TAYLOR’S COLLEGE

CHEMISTRY (9701)
AS Level

Chapter 5: Chemical Energetics

By: Mr. Chan M.H., Lucas

([email protected])
Introduction
• First Law - Energy can be neither created nor destroyed
but It can be converted from one form to another

• The bond breaking process:

H-H (g)→ 2H (g) ……………………Energy is absorbed

• The bond forming process:

2H (g) + 2 Cl (g) → 2H-Cl (g) ……..Energy is released

• Hence, there is a net change in energy in every chemical reaction

• ∆H = the enthalpy change of reaction

• The –ve sign (-) means that the reaction is exothermic, ie heat is release
• The +ve sign (+) means that the reaction is endothermic, ie heat is absorbed

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

 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 DH , “delta H ”

Enthalpy change (DH) = Enthalpy of products - Enthalpy of reactants

ENTHALPY

ENTHALPY
REACTION CO-ORDINATE REACTION CO-ORDINATE

Enthalpy of reactants > products Enthalpy of reactants < products

DH = - ve DH = + ve
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:- 101 kPa (1 atm)

A stated temperature 298K (25°C)

• as a guide, just think of how a substance would be under normal lab conditions
• Physical state symbols must be given [(g), (l) or (s) ]
• any solutions are of concentration 1 mol dm-3
• to tell if standard conditions are used we modify the symbol for DH .
• Units for is kJ mol-1
O

Enthalpy Change Standard Enthalpy Change

(at 298K)
• A thermochemical equation gives the amount (in moles) of
reactants and products, and also tells the quantity of energy involved
in the reaction

• 4NH3 (g) + 3O2(g) → 2N2(g) + 6H2O(l) ∆H° = -1260 kJmol-1

• For reaction,
− 1260
• NH3 (g) + ¾ O2(g) → ½ N2(g) + 3/2 H2O(l) ∆H° = kJ mol-1
4
= - 315 kJ mol-1
Standard Enthalpy Change

• Formation
• Combustion
• Neutralisation
• Atomisation
• Hydration
• Solution
• Reaction
Standard Enthalpy Change of
Formation
• Definition: the enthalpy change when 1 mole of a compound is
formed from its constituent elements in their standard states
under standard conditions of 298K and 1atm.

• Symbol: ∆HOf

• The ∆H°f for water is -286 kJ mol-1. This means that when 1 mol of
water (liquid) is formed by the combination of hydrogen and oxygen
gases, 286 kJ of heat is evolved.

H2 (g) + ½ O2 (g) → H2O (l) ∆H O

f= - 286 kJ mol-1
• The standard enthalpy of formation of a substance can be either positive or
negative:
2C (s) + H2 (g) → C2H2 (g) ∆H°f = +226 kJ mol-1
C(s) + O2 (g) → CO2 (g) ∆H°f = -394 kJ mol-1

• By definition, the standard enthalphy of formation of elements in its normal

physical state is zero. (Stable form under standard cond.)

• ∆H°f Is often used to predict the stability of a compound relative to its constituent
elements.

If ∆H°f < 0, compound is energetically more stable than its constituent elements
If ∆H°f > 0, compound is energetically less stable than its constituents elements
• Given:
HF (g) HCl (g) HBr (g) HI (g)

∆HØf /kJ mol-1 -269 -92 -36 +27

• Hence, stability decrease in order of:

HF > HCl > HBr > HI

½ N2 (g) + ½ O2 (g) → NO (g) ∆H°f = +90 kJ mol-1

• ∆H°f > 0, so NO (g) is energetically unstable with respect to N2 and

O2
• However, for elements that can exist in several allotropic form, only
the most stable form under standard conditions are given zero
standard enthalpies of formation.

Allotrope ∆H°f kJ mol-1

Graphite 0.0

Diamond +2.0

• Under standard conditions, graphite is the stable form

• The standard enthalpy of formation of some substance cannot be
directly measured from experiments

• Example (Production of ethyne, C2H2):

• C(s) + O2(g) → CO2(g) ∆H°= - 394kJ mol-1

• H2(g) + ½ O2(g) → H2O(l) ∆H°= - 286kJ mol-1
• C2H2(g) + 5/2 O2(g) → 2CO2 (g) + H2O(l) ∆H°= - 1300kJ mol-1

• The standard enthalpy of formation of ethyne is calculated from

other known enthalpy values using Hess law
Standard Enthalpy Change of
Combustion
• Definition: the enthalpy change of combustion is defined
as the enthalpy change when 1 mole of a element or
compound is completely burnt in excess oxygen
under standard conditions of 298K and 1atm.

