EXPERIMENT NO.

Calorimetry
Department of Chemical Engineering, College of Engineering

Calorimetry, constant pressure, enthalpy, adiabatic system

Results and Discussion
The Internal energy of a system is its total
energy content. It may be composed of thermal
energy, kinetic energy associated with random
molecular motion, and chemical energy,
energy associated with chemical bonds and
intermolecular attractions. As chemical
reactions progress, some chemical bonds are
broken and others are formed, and we
generally expect changes in the chemical
energy of the system as a result. Some of these
energy changes appear as heat. The evolution
of heat causes increase in temperature
(exothermic reaction), while the absorption of
heat causes decrease in temperature
(endothermic reaction). These changes in heat
content are equal to the Hrxn, called the
enthalpy change, if they are measured at a
constant pressure. If Hf is the enthalpy of the
final state and Hi of the initial state, the
enthalpy change for a chemical reaction is the
difference of Hf and Hi. [Eq. 1]
Here, the class examined the change in energy
of a reaction that occurred at constant pressure,
in an isolated system (that is, one that does not
exchange matter and energy with its
surroundings). A simple Styrofoam-ball set-up
is used to represent thus isolated system
because it is a good heat insulator, thus
allowing very little heat transfer between the
Grp.
No.
10

Trial

T,
(C)

qrxn,
(J)

qcal,
(J)

Ccal,
(J)

2.5

-279

279

111.6

Ave
Ccal,
(J)

122.2
2
2.1
- 279 279 132.9
Styrofoam and the immediate surroundings,
that is, the heat change is zero. [Eq. 2]
This process of measuring H is called
calorimetry, and the Styrofoam-ball set-up is
the device called calorimeter. In essence, a
calorimeter performs three functions: it
encloses a chamber in which a thermal
experiment is carried out; it measures the heat
exchange between the sample under test and

the calorimeter (and often other quantities are

being measured as well, such as temperature
and amount of substance); and it thermally
separates the experimental chamber from its
surroundings. To be able to have consistent
values of the heat capacity (Ccal) of the
calorimeter, it should be calibrated. This is
done by running in the calorimeter a reaction
of known H. [Eq. 3]
Ccal is determined by using H, moles of
limiting reactant, and change in temperature.
[Eq. 4]
To determine the heat involved in the
calorimeter, the reactants are placed inside the
calibrated calorimeter and the temperature
before and after the reaction are read. The
temperature difference will be used to
calculate for the heat released or absorbed by
the calorimeter. [Eq. 5]
From qrxn and number of moles of reaction that
took place, the enthalpy change per moles of
reaction can be calculated. [Eq. 6 & 7]
The experimental results showed deviation
from the theoretical values. These
discrepancies may be associated to human
error, like misreading the temperature or
mishandling of reagents, or that the reagents
used may have been contaminated.
The results and calculated values for the
calibration of the groups calorimeter are
shown in Table 1.
Table 1. Calibration of Calorimeter
The inaccuracy of the calorimeter can be
reduced by calibration. The key idea is to use
the very same parts of the calorimeter all
through out the experiment same Styrofoam
ball, test tube, stopper, and thermometer for
all the trials in order to have valid results.

The obtained heat of reaction assigned to the

group and other calculations are shown in
Table 2.

book.narod.ru/MISH/CH36.PDF.
(2011, Nov. 22)
Chang, R.(2006).Calorimetry.
General Chemistry.(2011, Nov. 22)
Petrucci, R. H., Herring, F. G., Madura, J.
D., Bissonnette, C.(2010).Heats of

Table 2. Determination of Heat of Reaction

Net
Ionic
Eq.

Grp.
No.

L
R

Trial

T,
(C)

nLR,
(mol)

qrxn,
(J)

Ca2+(aq) +
n
1
- 0.3
n/a
36.67
CO32-(aq)
10
o

ne
2
- 0.2
n/a
24.45
CaCO3(s)
The high % error obtained in the experiment is
mainly due improper method of transferring of
solutions to another vessel.

