As Chemistry “Unit II” London University

Topic 6: Energetics
 Enthalpy (H):
It is the total energy associated with the materials which react.

 Enthalpy change (∆H):

It is the heat energy transferred between the system and surroundings at constant
pressure. The standard conditions are 100 kPa and a specified temperature, usually 298 K.

 Exothermic reaction:
► During the exothermic reaction, heat energy is given out from
the system (chemicals). Therefore, the temperature rises up.
► The amount of energy released during bond making (formation)
is more than the energy absorbed during bond break.
► ΔH is negative because the energy of the products is less than
the energy of the reactants.
► The products have less energy than the reactants.

 Examples for Exothermic Processes:

1- Combustion of a fuel.
2- Respiration of human beings and animals where the energy in the food is released.
3- Displacement reaction.
4- Dissolving sodium hydroxide in water.
5- Adding concentrated sulfuric acid to water.

 Endothermic Reactions:
► During the endothermic reaction, heat energy is gained by the
system (chemicals) from surroundings. Therefore, the
temperature falls down.
► The amount of energy released during bond making is less than
the energy absorbed during bond break.
► ΔH is positive because the energy of the products is more than
the energy of the reactants.
► The products have more energy than the reactants.

 Examples for Endothermic Processes:

1- Thermal decomposition reaction.
2- The photosynthesis process in green plants.
3- The reaction between dilute ethanoic acid and solid sodium hydrogen carbonate
4- Dissolving ammonium nitrate, potassium iodide, urea and sodium thiosulphate in water.

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 Measuring the Enthalpy Change for a Reaction Experimentally

“Calorimetric method”

Calculating the enthalpy change of reaction, ∆Hr from experimental data

Energy change = mass of solution x heat capacity x temperature change
Q = m x c x ΔT
energy mass specific change in
change of water heat of water temperature
(J) (g) (4.18 J g-1 K-1) (K)
𝑯𝒆𝒂𝒕 𝑬𝒏𝒆𝒓𝒈𝒚 𝑪𝒉𝒂𝒏𝒈𝒆 (𝑸)
Molar Enthalpy Change(ΔH) = KJ mol-1
𝒏𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒎𝒐𝒍𝒆𝒔 (𝒏)
 The heat capacity of water is 4.18 J g-1K-1.
 In any reaction where the reactants are dissolved in water we assume that the heat capacity
is the same as pure water.
 Also assume that the solutions have the density of water, which is 1g cm-3.

 Enthalpy change of a Displacement Reaction:

The addition of 6.0 g (an excess) of magnesium metal to
100 cm3 of copper(II) sulphate “CuSO4(aq)” solution (2.0
mol dm-3) raised the temperature from 20.0°C to 65.0°C.
Calculate the enthalpy change of the reaction:
Mg(s) + CuSO4(aq) MgSO4(aq) + Cu(s)
● Specific heat capacity “c” of the solution = 4.18 J g-1 K-1.
● The density of the solution = 1.00 g cm-3

Answer:
1- Find the energy change:
The mass of the solution = 100 x 1.00 = 100 g
Energy gained to surroundings = m x c x ΔT
= 100 x 4.18 x (65 – 20)
= 18810 J
2- How many moles completely reacted:
Conc X V 2.00 X 100
Moles of CuSO4(aq) = = = 0.20 moles
1000 1000
3- Calculate the molar enthalpy change:

18810⁄
1000
ΔH = = – 94. 050 KJ/mol
0.20

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 Practical determination of the heat value of Ethanol:

A student carried out an experiment to determine the heat
value of ethanol. He got the following measurements:
● Mass of heated water = 670.0 g
● Initial mass of burner = 538.5 g
● Final mass of burner = 536.2 g
● Initial temp. of water = 25.0 °C
● Final temp. of water = 76.0 °C

1- Calculate the rise in temperature.

