ADNAN CHOWDHURY

CHEMISTRY TEACHER

UNIT 1 ENERGETICS
 UNIT 1: ENERGETICS

 When chemical reactions happen, some bonds are broken and some bonds are made.

 All types of chemical reaction involve changes in energy. When energy is emitted it can take a number
of forms, but the most common form is as heat energy.

 Heat energy is called enthalpy. Enthalpy change is represented by the symbol ∆H. This is the energy
transferred in a reaction at constant pressure. Unit: KJmol-1

 In general, when bonds break energy has to be supplied and when bonds form energy is given out.

 When heat energy is given out the reaction is described as EXOTHERMIC and this happens when more
energy is obtained from bonds being formed than is used by bonds being broken. The heat energy given
out can cause a temperature increase.

 Exothermic reactions give out energy.

 When the breaking of bonds in a reaction requires more energy than is given out by the formation of
new bonds, heat energy is taken in, and the reaction is said to be ENDOTHERMIC. The heat energy
taken in can cause a temperature decrease.

 Endothermic reactions absorb energy.

 Change in enthalpy = Σ Hproducts – Σ Hreactants

 For exothermic reactions Σ Hproducts < Σ Hreactants.

 For endothermic reactions Σ Hproducts > Σ Hreactants.

 The enthalpy of a substance depends upon:

1. The physical state of the substance (solid, liquid or gas).

2. The amount in moles of the substance.

3. The temperature and pressure.

Standard Conditions:

Since the amount of energy taken in or given out will vary depending on the pressure and temperature,
standard enthalpy changes are defined, which are measured under standard conditions. These are:

 1 atmosphere pressure

 temperature 298K (25°C)

 substances present in their standard states at 298K [e.g. H2O(l) not H2O(g) or H2O(s)]

 all solutions having a concentration of 1 moldm-3

ADNAN CHOWDHURY 1
 UNIT 1: ENERGETICS

Activation Energy:

This is the minimum amount of energy that the reactant molecules must possess to convert into product
molecules in a reaction.

Thermodynamic Stability & Kinetic Stability:

 For an exothermic reaction, reactants are at a higher energy level than products. So products are
more thermodynamically stable than reactants. So reaction is said to be thermodynamically feasible
(will take place).

 For an endothermic reaction, reactants are at a lower energy level than products. So reactants are
more thermodynamically stable than products. So reaction is said to be thermodynamically non
feasible (will not take place).

 For an exothermic reaction, if the activation energy is too high that the reactant molecules cannot
attain it then reactant becomes kinetically more stable than products.

Standard Enthalpy of Reaction, ∆Hθr:

The enthalpy change for the reaction occurring in molar quantities as written in the equation under standard
conditions in their standard states.

NH3(g) + HCl(g) → NH4Cl(s)

Fe(s) + CuSO4(aq) → Cu(s) + FeSO4(aq)

Standard Enthalpy of Formation, ∆Hθf:

The enthalpy change when one mole of a compound in its standard state is formed from its elements in
standard state, under standard conditions.

∆Hθf of C6H12O6(s): 6C(s) + 6H2(g) + 3O2(g) → C6H12O6(s)

𝟑
∆Hθf of SO3(l): S(s) + O2(g) → SO3(l)
𝟐

𝟏 𝟑
or S8(s) + O2(g) → SO3(l)
𝟖 𝟐

∆Hθf of MgO(s): Mg(s) + ½O2 (g) → MgO(s)

The process is normally exothermic.

By definition, the ∆Hθf value for an element in its standard state must be zero. (It takes no energy to form an
element is its standard state from its constituent element in its standard state).

Standard Enthalpy of Combustion, ∆Hθc:

The enthalpy change when one mole of an element or compound is completely burned in excess oxygen under
standard conditions.

∆Hθc of C6H12O6 (s): C6H12O6(s) + 6O2(g) → 6CO2(g) + 6H2O(l)

∆HθC of C8H18(l): C8H18(l) + 12½O2(g) → 8CO2(g) + 9H2O(l)

∆HθC of Mg(s): Mg(s) + ½O2(g) → MgO(s)

The process is always exothermic

Standard Enthalpy of Neutralisation, ∆Hθneut:

The enthalpy change that takes place when one mole of water is formed from the neutralisation reaction of
hydrogen ions (H+) by hydroxide ions (OH-) under standard conditions.

HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)

½H2SO4(aq) + NaOH(aq) → Na2SO4 + H2O(l)

ADNAN CHOWDHURY 2
 UNIT 1: ENERGETICS

Hess’s Law:

For a given chemical reaction, the overall enthalpy change will always be the same whether the change takes
place in one step or a number of steps. (It is independent of the route taken)

Example 1:

Example 2:

Calculate the enthalpy change for the following reaction:

H2(g) + O2(g) → H2O2(l)

Use the following data:

H2(g) + ½O2(g) → H2O(l) ∆Hθ1 = -285.9 kJmol-1

H2O2(l) → H2O(l) + ½O2(g) ∆Hθ2 = -98.3 kJmol-1

∆H = ∆H1 - ∆H2

Example 3:

ADNAN CHOWDHURY 3
 UNIT 1: ENERGETICS

From Enthalpy of Formation Data:

Example 4:

Example 5:

ADNAN CHOWDHURY 4
 UNIT 1: ENERGETICS

Example 6:

Example 7:

Example 8:

From Enthalpy of Combustion Data:

Example 9:

ADNAN CHOWDHURY 5
 UNIT 1: ENERGETICS

Example 10:

Example 11:

Example 12:

ADNAN CHOWDHURY 6
 UNIT 1: ENERGETICS

Example 13:

Example 14:

Bond Enthalpy:

Bond enthalpy is the enthalpy change when a bond in a gaseous molecule is broken or formed. Unit: KJmol-1.

 Bond breaking is endothermic.

 Bond formation is exothermic.

 The weaker the bond, the easier it is to break, and so the lower the bond enthalpy.

 Mean or average bond enthalpy is the enthalpy required per bond to break all the bonds of a
particular type in one mole of a gaseous molecule to give gaseous atoms, under standard conditions.

CH4(g) → C(g) + 4H(g) ∆H = +1646 kJ mol-1

Bonds broken = 4 (C-H)

Therefore 4 (C-H) = 1646

(C-H) = 1646 / 4 = 412 kJ mol-1

The bond enthalpy of (C-H) in CH4 is 412 kJ mol-1.

 Average bond enthalpies can be used to determine approximately the enthalpy change which will take
place in a particular reaction.

 ∆Hreaction = sum of bonds broken on left – sum of bonds made on right.

ADNAN CHOWDHURY 7
 UNIT 1: ENERGETICS

Example 15:

Example 16:

Example 17:

Example 18:

ADNAN CHOWDHURY 8
 UNIT 1: ENERGETICS

Example 19:

Example 20:

ADNAN CHOWDHURY 9
 UNIT 1: ENERGETICS

Enthalpy of Atomisation:

It is the amount of energy required to convert one mole of gaseous atoms from the elements in their standard
state under standard conditions which are 298k, 1atm pressure and 1moldm-3.

The process is always endothermic

Na(s) → Na(g)

½Cl2(g) → Cl(g)

½Br2(l) → Br(g)

S(s) → S(g)

1/8S8(s) → S(g)

ADNAN CHOWDHURY 10
 UNIT 1: ENERGETICS

Experimental method to determine the Enthalpy of Combustion of a liquid:

Measurements:

 Volume of water = V cm3

 Initial temperature of water = θ1 ºC

 Mass of spirit burner + fuel before burning = m1 g

 Mass of spirit burner + fuel after burning = m2 g

 Final temperature of water = θ2 ºC

Assumptions:

 Density of water = 1 gcm-3

 Specific heat capacity of water = 4.18 J g-1 ºC-1

 No heat is lost to the surrounding.

 No heat is absorbed by the metal container (copper calorimeter).

