Enthalpy (Heat) of Neutralisation

Key Concepts

Neutralisation is the name given to the reaction that occurs between an Arrhenius acid
and an Arrhenius base.
H+(aq) + OH-(aq) H2O(l)

When an acid is added to an aqueous solution of base, the temperature of the solution
increases.
Or, if a base is added to an aqueous solution of an acid, the temperature of the
solution increases.

Energy (heat) is produced when an acid reacts with a base in a neutralisation reaction.
Neutralisation reactions are exothermic.
H for a neutralisation reaction is negative.

Molar heat (enthalpy) of neutralisation is the energy liberated per mole of water
formed during a neutralisation reaction.
Hneut is the symbol given to the molar heat of neutralisation.
Hneut is usually given in units of kJ mol-1

Heat of neutralisation can be measured in the school laboratory:

heat produced = mass of reaction mixture x specific heat capacity of solution x
temperature change
enthalpy change for the reaction = -heat produced
molar heat of neutralisation = enthalpy change moles (of water produced)

Molar heat of neutralisation for reactions between dilute aqueous solutions of strong
acid and strong base is always the same.
No bonds need to be broken, but making the H-O bonds in H2O releases energy
(breaking bonds is an endothermic process, making bonds is an exothermic process)

Compared to strong acid-strong base reactions under the same conditions, less energy
is released when:
(a) a weak acid neutralises a strong base
(b) a strong acid neutralises a weak base
(c) a weak acid neutralises a weak base
because some of the energy is consumed in the process of breaking weak acid bonds
or weak base bonds

Example: Heat of Neutralisation for Strong Acid + Strong

Base
Strong Monoprotic Acid + Strong Monobasic Base
HCl(aq) is a strong monoprotic acid: HCl H+(aq) + Cl-(aq)
NaOH(aq) is a strong monobasic base: NaOH Na+(aq) + OH-(aq)
50.0 mL of 1.0 mol L-1 NaOH(aq) is placed in the styrofoam cup.
The temperature of the NaOH(aq) is recorded.

1.0 mol L-1 HCl(aq) at the same temperature is added 10.0 mL at a time.
The reaction mixture is stirred between each addition.
The maximum temperature the solution reaches is then recorded.
The results of the experiment are shown below:
Initially, the temperature of the reaction mixture in the calorimeter (styrofoam cup)
increases as HCl(aq) is added.
Energy (heat) is being produced by the reaction.
The reaction is exothermic.
Maximum temperature reached is 24.6oC when 50.0 mL of HCl(aq) had been added.
When 50.0 mL of the acid has been added, all the base has been neutralised.
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)
moles HCl(aq) added = moles of NaOH(aq) present in the calorimeter
Adding more acid doesn't increase the temperature in the calorimeter any further#.

We can calculate the molar heat of neutralisation for the reaction if we assume:

the density of each dilute aqueous solution is the same as water, 1 g mL-1 at 25o
so, the mass of solution in grams = volume of solution in mL

the heat capacity of each solution is the same as for water, 4.18 JoC-1g-1

a. Extract the data needed to calculate the molar heat of neutralisation for this reaction:
V(NaOH) = volume of NaOH(aq) in the calorimeter = 50.0 mL
V(HCl) = volume of HCl(aq) added to achieve neutralisation = 50.0 mL
c(NaOH) = concentration of NaOH(aq) = 1.0 mol L-1
c(HCl) = concentration of HCl(aq) = 1.0 mol L-1
Ti = initial temperature of solutions before additions = 18.0oC
Tf = final temperature of solution at neutralisation = 24.6oC
d = density of solutions = 1 g mL-1 (assumed)
Cg = specific heat capacity of solutions = 4.18 JoC-1g-1 (assumed)
q = heat liberated during neutralisation reaction = ? J
b. Check the units for consistency and convert if necessary:
Convert volume of solutions (mL) to mass (g): density x volume = mass
since density = 1 g mL-1: 1 x volume (mL) = mass (g)
mass(NaOH) = 50.0 g
mass(HCl) = 50.0 g
c. Calculate the heat produced during the neutralisation reaction:
heat produced = total mass x specific heat capacity x change in temperature
q = mtotal x Cg x T
mtotal = mass(NaOH) + mass(HCl) = 50.0 + 50.0 = 100.0 g
Cg = 4.18 JoC-1g-1
T = Tf - Ti = 24.6 - 18.0 = 6.6oC

