Chemical Energetics

Chemical Energetics

CONTENT
● Enthalpy changes: H; bond energy
● Hess' Law

LEARNING OUTCOMES
Candidates should be able to:
(a) explain that some chemical reactions are accompanied by energy changes, principally in the form of heat
energy; the energy changes can be exothermic (H negative) or endothermic (H positive)
(b) explain and use the terms:
bond energy (H positive, i.e. bond breaking);
(c) apply Hess' Law to construct simple energy cycles and carry out calculations involving such cycles and
relevant energy terms, with particular reference to average bond energies
(d) construct and interpret a reaction pathway diagram, in terms of the enthalpy change of the reaction and of
the activation energy
 Chemical Energetics

1. ENERGY CHANGES IN CHEMICAL REACTIONS

1.1 Enthalpy and Enthalpy Change

1. In a chemical reaction, energy is either given out or taken in from the surroundings,
principally in the form of heat.

Enthalpy of a substance is a measure of the heat content of the substance, given symbol H.
It reflects the energetic stability of the substance.

Absolute enthalpy cannot be measured, but the difference between the enthalpies of
reactants and products, i.e. the change in enthalpy accompanying a reaction, can be
measured.

2. Enthalpy change, H, is the change in heat content at constant pressure.

Consider a reaction: A + B → C + D
Enthalpy change, H = Hproducts − Hreactants = (HC + HD) − (HA + HB)

3. The Origin of Enthalpy Change of Reaction

In all chemical reactions,
● bonds in the reactant particles are broken and energy is absorbed to break these bonds
(endothermic process)
● new bonds are formed in the product particles and energy is given out when these bonds
are formed (exothermic process)

The enthalpy change of a reaction is the difference between the quantity of heat absorbed to
break bonds in the reactants and that evolved during the formation of new bonds in the
products.

1.2 Exothermic and Endothermic Reactions

Exothermic Reaction Endothermic Reaction

Figure 1(a) Energy Level Diagram for Figure 1(b) Energy Level Diagram for
Exothermic Reaction Endothermic Reaction

Products have a lower enthalpy (energetically ● Products have a higher enthalpy (energetically
more stable) than reactants. less stable) than reactants.
H (= Hproducts − Hreactants) is negative. H (= Hproducts − Hreactants) is positive.

● In an exothermic reaction, heat is released ● In an endothermic reaction, heat is absorbed

to the surroundings. from the surroundings.
temperature of surroundings rises (as the temperature of surroundings drops (as the
surroundings gains the heat released surroundings releases the heat needed for
from the reaction). the reaction).

● Example: 4Al(s) + 3O2(g) 2Al2O3(s) ● Example: N2(g) + O2(g) 2NO(g)

H = −1676 kJ mol−1 H = +180 kJ mol−1
 Chemical Energetics

2. ENTHALPY CHANGE OF REACTION, ΔH

2.1 Definition of Standard Enthalpy Change of Reaction

1. Enthalpy change of reaction, H, is the enthalpy change when molar

quantities of reactants, as specified by the balanced chemical equation,
react to form products

E.g. CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ΔH = −890 kJ mol−1

According to the thermochemical equation above, 890 kJ of heat is

evolved when 1 mole of CH4 gas reacts with 2 moles of O2 gas to form 1
mole of CO2 gas and 2 moles of liquid H2O under standard conditions.

Note: The use of “per mole” in the unit of ΔH does not imply “per mole of
any particular substance formed or used up”, but “per mole of equation”.

2. Enthalpy depends on the quantities of substances present.

⇒ magnitude of Hr is directly proportional to the amount of reactants
consumed in the reaction, e.g.
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ΔH = −890 kJ mol−1
2CH4(g) + 4O2(g) → 2CO2(g) + 4H2O(l) ΔH = 2(−890) kJ mol−1

3. Enthalpy change for a reaction is equal in magnitude, but opposite in sign,

to that for the reverse reaction, e.g.
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ΔH = −890 kJ mol−1
CO2(g) + 2H2O(l) → CH4(g) + 2O2(g) ΔH = +890 kJ mol−1

4. Enthalpy change for a reaction depends on the physical state of the

reactants and products, e.g.
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ΔH = −890 kJ mol−1
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g) ΔH = −802 kJ mol−1

The enthalpy change is different if the product is water vapour rather than
liquid water. Thus, it is important to specify the physical states of all
reactants and products in a thermochemical equation.

