ENERGY &

ENERGY
changes
Key Ideas:
 Enthalpy is a thermodynamic quantity which describes the energy of a system..
 Enthalpy change is the enthalpy change within a reaction system.
 Hess’s Law of constant heat summation states that the total enthalpy change of
chemical reaction is equal to the sum of all the individual enthalpy changes.
 Lattice energy the energy required to separate 1 mole of an ionic solid to gaseous ions.
 Bond dissociation energy the energy required to break a specific chemical bond within a
compound.
 Atomization energy the energy required to break all the bonds in one mole of a substance
to form individual atoms in the gas phase under standard conditions.
 Bond enthalpy is the average energy needed to split one mole of a specific type of
covalent bond in a gaseous molecule.
ENTHALPY CHANGE

o A system is the part of the Universe that we are focusing on in an experiment.

Everything else around it is called the surroundings.

There are three types of systems:

1. Open system: This can exchange both heat and matter with the surroundings.
An example is heating water in an open beaker.

2. Closed system: This can exchange heat, but not matter, with the surroundings. An
example is heating water in a covered beaker.

3. Isolated system: This cannot exchange heat or matter with the surroundings. An example
is a well-insulated thermos (like a calorimeter). It should be noted that no system can be
thought of as truly ideal, as some heat or matter will eventually escape to the surroundings.
It is a term used to describe systems which will exchange a negligible fraction of heat/matter with
their surroundings.
ENTHALPY CHANGE VIDEO
To measure how energy changes during a chemical reaction, scientists use a
special quantity called enthalpy (H). Enthalpy is a combination of the system’s
internal energy (U) and the product of its pressure (P) and volume (V).

Enthalpy has the same units as energy; Joules.

Mathematically, we write this as:

H = U + PV

This means that enthalpy depends on things like the pressure and volume of
the system. When the pressure stays the same, enthalpy is the amount of heat
energy that is added or removed during the reaction. This is quite common in
chemistry so is worth noting, an “isobaric” reaction.
 The enthalpy change (ΔH) in a chemical reaction is found by comparing
the enthalpy of the products (what we get after the reaction) with the
enthalpy of the reactants (what we started with).

Enthalpy change (ΔH) is therefore defined as:

Δ𝑯= 𝑯𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 - 𝑯𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔

ENTHALPY INTRODUCTORY VIDEO
Endothermic and Exothermic Reactions

When we study how energy changes during chemical reactions, we look at what is called the
enthalpy of reaction (ΔHrxn). This tells us whether a reaction gives off heat or takes in
heat.

 Exothermic reactions are reactions that release heat to the surroundings, making things
around them warmer. When this happens, the enthalpy of the system decreases as the
products have less energy/enthalpy than the reactants, and ΔHrxn is negative.

In exothermic reactions the system ends up with a lower heat content than the surrounding.

An example of an exothermic reaction is the combustion of methane

CH₄(g) + 2O₂(g) → CO₂(g) + 2H₂O(l) ΔH = -890.4 kJ/mol
 Endothermic reactions are reactions that absorb heat from the surroundings,
making things cooler.

In these reactions, the enthalpy of the system increases as the products have more
energy/enthalpy than the reactants, and ΔHₓₙ is positive.

In endothermic reactions, the system has more energy than the surroundings
because it took heat from them. The difference in energy comes from the heat the
system absorbs

An example of an endothermic reaction is the decomposition of calcium carbonate

CaCO₃(s) → CaO(s) + CO₂(g) ΔH = +177.8 kJ/mol
Figure 1: Energy profile diagram for exothermic and endothermic reactions
STANDARD ENTHALPY CHANGES

 When a chemical reaction happens, energy is either taken in or given off, and we measure this
energy change. But the amount of energy can change depending on the reaction conditions, like temperature and
pressure. In order to compare processes, scientists use standard conditions to measure these energy changes.
Standard conditions are used to measure and compare chemical reactions easily.

