Experiment 12: Determination of the enthalpy (heat) of reaction of a monobasic acid with

sodium hydroxide

Objective

To understand the enthalpy chemistry, to determine the calorimeter constant and the enthalpy of reaction
of acid-base reactions.

Introduction

In an open system, the pressure is constant. The change in enthalpy of a reaction is equal to the heat of
reaction. This can be defined by the equation “∆H=qp (the subscript “q” denotes that the change in
enthalpy is equal to the heat of reaction if and only if the pressure is constant)”. Hence, it enables us to
calculate the heat of reaction using Dewar flask, which is calorimeter.

Calorimeter is an apparatus for measuring the amount of heat involved in a chemical reaction or other
process. Calorimeter is used because it conveniently provides us with the accurate readings for the
calculations of heat of reaction that takes place within it. The reaction that takes place within a Dewar
flask is carried out adiabatically as well, which ,eases no heat is gained or lost by the system inside
Dewar flask and itself, which eases our job of obtaining the actual initial and final temperatures of the
solvent within the flask which is need to calculate the enthalpy of that particular reaction.

However, the calorimeter constant must first be determined. Calorimeter constant is defined by the
quantity of heat required to raise the temperature of the calorimeter and its contents by 1℃. It can be
measured by carrying out tests which will provide the calorimeter adding a known amount of
concentrated sulphuric acid. (Cann, 2015)

Apparatus
Dewar flask, stopwatch, thermometer, pipette, burette, conical flask, filter funnel and dropper

Materials

Sulphuric acid, concentrated nitric acid, 1M sodium hydroxide, 0.1M hydrochloric acid, methyl orange
indicator.
Procedure

A Dewar flask makes a suitable calorimeter

1. Calorimeter constant

100cm3of water been pipette into a Dewar flask. Stir the water slowly with a thermometer. Record down
the temperature at intervals of 1 min over a period of five min. Then add 2cm3 of conc. Sulphuric acid
into the Dewar flask using a measuring cylinder. Continue record the temperature in between 1 min than
record the temperature every 1 min until the temperature became constant. Allow the contents to cool.
Pipette 25 cm3 of the contents to a conical flask than add few drop of methyl orange indicator. Than
make a titration with 1M of sodium hydroxide.
2. Enthalpy of reaction

i) Mix 50 cm3 of sodium hydroxide and 50cm3 of water into a Dewar flask. Make the temperature
observation as described. Add 5 cm3 of 10M of nitric acid from a measuring cylinder. Continue the
temperature observation. Add few drop of methyl orange indicator in the solution to ensure the solution
is acid. If the solution is alkaline titrate it in calorimeter with 0.1 M of HCl to determine the amount of
alkaline.
ii) Repeat he experiment with described in i) above with change the solution to 100 cm3 of water.
Results and calculation

1. Calorimeter constant

Time (s) 0 60 120 180 240 300

Temperature of water ℃ 25.0 25.0 25.0 25.0 25.0 25.0

Time (s) 308 312 313 318 322 328 347 360 420 480 540 600
Temperature of 29.0 30.0 31.0 32.0 32.0 32.0 31.0 30.0 29.5 29.5 29.5 29.5
mixture ℃

Titration (15.30+15.40)
Average volume = = 15.35cm3
2
Titration 1 2
Starting point (cm3) 0.60 16.00
End point (cm3) 15.90 31.40
Temperature℃
Volume (cm3) 15.30 15.40
33.0

32.0

31.0

30.0
Time (s)

29.0

28.0

27.0

26.0

25.0

24.0
0 100 200 300 400 500 600 700
Temperature℃

Figure 1
2. Enthalpy of reaction
Part 1

Time (s) 0 60 120 180 240 300

Temperature of water + 1M NaOH ℃ 24.0 24.0 24.0 25.0 25.0 25.0

After adding of 10M of nitric acid

Time (s) 306 309 311 312 313 315 317 321 323 332
Temperature of 26.0 26.0 27.0 27.0 28.0 29.0 29.5 30.0 30.0 30.0
mixture ℃