Qn: Why is there a difference in ΔHr?

Exercise 1
Given H2(g) + Cl2(g) → 2HCl(g) H = −185 kJ mol−1
(a) 2 mol of hydrogen in excess chlorine H = ………………… kJ
(b) 0.5 mol of chlorine in excess hydrogen H = ………………… kJ
(c) 2HCl(g) → H2(g) + Cl2(g) H = ………………… kJ mol−1
 Chemical Energetics

3. HESS’ LAW OF CONSTANT HEAT SUMMATION

1. There are very few reactions whose enthalpy changes can be measured directly by
measuring the change in temperature in a calorimeter. The enthalpy changes of reactions
which cannot be determined by calorimetry can be calculated by the indirect method of
drawing energy cycles or energy level diagrams and applying Hess’ Law.

2. Hess' Law states that the enthalpy change of a chemical reaction depends only on the
initial and final states of the system and is independent of the pathway taken.
[Hess’ Law is simply a principle based on the Law of Conservation of Energy.]

An energy cycle (shown below) can be used to illustrate Hess’ Law.

How to construct an energy cycle:

1. Write the equation (including state symbols) for which the H is to be determined.

2. Complete the cycle by filling in equations which correspond to data given, ensuring that all
equations are balanced.

3. Write the corresponding H next to the arrows, taking particular care about the sign and the value.

Example 1
Given: CO2(g) + OH–(aq) → HCO3–(aq) H = –48.3 kJ mol−1
HCO3–(aq) + OH–(aq) → CO32–(aq) + H2O(l) H = –41.1 kJ mol−1
Calculate H for the reaction:

CO2(g) + 2OH–(aq) CO32–(aq) + H2O(l)

Example 2
Given: CaCO3(s) + 2HCl(aq) → CaCl2(aq) + CO2(g) + H2O(l) H = –15 kJ mol−1
CaO(s) + 2HCl(aq) → CaCl2(aq) + H2O(l) H = –194 kJ mol−1
194 not
Calculate H for the reaction:
all 9 H2Oe Cao 3 244 aq 4
CaCO3(s) CaO(s) + CO2(g)

0297 4206
Caco 3 12,497
2491994

202974206
ca0 3 24969

I f 9
Cachlag

AH 15m 194m

17945mol
 Chemical Energetics

Example 3
Given: I2(g) + 3Cl2(g) → 2ICl3(g) H = −214 kJ mol−1
I2(s) → I2(g) H = +38 kJ mol−1
With the aid of an energy level diagram, calculate the enthalpy change for the reaction:
½ I2(s) + 3/2Cl2(g) ICl3(g)

12197 302197 AH Imo

A
14 21422
ceg
II 3
1
13197

Exercise 3
(a) Given 2Fe(s) + 3/2 O2(g) → Fe2O3(s) H = −822 kJ mol−1
C(s) + O2(g) → CO2(g) H = −394 kJ mol−1
CO(g) + ½ O2(g) CO2(g) H = −284 kJ mol−1
Calculate H of the reaction: 3C(s) + Fe2O3(s) ⎯→ 3CO(g) + 2Fe(s)

(b) Given: K2CO3(s) + 2HCl(aq) → 2KCl(aq) + CO2(g) + H2O(l) H = −32.8 kJ mol−1

KHCO3(s) + HCl(aq) → KCl(aq) + CO2(g) + H2O(l) H = +23.3 kJ mol−1
Calculate H for the reaction: 2KHCO3(s) → K2CO3(s) + CO2(g) + H2O(l)
A
3C 3 30,197 Fezo s 30 g 2Fels 430cg

82zksmoi
4 3 394 m.it

310,197 areas 30,19 53 0 3coi'g areas 30219

g

2KHC03 3 Skaco 3 0,197 42069

246 2HCI
32.8451mi
AH
A 2002697 2420 7
m2KCI aq
a
 Chemical Energetics

4. BOND DISSOCIATION ENERGY / BOND ENERGY

1. Bond dissociation energy is the energy absorbed when one mole of particular covalent
bonds between atoms in a gaseous molecule is broken.

