Measuring Enthalpy Change of neutralisation

Calorimetry is a technique applied to measure enthalpy changes of some reactions. A simple

calorimeter can be:
- Polystyrene cup
- A vacuum flask
- A metal can
When carrying out calorimetry experiments, known amounts of reactants and known volumes of
liquids are used.
Calorimetry relies on the fact that it takes 4.18 joules of energy to increase the temperature of 1g
of water by 1C. Therefore the specific heat capacity of water is 4.18Jg -1C-1.
The energy transferred as heat (the enthalpy change) is given by the relationship
H = mcT
H = the energy transferred in joules
m = mass of water used or mass of mixture used. Note that the density of water = 1g/cm 3.
Volume of water or mixture is usually taken as mass.
T = Temperature change in C
With solutions, the assumptions made while measuring enthalpy changes are:
- 1 cm3 of solution has a mass of 1g
- The solution has the same specific heat capacity as water = 4.18Jg-1C-1.
Exercise:
(i)
Calculate the energy transferred when the temperature of 85cm 3 of water rises from 25C
to 50C.
(ii)
When 8g of NaCl is dissolved in 40cm3 of water, the temperature falls from 22C to
20.5C. Calculate the energy absorbed by the solution when NaCl completely dissolves.

Determination of enthalpy of neutralisation.

Thermometer (reading to 0.1C)
Plastic lid
polystyrene cup
Reaction mixture (H+(aq) + OH-(aq))

Procedure:
- Place 50cm3 of 1.0 moldm-3 hydrochloric acid in the polystyrene cup and record its
temperature.
- Add 50cm3 of 1.0 moldm-3 sodium hydroxide at the same temperature to the acid in the
polystyrene cup.
- Stirred reaction mixture continuously with a thermometer and record the highest temperature
attained. Note that enthalpy of neutralisation involves the formation of one mole of water i.e.
H+(aq) + OH-(aq) H2O(l).
The reaction is rapid thus experimental error due cooling is to an extent reduced.
Results and calculations:
Mass of solution = 50 + 50 = 100g
Specific heat capacity of mixture (solution)
Starting temperature of reactants
Highest temperature of product solution

= 4.18Jg-1C-1.
= 21.3C.
= 27.8C.

= 6.5C.

Temperature rise
H = mcT = 100 x 4.18 x 6.5 = 2717J
Moles of water formed =

1.0 x 50
concentration x volume (in cm 3 )
=
= 0.05mol
1000
1000

The formation of 0.05mol of water release 2717J of energy.

Thus formation of 1.0 mol of water release

2717J
= 54340Jmol-1.
0.05mol

To conclude, the enthalpy of neutralisation of HCl by NaOH is 54.3kJmol -1. This value is less
exothermic than the real value 57.1kJmol -1 in the data book due to heat loss to the air and
thermometer
The negative sign () before 54.3 is necessary since a neutralisation reaction is an exothermic
process.
Example 1:
In one such experiment, 25cm3 of 0.4moldm-3 NaOH on complete neutralisation by 25cm3 of 0.4moldm-3
HNO3 acid and caused a temperature rise from 25C to 26.75C. Calculate the heat of neutralisation of
NaOH by HNO3 given that the specific heat capacity of water is 4.18Jg-1 K-1.
Solution
H+(aq) + OH-(aq) H2O(l).
H = mcT; m = 50 + 50 = 100g
Cm = 4.2Jg-1K-1, = 300.5K 298K = 2.5K.
H = 50 x 4.18 x 2.75 = 574.75 J.
=> H = 574.75 joules.
Moles of water = moles of acid = moles of base =
0.01 mol
1 mol
x=

0.4 x 25
= 0.01mol.
1000

574.75 joules
x joules
=>

574.75J
57475 Jmol-1
= 57475 Jmol-1. => x =
= 57.475kJmol-1.
0.01mol
1000

Thus, the standard enthalpy of neutralisation of HNO3 by NaOH is about 57.5kJmol-1.