Calculations:

 Mass of water, M = density × volume = 1 × V = V g

 Change in temperature, Δθ = (θ2 - θ1) ºC

 Heat produced by the combustion of the fuel in Joules = M × c × Δθ

M = mass of water in the beaker (not the mass of fuel burnt).

c = specific heat capacity of water = 4.18 J g-1 ºC-1

Δθ = change in temperature.

 mass of fuel burnt, m = (m1 – m2) g

 Amount / Number of moles of fuel burnt = m/Mr

m = mass of fuel burnt

Mr = molar mass of fuel

𝒉𝒆𝒂𝒕 𝒑𝒓𝒐𝒅𝒖𝒄𝒆𝒅 𝒊𝒏 𝒌𝒊𝒍𝒐𝒋𝒐𝒖𝒍𝒆𝒔

 Enthalpy of Combustion = -
𝒏𝒐 𝒐𝒇 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒇𝒖𝒆𝒍 𝒃𝒖𝒓𝒏𝒕
The negative sign is due to the fact the reaction is exothermic.

ADNAN CHOWDHURY 11
 UNIT 1: ENERGETICS

Example 21:

Liquid Mass of burner Mass of burner Temperature at Temperature at

at start/g at end /g o o
start/ C end / C
Ethanal, C2H4O 115.78 115.59 21 29

Mass of water = 100g

Calculation:

Energy = m x C x Δθ = 100 x 4.2 x 8 = 3360 J Moles = 0.19 / 44 = 0.0043

ΔH = -3360 / 0.0043 = -781,395 J/mol = -781 kJ/mol (3 sig fig).

If the experiment is repeated with a number of alcohols, it can be shown that the values of the enthalpies of
combustion of successive alcohols differ by a similar amount. This is because each member of a homologous
series differs from the next by –CH2–. The combustion of this unit should result in the same release of energy
(about 650 kJmol-1) whatever the homologous series being investigated.

Example 22:

Example 23:

Alternative Accurate Method:

 The temperature of the water in the calorimeter is measured every minute for three minutes.

 The burner is lit after 3.5 minutes.

 The temperature of the water is continued recording every minute.

ADNAN CHOWDHURY 12
 UNIT 1: ENERGETICS

 When the temperature has reached a suitable rise, the flame in the spirit burner is extinguished and
the burner immediately reweighed.

 The temperature readings are stopped 5 minutes after the temperature has reached a maximum value.

Sources of Errors:

 As the experiment takes a long time, not all the heat lost to the surroundings is compensated for the
extrapolation of the graph.

 Some of the heats released in burning heats up the air and not the water.

 The beakers absorb some of the heat produced.

 Some of the ethanol may not burn completely to carbon dioxide and water. Incomplete combustion
would cause black soot to be deposited on the bottom of the container.

 The conditions are not standard. Water vapour, and not liquid water, is produced.

 Assuming the volume (and therefore mass) of water used in the calculation is the same as the volume
of the solution used in the reaction.

Improvements:

 The copper calorimeter should be first weighed empty and then when containing water. Alternatively,
water could be added to the calorimeter using a pipette, not a measuring cylinder. If the volume of
water is measured, the mass is calculated using the density of water, which is 1 gcm-3.

 A screen should be placed around the calorimeter to maximize the transfer of heat from the hot
combustion gases to the beaker of water.

 To ensure an even temperature throughout, the water in the calorimeter must be stirred continually.

 The temperature of the water should be measured for several minutes before lighting the fuel and for
several minutes after putting out the burner flame.

 The temperature-time measurements are used to plot a graph from which the theoretical temperature
rise is estimated by extrapolation. This reduces the error caused by heat loss from the beaker to the
surroundings.

 The burner and its contents should be weighed before and immediately after the experiment, using a
balance that reads to an accuracy of 0.01 g or better.

 A bomb calorimeter can be used.

ADNAN CHOWDHURY 13
 UNIT 1: ENERGETICS

An experiment to measure Enthalpy of Neutralisation:

 Using a measuring cylinder, 30 cm3, 1.0 moldm-3 of dilute hydrochloric acid is placed into an
expanded polystyrene cup.

 A thermometer is placed in the solution and the temp is recorded every minute for 3 minutes.