▪ Bond dissociation energies are always endothermic because energy is required to

break bonds.
▪ The same amount of energy is given off when one mole of the bonds is formed in the
reverse process.

2. For Diatomic Molecules

A gaseous diatomic molecule has only one value for its bond dissociation energy.
Examples: H−H(g) → 2H(g) E(H−H) = +436 kJ mol−1
O=O(g) → 2O(g) E(O=O) = +496 kJ mol−1
H−Cl(g) → H(g) + Cl(g) E(H−Cl) = +431 kJ mol−1

3. For Polyatomic Molecules

A polyatomic molecule has first, second, third, etc. bond dissociation energies. These
values are different because the strength of a covalent bond is influenced by the
neighbouring atoms present.

Example: H−OH(g) H(g) + OH(g) H = +494 kJ mol−1

O−H(g) H(g) + O(g) H = +430 kJ mol−1
∴The average bond dissociation energy of the O−H bond in H2O
= ½ [(+494) + (+430)] = +462 kJ mol−1

4. Bond energy is the average energy absorbed when one mole of covalent bonds
between atoms in a gaseous molecule is broken (all species being in the gas phase).

5. The bond energy of a particular bond quoted in tables represents the average bond
dissociation energy of that particular bond in the full range of molecules that contain the
bond.
For example, the O−H bond energy given in the Data Booklet is 460 kJ mol−1,
which is found by considering the O−H bond dissociation energy in various compounds
containing the bond, including H2O (H−O−H), H2O2 (H−O−O−H), CH3O−H, etc.
 Chemical Energetics
−1
Bond Energy in kJ mol
Diatomic molecules Polyatomic molecules
Bond Energy/kJ mol−1 Bond Energy/kJ mol−1
H−H 436 C−C 350
D−D 442 C=C 610
N≡N 994 C≡C 840
O=O 496 C C (benzene) 520
F−F 158 C−H 410
Cl−Cl 244 C−Cl 340
Br−Br 193 C−Br 280
I−I 151 C−I 240
H−F 562 C=N 610
H−Cl 431 C≡N 890
H−Br 366 C−O 360
H−I 299 C=O 740
N−H 390
N−N 160
N=N 410
O−H 460
O−O 150
Si−Cl 359
Si−H 320
Si−O 444
Note:
▪ Bond energies give information about the strength of the covalent bonds − the higher the bond
energy, the stronger the bond.
▪ Enthalpy changes estimated using bond energy values can vary from experimentally determined
values due to the chemical environment which affect covalent bond strength, or when covalent
bonds are highly polarised, resulting in ionic character in the covalent bond.

6. Bond energies can be used to estimate the enthalpy change for reactions
involving gaseous reactants and products.

Calculation of enthalpy change of reaction is based on:

Hr = Energy change in bond breaking + Energy change in bond forming
▪ energy is absorbed in breaking bonds in reactants ⇒ ΔH is positive

▪ energy is evolved in forming bonds in products ⇒ ΔH is negative

Hr = Σ HBE(bonds broken) − Σ HBE(bonds formed)

 Chemical Energetics

Example 4
(a) Calculate the enthalpy change of the following reaction using bond energy values on the
previous page.
N2H4(g) + O2(g) ⎯⎯→ N2(g) + 2H2O(g)
H H
N N
0 0 NEN 2H O H
H H

Bonds broken Bonds formed

994 2 460
AH 43907 160 496
302451mmol

(b) Use bond energy values from the previous page to calculate the enthalpy change of the
following reactions.

(i) CH4(g) + 2O2(g) → CO2(g) + 2H2O(g) 0

2 854
4 410 2 1496 2 740 4 460
688k not

(ii) N2(g) + 3H2(g) → 2NH3(g)

994 3 436 213390