• Symbol: ∆H O
c (always –ve)

Example(s)

C(s) + O2(g) → CO2(g) ∆H O c = -394 kJ mol-1

C2H4(g) + 3O2(g) → 2CO2(g) + 2H2O(l) ∆H O c = -1411 kJ mol-1
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(l) ∆H O c = -2202 kJ mol-1
Standard Enthalpy Change of
Neutralisation
• Definition: The standard enthalpy change of neutralisation is defined
as the enthalpy change when 1 mole of water is formed in
neutralisation between an acid and an alkali under standard
conditions. (Reaction in aqueous solution)

• NaOH (aq) + HCl (aq) → NaCl (aq) + H2O(l) ∆H O

n = -57.3 kJ
mol-1

• Enthalpy change of reaction = enthalpy change of neutralisation of

NaOH with HCl

• The enthalpy change of neutralisation of a strong acid with a strong

alkali is almost the same

• H+(aq) + OH-(aq) → H2O(l)

Standard Enthalpy Change of
Atomisation
• Definition: The standard enthalpy change of atomisation of an
element is the heat energy required when 1 mole of free gaseous
atoms is formed from its element under standard conditions.

• Example:

• Fe(s) → Fe(g) ∆H°at = +418 kJ mol-1

• ½ Cl2(g) → Cl(g) ∆H°at = +121 kJ mol-1

• Why the enthalpy changes of atomisation are positive?

• What is the standard enthalpy change of atomisation of Helium
and Argon?
Standard Enthalpy Change of
Hydration
• Definition: The standard enthalpy change of hydration (ΔHhydº) of an
ion is defined as the enthalpy change when one mole of the
gaseous ions is dissolved in a large quantity of water to form
aqueous ions under standard conditions.

• Example:

• Na+ (g) + water → Na+ (aq) ∆H°hyd = -406 kJ mol-1

• The heat produced in the hydration of ions comes from the bonds
formed between the ions and the dipole on the water molecules.
Enthalpy change is always –ve. Why?
Standard Enthalpy Change of
Solution
• Definition: The standard enthalpy change of solution (ΔHsolº) is
defined as the enthalpy change when one mole of a substance
dissolves in water to form aqueous compound or ions under
standard conditions.

• Example;

• NaCl(s) + aq → Na+ (aq) + Cl- (aq) ∆H°Sol = +6 kJ mol-1

• NH3(g) + aq → NH3(aq)

• Enthalpy change can be +ve or -ve

Standard Enthalpy Change of
reaction
• The standard enthalpy change of reaction is the enthalpy
change when the amounts of reactants shown in the
equation react to give products under standard
conditions.
• The reactants and products must be in standard states.
• Symbol: ∆H°r
Determination of the Standard
Enthalpy of Combustion
• The enthalpy change of combustion of a compound can be found by
using a bomb calorimeter

thermometer

ignition
unit
dewar

O2
stirrer
water sample
bomb

• The bomb consist of a steel cylinder surrounded by a known quantity of water

• Sample is placed on a platinum crucible
• Oxygen, under a pressure about 25 atm is forced into the bomb
• The substance is burned by a hot filament.
• Heat is recorded by the thermometer.
• http://www.chm.davidson.edu/ronutt/che115/Bomb/Bomb.htm
 mass of compound burnt
• No. of moles of compound burnt =
relative molecular mass of compound

= x moles

• Heat produced in the combustion =

Mass of water in grams x Specific heat capacity of water x temperature rise
(= v of water in cm3) (4.18JK-1g-1) (In oC)
=yJ

=
y kJ
1000

Hence if x mole of the compound was burnt, the heat produced

y
=- kJ/mol = the enthalpy change of combustion
1000 x
• 1.80 g of glucose was completely burnt in oxygen. The heat produced was
found to raise the temperature of 5.0dm 3 of water by 1.34oC. Calculate the
enthalpy change of combustion of glucose. (relative molecular mass of glucose = 180;
specific heat capacity of water = 4.18 JK-1g-1)

• Heat absorbed by water = 5000 x 4.18 x 1.34

= 5000 X 4.18 X 1.34

= 28 006 J

1.8
• Number of moles of glucose that was burnt = = 0.01 mole
180

• Hence 1 mole of glucose would produce 28006 J

0.01 x 1000

• The enthalpy change of combustion of glucose, ∆H° = - 2800 kJ mol-1

Sample question
Sample question

N19/P21/Q3
Sample question
• Use a measuring cylinder to measure 50.0 cm 3 of 0.2M of CuSO4
solution and transfer it into the polystyrene cup. Weigh exactly 1.00g
of Zn powder by using the weighing balance. Record the initial
temperature (27.0°C) and transfer the Zn powder into the CuSO4
solution. Stir the mixture with the thermometer throughout the
experiment. Record the final temperature (35.0°C). Calculate the
enthalpy change of this reaction.
Sample question

March 2017, P12

• Refer June 2017 P32/Q2 for acid-base

Hess’s Law
• Many chemical reactions occur in a series of steps rather than a
single step.