 The rise in temperature = 76 - 25 = 51°C
2- Calculate the heat gained (in kJ) by water(C = 4.2 J/°K.g).
 Heat gained = M x C x T
= 670 x 4.2 x 51
= 143514 J
= 143.514 kJ
3- Assuming that the heat produced from the fuel is completely absorbed by water.
i- Calculate the mass of the used fuel in this experiment.
 Mass of fuel = 538.5 - 536.2 = 2.3 g
ii- Calculate the ethanol moles.
2.3
 The ethanol mole = = 0.05 mol
46
iii- Calculate the molar enthalpy change of ethanol measured in kJmol-1.
143.514
 The heat value = = - 2870.28 kJmol-1
0.05

General method
1. Calculate energy change for quantities using Q = m x cp x ∆T
2. Work out the moles of the reactants used
3. Calculate ∆H by dividing Q by the number of moles of the reactant
4. Add a sign and unit (divide by a thousand to convert Jmol-1 to kJmol-1)

Errors in measuring enthalpy change for Errors in measuring enthalpy change for
reactions combustion

• Energy transfer to or from surroundings. • Energy losses from calorimeter

• Reaction or dissolving may be incomplete or slow. • Incomplete combustion of fuel
• Density of solution is taken to be the same as • Incomplete transfer of energy
water. • Evaporation of fuel after weighing
• Approximation in specific heat capacity of solution. • Heat capacity of calorimeter not included
• The method assumes all solutions have the heat • Measurements not carried out under standard
capacity of water. conditions
• Neglecting the specific heat capacity of the (as H2O is gas, not liquid, in this experiment)
calorimeter.
• We ignore any energy absorbed by the apparatus.

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Examples
1. Calculate the enthalpy change of reaction for the reaction where 25cm3 of 0.2 M copper
sulphate was reacted with 0.01mol (excess of zinc). The temperature increased 7 oC .
Solution:
Q = m x cp x ∆T = 25 x 4.18 x 7 = 731.5 J
Moles of CuSO4 = conc x volume = 0.2 x 25/1000 = 0.005 mol
∆H = Q / no of moles = 731.5 / 0.005 = 146300 J mol-1
= 146 kJ mol-1 to 3 sf
Finally add in the sign to represent the energy change: if temp increases the reaction is
exothermic and is given a minus sign e.g. –146 kJ mol-1.

2. 25cm3 of 2M HCl was neutralised by 25cm3 of 2M NaOH. The Temperature increased 13.5oC
What was the energy change per mole of HCl?
Solution:
Q = m x cp x ∆T = 50 x 4.18 x 13.5 = 2821.5 J
moles of HCl = conc x volume = 2 x 25/1000 = 0. 05 mol
∆H = Q / no of moles = 2821.5 / 0.05 = 564300 J mol-1
= - 56.4 kJ mol-1

3. Calculate the enthalpy change of combustion for the reaction where 0.65g of propan-1-ol was
completely combusted and used to heat up 150g of water from 20.1 to 45.5oC
Solution:
Q = m x cp x ∆T = 150 x 4.18 x 25.4 = 15925.8 J
moles of propan-1-ol = mass / Mr = 0.65 / 60 = 0.01083 mol
∆H = Q/ no of moles = 15925.8/0.01083 = 1470073 J mol-1
= 1470 kJ mol-1 to 3 sf
= –1470 kJ mol-1

4. Methane is burned in presence of oxygen as fuel according to the equation:

CH4 + 2 O2 CO2 + 2 H2O

Decide whether the reaction is exothermic or endothermic and calculate the overall energy
change for this reaction. The table gives some average bond dissociation energies.
Bond C−H O=O C=O O−H
Average bond dissociation energy (KJ/mol) 410 498 740 460

 Energy absorbed during bond break = ………………………………………………………………………………………………. KJ

 Energy released during bond formation = ……………………………………………………………………………………………….KJ
 The overall energy change = ……………………………………………………………………………………………….KJ
 The reaction is ……………………………………………………………… as ……………………………………………………………………………………………
…..………………………………………………………………………..……………………………………………………………………………………………………………………

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Calorimetric method
One type of experiment is one in which substances are mixed in an insulated container and the
temperature rise measured as reaction between two solutions.

General method
 Washes the equipment (cup and pipettes etc) with the solutions to be used.
 Dry the cup after washing.
 Put polystyrene cup in a beaker for insulation and support.
 Measure out desired volumes of solutions with volumetric pipettes and transfer to insulated cup.
 Clamp thermometer into place making sure the thermometer bulb is immersed in solution measure
the initial temperatures of the solution or both solutions if 2 are used
 Do this every minute for 2-3 minutes
 At minute 3 transfer second reagent to cup.
 If a solid reagent is used then add the solution to the cup first and then add the solid weighed
out on a balance.
 If using a solid reagent then use ‘before and after’ weighing method
 Stirs mixture (ensures that all of the solution is at the same temperature)
 Record temperature every minute after addition for several minutes.