The Standard conditions are:

• Pressure: 1 atmosphere (1 atm or 101.3 kPa)
• Temperature: 298 K (which is the same as 25°C or room temperature).

When we measure energy changes under these conditions, we call it standard enthalpy change.
It shows how much energy (heat) is gained or lost during a reaction when everything is at the
same pressure and starting temperature. We usually measure this energy in kilojoules per mole
(kJ/mol), and we use the symbol ΔH° to show standard enthalpy change.
 Standard State: This means the most stable form of an element or compound at room
temperature and 1 atmosphere of pressure. For example, oxygen's standard state is O₂ gas
because that’s how it exists in the air.

For water, the standard state is liquid because that’s its most stable form at room temperature.

For reactions in solutions, scientists also use a standard concentration, which is usually:
1.0 mol/dm³ (This means 1 mole of a substance is dissolved in 1 dm3 of water).
Types of standard enthalpy changes

1. Standard enthalpy change of reaction

It is the quantity of heat involved when any valid stoichiometric molar quantities of reactants
combine to form products under standard conditions.

Any heat change measured under standard conditions is described as a standard enthalpy change of reaction. It is dependent on the
stoichiometry of the balanced chemical equation. Changes in the balanced coefficients of reactants and products in any chemical reaction
will change the value of its enthalpy changes accordingly. It has a unit of J/mol (or kJ/mol).

For example,
𝑜
N2(g) + 3H2(g) → 2NH3(g) ∆𝐻𝑟𝑥𝑛 = -92.38 𝑘 𝐽𝑚𝑜𝑙-1
1 3 𝑜
N2(g) + H2(g) → 2NH3(g) ∆𝐻𝑟𝑥𝑛 = -46.19 𝑘 𝐽𝑚𝑜𝑙-1
2 2
𝑜
3N2(g) + 9H2(g) → 6NH3(g) ∆𝐻𝑟𝑥𝑛 = -277.14 𝑘 𝐽𝑚𝑜𝑙-1

Notice here this is the same reaction, the standard enthalpy of reaction changes based upon
how much of the substances react. The value is not constrained in any way.
2. Standard enthalpy change of formation
The standard enthalpy change of formation of a compound is the enthalpy
change that results when one mole of the compound is formed from its
elements under standard conditions. (298K and 101.3 kPa), all reactants and
𝑜
products being in their standard states. It is given the symbol ∆H𝑓
𝑜
E.g. C(s) + 2H2(g) → CH4(g), ∆H𝑓(CH4) = -74.8 kJmol-1.
The standard enthalpy of formation of methane is -74.8 kJmol-1.

The standard enthalpy of formation of all elements in their standard states is zero.

Using oxygen as an example, it exists in the most stable form as a diatomic molecule (𝑂2) in the
gaseous form as compared to the other allotropic forms such as ozone (𝑂3).
𝑜 𝑜 𝑜
As such ∆H𝑓 (O2) = 0 but ∆H𝑓 (O3) = 142.2 kJ/mol while ∆H𝑓(𝑂) = 249.4 kJ/mol.
The most stable form of carbon under standard conditions is graphite,
therefore ∆H𝑜𝑓 (C(graphite)) = 0
 Table 1.1: Describes some elements in their standard state,
any other states will have associated enthalpies of formation

Substance ∆H 𝑜𝑓 Substance ∆H 𝑜𝑓
𝑂2(𝑔) 0 𝐶(𝑔𝑟𝑎𝑝ℎ𝑖𝑡𝑒) 0
𝑁2(𝑔) 0 𝑆(𝑟ℎ𝑜𝑚𝑏𝑖𝑐) 0
𝐻2(𝑔) 0 𝐴𝑔(𝑠) 0
𝐹2(𝑔) 0 𝐶𝑎(𝑠) 0
𝐼2(𝑔) 0 𝐶𝑢(𝑠) 0
𝐶𝑙2(𝑔) 0 𝐻𝑔(𝑙) 0

