Experiment Title

:
Exp 12-Determination Of The Enthalpy (Heat) Of Reaction Of A
Monobasic Acid With Sodium Hydroxide

Subject

UDEC 1134 CHEMISTRY LABORATORY I

Course

Bachelor of Science (Hons) Chemistry

Name of Student

Name of Partners
:
Student ID No

Year and Trimester :

Y1S2

Received by:-

03.02.2016

________________________

Date of Experiment:
(Dr Sim Yoke Leng)

Name of Lecturer :
Dr Sim Yoke Leng
Date of Submission
:

Objectives

1. To understand the enthalpy chemistry.

2. To determine the calorimeter constant.
3. To determine the enthalpy of reaction of acid-base reactions.
4. To study the exothermic reactions.
Introduction
Enthalpy, H, is defined as H= U+ pV
Where p is the pressure of the system and V is its volume. Because U, p, and V are all state
functions, the enthalpy is a state function too. As is true of any state function, the change in
enthalpy, H, between any pair of initial and final state is independent of the path between them.
For a measurable change, H=q
q = U + W (1)
U = q W
U = q - PV (2)

W=PV

H = U + W
H = U + PV
H =U + PV + VP (3)
Equation (2) sub into (3)
H = (q - PV )+ PV + VP
H = q + VP
In constant pressure, q = H

PV also same as (PV)

The enthalpy is normally measure with S.I. unit of Joule, J, although other units still in use such
as Calorie, C and calorie, c. However, we often measure the change in enthalpy, H instead of
measuring the enthalpy, H because the total enthalpy cannot be measured directly.
Enthalpy change is defined by the following equation:

H = HFinal HInitial
H = Enthalpy change

HFinal

= Final enthalpy of the system. In a chemical reaction,

HFinal

is the enthalpy of the

products.

HInitial

= Initial enthalpy of the system. In a chemical reaction, HInitial is the enthalpy of the

reactants.
Enthalpy change is in positive values in endothermic reaction and negative values in exothermic
reaction. Exothermic reactions involve energy released as heat into its surroundings, causing the
temperature of the surroundings to rise while endothermic reactions involve energy acquired
from its surroundings as heat, causing the surrounding temperature to drop. Change in enthalpy
that occurs as a result of a chemical reaction is numerically equal to the heat of reaction under
constant (atmospheric) pressure conditions (H = q). The heat of reaction is conveniently
measured adiabatically in a Dewar calorimeter by the rise or fall in temperature of the products
produced by the reaction in solution. Dewar flask is used because it is designed to preserve heat
and minimize heat loss to the surrounding. In addition, isolated system is also required in this
experiment to obtain an accurate data. Since every Dewar flask has different calorimeter constant
because of different substances used, so the calorimeter constant must first be determined, that is
the quantity of heat required to increase the temperature of the calorimeter and its content by 1
C.

The constant is measured by supplying the calorimeter and contents with a definite known
quantity of heat. This can be done electrically or by adding a known amount of concentrated
sulphuric acid.
Apparatus & Materials
Dewar flask, stopwatch, thermometer (5 to +50C, graduated in 1/10C), 50cm 3 graduated pipette
fitted with a suction bulb, 10cm3 graduated cylinder, conc. Sulphuric acid (specific gravity 1.84,
98.5% H2SO4), conc. Nitric acid, 1M sodium hydroxide, 0.1M hydrochloric acid, methyl orange
indicator.
Experimental Procedure
A Dewar flask makes a suitable calorimeter
1. Calorimeter constant
Pipette 100cm3 of water into the Dewar flask. Stir the water slowly and regularly with a
1/10C thermometer (CAUTION: the thermometer bulb is very fragile). Note the
temperature at intervals of 1 minutes over a period of five minutes or so. At the end of
this period introduce into the calorimeter about 2cm3 of conc. Sulphuric acid using a
graduated cylinder. Continue recording the temperature at 1 minute intervals whilst
continuing to stir until the rate of rise of temperature has become constant about 10
minutes. Allow the contents of the calorimeter to cool. Titrate 50cm 3 of the solution
against 1M sodium hydroxide to determine the molarity of the solution.
2. Enthalpy of reaction
i)

Mix in the calorimeter of known constant 50cm 3 of 1M sodium hydroxide and 50

cm3 of water. Make temperature observations as already described. At a known
time, add 5cm3 of 10M nitric acid from a graduated pipette. (Prepared 10M acid
by diluting 65cm3 conc. nitric acid to 100cm3 with distilled water). Continue the
temperature observations. Add to the solution in the calorimeter a few drops of
methyl orange indicator to ensure that the solution is acid. If the solution is

alkaline titrate it in the calorimeter with 0.1M hydrochloric acid to determine the
exact amount of alkali neutralized during the experiment.
ii)

Repeat the experiment described in (i) above but substitute 100cm 3 of distilled
water for the (50cm3 1M sodium hydroxide+ 50cm3 water)mixture.

