Determination of the heat capacity of a calorimeter

Theory:
Chemical reactions involve the release or consumption of energy, usually in the
form of heat. Reactions that give off energy as heat are called exothermic heat
exits the system, while reactions that absorb heat from their surroundings as
they occur are called endothermic heat goes into the reaction system.
Calorimetry is the study of heat transferred in a chemical reaction, and a
calorimeter is the tool used to measure this heat. It is an insulated apparatus
containing a liquid reservoir in which the reaction occurs. The reservoirs heat
capacity relates the temperature change, T in the reservoir due to heat
transferred into or out of it, qres, as shown in the following equation:
qres= (Heat capacity) T

..(1)

Thus if the heat capacity of the reservoir is known, qres can be calculated from
the difference in the temperature of the reservoir measured before (Tinitial) and
after (Tfinal) the reaction occurs. That is T= Tfinal- Tinitial .
The specific heat capacity is the heat capacity per gram of the reservoir liquid
and is given the symbol, C. Then the equation above becomes
qres= C mass T

..............(2)

However, the transfer of heat that results from an acid/base neutralization

reaction carried out at constant pressure is called the enthalpy of neutralization,
Hneutralization and is expressed in units of kJ/mol. The reaction to be studied is:
NaOH(aq) + HCl(aq) H2O(l) + NaCl(aq)

(3)

As with any chemical reaction, the extent of the reaction is dependent on the
amount of limiting reactant present. Given the moles of limiting reactant
undergoing reaction and the measured heat of the reaction, Hneutralization can be
determined as shown below, keeping in mind that heat of reaction = qres.

H =

heat of reaction
moles reactetd

(4)
Knowing the heat of neutralization the heat capacity of a calorimeter can be
evaluated using the following expression

Hneutralization = (Cs m T ) + (Cc T )

..(5)

Where Cs is the specific heat of the solution, m is the mass of the solution Cc is
the specific heat of the calorimeter and T is the temperature change

Procedure
About 80 cm3 of 1.0 M HCl were placed in a calorimeter A and also 80 cm3 of
1.0M NaOH were placed in calorimeter B .Lids were used to close each of the
calorimeters and both systems were allowed to equilibrate for about one
minute with the thermometers inside the calorimeters, the temperature was
recorded for three minutes at one minute intervals for both calorimeters and at
the end of the 4th minute the NaOH solution in calorimeter B was transferred to
calorimeter A and at the end of 5th minute temperature was recorded at one
minute interval again up to 10th minute. After the reaction both calorimeters
were rinsed with distilled water and the procedure was repeated using oxalic
acid and NaOH.

Results and calculations

Calorimeter B (NaOH)
Temperature (C)
18
18
18

Temperature (C)
23
23
23
23
22.5
22.5

Time (mins)
1
2
3

Calorimeter A (NaOH + HCl)

Time (mins)
5
6
7
8
9
10

Calorimeter A (oxalic acid)

Temperature (C)
16
16
16

Temperature (C)
22.5
22.5
22.5
22.5
22.5
22.5

calorimeter A (HCl)
Temperature (C)
16
16
16

Time (mins)
1
2
3

calorimeter B (NaOH)
Temperature (C)
17
17
17

Calorimeter A (NaOH + oxalic acid)

Time (mins)
5
6
7
8
9
10

Since we are given the following data : Hneutralization

= -55.836KJmol-1
= 4.092 J K-1 g-1

Cs

Density of NaOH = 1.097 g cm-3

Density of HCl

= 1.004 g cm-3

Density of H2C2O4 = 1.03 g cm-3

Concentration of HCl = 0.9825 M
Concentration of NaOH= 0.9904 M
Concentration of oxalic = 0.500M
TA(HCl + NaOH) is the temperature change inside calorimeter A when the solution
is (HCl + NaOH)
= 23C 16C = 7C

TA(oxalic + NaOH) is the temperature change inside calorimeter A when the solution
(Oxalic + NaOH)
= 22.5C - 16C= 6.5C
From the above data mass of oxalic acid used can be calculated as follows
m= v
m=

1.03 g
80 ml
ml

= 82.4g

Mass of sodium hydroxide used can be calculated as follows

m= v
m=

1.097 g
80 ml
ml

= 87.76g

Mass of hydrochloric acid used can also be calculated as follows

m= v
m=

1.004 g
80 ml
ml

= 80.32g

Now Cc can be evaluated using the above data:

For calorimeter A with a solution of HCl and NaOH

Number of moles of NaOH = concentration volume
= 0.9904 0.16 = 0.1585 moles
Number of moles of HCl = 0.9825 0.16 = 0.1572 moles
Therefore the limiting reagent is HCl

Now we calculate the amount of energy that gets released through the reaction,
but viewed from the environment not the reaction
-q = Hneutralization n =0.1572 mol -55.836 KJ mol-1 = -8.777 KJ
Since we now know the heat released, we expand q = (Cs m T) + (Cc T)
and solve for Cc

Cc =

qCs m T
T

8777 J

= 566 J K-1

4.092 J
168.08 g 7 K
gK
7K

Discussion
Neutralization is name given to the reaction that occurs between an Arrhenius
acid Arrhenius base .
H(aq)+

OH-(aq)

H2O(l)

When a base is added to an aqueous solution of an acid or vice versa, the

temperature of the solution increases. Molar heat of neutralisation is the energy
liberated per mole of water formed during a neutralisation reaction. When
NaOH was added to HCl Initially, the temperature of the reaction mixture in the
calorimeter increased, indicating an exothermic reaction, the maximum
temperature reached was 23C however the temperature recorded at the 10th
minute was 22.5C, the drop in temperature suggests that the temperature was
dropping back to room temperature as the reaction was finished. The heat of
neutralization for the reaction between NaOH and HCl was given as -55.836 K
Jmol-1 and this value was used to calculate the heat capacity of the calorimeter
which was found to be 566 JK-1.

The experiment described above was repeated using the same base and oxalic
acid. Initially, the temperature of the reaction mixture in both experiments
increases as the base was added. Maximum temperature reached for the reaction
with oxalic acid is much less than the maximum temperature reached for the
reaction with HCl but volume of oxalic acid added to reach the maximum
temperature was the same as the volume of HCl needed to reach maximum
temperature (both volumes were 80.0 ml).the reason for this is because some of
the energy was consumed in the process of breaking weak acid bonds.

A perfect
calorimeter absorbs no heat from the solution that it
contains, nor loses any heat to
the surroundings. No calorimeter is
perfect, however.