 30cm3, 1.1 moldm-3 of sodium hydroxide solution is measured out. Sodium hydroxide is taken in slight
excess to ensure complete neutralisation of the acid.

 At 3.5 minutes the sodium hydroxide solution is added.

 The mixture is stirred continuously.

 Readings continue to be taken every minute up to ten minutes.

 A graph of the readings is plotted and the lines extrapolated as shown in the diagram below.

Assumptions:

 Density of solution = 1 gcm-3

 Specific heat capacity of water = 4.18 J g-1 ºC-1

 No heat is lost to the surrounding.

 No heat is absorbed by the polystyrene cup.

Calculations:

HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)

 Total volume, V = 30 + 30 = 60cm3

 Total mass of solution, M = density × volume = 1 × V = V g

 Change in temperature, Δθ is recorded from graph.

 Heat produced in Joules = M × c × Δθ

M = total mass of water in the beaker (not the mass of fuel burnt).

c = specific heat capacity of solution = 4.18 J g-1 ºC-1

Δθ = change in temperature.

 Amount / Number of moles of H2O = Amount / Number of moles of HCl = Concentration × Volume

𝒉𝒆𝒂𝒕 𝒑𝒓𝒐𝒅𝒖𝒄𝒆𝒅 𝒊𝒏 𝒌𝒊𝒍𝒐𝒋𝒐𝒖𝒍𝒆𝒔

 Enthalpy of Neutralisation = -
𝒏𝒐 𝒐𝒇 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒘𝒂𝒕𝒆𝒓
The negative sign is due to the fact the reaction is exothermic.
ADNAN CHOWDHURY 14
 UNIT 1: ENERGETICS

Example 24:

Example 25:

Example 26:

ADNAN CHOWDHURY 15
 UNIT 1: ENERGETICS

Example 27:

Displacement Reactions and Enthalpies of Solution:

 In both displacement reactions and experiments to determine the enthalpy of solution, a solid is added
to a liquid or solution and temperature change is measured.

 Temperature – time graphs are necessary because the reactions are not instantaneous.

Errors can be reduced by:

 Using powdered solids rather than lumps. This speeds up the reaction, so there is less time for cooling.

 Making sure that, for displacement reactions, enough metal is taken to ensure that the solution of the
salt of the less reactive metal is the limiting reagent (so that it reacts completely). For enthalpy of
solution experiments, the water must be in large excess to ensure that all the solid dissolves.

 Measuring the temperature for several minutes before the start of the reaction and for several minutes
after the reaction has finished. The measurements are used to plot a graph, which is extrapolated to
find the theoretical temperature rise.

 Continually stirring the contents of the expanded polystyrene cup.

 Placing a lid on the cup to prevent heat loss through evaporation.

 Weighing the cup empty and then, before the reaction starts, weighing it containing the solution. This
gives an accurate value of the mass of the solution. The assumption that the density of a solution is 1
gcm-3 is not wholly accurate.

 Measuring the volume of solution using a pipette rather than a measuring cylinder, so that the amount
(moles) can be accurately determined. This is not necessary for enthalpy of solution determinations.

Calculation:

 Heat produced or lost by the reaction in Joules = m × c × ΔT

m = mass of solution in the cup (not the mass of solute reacted).

c = specific heat capacity of water, 4.18 J g-1ºC-1

ΔT = change in temperature.

ADNAN CHOWDHURY 16
 UNIT 1: ENERGETICS

 Amount / Number of moles of solution reacted = concentration (moldm-3) × volume (dm3)

𝒉𝒆𝒂𝒕 𝒑𝒓𝒐𝒅𝒖𝒄𝒆𝒅 𝒐𝒓 𝒍𝒐𝒔𝒕 𝒊𝒏 𝒌𝒊𝒍𝒐 𝑱𝒐𝒖𝒍𝒆𝒔

 Enthalpy of Reaction, ΔHr =
𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏 𝒓𝒆𝒂𝒄𝒕𝒆𝒅
If there is a temperature rise, ΔH is negative; if the temperature falls, ΔH is positive.