Standard enthalpies of formation values help in calculating the standard enthalpy of reaction
𝑜
(ΔHrxn), defined as the enthalpy of a reaction carried out under standard conditions
For example, consider the hypothetical reaction;

aA + bB → cC + dD
where a, b, c, and d are stoichiometric coefficients.
𝑜
For this reaction, ΔHrxn is given by
𝑜 𝑜 𝑜 𝑜 𝑜
ΔH rxn = [𝑐∆H𝑓(𝐶) + 𝑑∆H𝑓(𝐷)] - [𝑎∆H𝑓(𝐴) + 𝑏∆H𝑓(𝐵)]
𝑜 𝑜
We can generalize; ΔH rxn = 𝛴𝑛∆H𝑓 (𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) - 𝛴𝑚∆H𝑓 (𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)
where m and n are the stoichiometric coefficients for the reactants and products,
respectively, and Σ (sigma) means “the sum of.”

Standard enthalpy of formation values also give a measure of the stability of compounds
upon their formation. Compounds with negative ∆H𝑜𝑓 values are more stable than
compounds with positive ∆H𝑜𝑓 values.
3. Standard enthalpy change of combustion

The standard enthalpy of combustion of a substance is defined as the enthalpy change that
occurs when one mole of a substance is combusted completely in oxygen under
standard conditions. (298K and 101.3 kPa), all reactants and products being in their standard
states.
𝑜
It is given the symbol ∆H𝑐

1 𝑜
Eg. H2(g) + O 2(g)→ H2O(l), ∆H𝑐(H2(g)) = -285.8 kJmol-1.
2
The standard enthalpy of combustion of hydrogen is -285.8 kJmol-1.

Notice here that fractional values for stoichiometric co-efficients can be used to
balance the equation. This ensures only 1 mole of the substance is combusted.
 Respiration and Combustion

Respiration is like a slow burning process in your body, where the food you eat gets
"burned" to release energy that you need for daily activities. The amount of energy
you get from food depends on what you eat.

The main energy-giving foods are carbohydrates and fats. In nutrition, the energy
from these foods is measured in Calories. If you eat more carbohydrates than your
body needs, the extra energy gets stored as fat. Eating too much can cause your body
to store too much fat, which can lead to obesity.

In industries, the enthalpy of combustion is used to measure how efficiently

machines like power plants or engines turn fuel into energy. Fuels with higher energy
𝑜
(higher ∆H𝑐) are better for creating power. It also helps compare different fuels and
even different forms of the same material, like allotropes.
4. Standard 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. It is assigned the symbol ∆H𝑜𝑛.

When one mole of a monobasic acid reacts with one mole of a monobasic base
under standard conditions the amount of energy released is almost the same as
the enthalpy of formation of water from its ions.
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l) ∆H = - 57.5 kJ/mol
HNO3(aq) + KOH(aq) → KNO3(aq) + H2O(l) ∆H = - 57.3 kJ/mol
 Enthalpy of formation of water from its ions is represented by the
equation;

H+(aq) + OH-(aq) → H2O(l) ΔH = - 57.4 kJ/mol

Strong acids and strong bases ionise completely in aqueous solution to give off hydrogen ions
and hydroxyl ions therefore they tend to have higher enthalpies of neutralisation than the
weak acid and weak bases (which do not fully ionise).
5. Standard enthalpy of solution and hydration.