For example, the following reaction describes the burning

(combustion) of carbon:
(1) C (s) + O2(g) → CO2(g) ΔH = -393 kJ mol-1

If not enough oxygen is present, CO rather than CO2 is produced:

(2) C (s) + ½ O2(g) → CO (g) ΔH = -110.0 kJ mol-1

If more oxygen is now added, CO will undergo further combustion

with oxygen:
(3) CO (g) + ½ O2(g) → CO2 (g) ΔH = -283.0 kJ mol-1

Watch what happens if we add together the second and third

reaction:
(2) C (s) + ½ O2(g) → CO (g) Be sure you see how these
equations can be added together

(3) CO (g) + ½ O2(g) → CO2 (g) Add things that are on the same side of the equation:
½O + ½O = 1 O 2 2 2
______________________________________________________________________________________ and cross things out on opposite side of the equation
(1) C (s) + O2(g) → CO2(g) (the CO)
Hess’s Law
• Now compare the total energy released in the second and third
reactions with the amount of energy released in the original reaction:

ΔH Reaction2 + ΔH Reaction3 = ΔH Reaction 1

-110.0 kJ mol-1 + (-283.0 kJ mol-1) = -393.0 kJ mol-1

- 393.0 kJ mol-1 = -393.0 kJ mol-1

• The end result is that it doesn't matter if the reaction proceeds all at
once or in series of steps; the net energy change is the same.

• This illustrates Hess's Law

Hess’s Law
• Definition: The total enthalpy change for a chemical
reaction is independent of the route taken provided the
initial and final conditions are the same.

• 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.
Hess’s Law

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

the enthalpy change.

e.g. ΔH2 = - ΔH1 + ΔHr - ΔH3

The values of ΔH1 and ΔH3 have been subtracted because the route
involves going in the opposite direction to their definition.
Hess’s Law
• Tips for for Using Hess's Law:

– Write balanced equation on top

– Draw cycle with elements or compound form at the
bottom
– Draw arrows, make sure they are in the correct
direction
– Apply Hess’s law, taking into account the number of
moles of each reactant and products.
Hess’s Law (Example)
You are given the following two reactions (Reactions 1 and 2):

(1) C2H2(g) + 5/2 O2(g) → 2 CO2(g) + H2O(l) ΔH = -1299 kJ mol-1

(2) C6H6(l) + 15/2 O2(g) → 6 CO2(g) + 3 H2O(l) ΔH = -3267 kJ mol-1

Find ΔH for the following reaction (Reaction 3) and tell whether it is

exothermic or endothermic:

(3) 3 C2H2(g) → C6H6(l)

Solution:
1.Reverse equation 2. Why? Remember to change the sign of ΔH.

2.Balance the overall equation. Multiply equation (1) by 3 in order to end up

with the correct number of moles for the final equation. Also multiply ΔH by 3.

3. Add the equations together

 Hess’s Law (Example)
You are given the following two reactions (Reactions 1 and 2):

(1) C2H2(g) + 5/2 O2(g) → 2 CO2(g) + H2O(l) ΔH = -1299 kJ

(2) C6H6(l) + 15/2 O2(g) → 6 CO2(g) + 3 H2O(l) ΔH = -3267 kJ

Find ΔH for the following reaction (Reaction 3) and tell whether it is

exothermic or endothermic:

(3) 3 C2H2(g) → C6H6(l)

3 C2H2(g) + 15/2 O2(g) → 6 CO2(g) + 3 H2O(l) ΔH = 3(-1299) = -3897kJ mol-1

6 CO2(g) + 3 H2O(l) → C6H6(l) + 15/2 O2(g) ΔH = + 3267 kJ mol-1

___________________________________________________________
3 C2H2(g) → C6H6(l) ΔH = -630 kJ mol-1
By Hess’ Law Alternatively,
Lets say ∆Hof = a ΔH= ∑ΔHc(reactant) - ∑ΔHc(product)
∆ H = -393.4 + 2(-285.7) – (- 890.2)
a + (-890.2) = -393.4 + 2(-285.7)
= -74.6 kJ mol-1
a = -393.4 + 2(-285.7) + 890.2
a = ∆Hof = -74.6 kJ mol-1
• Draw an enthalpy cycle to calculate ΔH of formation of ethane
given that enthalpy change of combustion of carbon,
hydrogen and ethane is -393.5 kjmol-1, - 285.8 kjmol-1 and
-1559.7 kjmol-1
By Hess’ Law
Lets say ∆H = y