Results
1. Calorimeter constant
Table 1: Temperature of water and temperature of mixture after the addition of 2cm 3
of concentrated sulphuric acid
1st minutes 2nd
Temperature of 23.5

minutes
23.5

3rd

4th

5th

minutes
23.5

minutes
23.5

minutes
23.5

3rd

4th

5th

minutes
27.0

minutes
27.0

minutes
27.0

water C
1st minutes 2nd
Temperature of 27.0

minutes
27.0

mixture, C
Initial reading of 1M of sodium hydroxide on burette= 50cm3
Final reading of 1M of sodium hydroxide on burette= 75cm3
Volume of 1M sodium hydroxide needed for titration= 75cm3-50cm3=25cm3

2. Enthalpy of reaction
Table 2: Temperature of distilled water with 50cm 3 sodium hydroxide and 50cm3
distilled water and after the addition of 5cm3 of nitric acid:
1st

2nd

minutes minutes

3rd

4th

5th

minutes

minutes

minutes

Temperature

of 23.5

23.5

23.5

23.5

23.5

2nd

3rd

4th

5th

minutes
30.0

minutes
30.0

minutes
30.0

water + sodium
hydroxide (C)
1st
Temperature

minutes minutes
of 29.0
30.0

mixture (water+
sodium
hydroxide+
conc.nitric acid)
(C)
Initial volume=9.30cm3
Final volume=23.60cm3
Volume used for titrate= 23.60cm3- 9.30cm3 = 14.30cm3
The colour change from red to yellow.

ii.

Table 3: Temperature of 100cm3 of distilled water before and after addition of 5cm 3
of nitric acid (substitute 50cm3 1M sodium hydroxide and 50cm3 of water)

Temperature

1st

2nd

3rd

4th

5th

minutes
24.0

minutes
24.0

minutes
24.0

minutes
24.0

minutes
24.0

1st

2nd

3rd

4th

5th

minutes

minutes

minutes

minutes

minutes

of water (C)

Temperature
of

24.0

24.0

24.5

24.5

24.5

mixture

(C)
The colour change from yellow to orange.

Calculations:
From 1st part of the experiment (reaction of 1M sodium hydroxide with concentrated sulphuric
acid and water):
Volume of NaOH needed for titration = 25cm3
From graph 1, the change in temperature of solution = final temperature - initial temperature
= 27.0C 23.5C
= 3.5C
mv
No of moles of NaOH = 1000

1.0 X 25
1000

= 0.025 mol
No. of moles of hydroxide ions = 0.025mol
1 mole of sulphuric acid produces 2 mole of hydroxonium ions when dissolved in water.
1 mole of hydroxonium ions react with 1 mole of hydroxide ions
0.025mol of hydroxonium ions react with 0.025 mol of hydroxide ions

No. of moles of sulphuric acid =

0.025
2

Hence, the molarity of sulphuric acid =

= 0.0125 mol

no of moles of sulphuric acid X 1000

volume of sulphuric acid that under went titration

0.0125 X 1000
50

= 0.25M
Graph 2 features the heat liberated when various quantities of conc. sulphuric acid was added to
100cm3 of distilled water, based on the table given:
Table 4: The given values of different molarities of diluting concentrated sulphuric acid during
certain experiment and heat liberated during the process
Acid added/cm3
Molarity of solution/M
Heat liberated/ kJ
0.6
0.108
0.802
0.75
0.138
1.016
1.5
0.276
1.987
2.3
0.421
3.016
2.5
0.459
3.293
Based on the second graph, when molarity solution is 0.25M, the heat released during the
reaction is 1.825 kJ.

1g = 1cm3
2 cm3 of conc. sulphuric acid =2g and 100cm3 of water=100g
2cm3 of conc. sulphuric acid add in 100cm3 of water, thus

Mass=100g+2g=102g

Hence, the calorimeter constant,

Ccal =

q
m. T

1.825
102 X 4

= 4.4730X10-3 kJg-1C-1
= 4.4730Jg-1C-1
From graph 3, the change in temperature of the solution = final temperature initial temperature
= 30.0C 23.5C
= 6.5C
1g = 1cm3
5 cm3 of nitric acid =2g and 100cm3 of water =100g
5cm3 of nitric acid add in 100cm3 of water, thus
Mass=100g+5g=105g

Since the calorimeter constant,

Ccal =

q
m. T

The change in heat enthalpy change of neutralization, Hneutralization = q

So, the solution to find q is m.Ccal.T = 105x4.4730x6.5

= 3052.823J
Since the heat of neutralization is undergoes exothermic reaction, therefore

Hneutralization = - 3052.823J
The change in heat enthalpy change of neutralization, Hdilution = 105x4.4730x0.5
= 234.833J
Since the heat of neutralization is undergoes exothermic reaction ALSO, therefore