The standard enthalpy of solution is the enthalpy change when one mole of an ionic
substance is dissolved in excess water under standard conditions such that no further
addition of water produces a further change in energy.
𝑜
It is assigned the symbol ∆H𝑠𝑜𝑙𝑛.

e.g. NaCl (s) + H2O(l) → Na+ (aq) + Cl– (aq) ΔH = - 3.9 kJ/mol

Standard enthalpy of hydration is the enthalpy change when one mole of gaseous ions is
dissolved in water to give one mole of aqueous ions and a solution of infinite dilution. It
can also be defined as the energy evolved when one mole of a gaseous ion is surrounded,
coordinated and stabilised by a sheath of water molecules under standard conditions.

e.g. Na+(g) + H2O(l) → Na+ (aq) ΔH = - 406 kJ/mol

SUMMARY OF ENTHALPY TYPES
Calculating standard enthalpy change:

a. Standard enthalpy change of reaction (∆H𝑜𝑟)

Formula: ∆H𝑜𝑟 = Σ∆H𝑜𝑓 (products) - Σ∆H𝑜𝑓(reactants)

Let’s calculate the enthalpy change for the reaction:

H2(g) + Cl2(g) → 2HCl(g)
Given:
∆H𝑜𝑓 of HCl(g) = -92 kJ/mol
∆H𝑜𝑓 of H₂(g) and Cl₂(g) = 0 kJ/mol
(because they are elements in their standard states).
Calculation:

∆H𝑟 = Σ∆H𝑜𝑓 (products) - Σ∆H𝑜𝑓(reactants) = [2(-92)] - [0 + 0] = -184 𝑘𝐽/𝑚𝑜𝑙

The reaction releases 184 kJ of energy.

b. Standard enthalpy change of combustion (∆H𝑐)

Formula: ∆H𝑜𝑐 = Σ∆H𝑜𝑓 (products) - Σ∆H𝑜𝑓(reactants)

Calculate standard enthalpy of combustion of methane (CH₄):

Given: CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
𝑜
∆H𝑓 of CH4(g) = -74.8 kJ mol-1,
∆H𝑓 of CO2(g) = -393.5 kJmol-1,
∆H𝑜𝑓 of H2O(l) = -285.8 kJmol-1
Using the equation below, substitute the values into the equation.
∆H𝑜𝑐 = Σ∆H𝑜𝑓 (products) - Σ∆H𝑜𝑓 (reactants)
EXPERIMENTAL DETERMINATION OF ENTHALPY CHANGE

Experimental determination of heat of combustion of alcohol

Materials needed: Alcohol burner (containing ethanol), calorimeter (or a metal can),
thermometer, Water (200 ml), balance, retort stand and clamp, heatproof mat.

Procedure:
1. Measure initial mass of alcohol burner with the alcohol inside.
2. Add 200 ml of water to the calorimeter (or metal can).
3. Place the calorimeter on a stand above the alcohol burner, ensuring there is enough space
for the flame to heat the water effectively.
4. Record initial temperature of water:
5. Light the alcohol burner and let the flame heat the water.
Stir the water gently to ensure even heating.
6. Allow the alcohol to burn until the temperature of the water rises by about 15–20 °C.
Extinguish the flame by capping the burner.
7. Record the final temperature of the water after extinguishing the flame.
8. Weigh the alcohol burner again to find the final mass of alcohol left in the burner.
ALCOHOL EXPERIMENT VIDEO
Data:
1. Initial mass of alcohol burner (minitial = x g).
2. Final mass of alcohol burner (mfinal = y g).
3. Initial temperature of water (Tinitial = Ti).
4. Final temperature of water (Tfinal = Tf).
5. Mass of water = z g.

Calculations:
1. Calculate Mass of Alcohol Burned:
Mass of alcohol burned = (x - y) 𝑔

2. Calculate Temperature Change:

ΔT = T 𝑓 - T𝑖

3. Calculate Energy Transferred to Water: Use the formula:

Q = m(water) ⋅ c ⋅ ΔT Where:
Q is the heat absorbed by the water (in joules), m(water) is the mass of the water,
c is the specific heat capacity of water (4.18 J/g°C), ΔT is the temperature change of the water.
Calculate Heat of combustion of the alcohol:
i. Convert Q from joules to kilojoules (kJ) by dividing by 1,000.
ii. Calculate the heat of combustion per gram of alcohol:
Q
Heat of combustion per gram =
mass of alcohol burned