-1220 + (-814) + y = 2(-271) + (-1434)

y=
y = ∆H = +58 kJ mol-1
• Draw an enthalpy cycle to calculate enthalpy change of
reaction of

2Al(s) + Fe2O3(s) → 2Fe(s) + Al2O3(s)

• given that enthalpy change of formation of Fe 2O3, and

Al2O3 is -824.2 kjmol-1, and -1675.7 kjmol-1
Bond Energy
• The bond energy is the amount of energy (in kJ mol-1) required to
break one mole of a covalent bond, between two atoms in the
gaseous state

A---B → A(g) + B(g) ∆H = +ve (kJ per mole)

• Each bond has a typical value, e.g. to break 1 mole of C-H bonds is
on average about +410 kJ/mol,
• The C=O takes an average +740 kJ/mol,
• What happens if molecule has a large bond energy?

• Bond energies (enthalpies) are use to:

– calculate what the net energy change is for that reaction (energy to
break bonds and to form a bond)

– determine whether the reaction is exothermic or endothermic

Bond energy (kJ/mol)
 Bond Energy
Theory During a reaction, all the bonds of reacting species are broken
and the individual atoms join up again but in the form of products.
Overall energy change will depend on the difference between the energy
required to break the bonds and that released as bonds are made.

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

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 DHr = Step 1 - Step 2

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

DH2 1 x C=C bond @ 610 = 610 kJ

4 x C-H bonds @ 410 = 1640 kJ
1 x H-H bond @ 436 = 436 kJ
Total energy to break bonds of reactants = 2686 kJ

DH3 1 x C-C bond @ 350 = 350 kJ

6 x C-H bonds @ 410 = 2460 kJ
Total energy to break bonds of products = 2810 kJ

Applying Hess’s Law DH1 = DH2 – DH3 = (2686 – 2810) = – 124 kJ mol-1
Example
Hydrogen + Chlorine → Hydrogen Chloride

The symbol equation is: H2(g) + Cl2(g) → 2HCl(g)

but think of it as: H-H + Cl-Cl → H-Cl + H-Cl

(- represents the chemical bonds to be broken or formed)

the bond energies in kJ/mol are: H-H: 436; Cl-Cl: 242; H-Cl: 431

Energy to break bonds = 436 + 242 = 678 kJ

Energy on bond formation = 2(-431) = 862 kJ

∆Hor = 678 – (862)

= - 184 kJ mol-1
(- 92 kJ per mole of HCl formed)

More energy is given out than taken in, so the reaction is

exothermic.
Example
Hydrogen Bromide → Hydrogen + Bromine

The symbol equation is: 2HBr(g) → H2(g) + Br2(g)

but think of it as: H-Br + H-Br → H-H + Br-Br

(where - represents the chemical bonds to be broken or formed)

the bond energies in kJ/mol are: H-Br 366; H-H 436; Br-Br 193

Energy to break bonds = 366 + 366 = 732 kJ

Energy on bond formation = -436 +(-193) = 629 kJ

∆Hor = 732 – (629)

= + 103 kJ mol-1
(+51.5kJ per mole of HBr decomposed)

More energy is taken in than given out, so the reaction is

endothermic
Example
Nitrogen + Hydrogen → Ammonia

N2(g) + 3H2(g) ↔ 2NH3(g)

or N N + 3 H-H ↔ 2

bond energies in kJ/mol:

N N is 944
H-H is 436
N-H is 390
Example (cont.)
bonds broken:
(1 x N- N) + (3 x H-H) = (1 x 944) + (3 x 436)
= 2252 kJ

bonds made:
2 x (3 x N-H) = 2 x 3 x (-390)
= 2340 kJ
or
∆H o = 2252 – (2340) = - 88 kJ mol-1
( -44 kJ per mole of ammonia formed)

since more energy is given out than taken in, the reaction is
exothermic.
Example
methane + oxygen → carbon dioxide + water

CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)

or

bond energies in kJ/mol:

– C-H single bond is 412, O=O double bond is 496, C=O double
bond is 805, H-O single bond is 460

bonds broken
(4 x C-H) + 2 x (1 x O=O) = (4 x 412) + 2 x (1 x 496)
= 1648 + 992 = +2640 kJ

bonds formed
(2 x C=O) + 2 x (2 x O-H) = 2(805) + [2 x 2(460)]
= 1610 +(1852) = 3450 kJ
Example (cont.)
overall energy change is:

∆Ho = 2640 – (3450) = - 810 kJ mol-1 given out per mole methane
burned,

since more energy is given out than taken in, the reaction is
exothermic.

At AS level this will be expressed as enthalpy of combustion =

ΔHc = - 810 kJ mol-1

• N10/P12/Q4
• J03/P1/Q7