Time (s) 340 352 360 420 480 540 600

Temperature of 30.5 30.5 31.0 31.0 31.0 31.0 31.0
mixture ℃
The methyl orange solution turned red
Temperature℃
32

31

30

29
Time (s)

28

27

26

25

24

23
0 100 200 300 400 500 600 700

Temperature℃

Figure 2
Part 2

Time (s) 0 60 120 180 240 300

Temperature of water ℃ 25.0 25.0 25.0 25.0 25.0 25.0

Time (s) 360 420 480 540 600

Temperature of mixture ℃ 25.5 25.5 25.5 25.5 25.5
The methyl orange solution turned red

Temperature℃
25.6

25.5

25.4

25.3
Time (s)

25.2

25.1

25

24.9
0 100 200 300 400 500 600 700
Temperature℃

Figure 3
From the first experiment (reaction of 1M NaOH with conc. Sulphuric acid and water)
Volume of NaOH needed for titration = 15.35 cm3
From figure 1, the change in temperature of solution = final temperature – initial temperature
= 29.5℃ – 25.0℃
= 4.5℃
No. of moles of NaOH = MV/1000
= (1.00)(15.35)/1000
= 0.015 mol
2NaOH + H2SO4  Na2SO4 + 2H2O
2 mole of NaOH : 1 mole of H2SO4
Therefore, 0.015 mol of NaOH : 0.0075 mol of H2SO4

No.of mole of H2SO4 = MV/1000

0.0075 mol = M25.0/1000
M = 0.3 M
Table: The given value of different molarities of diluting concentrated sulphiric acid during certain
experiment and heat liberated during the process
Acid added/cm3 Molarity of solution/M Heat liberated/ kJ
0.60 0.108 0.802
0.75 0.138 1.010
1.50 0.276 1.987
2.30 0.421 3.016
2,50 0.459 3.293

Based on the graph, when molarity of solution = 0.3 M

The heat release during the reaction = 2.160kJ
1 g = 1cm3
∴ mass, m = 100 g + 2 g = 102g
 𝑞
Hence, the calorimeter constant, Ccal =
𝑚.∆T
2.160𝑘𝐽
=
102 𝑔 ×4.5℃
=4.7059 x 10-3 kJ g-1 ℃-1
= 4.7059 J g-1 ℃-1
From figure 2, the change of temperature of the solution = Final temperature – Initial temperature
= 31.0℃ - 24℃
= 7.0℃
Mass, m = 100 g + 5 g = 105 g
q = mc∆T
= 105 x 4.7095 x 7.0
= 3461.483 J
Since the reaction is exothermic, ∆Hneutralisation = -3461.483 J
This is not the correct enthalpy change value. Enthalpy of dilution of nitric acid must be considered.
This is because dilution is also an exothermic reaction. Hence, change in heat enthalpy of dilution must
be soleved in order to get the change in heat enthalpy of the reaction.
From figure3, change in temperature of solution = 25.0℃– 25.5℃
= 0.5℃
Mass, m = 100 g + 5 g = 105 g
The change in heat enthalpy of dilution, ∆Hdilution = 105 x 4.7095 x 0.5
= 247.249 J
Since the reaction is exothermic, ∆Hdilution = - 247.249 J
Change in heat enthalpy of reaction, ∆Hreaction = ∆Hneutralisation - ∆Hdilution
= (-3461.483 J) - (-247.249 J)
= -3214.234 J
= -3.214 kJ
Discussion
Calorimeter constant is defined by the heat required to raise the temperature of both the calorimeter and
its content by 1℃, or a constant that quantifies the heat capacity of a calorimeter. When reaction such as
the neutrlisation of alkali by acid or dilution of acid occur in a calorimeter, chemically, heat released
during the neutralisation process and dilution process as new bonds are formed to create new types of
molecules or chemicals. The heat is released to the calorimeter as no heat can be lost or gained from the
surroundings by the calorimeter. But since addition of chemical or reagents into the calorimeter must be
performed in this experiment, the calorimeter is opened to an extent by its cap and hence, heat may be
lost to the surroundings. (Silberberg, 2009)
To calculate and identify the change in enthalpy of neutralisation reaction and dilution, the calorimeter
constant must be identified first so that we can understand how much heat must be applied on the
calorimeter and also its contents for them to raise their temperature by 1 degree Celsius. The dilution of
concentrated sulphuric acid in first part of the experiment is useful for this purpose of identification
because the dilution of concentrated sulphuric acid releases a large amount of heat. In other words, the
dilution reaction is exothermic.
The first part of this experiment focused on diluting the concentrated sulphuric acid first before titrating
it using 1M sodium hydroxide. However, for this experiment, the enthalpy of reaction between a
monobasic acid with sodium hydroxide is to be determined instead of dibasic acid like sulphuric acid
itself, the calculated molarity of sulphuric acid was divided by two. This is because during the
neutralisation of sulphuric acid by sodium hydroxide, sulphuric acid releases 2 hydrogen ions and extra
there must be two mole of sodium hydroxide for the full titration of sulphuric acid by sodium hydroxide.
The molarity of sulphuric acid is divided by 2 because for the neutralization between nitric acid and
sodium hydroxide, only 1 hydrogen ion was dissociated from the bonds in nitric acid and the hydrogen
ion is to be donated to the hydroxide ion in sodium hydroxide to form water molecule. A monobasic
acid is defined by an acid that has one replicable hydrogen atom, whereas a dibasic acid is defined by an
acid that has two hydrogen ions to donate to a base in an acid-base reaction. Hence, the molarity of the
sulphuric acid in this experiment was divided by 2 as it is only used for the calculation of the calorimeter
constant of the Dewar flask that had been used during the experiment.
In the first part of experiment,
2NaOH(aq) + H2SO4(aq)  Na2SO4(aq) + 2H2O(l)