iii. If you want the heat of combustion per mole, multiply by the molar mass
of the alcohol. (for ethanol, C2H5OH, molar mass 46 g/mol)
Example Calculation:
𝑚𝑖𝑛𝑡𝑖𝑎𝑙 = 𝑥 = 120 𝑔
𝑚𝑓𝑖𝑛𝑎𝑙 = 𝑦 = 119 𝑔
𝑇𝑖𝑛𝑡𝑖𝑎𝑙 = 𝑇𝑖 = 22℃
𝑇𝑓𝑖𝑛𝑎𝑙 = 𝑇𝑓 = 42℃
Mass of alcohol burned = (x - y) = 120 - 119 = 1.0 𝑔
ΔT = T 𝑓 - T𝑖 = 42 - 22 = 20℃

Energy transferred to water:

c
Q = mwater ⋅ ⋅ ΔT
= 200 𝑔 × 4.18 Jg-1°C-1 × 20℃ = 16,720 J = 16.72 kJ

Q
Heat of combustion per gram = = 16.72 1 𝑔 = 16.72 𝑘J g-1
mass of alcohol burned

Heat of combustion per mole (for ethanol, C2H5OH, molar mass 46 g/mol Heat of
combustion per mole = 16.72 kJg-1 × 46 g mol-1 = 769.12 kJ mol-1
 Standard enthalpy of Neutralisation
It is the heat released when one mole of an acid is neutralised by an alkali to produce
one mole of water under standard conditions.

Calculating the Enthalpy of Neutralization

1. Find the heat released
Use the formula: Q = 𝑚 × c × ΔT

Where: Where:
Q is the heat released,
m is the total mass of the solution,
c is the specific heat capacity of water (4.18 J/g°C), here we will approximate the specific
heat of the solution to that of water.
ΔT is the temperature change of the solution

2. Calculate enthalpy of neutralization

Divide the heat released by the number of moles of acid or base that reacted to find the
enthalpy of neutralization in kJ/mol.
Example
If you get a temperature rise of 6°C with 100 g of solution,
plug it into the formula: Q = 100 × 4.18 × 6 = 2508 J
Divide by the moles of acid or base used to get the enthalpy of
neutralization.
Standard enthalpy of solution
It is the heat absorbed or released when one mole of an ionic substance is dissolved in excess
water such that no further addition of water produces further heat change under standard
conditions.

Mass of the solute (like salt)

Temperature change (final - initial temperature)
Specific heat capacity of water (4.18 J/g°C, a constant that tells us how much heat is needed
to change water temperature).
Calculation:
Using the data, we can calculate the heat energy (Q) absorbed or released: Q = 𝑚 × c × ΔT

Where:
Q is the heat released,
m is the total mass of the solution,
c is the specific heat capacity of water (4.18 J/g°C), ΔT is the temperature change of the
water.

Next, calculate the enthalpy change per mole by dividing Q by the moles of solute added
(n = m/RAM).
HESS’S LAW OF CONSTANT HEAT SUMMATION

Some compounds can’t be easily made by mixing their basic elements because the reaction is
either too slow or creates the wrong products through unwanted side reactions. In these cases,
scientists use an indirect method to figure out the energy change, called ∆𝐻𝑓°. This method is
based on Hess’s law.

Hess’s law states that if a reaction happens in several steps, the total energy change is
the sum of the energy changes of each step.

Hess’s law helps to calculate the energy even if the reaction doesn’t happen in one step.
Calorimetry can be used to measure enthalpy changes (ΔH) for many chemical
processes, but not all. Consider the hypothetical reaction below:

A+B→D
Where A and B are the reactants, D is the product

The overall energy change (ΔH) for a chemical reaction remains constant,
regardless of the reaction pathway.

