Chem Factsheet

www.curriculum-press.co.uk Number 206

Enthalpy change of neutralisation, ∆Hn or ∆Hneut
Neutralisation is the name given to a reaction between an acid (a proton Measuring an Enthalpy Change of Neutralisation
donor) and a base (a proton acceptor) to form a salt and water. This is achieved by a technique called calorimetry.
e.g.1 HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l) Known quantities of acid and base (alkali) are mixed in a calorimeter.
In a simple experiment, a polystyrene cup fitted with a lid is used –
e.g.2 H2SO4(aq) + 2KOH(aq) → K2SO4(aq) + 2H2O(l) polystyrene is a very good thermal insulator and its use minimises heat
loss during such experiments. Temperatures before and after mixing
e.g.3 2HNO3(aq) + Ba(OH)2(aq) → Ba(NO3)2(aq) + 2H2O(l)
are also recorded. These data, along with a value for the specific heat
e.g.4 HCOOH(aq) + NaOH(aq) → HCOONa(aq) + H2O(l) capacity of water, allow the enthalpy change of neutralisation to be
calculated.
e.g.5 HCl(aq) + NH4OH(aq) → NH4Cl(aq) + H2O(l)
Fully standardised, accurate enthalpy changes
e.g.6 H3PO4(aq) + 3NaOH(aq) → Na3PO4(aq) + 3H2O(l)
such as measured at the National Physical
There may be several bonding changes taking place (see later) during Laboratory (NPL) are measured using an
these reactions but the most important change is the combination of electrically calibrated and compensated
H+ and OH- ions to form covalent water. calorimeter such as that illustrated here.

i.e. H+(aq) + OH-(aq) → H2O(l)

Experiment thermometer
This involves the formation of a covalent bond between the H+ and 1. Pipette 50.0cm 3 of 1.00 stirrer lid
O of the OH- ion. m o l d m -3 a c i d i n t o a
polystyrene cup, stir it
- polystyrene cup
with a thermometer and
record its steady initial reaction mixture
H+ + O H → H O H temperature to 0.1°C – Tacid.

2. Pipette 50.0cm3 of 1.05 moldm-3 alkali into a second polystyrene

Consequently, since any bond formation is an exothermic process, then cup, stir it with a thermometer and record its steady initial
all neutralisation reactions are exothermic. temperature to 0.1°C – Talkali.
3. Quickly pour the acid in to the alkali and fit a polystyrene lid. Stir
Definition
the reacting mixture and record the maximum temperature achieved
Like any enthalpy change (an energy change measured at constant
to 0.1°C – Tmixture.
pressure) it needs to be standardised in terms of definition and
conditions of measurement to ensure that any person in any part of The temperature will always increase because the acid and alkali
the world is referring to the same process. release energy as they react (see above). This energy is transferred
to the water present resulting in a rise in temperature.
The definition focuses on the common factor for all neutralisations
– the formation of water! Apart from that, temperature, pressure and 4. Calculate the average temperature change (∆T) using:
concentrations are fixed as in all other standard enthalpy changes. ∆T = Tmixture - [(Tacid + Talkali)/2]
Hence, the standard enthalpy change of neutralisation, (∆Hn or 5. Repeat the experiment until concordant (agree within 0.1°C) DT
∆Hneut.) is defined as follows: values are obtained.
Sample Results
The standard enthalpy change of neutralisation is the enthalpy
Acid used = 50.0 cm3 1.00 moldm-3 HCl(aq)
change when solutions of an acid and an alkali react together to
Alkali used = 50.0 cm3 1.05 moldm-3 NaOH(aq)
produce 1 mole of water, measured at 298K and 100kPa pressure

using 1.00moldm-3 solutions.
Experiment Tacid/°C Talkali/°C Tmixture/°C ∆T/°C Concordant?
Hence, for the previous examples: 1 20.0 19.6 26.7 6.9 Yes
e.g.1 HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l) ; ∆Hn
2 21.4 20.6 27.2 6.2 No
e.g.2 H2SO4(aq) + 2KOH(aq) → K2SO4(aq) + 2H2O(l) ; 2∆Hn
3 19.8 20.4 26.9 6.8 Yes
e.g.3 2HNO3(aq) + Ba(OH)2(aq) → Ba(NO3)2(aq) + 2H2O(l) ; 2∆Hn
e.g.4 HCOOH(aq) + NaOH(aq) → HCOONa(aq) + H2O(l) ; ∆Hn
e.g.5 HCl(aq) + NH4OH(aq) → NH4Cl(aq) + H2O(l) ; ∆Hn
e.g.6 H3PO4(aq) + 3NaOH(aq) → Na3PO4(aq) + 3H2O(l) ; 3∆Hn

