I.

Theoretical Background

Calorimetry is the measurement of heat changes, and a calorimeter is used to measure the
heat involved in any physical and chemical processes. The following heats of reaction can be
measured using a calorimeter:

a. Combustion
b. Dissolution, dilution or mixing
c. Neutralization etc.

There are two basic types of calorimeters: the open-type (constant pressure) and the bomb
calorimeter (constant volume). Figure 1 shows inner sections of various calorimeters:

Figure 1a. OPEN TYPE CALORIMETER Figure 1b. BOMB TYPE CALORIMETER

From the statement of the First Law of Thermodynamics, the change in the internal
energy is due to the exchange of heat and work across the boundary of the closed system.
Mathematically, ∆ U =Q+W where ∆ U is the sum of the kinetic and potential energy at a system
due to microscopic position and movement and Q and W (equal to −P ∆ V ) are heat and work
that is either absorbed or released, and done on or done by the system, respectively. The sign
convention for Q and W are assigned as follows:

HEAT (Q) WORK (W)

released by the system

- work done by the system -
(exothermic)
absorbed by the system
+ work done on the system +
(endothermic)
 The enthalpy of a system is a thermodynamic function so defined to express U + PV in
flow processes. Thus, ∆ H =∆ U + P ∆ V at constant pressure. Since ∆ U =Q−P ∆ V the two
equations can be simplified to:

∆ H =∆ U + P ∆ V =Q

∆ H =Q p

This simply implies that, heat released or absorbed at constant pressure is a measure of
the change in enthalpy of a system. Therefore, heat measured in an open-type calorimeter is a
measure of ∆ H .

At constant volume, ∆ V =0…

∆ U =Q−P ∆ V =Q

∆ U =Qv

Similarly, the heat released or absorbed at constant volume is a measure of the change in
internal energy so as in bomb calorimeters.

For solids and liquids, ∆ H is approximately equal to ∆ U since changes in volume are
assumed to be negligible when heat and work are applied.

For gases, assuming that ideal behavior, the ideal gas equation can be applied thus,

∆ H =∆ U + ( ∆ n g ) RT

Where ∆ ng=ngas ,constant −n gas, reactant

In bomb calorimeters, reaction occurs in a vessel immersed in a known mass of water.

The whole assembly is insulated so as to avoid heat transfer from the surroundings. When a
reaction releases heat, water and the calorimeter absorb the heat. No heat is assumed to be
dissipated to the surroundings. In so doing, the temperature of water and the calorimeter will rise.
A stirrer is installed to ensure the uniformity of the temperature. Thus,

Qreaction +Qcalorimeter +Qwater =0

Qreaction =−( Q calorimeter +Qwater )

∆ U =Qreaction =−[ ( C cal ∆ T ) + ( mC ∆ T )water ]

Heat Capacity (C) of a substance is the amount of heat required to raise the temperature
of a substance by one degree temperature. Specific Heat (c) is the amount of heat required to
raise the temperature of a unit-mass of a substance by 1 ℃. A British Thermal Unit (BTU) is the
heat required to raise the temperature of 1 pound-mass of a substance by 1 ℉ . Thus, at constant
pressure, ∆ U =C v dT and at constant volume, ∆ H =C p dT .

In this experiment, the heat capacity of the calorimeter is determined along with the heats
of neutralization, dilution and neutralization using a constant pressure calorimeter.

II. Procedure
A. Thermometer Calibration
1. Label two thermometers as thermometer A and thermometer B to be used for
calorimeter A and calorimeter B, respectively.
2. Dip both thermometers in a beaker filled with distilled water. Record the temperature
readings on both thermometers.
3. For thermometer B, account for any difference and record difference as correction
factor in relation to thermometer A. add the difference to all readings of thermometer
B. otherwise subtract the difference from all readings of thermometer B.

B. Determination of Heat Capacity of Calorimeter

1. Dry the Styrofoam cups and fill calorimeter A with 25 mL water at a temperature
above 70°C and calorimeter B with 25 mL distilled water at room temperature.
2. With the cover and thermometer in place, transfer the contents of calorimeter B to
calorimeter A and cover it immediately.
3. Record the temperature reading of thermometer A until a constant value is attained
that lasts for two minutes.

C. Heat of Neutralization
1. Prepare 25 mL of 1.0 M of HCl solution in calorimeter A and 25 mL of 1.0 M of
NaOH solution in calorimeter B. Allow to stand until both solutions attain room
temperature.
2. Quickly pour the contents of calorimeter B to calorimeter A.
3. Record the temperature reading of thermometer A until a constant value is attained
that last for two minutes.

