Η°r will be...

REACTANTS PRODUCTS
[ (1 x ∆Η c of C) + (2 x ∆Η c of H2) ] minus [ 1 x ∆Η c of CH4]

∆Η°r = 1 x (-394) + 2 x (-286) - 1 x (-890)

ANSWER = - 76 kJ mol-1
 MEASURING ENTHALPY CHANGES
Calorimetry involves the practical determination of enthalpy changes
usually involves heating (or cooling) known amounts of water
water is heated up reaction is EXOTHERMIC
water cools down reaction is ENDOTHERMIC

Calculation The energy required to change the temperature

of a substance can be calculated using... q = m x c x ∆Τ

where q = heat energy kJ

m = mass kg
c = Specific Heat Capacity kJ K -1 kg -1 [ water is 4.18 ]
∆Τ = change in temperature K
 MEASURING ENTHALPY CHANGES
Calorimetry involves the practical determination of enthalpy changes
usually involves heating (or cooling) known amounts of water
water is heated up reaction is EXOTHERMIC
water cools down reaction is ENDOTHERMIC

Calculation The energy required to change the temperature

of a substance can be calculated using... q = m x c x ∆Τ

where q = heat energy kJ

m = mass kg
c = Specific Heat Capacity kJ K -1 kg -1 [ water is 4.18 ]
∆Τ = change in temperature K

Example On complete combustion, 0.18g of hexane raised the temperature of

100g water from 22°C to 47°C. Calculate its enthalpy of combustion.

Heat absorbed by the water (q) = 0.1 x 4.18 x 25 = 10.45 kJ

Moles of hexane burned = mass / Mr = 0.18 / 86
= 0.00209
Enthalpy change = heat energy / moles = 10.45 / 0.00209
ANS = 5000 kJ mol -1
 MEASURING ENTHALPY CHANGES
Example 1 - graphical
The temperature is taken every half
minute before mixing the reactants.

Reactants are mixed after three minutes.

Further readings are taken every half

minute as the reaction mixture cools.

Extrapolate the lines as shown and

calculate the value of ∆Τ.
 MEASURING ENTHALPY CHANGES
Example 1 - graphical
The temperature is taken every half
minute before mixing the reactants.

Reactants are mixed after three minutes.

Further readings are taken every half

minute as the reaction mixture cools.

Extrapolate the lines as shown and

calculate the value of ∆Τ.

Example calculation
When 0.18g of hexane underwent complete combustion, it raised the temperature of
100g (0.1kg) water from 22°C to 47°C. Calculate its enthalpy of combustion.

Heat absorbed by the water (q) = m C ∆Τ = 0.1 x 4.18 x 25 = 10.45 kJ

Moles of hexane burned = mass / Mr = 0.18 / 86 = 0.00209

Enthalpy change = heat energy / moles = 10.45 / 0.00209 = 5000 kJ mol -1
 MEASURING ENTHALPY CHANGES
Example 2
25cm3 of 2.0M HCl was added to 25cm3 of 2.0M NaOH in an insulated beaker. The initial
temperature of both solutions was 20°C. The highest temperature reached by the
solution was 33°C. Calculate the Molar Enthalpy of Neutralisation. [The specific heat
capacity (c) of water is 4.18 kJ K -1 kg -1]

NaOH + HCl ——> NaCl + H2O

 MEASURING ENTHALPY CHANGES
Example 2
25cm3 of 2.0M HCl was added to 25cm3 of 2.0M NaOH in an insulated beaker. The initial
temperature of both solutions was 20°C. The highest temperature reached by the
solution was 33°C. Calculate the Molar Enthalpy of Neutralisation. [The specific heat
capacity (c) of water is 4.18 kJ K -1 kg -1]

NaOH + HCl ——> NaCl + H2O

Temperature rise (∆Τ) = 306K – 293K = 13K

Volume of resulting solution= 25 + 25 = 50cm3 = 0.05 dm3
Equivalent mass of water = 50g = 0.05 kg
(density is 1g per cm3)
Heat absorbed by the water (q) = m x c x ∆Τ = 0.05 x 4.18 x 13 =
2.717 kJ
 MEASURING ENTHALPY CHANGES
Example 2
25cm3 of 2.0M HCl was added to 25cm3 of 2.0M NaOH in an insulated beaker. The initial
temperature of both solutions was 20°C. The highest temperature reached by the
solution was 33°C. Calculate the Molar Enthalpy of Neutralisation. [The specific heat
capacity (c) of water is 4.18 kJ K -1 kg -1]

NaOH + HCl ——> NaCl + H2O

Temperature rise (∆Τ) = 306K – 293K = 13K

Volume of resulting solution= 25 + 25 = 50cm3 = 0.05 dm3
Equivalent mass of water = 50g = 0.05 kg
(density is 1g per cm3)
Heat absorbed by the water (q) = m x c x ∆Τ = 0.05 x 4.18 x 13 =
2.717 kJ

Moles of HCl reacting = 2 x 25/1000 = 0.05 mol

Moles of NaOH reacting = 2 x 25/1000 = 0.05 mol
Moles of water produced = 0.05 mol

Enthalpy change per mol (∆Η) = heat energy / moles of water = 2.717 / 0.05
= 54.34 kJ mol -1
 REVISION CHECK
What should you be able to do?
Explain the difference between an endothermic and exothermic reaction
Understand the reasons for using standard enthalpy changes
Recall the definitions of enthalpy of formation and combustion
Write equations representing enthalpy of combustion and formation
Recall and apply Hess’s law
Recall the definition of bond dissociation enthalpy
Calculate standard enthalpy changes using bond enthalpy values
Calculate standard enthalpy changes using enthalpies of formation and combustion
Know simple calorimetry methods for measuring enthalpy changes
Calculate enthalpy changes from calorimetry measurements

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 EN THA LP Y
CHAN GE S
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© 2003 JONATHAN HOPTON & KNOCKHARDY PUBLISHING