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206. Enthalpy change of neutralisation, ∆Hn or ∆Hneut Chem Factsheet

Calculation In general, measured enthalpy changes using this sort of apparatus

The heat released (q) during the experiment is calculated using: tend to be lower than standardised values because:
q = m × C × ∆T 1. heat is lost to the surroundings
2. the reaction is incomplete
where m = the mass of the reaction mixture 3. other reactions may occur
C = the specific heat capacity of the reaction mixture
∆T = the temperature change during the experiment. For neutralisation reactions, only heat loss is significant. This means
the maximum temperature achieved by the reaction mixture will
1. It is assumed that the mass of the reaction mixture is the same be lower than it should be.
as the mass of water in the mixture.
Heat losses can be compensated for by plotting a cooling curve during
2. It is assumed that this mass of water in the mixture is numerically the experiment. Since neutralisation reactions are very fast, this would
equal to the volume of the reaction mixture. This is based on need to be carried out using a thermocouple linked to data-logger and
assuming that the density of the mixture is the same as that of computer.
water at 25°C. i.e. 1.0 gcm-3.
This would automatically produce a graph of the temperature of the
3. It is assumed that the specific heat capacity of the mixture is reaction mixture against the time from the start of the experiment to
same as the specific heat capacity of water. i.e. 4.18 Jg-1°C-1. well after the maximum observed temperature, measured say every
0.1s. Such a graph is shown below.
Hence, m = 50.0 + 50.0 = 100g
C = 4.18 Jg-1°C-1
∆T = 6.9 + 6.8 / 2 = 6.85°C. final compensated temperature
→ q = 100 × 4.18 × 6.85 = 2863J = 2.863 kJ

Moles HCl used = CV/1000 = 1.00 × 50.0 / 1000 = 0.0500

Temperature /oC

and moles NaOH used = CV/1000 = 1.05 × 50.0 / 1000 = 0.0525

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

→ Moles water formed = moles HCl (NaOH slight excess) used

= 0.05 start temperature
→ ∆Hneut = -2.863 / 0.05 = -57.3 kJmol-1.
Remember to insert “-“ to show that the reaction is exothermic. reaction started
q does not have a “+” or “-“ sign!
Time / s

Example 1
The cooling part of the curve is extrapolated back to the start of the
In a laboratory experiment to determine the molar enthalpy of
reaction to give the “final compensated temperature” – this corresponds
neutralisation, 25.0 cm3 of 1.00 mol dm–3 sulphuric acid and 50.0 cm3
to the temperature that the mixture should have reached had the reaction
of 1.00 mol dm–3 sodium hydroxide, each at a temperature of 21.0 °C,
been instantaneous with no heat loss. ∆T can be read from the graph
were mixed together in a calorimeter.
and used in calculations as before.
The final temperature of the mixture was 30.1°C, and the following
reaction occurred: Variations in ∆Hneut Values
2NaOH(aq) + H2SO4(aq) → Na2SO4(aq) + 2H2O(l) This mostly depends on whether the acids and bases are strong or weak.
In other words, whether they are fully or partially ionised in solution.
Calculate the molar enthalpy of neutralisation from the above data.
Reactions involving strong acids and alkalis invariably give ∆Hneut
[Assume that all solutions have a density of 1.00 g cm–3 and a specific values between -57 and -58 kJmol-1. They vary only slightly with
heat capacity of 4.18 J°C–1g–1]. different acid-alkali combinations.

Example 2 Strong acids and strong alkalis are fully ionised in solution and the
During a thermochemical experiment, 100cm of 2.00 moldm 3 -3 ions behave independently of each other. For example hydrochloric
CH3COOH is reacted with 110 cm3 2.00 mol dm-3 KOH. Given that acid contains separate hydrogen ions and chloride ions in solution
the enthalpy change of neutralisation for this reaction is -54.0 kJmol-1, while sodium hydroxide solution consists of separate sodium ions and
calculate the average temperature rise during the experiment. hydroxide ions in solution. When reacted, the hydrogen and hydroxide
ions combine to form water and the remaining ions remain free in
The equation for the reaction is: solution – they are “spectator ions”, taking no part in the reaction.
CH3COOH(aq) + KOH(aq) → CH3COOK(aq) + H2O(l)
H+(aq) + Cl-(aq) + Na+(aq) + OH-(aq) → Na+(aq) + Cl-(aq) + H2O(l)
[Assume that all solutions have a density of 1.00 gcm–3 and a specific
heat capacity of 4.18 J°C–1g–1]. Hence, the equation for any strong acid being neutralised by a strong
alkali is essentially: H+(aq) + OH-(aq) → H2O(l)
This means that reactions between any strong acid and any strong alkali
will have the same enthalpy change of neutralisation, about -57 kJmol-1.

