Calorimetry – Heat of Reaction

Calorimetry is a method of determining heats of reaction. The heat generated by a

reaction causes the temperature of a solution to rise. By measuring this temperature change,
and relating it to the heat capacity, one can find the amount of heat generated in a reaction.

If two samples of matter, initially at different temperatures (T H and TC, respectively), are
placed in thermal contact, heat will be lost by the hotter sample (T H) and gained by the cooler
one (TC). This exchange of heat will take place until both samples achieve the same final
temperature, TF, so that TH > TF > TC. This is known as the Zeroth Law of Thermodynamics.
During heat exchange (or, as we shall see, during a chemical reaction), heat is neither created
nor destroyed (The First Law of Thermodynamics). Thus, heat lost equals heat gained, if the heat
exchange can be sufficiently insulated from the surroundings so that not very much heat escapes
to the surroundings.

�� ������ = −���������� (1)

A vessel that provides adequate heat insulation from its surroundings, and in which
temperature changes are measured in order to determine specific heats (or heats of chemical
reactions) is called a calorimeter. A typical calorimeter is made of two nested Styrofoam cups,
and looks like the one shown below:

A perfect calorimeter absorbs no heat from the solution that it contains, nor loses any heat to the
surroundings. No calorimeter is perfect, however.
In this experiment, a simulation of an ideal constant-pressure calorimeter will be used to
study two reactions: 1) the reaction of a strong acid with a strong base and 2) the dissolution of
salt in water. We assume that no heat went into warming the calorimeter vessel and that no heat
was lost to the surroundings. Since water serves as the surroundings,

�� �������� = ������������ (2)

The heat that is exchanged with the water causes a temperature change of ΔT water in the water as
shown in equation 3.

�� ���������� = (������������)(������������) (3)

where Cwater is the heat capacity of the water, the amount of heat needed to raise the temperature
of the water by 1°C. The units of C are J/°C. ΔT is the temperature change, defined as ΔT = TH –
TC. Heat capacities depend upon the mass of the sample, so the specific heat, the amount of
heat needed to raise the temperature of one gram of a substance by 1°C, is often used instead.
The symbol for specific heat is Sp ht. The specific heat of water is 4.184
J/g · °C. The heat capacity of the water equals the mass of water times the specific heat of
water, i.e., Cwater = mwater · Sp htwater. Substitution into equation 3 yields equation 4:

�� ���������� = (������������)(���� ℎ������������)

(Δ������������) (4) Combining equations 1 – 3, we have

(������������)(���� ℎ������������)(Δ������������) = −
(������������)(���� ℎ������������)(Δ������������) or (5)
(����) (4.184 ���� ��) (���� − ����) = −(����) (4.184 ���� ��) (���� −
����)
where subscript F refers to the final temperature after mixing.
In the neutralization reaction, if equimolar amounts of a strong acid and strong base were
mixed, the reaction produces heat which causes the temperature in the calorimeter to increase.
After complete reaction, the calorimeter will contain a dilute solution of salt. We can assume that
the specific heat is still that of water (4.184 J/goC) without producing much error and we can
assume that the density of the dilute salt solution is that of water, 1.00 g/mL. The heat exchange
equation is:
heat given off by the reaction = heat gained by the water

If the calorimeter and the reactant solutions all start at the same initial temperature (T I ) and
warm to a final temperature (Tf), then

heat given off by the reaction = (mwater) (4.184 J/g °C)(TF – TI) (6) = (Vwater in mL) (1.00
g/mL)(4.184 J/g °C) (TF – TI) (7) (Note: We assume that the V water is the final volume of the
solution after mixing)
At constant pressure, the heat given off by the reaction is equal to the change in enthalpy (ΔH) of
neutralization (in kJ/mol) given by the equation:
− ��������,��
∆������������������������������ = (
�� ����
�������� ����������)(

�������� ��) (8)

The minus sign is inserted to indicate that the reaction is exothermic.

For the enthalpy of solution, the heat released by the dissolving process is equivalent to
the heat gained by the water.

−�������� = (�������� ���� ���������������� +

�������� ���� ����������)(���� ℎ������������)(Δ��)

(9) and the ΔH of solution is
Δ�������� =−��������
���������� ���� ������ ���������� ���������������� (10)
Instruction:
 1. On your browser go to:
https://media.pearsoncmg.com/bc/bc_0media_chem/chem_sim/calorimetry/Calor.ph p
2. Run a demonstration by following the instructions given to you in order to see how the
simulation goes.
3. After you are done, reset the page and select “Run Experiment”. Use the simulator to
carry out the succeeding experiments.

A. Determination of Enthalpy of Neutralization

(Refer to your instructor for the acid and base solutions assigned to you.)

1. Measure 50.0 mL of a 2.0 M strong acid solution and pour it into a clean, dry beaker.
(Caution: HCl is corrosive and, if spilled on the skin, should be washed away immediately
with copious amounts of water.)

2. Measure 50.0 mL of a 2.0 M strong base solution and pour it into the calorimeter. (Caution:
NaOH is corrosive and, if spilled on the skin, should be washed away immediately with
copious amounts of water.)

3. Record the initial temperature of the solutions (TI).

4. Pour the strong acid solution into the calorimeter, replace the top, and stir until the
temperature no longer changes (TF).

5. Use these temperatures to calculate the heat evolved and ∆H of neutralization.

B. Determination of Enthalpy of Solution

(Refer to your instructor for the solid compound assigned to you.) 1.

In a dry beaker, weigh 5.0 grams of your assigned solid compound.

2. After thoroughly rinsing and drying your calorimeter, measure 100.0 mL of deionized water
in a clean graduated cylinder and add this to the calorimeter.

3. Record the initial temperature as TI.

4. Cover the calorimeter and stir. Continue swirling until the temperature no longer changes.
Record this temperature as TF

5. Use these temperatures to calculate the heat evolved and ∆H of solution.

Name: ____________________________________ Subject/Section: _________

Calorimetry – Heat of Reaction

A. Determination of Enthalpy of Neutralization

Acid: __________
 Base: __________
Acid Base

Concentration, M

Initial Volume

Initial Temperature (TI), oC

Final Temperature (TF), oC

Final volume after mixing

Balanced chemical equation: __________________________________________

Calculate:
a) Heat lost by the reaction, kJ

qrxn =

b) Moles of water formed =

c) Enthalpy of neutralization, kJ/mol

ΔH =
B. Determination of Enthalpy of Solution

Name and chemical formula of the solid compound: _______________________

Molar mass, g/mol: _______________________
Solid compound Water

Mass, g

Initial Temperature (TI), oC

Final Temperature (TF), oC

Mass (solid compd + water)

Balanced chemical equation: __________________________________________

Calculate:
a) Heat absorbed by the calorimeter, kJ

qcal =

b) Moles of the solid compound =

c) Enthalpy of solution, kJ/mol

ΔH =

d) Is the process exothermic or endothermic? _________________

What is the major source of error in this experiment?