 If the reaction is slow then the exact temperature

rise can be difficult to obtain as cooling occurs
simultaneously with the reaction.
 To counteract this we take readings at regular time
intervals and extrapolate the temperature
curve/line back to the time the reactants were
added together.
 We also take the temperature of the reactants for
a few minutes before they are added together to
get a better average temperature.
 If the two reactants are solutions then the
temperature of both solutions need to be
measured before addition and an average
temperature is used.

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 Standard Enthalpy Changes of Reaction ( ΔHrӨ):

It is the enthalpy change which occurs when one mole of a substance is formed from its
elements in their the quantities of substances mentioned in a balanced equation react
under standard conditions, and with everything in its standard state.

 Standard conditions are:

 100 kPa pressure (= 105Pa nearly equal 1atm )
 298 K (room temperature or 25oC)
 Solutions at 1mol dm-3
 All substances should have their normal state at 298K

 Standard Enthalpy Change of Formation (ΔH𝑓Ө )

It is the enthalpy change when 1 mole of a compound is formed from its constituent
elements in their standard states and under standard conditions.
2Fe (s) + 1.5O2 (g) → Fe2O3 (s) 𝚫𝐇𝒇Ө = -824.2 KJ mol-1
The standard enthalpy of formation of an element = 0 kJ mol-1

 Standard Enthalpy Change of Combustion (ΔH𝑐Ө )

It is the enthalpy change which occurs when one mole of the compound is burned
completely in excess of oxygen under standard conditions.
CH4 (g) + 2O2 (g) → CO2 (g) + 2 H2O (l) ∆ 𝐇𝐜𝛉 = -890.3 KJ mol-1
 Incomplete combustion will lead to soot (carbon), carbon monoxide and water. It will be less
exothermic than complete combustion.

Standard Enthalpy Change of Neutralisation (ΔH𝑛Ө )

It is the enthalpy change when an acid neutralises an alkali under standard conditions to
produce 1 mole of water.
HCl (aq) + NaOH (aq) → NaCl (aq) + H2O (l) ∆ 𝐇𝐧𝛉 = -57.1 KJ mol-1
 Enthalpy changes of neutralisation for strong acids and alkalis, the values are similar,
with values between -56 and -58 kJ mol-1 and decreases for the neutralisation between
weak acids and weak bases.

Standard Enthalpy Change of Atomisation (ΔH𝑎𝑡

Ө
)
It is the enthalpy change when 1 mole of gaseous atoms is formed from its element under
standard conditions.
𝛉
Na (s) → Na (g) ∆ 𝐇𝐚𝐭 = +107 KJ mol-1
 Enthalpy change of atomisation is always endothermic (has positive value) as it involves
increasing the separation between atoms which requires energy.

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 Hess’s Law
Hess’s law states that total enthalpy change for a reaction is independent of the route by
which the chemical change takes place as long as the initial and final conditions are the same.
It is used to calculate the ∆Hf for substance difficult to measure and to determine the
stability of compounds.

This means that the enthalpy to go from A to B

doesn’t depend on the route taken.
As formula: ∆Hr = ∆H1 + ∆H2

Example 1

Example 2

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Using Hess’s law to determine enthalpy changes from enthalpy

changes of formation.

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Using Hess’s law to determine enthalpy changes from enthalpy

changes of combustion.

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 Bond enthalpy and Mean Bond enthalpy

 The bond enthalpy ΔHB is the enthalpy change when one mole of a bond in the
gaseous state is broken.
 The mean bond enthalpy is the enthalpy change to break one mole of a bond
averaged out over many different molecules is broken in the gaseous state.

 These values are positive because energy is required to break a bond.

 The definition only applies when the substances start and end in the gaseous state.
 We use values of mean bond energies because every single bond in a compound has a slightly
different bond energy.
 'Average' refers to the fact that bond enthalpy is different in different molecules.

Example:
In CH4 , there are 4 C-H bonds. Breaking each one will require a different amount of
energy. However, we use an average value for the C-H bond for all hydrocarbons.

For diatomic molecules as : Cl2(g) → 2Cl(g) ΔBH = +243 kJmol-1

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Remember:
Calculated values of enthalpy of combustions from enthalpy of formation data will be more
accurate than if calculated from average bond enthalpies.
Because average bond enthalpy values are averaged values of the bond enthalpies from
various compounds.

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Summary
Using Hess’s law to determine enthalpy changes from enthalpy changes of
formation.

Using Hess’s law to determine enthalpy changes from enthalpy changes of

combustion.

Using Hess’s law to determine enthalpy changes from enthalpy changes for bond
energies.

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