A+B→C ΔH1
C+B→D ΔH2
Then A + 2B → D ΔH3
ΔH3 = ΔH1 + ΔH2

Consider the example below, the oxidation of carbon to form carbon monoxide.
1
C(s) + O2(g) → CO(g)
2
The oxidation of carbon to carbon (IV) oxide. This reaction occurs in two steps:

Step 1: the oxidation of C(s) to CO(g) (Equation 1) and

Step 2: the oxidation of CO(g) to CO2(g) (Equation 2).

Adding the two equations to gives the overall equation for the oxidation of C(s) to
CO2(g) (Equation 3).

Equation 1: C(s) + 1 ⁄2 O2(g) → CO(g) ° ∆𝐻𝑟𝑥𝑛1 = ?

Equation 2: CO(g) + 1 ⁄2 O2(g) → CO2(g) ∆𝐻𝑟𝑥𝑛2 = -283.0 kJ/mol
Equation 3: C(s) + O2(g) → CO2(g) ∆𝐻𝑟𝑥𝑛3 = -393.5 kJ/mol

Hess’s law says that the enthalpy change for the overall reaction that is equation 3 is the
sum of the enthalpy changes for reactions that equations 1 and 2. these values are then
used to calculate the enthalpy change for reaction 1.

∆𝐻𝑟𝑥𝑛 ° 3 = ∆𝐻𝑟𝑥𝑛 1 + ∆𝐻𝑟𝑥𝑛 2

-393.5 kJ/mol = ∆𝐻𝑟𝑥𝑛 1 + (-283.0 kJ/mol) ∆𝐻𝑟𝑥𝑛 1 = -110.5 kJ/mol
 Rules for Manipulating Thermochemical Equations
i. The opposite of an exothermic reaction is an endothermic reaction. As a result, the sign
of an equation's enthalpy must likewise be reversed or negated when it is stated in the
other direction.
To illustrate, the reverse of the equation:
A + B → C ΔH = +x J/mol is the following equation:
C → A + B ΔH = -x J/mol
Only when a substance is in the same physical state can it be
ii.
eliminated from both sides of an equation.
If all the coefficients of an equation are multiplied by a factor, the value of
iii.
its enthalpy must be multiplied by the same factor.
a. To illustrate, the factors of an equation: A + B → C ΔH = +x J/mol
When an equation is multiplied by 2: 2A + 2B → 2C ΔH = 2 (+x J/mol)
iv. When equations are added, the enthalpy changes are also added accordingly with proper signs
A + B → C ΔH1
C + B → D ΔH2
Then A + 2B → D ΔH3 = ΔH1 + ΔH2
Example: using Hess’s law to calculate the enthalpy change (∆𝐻𝑟𝑥𝑛 °) of the
following reaction:

C (graphite) + 2 H2(g) → CH4(g) Data given from the table below:

Reactions ∆𝐻

(i) C (graphite) + O2(g) → CO2(g) ∆𝐻𝑓 ° (i) = – 393.5 kJ mol–1

(ii) H2 (g) + 12O2(g) → H2O(l) ∆𝐻𝑓 ° (ii) = – 285.8 kJ mol–1

(iii) CH4 (g) + 2 O2(g) → CO2(g) +2 H2O(l) ∆𝐻𝑟𝑥𝑛 ° (iii) = – 890.3 kJ mol–1
Solution.

C (graphite) + 2 H2(g) → CH4(g) ∆𝐻𝑟𝑥𝑛 ° (A) =?

∆𝐻𝑟𝑥𝑛 ° = ∆𝐻𝑓 ° (products) – ∆𝐻𝑓 ° (reactants)

(∆𝐻𝑟𝑥𝑛 °) = -890.3 kJ/mol

∆𝐻𝑓 ° product = ∆𝐻𝑓 ° (CO2) + 2 x ∆𝐻𝑓 ° (H20)

= -393.5 + 2(-285.8) = - 965.1

∆𝐻𝑓 ° reactants = x + 0
-890.3 = -965.1 – (x)
X = -965.1 + 890.3
= - 74.8 kJ/mol
 Alternatively, using the rearrangement method,

Maintain equation (i)