D. Heat of Solution
1. Measure 400 mg of NH4Cl in calorimeter A and 50 mL of distilled water in
calorimeter B.
2. Pour water in calorimeter A to calorimeter and record the temperature reading of
thermometer A until a constant value is attained that lasts for two minutes.
 III. Results

A. Thermometer Calibration

Thermometer A Reading 30 °C

Thermometer B Reading 26 °C

Correction Factor for Thermometer B 4 °C

B. Determination of Heat Capacity of Calorimeter

Temperature of Water in Calorimeter A (°C) 76 °C

Density of Water in Calorimeter A (g/mL) 1 g/mL

Temperature of Water in Calorimeter B (°C) 30 °C

Density of Water in Calorimeter B (g/mL) 1 g/mL

Temperature of Mixture in Calorimeter A (°C) 48 °C

Heat Capacity of Calorimeter A 58.111 J/°C

C. Heat of Neutralization

Temperature of HCl(aq) in Calorimeter A (°C) 32 °C

Temperature of NaOH(aq) in Calorimeter B (°C) 30 °C

Temperature of Mixture in Calorimeter A (°C) 38 °C

Heat of Neutralization per mole H2O Produced 13.947 kJ/mol

D. Heat of Solution

Mass of NH4Cl (grams) 0.4024 g

Temperature of H2O in Calorimeter B (°C) 28 °C

Density of Water in Calorimeter B (g/mL) 1 g/mL

Heat of Solution per mole NH4Cl Dissolved -15.448 kJ/mol

Final Temperature of Solution (°C) 26 °C

Calculations:

( 25 g ) ( 4.184
g∙℃ )
J
(76−48 ) ℃−( 25 g ) (
g∙℃ )
4.184 J
( 48−30 ) ℃=HC calorimeter ( 48−30 ) ℃

2928.8 J −1882.8 J =HC calorimeter (18 ℃)

 HC calorimeter =58.111 J /℃

Q C ∆T
∆ H neutralization= =
n n

n=25 mL ( 1000L mL )( molL )=0.025 mol NaOH =0.025 mol H O 2

( 58.111 J /℃ ) ( 38−32 ) ℃
∆ H neutralization=
0.025 mol
∆ H neutralization=13946.667 J /mol

∆ H neutralization=13.947 kJ /mol

Q C ∆T
∆ H solution= =
n n

n=0.4024 g ( 53.491
mol
g)
=0.00752mol N H Cl 4

( 58.111 J /℃ )( 26−28 ) ℃
∆ H solution=
0.00752 mol N H 4 Cl

∆ H solution=−15449.411 J /mol

∆ H solution=−15.448 kJ /mol

IV. Discussion
The thermometer calibration is an adjustment that ensures accuracy of temperature
readings for the experiment since we use two different thermometers. Thermometer A recorded
30 °C, while Thermometer B recorded 26 °C, showing a correction factor of 4 °C.

The heat capacity of the calorimeter is the ability to absorb or release heat. By mixing
two different temperatures of water, 76 °C and 30 °C respectively, the final temperature showed
48 °C. Determining that the heat capacity using our data is 58.111 J/°C.

The heat of neutralization is the energy absorbed or released when mixing acid and base.
The temperatures of HCl(aq) and NaOH(aq) were 32 °C and 30 °C, respectively. By mixing
them, it showed a temperature of 38 °C. Determining that the heat of neutralization per mole of
H2O produced is 13.947 kJ/mol.

The heat of solution is about the heat exchange when mixing solute and solvent. Using
0.4024 g of NH4Cl dissolved in water, and with the initial temperature of water in calorimeter B
at 28 °C, the heat of solution per mole of NH4Cl dissolved was determined to be -15.448 kJ/mol.

V. Conclusion
VI. Recommendations

VII. Prelab Exercises

1. Calculate the standard enthalpy of reaction of the following:

3
a. C 2 H 2(g) + O 2( g) → 2 CO(g) + H 2 O (l)
2
b. NaOH (s) + HCl(g) → NaCl(s) + H 2 O(l)
c. H 2 SO4(l) +2 NaOH (s) → Na2 S O4(s) + H 2 O(l)

2. What are the two basic types of calorimeters? Differentiate these calorimeters.
The two basic types of calorimeters are open type calorimeter and bomb
calorimeter. An open type of calorimeter is a device used to study changes in
temperature and reactions carried out in the system at a constant atmospheric
temperature. It is also called constant-pressure calorimeter, which we often
encounter since we only use coffee cup calorimeter in our school laboratories,
which utilizes constant atmospheric pressure using a coffee cup as the container,
lid, stirring rod, and thermometer. A coffee cup is used as it was accessible and a
good insulator.
A bomb or constant-volume calorimeter on the other hand, is a device
used to measure heat energy released by combustion reactions carried out in the
system while holding a constant volume. This device has more intricate design
than open type calorimeter, thus, it is harder to operate but will produce more
accurate results. This device is designed to withstand large amounts of pressure
from combustion reaction. Those reactions may produce explosions; thus, it is
called bomb calorimeter.

3. Write the thermochemical equations of the following reactions at 25 °C.

a. Formation of CH 4(g)
C(s )+ 2 H 2(g) →CH 4(g)
b. Combustion of CH 3 OH (l)
CH 3 OH (l) +3 O2(g) →CO 2( g) +2 H 2 O(l )
c. Dissolution of SO 3(g ) in H 2 O(l)
SO3(g )+ H 2 O(l ) → H 2 S O4(aq)
4. The molar heat of combustion of liquid ethyl alcohol is -1336.91 kcal/mole. If
300 mg of ethyl alcohol is burned in a calorimeter causes a rise in temperature of
2.225 °C, what is the total heat capacity of the calorimeter?

∆ H combustion=−1336.91 kcal /mol

Q C ∆T
∆ H combustion= =
n n
−1336.91 kcal −C ( 2.225 ℃ )
=
mol
0.3 g (
mol
46.068 g )
C=3.912 kcal/℃