Conclusion
Calorimetry connects chemical and physical
processes as well as heat change that are
essential in understanding chemical relativity
and physical property. The adiabatic nature of
the Styrofoam-ball calorimeter (for constant
pressure) makes it convenient for people to
carry out and trace changes of heats of
reactions under the normal atmospheric
pressure. But human errors cannot be
neglected since these errors contribute greatly
on the finals results acquired.

qcal,
(J)

Hrxn
(kJ/mol)

-36.67

36.79

-24.45

24.53

Ave.
Hrxn
(kJ/mol)

30.66

Theo
Hrxn
(kJ/mol)

%
Error

13.07

134.6

Reaction and Calorimetry.General

Chemistry.(2011, Nov. 22)
The Law of Conservation of
Mass.Retrieved from
http://www.mi.mun.ca/users/edurnfor/
1100/atomic%20structure/tsld004.htm.
(2011, Nov. 22).
Working Equations
!"# = ! ! (1)
!"#$%&'( !"!#$% = !"# + !"# 2
=0
!

!"

+ ! !" ! ! (3)
= 55.8

Applications
Ceramics
The energetic study of ceramics or solid
solution is able to reveal information about the
thermodynamics and properties of material
and further provide instructions to the
synthesis and application.
References
Application of Calorimetry.Retrieved
from
http://chemwiki.ucdavis.edu/Physical_
Chemistry/Thermodynamics/Calorime
try/Application_of_calorimetry.
(2011, Nov. 22)

!"# =

!"

where Ccal = heat capacity of the

calorimeter (J/C);
H = enthalpy change of rxn
(kJ/mol);
nLR = moles of limiting
reactant (mol);
coeff = coefficient of limiting
reactant; and
T = change in temperature (C)
!"# = !"# (5)

Calorimetry Measurement.Retrieved
from http://www.dsp

For reactions without solid reactants and/or

products:
!"#
!"# =
6
!"

Use [Equation 5] to compute for qcal:

!"# = !"# (5)
Trial 1:
!"# =

For reactions without solid reactants and/or

products:
!"#
!"# +
=

Trial 2:
!" !"#$% !"#$%#&%

!"#$% !"#$%&'

!"

!"# =

(7)

In the Calibration part of the experiment, to

calculate for the heat capacity of the
calorimeter (Ccal), the group used [Equation 4]
and referred to [Equation 3] for :
!"

!"# =
4

!"# = 279
132.9

2.1

Use [Equation 2] for both trials to find qrxn:

!"# + !"# = 0 2
Trial 1:
!"# + 279 = 0
!"# = 279
Trial 2:
!"# + 279 = 0

Trial 1:

55.8

0.005
1
2.5

1000
1

Trial 2:
!"# =

55.8

0.005
1
2.1

!"# = 279

In the Determination of Heats of Reaction part

of the experiment, the group was assigned the
reaction

!"# = 111.6 /
1000
1

Na2CO3(aq) + CaCl2(aq)
2NaCl(aq) + CaCO3(s)

To compute for Average Ccal, sum up the

obtained values from Trial 1 and Trial 2, and
divide by 2:
. !"#
!"# (!"#$% !) + !"# (!"#$% !)
=
(8)
2
. !"# =

111.6 / + 132.9 /
2

. !"# = 122.2 /

(9)

Net ionic equation:

!"# = 132.9 /

! !! (!") + !!

!"

! (!)

and was instructed to get the theoretical !"#

using the given standard heats of formation of
some substances, that is,
!"# =
!"# =
1

1206.9

1
1

2.5

!"# = 279

Sample Calculations

!"# =

()

111.6

! !

!"
!"#

! ! (10)

677.14
542.83

!"
!"#
!"

!"#

 !"# = 13.07

!"

!"#

!"#

122.2
=

qcal is calculated by using [Equation 5] for both

trials (use average Ccal in computation).
!"# = !"# (5)

Trial 2:
!"#

Trial 1:

122.2

!"# = 122.2 / 0.3

!"# = 36.67

Trial 2:
!"# = 122.2 / 0.2
!"# = 24.45

+ 0 + 0.50044

1

!"# = 36.79

0.8181

0.3

+ 0 + 0.50044

1

!"# = 24.53

0.8181

0.2

To compute for Average !"# , sum up the

obtained values from Trial 1 and Trial 2, and
divide by 2:

Use [Equation 2] for both trials to find qrxn:

!"# + !"# = 0 2

. !"#
!"# (!"#$% !) + !"# (!"#$% !)
=
(12)
2

Trial 1:
!"# + (36.67) = 0
!"# = 36.67

. !"# =

Trial 2:
!"# + (24.45) = 0

. !"# = 30.66

!"# = 24.45

The % error is given by this Equation:

To calculate for !"# , use [Equation 7]

because the reaction yields solid products. But
first, the mass of the product must be known.