Multiply equation (ii) by 2

Reverse equation (iii)

(iv) 2H2 (g) + O2(g) → 2H2O(l) ∆𝐻𝑟𝑥𝑛 ° (iv) = – 2×285.8 kJ mol–1 = -571.6 kJ mol–1
(v) CO2(g) + H2O(l) → CH4 (g) + 2 O2(g) ∆𝐻𝑟𝑥𝑛 ° (v) = + 890.3 kJ mol–1
equations (i) + (iv) + (v) with corresponding ∆𝐻𝑟𝑥𝑛 ° values, to get equation (vi)

(vi) [C (graphite) + O2(g)] + [2H2 (g) + O2(g)] + [CO2(g) +2 H2O(l)] → CO2 (g) + 2 H2O(l) + [CH4(g) + 2O2(g)]

∆𝐻𝑟𝑥𝑛 ° (vi) = ∆𝐻𝑟𝑥𝑛 ° (iv) + ∆𝐻𝑟𝑥𝑛 ° (v) + ∆𝐻𝑟𝑥𝑛 ° (i)

21 = (– 393.5 + (– 2×285.8 + 890.3) kJ mol–1
= –74.8 kJ mol–1
cancel the common terms on the two sides of equation (vi), we get equation (vii)
(vii) C (graphite) + 2H2 (g) → CH4(g) ∆𝐻𝑟𝑥𝑛 ° (vii) = –74.8 kJ mol–1
BORN – HABER CYCLES

Hess' law is used to draw Born-Haber cycles, which are energy cycles for ionic molecules. Ionic compounds
are created when constituent elements undergo a sequence of events for which, with the exception of the
lattice energy, the majority of energy changes are directly measurable.

A Born-Haber cycle is used to calculate lattice energy from the enthalpy data. Ionization
energies, electron affinities, sublimation energies, bond dissociation energies, and their
enthalpy of formation are all related to the lattice energies of ionic compounds.
Consider the reaction between lithium and fluorine: Li(s) + 1/2 F2(g) → LiF(s)
For this reaction, the standard enthalpy change is -594.1 kJ/mol.

Five distinct steps can be used to track the production of LiF from its constituent elements, and the sum
of the enthalpy changes for the steps equals the enthalpy change for the entire reaction (-594.1 kJ/mol).
Using Hess's law, this pathway aids in the analysis of the energy shifts involved in the synthesis of ionic
compounds.
1. Convert solid lithium to lithium vapor (the direct conversion of a solid to a gas is called
sublimation):
Li(s) → Li(g) ΔH° = +155.2 kJ/mol
The energy of sublimation for lithium is 155.2 kJ/mol.

2. Dissociate ½ mole of F2 gas into separate gaseous F atoms:

1/2 F2(g) → F(g) ΔH° = +75.3 kJ/mol
The energy needed to break the bonds in 1 mole of F2 molecules is +150.6 kJ.
Here we are breaking the bonds in half a mole of F2, so the enthalpy change is 150.6 2 , or 75.3 kJ.

3. Ionize 1 mole of gaseous Li atoms:

Li(g) → 𝐿𝑖+(𝑔) + 𝑒 - ΔH° = +520 kJ/mol
This process corresponds to the first ionization of lithium.

4. Add 1 mole of electrons to 1 mole of gaseous F atoms.

F(g) + 𝑒- → 𝐹(𝑔)- ΔH° = - 328 kJ/mol

5. Combine 1 mole of gaseous 𝐿𝑖+ and 1 mole of 𝐹- to form 1 mole of solid LiF: 𝐿𝑖+(g) + 𝐹-(g) → LiF(s) ΔH° = ?
The reverse of step 5, energy + LiF(s) → 𝐿𝑖+(g) + 𝐹 -(g)
According to Hess’ law