Example 28:

Example 29:

ADNAN CHOWDHURY 17
 UNIT 1: ENERGETICS

Example 30:

Instantaneous Reactions:
 Neutralisation and precipitation reactions are neutralisation reactions.

Errors can be reduced by:

 Using pipettes, rather measuring cylinders, to measure out the volume of the two liquids.

 Making sure that one of the reactants is in excess. The value of ΔH can then be worked out using the
amount in moles of the limiting reagent.

 For neutralisation reactions only, weighing the expanded polystyrene cup empty and after the reaction.
This is a more accurate way of obtaining the mass of solution than using a pipette and assuming that
the solution has a density of 1 gcm-3.

 Measuring the temperature of both liquids before mixing and averaging the two values.

 Stirring immediately on mixing the two solutions.

 Reading the maximum temperature reached.

Calculation:

 Heat produced or lost by the reaction in Joules = m × c × ΔT

m = total mass of the two solutions in the cup (not the mass of solute reacted).

c = specific heat capacity of water, 4.18 J g-1 ºC-1

ΔT = change in temperature.

 Amount / Number of moles of limiting solution = concentration (moldm-3) × volume (dm3)

𝒉𝒆𝒂𝒕 𝒑𝒓𝒐𝒅𝒖𝒄𝒆𝒅 𝒐𝒓 𝒍𝒐𝒔𝒕 𝒊𝒏 𝒌𝒊𝒍𝒐 𝑱𝒐𝒖𝒍𝒆𝒔

 Enthalpy of Reaction, ∆Hr =
𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒍𝒊𝒎𝒊𝒕𝒊𝒏𝒈 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏
If the temperature rises, ΔH is negative; if the temperature falls, ΔH is positive.

ADNAN CHOWDHURY 18
 UNIT 1: ENERGETICS

Enthalpy Titration:
 The concentration of a solution can be determined by measuring the temperature change when an
alkaline solution of known concentration is added gradually, until it is in excess.

 25 cm3 of the acid solution is pipetted into an expanded polystyrene cup.

 The temperature of the acid is recorded with a thermometer.

 Standard 1 moldm-3 solution of sodium hydroxide is added from a burette in 2cm3 portions, stirring
and measuring the temperature after each addition.

 Sodium hydroxide is continued adding after the maximum temperature is reached.

 A graph of temperature against volume of sodium hydroxide is plotted.

 This method is suitable for a weak acid weak base titration where no indicator is suitable.

Example 31:

Example 32:

CuSO4 is the (nearly) the white form of copper (II) sulfate. It turns blue on the addition of water- but it
would be very difficult to add exactly the right amount of water to just hydrate all the powder. However,
the enthalpy changes can be measured by dissolving the anhydrous and hydrated form of copper (II) sulfate
separately in water, and using a Hess’s cycle to find the enthalpy of formation of CuSO4.5H2O.

ADNAN CHOWDHURY 19
 UNIT 1: ENERGETICS

Problem 1:

ADNAN CHOWDHURY 20
UNIT 1: ENERGETICS

ADNAN CHOWDHURY 21
 UNIT 1: ENERGETICS

Problem 2:

Problem 3:

ADNAN CHOWDHURY 22
 UNIT 1: ENERGETICS

Problem 4:

Problem 5:

ADNAN CHOWDHURY 23
 UNIT 1: ENERGETICS

Problem 6:

ADNAN CHOWDHURY 24
 UNIT 1: ENERGETICS

Problem 7:

ADNAN CHOWDHURY 25
 UNIT 1: ENERGETICS

Problem 8:

ADNAN CHOWDHURY 26
UNIT 1: ENERGETICS

ADNAN CHOWDHURY 27
UNIT 1: ENERGETICS

ADNAN CHOWDHURY 28
 UNIT 1: ENERGETICS

Problem 9:

Problem 10:

Problem 11:

ADNAN CHOWDHURY 29
UNIT 1: ENERGETICS

ADNAN CHOWDHURY 30
 UNIT 1: ENERGETICS

Problem 12:

Problem 13:

Problem 14:

Problem 15:

ADNAN CHOWDHURY 31
UNIT 1: ENERGETICS

ADNAN CHOWDHURY 32