q = 100.0 x 4.18 x 6.6 = 2758.8 J

d. Calculate the moles of water produced:
OH-(aq) + H+(aq) H2O(l)
1 mol OH-(aq) + 1 mol H+(aq) 1 mol H2O
moles(H2O) = moles(OH-(aq))
moles(OH-(aq)) = concentration (mol L-1) x volume (L) = 1.0 x 50.0/1000 = 0.050 mol
moles of water produced = 0.050 mol
e. Calculate the heat liberated per mole of water produced, Hneut :
Hneut will be negative because the reaction is exothermic
Hneut = heat liberated per mole of water = -1 x q moles of water
Hneut = -1 x 2758.8 0.050 = -55176.0 J mol-1
We can convert J to kJ by dividing by 1000:
Hneut = -55176.0 1000 = 55.2 kJ mol-1
Strong Diprotic Acid and Strong Monobasic Base
The experiment described above is repeated using 50.0 mL of 1.0 mol L-1 sodium hydroxide, a
strong monobasic base, and 1.0 mol L-1 sulfuric acid, a strong diprotic acid, instead of 1.0 mol
L-1 hydrochloric acid, a strong monoprotic acid.
The second experiment's results look different when compared to the first experiment's
results:
Initially, the temperature of the reaction mixture in both experiments increases as acid is
added.
Energy (heat) is being produced by the reaction. The reaction is exothermic.
Maximum temperature reached for the reaction with H2SO4(aq) is higher than the maximum
temperature reached for the reaction with HCl(aq).
Volume of H2SO(aq) added to reach the maximum temperature is less than the volume of
HCl(aq) needed to reach maximum temperature.
For the reaction HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)
we found that H = -55.2 kJ mol-1 (per mole of water formed)
So, H+(aq) + OH- H2O(l) Hneut = -55.2 kJ mol-1
For the reaction H2SO4(aq) + 2NaOH(aq) Na2SO4(aq) + 2H2O(l)
2H+(aq) + 2OH-(aq) 2H2O(l)
so, H+(aq) + OH-(aq) H2O(l)
We predict that Hneut = -55.2 kJ mol-1
We can use the results of the second experiment to calculate the value for the molar heat of
neutralisation (Hneut), and see if they agree with our prediction.

Calculate the molar heat of neutralisation for the reaction: H2SO4(aq) + 2NaOH(aq)
Na2SO4(aq) + 2H2O(l)
a. Extract the data needed to calculate the molar heat of neutralisation for this reaction:
V(NaOH) = volume of NaOH(aq) in the calorimeter = 50.0 mL
V(H2SO4) = volume of H2SO4(aq) added to achieve neutralisation = 25.0 mL
c(NaOH) = concentration of NaOH(aq) = 1.0 mol L-1

c(H2SO4) = concentration of H2SO4(aq) = 1.0 mol L-1

Ti = initial temperature of solutions before additions = 18.0oC
Tf = final temperature of solution at neutralisation = 26.9oC
d = density of solutions = 1 g mL-1 (assumed)
Cg = specific heat capacity of solutions = 4.18 JoC-1g-1 (assumed)
q = heat liberated during neutralisation reaction = ? J
b. Check the units for consistency and convert if necessary:
Convert volume of solutions (mL) to mass (g): density x volume = mass
since density = 1 g mL-1: 1 x volume (mL) = mass (g)
mass(NaOH) = 50.0 g
mass(H2SO4) = 25.0 g
c. Calculate the heat produced during the neutralisation reaction:
heat produced = total mass x specific heat capacity x change in temperature
q = mtotal x Cg x T
mtotal = mass(NaOH) + mass(H2SO4() = 50.0 + 25.0 = 75.0 g
Cg = 4.18 JoC-1g-1
T = Tf - Ti = 26.9 - 18.0 = 8.9oC
q = 75.0 x 4.18 x 8.9 = 2790.2 J
d. Calculate the moles of water produced:
OH-(aq) + H+(aq) H2O(l)
1 mol OH-(aq) + 1 mol H+(aq) 1 mol H2O
moles(H2O) = moles(OH-(aq))
moles(OH-(aq)) = concentration (mol L-1) x volume (L) = 1.0 x 50.0/1000 = 0.050 mol
moles of water produced = 0.050 mol
e. Calculate the heat liberated per mole of water produced, Hneut :
Hneut will be negative because the reaction is exothermic
Hneut = heat liberated per mole of water = -1 x q moles of water
Hneut = -1 x 2790.2 0.050 = -55803 J mol-1 (of water produced)
We can divide J by 1000 to convert this enthalpy change to kJ per mole:
Hneut = 55803 J mol-1 1000 J/kJ = 55.8 kJ mol-1 (of water produced)
f.

Compare the molar heat of neutralisation for:

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

Hneut = -55.2 kJ mol-1 (of water)

H2SO4(aq) + 2NaOH(aq) Na2SO4(aq) + 2H2O(l)

Hneut = -55.8 kJ mol-1 (of water)

g.
There is close agreement between the two values for molar heat of neutralisation, so
we can generalise and say that the molar heat of neutralisation for the reaction
between a strong acid and a strong base is a constant.
Weak Acid + Strong Base
The experiment described above is repeated using 50.0 mL of 1.0 mol L-1 sodium hydroxide,
a strong monobasic base, and 1.0 mol L-1 hydrogren cyanide (HCN), a weak monoprotic acid
(Ka 6 x 10-10), instead of 1.0 mol L-1 hydrochloric acid, a strong monoprotic acid.