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206. Enthalpy change of neutralisation, ∆Hn or ∆Hneut Chem Factsheet

Hence, for the previous examples: The difference between a ∆Hneut for a weak acid / alkali and the standard
e.g.1 -57 kJmol-1 for a strong acid-alkali neutralisation can be used as a net
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l); ∆HR = -57 kJmol-1. measure of the energy required to complete the initial ionisation.

e.g.2 Using Hess’s Law and the energy cycle shown, this can be seen to be
H2SO4(aq) + 2KOH(aq) → K2SO4(aq) + 2H2O(l); ∆HR = -114 kJmol-1. +3kJmol-1 for methanoic acid. This is a fairly small value because the
endothermic O-H bond ionisation must be mostly cancelled by the net
e.g.3 exothermic hydration changes – the changes from hydrated HCOOH
2HNO3(aq) + Ba(OH)2(aq) → Ba(NO3)2(aq) + 2H2O(l); ∆HR = -114 kJmol-1. molecules to more hydrated H+ and HCOO- ions.
e.g.4
H3PO4(aq) + 3NaOH(aq) → Na3PO4(aq) + 3H2O(l); ∆HR = -171 kJmol-1. Answers
Any slight variations are due to minor changes in the hydration of the Example 1
different spectator ions during the mixing process. m = 25.0 + 50.0 = 75g
C = 4.18 Jg-1°C-1
Reactions involving weak acids and/or alkalis invariably give DHneut ∆T = 30.1 – 21.0 = 9.1°C.
values which are less exothermic than those for strong acid-strong → q = 75 × 4.18 × 9.1 = 2853J = 2.853 kJ
alkali reactions. Furthermore they vary significantly for different acids
and alkalis. Moles H2SO4 used = CV/1000 = 1.00 × 25.0 / 1000 = 0.0250
and moles NaOH used = CV/1000 = 1.00 × 50.0 / 1000 = 0.0500
e.g.1
HCOOH(aq) + NaOH(aq) → HCOONa(aq) + H2O(l) ; ∆Hneut = -54 kJmol-1. 2NaOH(aq) + H2SO4(aq) → Na2SO4(aq) + 2H2O(l)
e.g.2 → Moles water formed = moles NaOH used = 0.05
HCl(aq) + NH4OH(aq) → NH4Cl(aq) + H2O(l) ; ∆Hneut = -52 kJmol-1. → ∆Hneut = -2.853 / 0.05 = -57.1 kJmol-1.
e.g.3
HCN(aq) + NaOH(aq) → NaCN(aq) + H2O(l) ; ∆Hneut = -12 kJmol-1. Example 2
m = 100.0 + 100.0 = 200g
In a weak acid such as methanoic acid, at ordinary concentrations, only C = 4.18 Jg-1°C-1
about 1% of the molecules are ionised. This means that the enthalpy ∆T = × °C.
change of neutralisation will include other enthalpy change terms for the
ionisation of the acid as well as the reaction between the hydrogen ions Moles CH3COOH used = CV/1000 = 2.00 × 100.0 / 1000 = 0.20
and hydroxide ions. Since such ionisations involve bond breaking, they and moles KOH used = CV/1000 = 2.00 × 110.0 / 1000 = 0.22
will be endothermic giving an overall less exothermic enthalpy change.
CH3COOH(aq) + KOH(aq) → CH3COOK(aq) + H2O(l)
“Weak” does not mean the acid reacts less or more slowly giving → Moles water formed = moles CH3COOH (KOH slight excess)
a less exothermic reaction. It is important to realise that the weak used = 0.20
acid DOES react completely. The acid is in equilibrium with its
ions: CH3COOH(aq)  CH3COO-(aq) + H+(aq) → q = ∆Hneut × Moles H2O formed = 54000 × 0.20 = 10800J.

As the alkali is added, OH- ions combine with and remove the → 10800 = 200 × 4.18 × ∆T
H+ ions thus, by Le Chatelier’s Principle, pulling the equilibrium → ∆T = 10800 / 200 × 4.18 = 12.9°C.
completely to the right. Energy is absorbed as the CH3COOH
molecules ionise during this shift.

Similarly, in a weak alkali such as ammonia solution, the ammonia is

also present mostly as ammonia molecules.
NH3(aq) + H2O(l)  NH4+(aq) + OH-(aq).
Again, there will be other endothermic enthalpy changes involved in
forming these ions, apart from the simple formation of water from
hydrogen ions and hydroxide ions.

HCOO-(aq) + H+(aq) + OH-(aq)

∆Hionise
Enthalpy HCOOH + OH-(aq) −57 kJmol­-1

−54 kJmol­-1 Acknowledgements: This Factsheet was researched and written by Mike Hughes.
Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1
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