Hdilution = - 234.833J
Change in heat enthalpy of reaction Hreaction = Hneutralization = -3052.823J

Hdilution

- (-234.833J)

= -2817.99 J or -2.82 kJ
Dicussion
Calorimeter constant is defined by the heat require to raise the temperature of both the
calorimeter and its content by 1C, or a constant that quantifies the heat capacity of a calorimeter.
When reaction such as the neutralization of alkali by acid or dilution of acid in calorimeter, there
was the heat released in these reaction because new bond are formed to create new chemical
product. Finally the reaction is undergoes exothermic reaction due to the heat is released to the
calorimeter itself and also the solution. However, if adiabatic process occur in calorimeter, there
is no heat to be released or absorb from the surrounding by the calorimeter. But, when in this
experiment have to added the chemical substances or chemical reagents in the calorimeter.
Meanwhile, the cap also keep on open, thus, in certain circumstances the heat lost to the
surroundings will be take place in this experiment.

To calculate the change in enthalpy of a neutaralization and dilution, first we have to be

know the calorimeter constant only we can be carry out the calculation as well. Once we know
the calorimeter constant, automatically can also know how much heat must be applied on the
calorimeter and also its contents for them to raise their temperature by 1C. The dilution of conc.
sulphuric acid in the first part is very useful for this purpose of identification, because this
reaction will be liberated a large amount of heat or in other word to say it is an exothermic
reaction.
The first part of the experiment focused on the dilution of conc. sulphuric acid and then
only do the titration which is titrating it by using 1 M sodium hydroxide. But, for the heat of
reaction between the monobasic acid with sodium hydroxide is to be determined instead of
dibasic acid such as conc. sulphuric acid itself, the calculated molarity of sulphuric acid was
divided by 2 because when the neutralization of sulphuric acid by sodium hydroxide, 2 hydrogen
ions will be released from the sulphuric acid. In addition, there must be 2 moles 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 ws 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 replaceable hydrogen atom,
whereas a dibasic acid is defined by an acid that has two hydrogen ions to donate to a base in
acid-base reaction. Hence, the molarity of the sulphuric acid in this experiment was dicided 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 the experiment:

H2SO4(aq)+2NaOH(aq)

Na2SO4(aq)+2H2O(l)

In the second part of the experiment,

HNO3(aq)+NaOH(aq)

NaNO3(aq)+H2O(l)

A graph 2 was plotted with given values of both heat liberated and difference molarities
of sulohuric acid on table 4 and from there, the heat released by the experimented sulphuric acid
when the dilution process occurred was determined by using the calculated molarity of the
sulphuric acid (0.26M) from the first table and its calculations, At first, the formula of the
H
calorimeter constant was introduced as Ccal = T

In this case, the mass measure must be 1 kg only can be used that formula to do the
calculation. But, this is not equal to 1 kg so that formula is not suitable use for calculate the
calorimeter constant. Since q at constant atmospheric pressure is equal to H and we may
rearrange the formula to this form

q = mCcalT and by using this formula we can calculate

the calorimeter constant. Since we can obtain the value of q from the graph, the mass and we also
know the temperature difference so we able to find the calorimeter constant:-

Ccal =

q
m T

The dilution of acid and the neutralization process both are in exothermic reaction. The
heat enthalpy change of the reaction (Hreaction) of a monobasic acid (in this experiment, the
monobasic acid is nitric acid) with sodium hydroxide is determined by subtracting the enthalpy
of dilution (Hdilution) by the enthalpy change of neutralization (Hneutralization). Hence the
enthalpy (heat) of reaction for the process of the nitric acid and sodium hydroxide in this
experiment is -2.82kJ.
When handling the conc. sulphuric acid during the first part of the experiment, extra care
was given when it was added to the distilled water in the Dewar flask as droplets of the acid can

be sprayed into the air. When measure the chemical and reagents, observer eye must
perpendicular to the mark level to avoid parallax error occur.

Conclusion
The change in enthalpy (heat) of reaction of nitric acid (monobasic acid) with sodium
hydroxide is -2.413kJ. It was calculated by subtracting the enthalpy of neutralization between
nitric acid and the sodium hydroxide by the enthalpy of dilution of nitric acid. The enthalpy of
dilution of nitric acid must be considered because dilution of the acid is an exothermic process
just like the neutralization process. It must be also considered for the purpose of obtaining a
more accurate enthalpy of reaction value.
References
1.

Calorimeter Constant.
(n.d.). Retrieved February 24,
http://chemistry.oregonstate.edu/courses/ch361-464/ch362/calorim2.htm

2016,

from

2. Monobasic, Dibasic and Tribasic Acids : Wizznotes.com- Free GCSE and CXC:
Tutorials, Past Papers and Quizzes. (n.d.). Retrieved February 24, 2016, from
http://wizznotes.com/chemistry/acid-bases-and-salts/monobasic-dibasic-and-tribasicacids