The results of these experiments is shown below:

Initially, the temperature of the reaction mixture in both experiments increases as acid is
added.
Energy (heat) is being produced by the reaction. The reaction is exothermic.
Maximum temperature reached for the reaction with HCN(aq)is much less than the maximum
temperature reached for the reaction with HCl(aq).
Volume of HCN(aq) added to reach the maximum temperature is the same as the volume of
HCl(aq) needed to reach maximum temperature (both volumes are 50.0 mL).
For the reaction HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)
we found that H = -55.2 kJ mol-1 (per mole of water formed)
So, H+(aq) + OH- H2O(l) Hneut = -55.2 kJ mol-1
For the reaction HCN(aq) + NaOH(aq) NaCN(aq) + H2O(l)
Will H for this reaction be the same (-55.2 kJ mol-1) ?
We can use the results of the HCN experiment to calculate the value for the molar heat of
neutralisation (Hneut), and see.

a. Extract the data needed to calculate the molar heat of neutralisation for this reaction:
V(NaOH) = volume of NaOH(aq) in the calorimeter = 50.0 mL
V(HCN) = volume of HCN(aq) added to achieve neutralisation = 50.0 mL
c(NaOH) = concentration of NaOH(aq) = 1.0 mol L-1
c(HCN) = concentration of HCN(aq) = 1.0 mol L-1
Ti = initial temperature of solutions before additions = 18.0oC
Tf = final temperature of solution at neutralisation = 19.2oC
d = density of solutions = 1 g mL-1 (assumed)
Cg = specific heat capacity of solutions = 4.18 JoC-1g-1 (assumed)
q = heat liberated during neutralisation reaction = ? J
b. Check the units for consistency and convert if necessary:
Convert volume of solutions (mL) to mass (g): density x volume = mass
since density = 1 g mL-1: 1 x volume (mL) = mass (g)
mass(NaOH) = 50.0 g
mass(HCN) = 50.0 g
c. Calculate the heat produced during the neutralisation reaction:
heat produced = total mass x specific heat capacity x change in temperature
q = mtotal x Cg x T
mtotal = mass(NaOH) + mass(HCN) = 50.0 + 50.0 = 100.0 g
Cg = 4.18 JoC-1g-1
T = Tf - Ti = 19.2 - 18.0 = 1.2oC
q = 100.0 x 4.18 x 1.2 = 501.6 J
d. Calculate the moles of water produced:
NaOH(aq) + HCN(aq) NaCN(aq) + H2O(l)
moles(H2O) = moles(NaOH)
moles(NaOH(aq)) = concentration (mol L-1) x volume (L) = 1.0 x 50.0/1000 = 0.050 mol

moles of water produced = 0.050 mol

e. Calculate the heat liberated per mole of water produced, Hneut :
Hneut will be negative because the reaction is exothermic
Hneut = heat liberated per mole of water = -1 x q moles of water
Hneut = -1 x 501.6 0.050 = -10032 J mol-1
We can convert J to kJ by dividing by 1000:
Hneut = -10032 1000 = -10.0 kJ mol-1
f.

Compare the molar heat of neutralisation for:

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

Hneut = -55.2 kJ mol-1 (of water)

HCN(aq) + NaOH(aq) NaCN(aq) + H2O(l)

Hneut = -10.0 kJ mol-1 (of water)

g.
The heat released per mole of water for the hydrogen cyanide reaction is much less
than the heat released per mole of water for the hydrochloric acid reaction.
The difference in molar heats of neutralisation is due to the type of reaction taking place:

Strong Acid + Strong Base Reaction:

Strong base, NaOH, fully dissociates in water. The reacting species is OH-(aq)
Strong acid, HCl, fully dissociates in water. The reacting species is H+(aq)
The reaction is therefore an Arrhenius neutralisation reaction:
H+(aq) + OH-(aq) H2O(l)

No bonds need to broken in the strong acid or strong base, no energy is lost in
breaking bonds.
Energy is produced when the H-O bonds form in the H2O product.

Weak Acid + Strong Base

Strong base, NaOH, fully dissociates in water. The reacting species is OH-(aq)
Weak acid, HCN, only partially dissociates in water.
Most of the acid species in solution are undissociated HCN molecules.
The reaction is therefore a Brnsted-Lowry proton transfer reaction:
HCN(aq) + OH-(aq) CN-(aq) + H2O(l)

In order for this reaction to occur, H-C bonds in HCN molecules must be broken
before H2O molecules can be produced.
Breaking covalent bonds requires energy.
So, even though we might expect the same amount of energy to be produced in
both the HCl and HCN reactions because both reactions are producing the same
number of moles of H2O, we see that energy will be consumed in breaking bonds in
HCN so the amount of energy produced overall will be less than that for the HCl +
NaOH reaction.
The heat liberated per mole when a weak acid neutralises a strong base is less than the
amount of heat liberated per mole when a strong acid neutralises a strong base.