In the second part of the experiment

HNO3 (aq) + NaOH (aq)  NaNO3 (aq) + H2O (l)
A graph was plotted with given values of both heat liberated and different molarities of sulphuric acid,
the heat released by the experimented sulphuric acid when the dilution process occurred was determined
by using calculated molarity of the sulphuric acid (0.3M) from the first table and its calculations. At
first, the formula of the calorimeter constant was introduced as:
∆H
Ccal = ; where Ccal is calorimeter constant.
∆T
However, the condition in using that formula is that the mass measured must be equal to 1 kg, which
was nor suitable to be used for the calculation of calorimeter constant in this experiment. Since q ay
constant atmospheric pressure is equal to ∆H, hence we may rearrange the formula q = mc∆T to:
q = mCcal∆T
𝑞
Ccal =
𝑚.∆T
Understand that the dilution of acids and the neutralisation process between acid and base are
both exothermic reaction (∆Hreaction) of a monobasic acid with sodium hydroxide is determined by
subtracting the enthalpy od dilution (∆Hdilution) by the enthalpy change of neutrlisation (∆Hneutralisation).
Hence, the enthalpy of reaction for the process of the nitric acid and sodium hydroxide in this
experiment is -3.214kJ.
When handling concentrated sulphuric acid during the first part of experiment, extra care was given
when it was added into the distilled water in the Dewar flask as droplets of the acid can be sprayed into
the air. The eye level when measuring the chemicals and reagents such as nitric acid, sulphuric acid and
also distilled water must be on the same level as the chemicals’ level in the measuring cylinder to
prevent parallax error.

Conclusion
The change in enthalpy of reaction of nitric acid with sodium hydroxide is -3.214 kJ. It was calculated
by subtracting the enthalpy change of neutraisation of nitric acid and sodium hydroxide by the enthalpy
of dilution of nitric acid. The enthalpy of dilution of nitric acid must be consider because dilution of the
acid is an exothermic process just like the neutralisation process. It must also be considered for the
purpose of obtaining a more accurate enthalpy of reaction value.

References

Cann, P. a. H. P., 2015. Cambridge International AS and A Level Chemistry (9701). s.l.:Hodder
Education.
Silberberg, M., 2009. Principles of General Chemistry. s.l.:s.n.