%
. !"# !"#
=
(13)
!"#

*There are no limiting reactants in the

reaction. One may use either of the reactants to
compute for the mass of the product.

% =

1 !

1000 !
1 !
100.088 !


1 !
1 !
= 0.50044 ! 11

Answers to Questions

The specific heat of CaCO3(s) is 0.8181.

Trial 1:

+
!"

!" !"#$% !"#$%#&%

!"#$% !"#$%&'

30.66 13.07

13.07

% = 134.6 %

5 !

!"#
!"# +
=

36.79 + 24.53
2

()

1. After obtaining experimental values of

Hrxn explain any discrepancy of the
values to the theoretical. Give some
possible sources of errors.
(7)

The discrepancy of the

calculated values is mainly caused by
human error. Groups who prepared
their assigned solutions might have
been inaccurate in measuring the
solutes or solvents they used. Also,

when transferring or pouring out

solutions from one container to
another, spilled portions can alter the
expected experimental values.
In performing the actual
experiment, a lot of factors can cause
this discrepancy. One is that when
pouring the remaining reactant, the
cork is removed from the test tube
while there is already an occurring
reaction inside the calorimeter,
causing heat to escape from the
adiabatic system. Secondly, in reading
the initial temperature, the group
might have recorded a Tinitial while
reaction has already started, making
the Tinitial inaccurate. On the other
hand, in reading the final temperature,
the group might have recorded a Tfinal
without making sure that the solutions
reacted completely, making Tfinal
wrong. Moreover, when in reading
these said temperatures with the
thermometer, the group might obtain a
parallax error.
2. In the procedure for the determination
of H, explain why it is important:
a. that the volume of the resulting
solution be 15 mL
The volume of the resulting
solution must be exactly 15 mL or the
same with the sum of the volumes of
the two reactant solutions. This must
be true in accordance with The Law of
Conservation of Mass, which states
that the mass of the substances
produced by a chemical reaction is
always equal to the mass of the
reacting substances.
b. to know the exact concentrations
of the reactants?

c. to know the exact weight of the

metal solids used?
Knowing the exact weight of the
metal solids is significant in
calculating the concentrations, the
number of moles, the theoretical
amount of products, and other values
the group encountered in this
experiment.
3. The neutralization of 200 mL of 0.05
M HA by sufficient amount of NaOH
evolves 6.0 kJ of heat.
a. Calculate the enthalpy change for
the neutralization of 1 mole HA.
Hrxn = qrxn / nrxn
Hrxn = (-6.0 kJ) / (0.1 mole)
= -60 kJ/mol
b. Is HA a weak or strong acid?
Justify your answer using
thermochemical equations.
HA + NaOH NaH + H2O(l)
HA is a strong acid, since it was
fully ionized in aqueous
solution.
c. Write the net ionic equation for
the reaction between HA and
NaOH.
H+(aq) + OH-(aq)H2O (l)
4. A calorimeter similar to your
Styrofoam-ball calorimeter was used
to determine the enthalpy change
associated with the reaction between
Cu2+ and Zn(s). The reaction between
20 mL of 0.450 M CuSO4 and 0.264 g
Zn(s) resulted to a temperature change
of 8.83 C.
Prior to the analysis, the calorimeter
was calibrated using the reaction
between 15 mL of 2.0 M HCl and 5

It is important to know the exact

concentrations of the reactants since it
is the key in calculating the number of
moles of the reactants present in the
solution.

mL of 2.0 M NaOH, which brought

about a temperature change of 5.60C.
a. Write the net ionic equation for
the calibration reaction.

H+(aq) + OH-(aq)H2O (l)

b. Write the ionic reaction for the
displacement reaction.
Cu2+(aq)+Zn(s)Cu(s)+Zn2+(aq)
c. Calculate Ccal.
Ccal = -H (nLR/coeff.)
T
Ccal = -(-55.8 kJ/mol)(0.01 mol)
5.60C

Ccal = 99.64 J/ C
d. Calculate the enthalpy change (per
mole) for the displacement
reaction.
The enthalpy change (per mole) is 55.8 kJ.
5. Given that the standard enthalpy of
formation of liquid water, Hf,H20 is 285 kJ/mol, calculate the Hf of OH(aq).
Hrxn= Hf [H2O] ( Hf [H+]+ Hf
[OH-])
-55.8 kJ = -285 kJ (0 + Hf [OH-])
Hf [OH-]= -229.2 kJ