Δ𝐻(𝑜𝑣𝑒𝑟𝑎𝑙𝑙)= Δ𝐻1 + Δ𝐻2 + Δ𝐻3 + Δ𝐻4 + Δ𝐻5

-594.1 = 155.2 + 75.3 + 520 - 328 + 𝑥
𝑥 = -594.70 - 422.5
𝑥 = -1016.6 𝑘𝐽/𝑚𝑜l
BOND ENERGY

One or more pure compounds can be transformed into one or more other chemical
substances through chemical reactions.
In most cases, chemical bonds are produced in the products and broken in the
reactants. These bond-breaking and bond-forming mechanisms are primarily responsible
for the enthalpy change for any chemical reaction.
A chemical bond must be broken with energy, and when a chemical bond is
formed energy is liberated.
Bond formation is an exothermic activity that releases energy, whereas bond
breaking is an endothermic process that absorbs energy.
Consequently, estimating the total enthalpy change in a chemical reaction can be
aided by knowledge of the energies of the individual bonds.

The average energy needed to break one mole of a specific type of covalent
bond in a molecule is known as the bond enthalpy.
The energy absorbed to break one mole of a specific kind of covalent bond in a gaseous molecule
into free radicals under standard circumstances is known as the standard bond dissociation
energy.

The enthalpy shift that occurs when a compound's bonds are broken and its constituent atoms split
apart into single atoms is known as the enthalpy of atomization. It can alternatively be described
as the energy shift that takes place when a compound's chemical bonds are broken, producing one
mole of gaseous atoms as byproducts.

Simple diatomic molecules like H2, O2, and Cl2 often have their bond enthalpies determined
spectroscopically; however, complex compounds use Hess's law to calculate bond enthalpies based on
thermochemical data.
The experimentally determined bond enthalpy of the diatomic hydrogen molecule, for example, is

H2(g) → H(g) + H(g) ΔH° = + 436.4 kJ/mol

According to this equation, breaking the covalent bonds in 1 mole of gaseous H2 molecules
requires 436.4 kJ of energy.

For the less stable chlorine molecule, Cl2(g) → Cl(g) + Cl(g) ΔH° = + 242.7 kJ/mol

Bond enthalpies can also be directly measured for heteronuclear diatomic molecules, such as HCl,
HCl(g) → H(g) + Cl(g) ΔH° = + 431.9 kJ/mol
as well as for molecules containing multiple bonds: O2(g) → O(g) + O(g) ΔH° = + 498.7 kJ/mol
 The table below shows the bond enthalpies of
some diatomic molecules
Bond Bond Enthalpy (kJ/mol)
H–H +436.4
O=O +498.7
Cl – Cl +242.7
H–O +460

∆𝐻𝑟𝑥𝑛 ° = ∑Δ𝐻 𝑜 𝑏𝑜𝑛𝑑𝑠 𝑏𝑟𝑜𝑘𝑒𝑛 - ∑Δ𝐻 𝑜 𝑏𝑜𝑛𝑑𝑠 𝑓𝑜𝑟𝑚𝑒𝑑

Example: Calculate the enthalpy of reaction when one mole of water is formed from hydrogen gas and
oxygen gas.

[Bond enthalpies in kJ/mol are H – H = +436, O = O = +498, H – O = +464]

Solution

𝐻2 + 1/ 2 𝑂2 → 𝐻2𝑂
Bonds broken: one mole of (H – H) and half of (O = O)
= 436 + 1/ 2 (498)
= +685
Bonds formed: H – O – H which is twice (H – O)
= 2(464) = +928
∆𝐻𝑟𝑥𝑛 ° = ∑Δ𝐻 𝑜 𝑏𝑜𝑛𝑑𝑠 𝑏𝑟𝑜𝑘𝑒𝑛 - ∑Δ𝐻 𝑜 𝑏𝑜𝑛𝑑𝑠 𝑓𝑜𝑟𝑚𝑒𝑑
∆𝐻𝑟𝑥𝑛 ° = 685 - 928
∆𝐻𝑟𝑥𝑛 ° = - 243 k𝐽/𝑚𝑜l