Activity 5

Heats of Reactions

Objectives

At the end of the exercise, the students must be able to:

1. test for the heat of solution of sodium hydroxide.
2. calculate for the heat of reaction for the neutralization of sodium hydroxide and
hydrochloric acid.

Changes in matter, be it physical or chemical change, are always accompanied by

change in energy. This energy change at constant pressure it is defined as heat of
reaction or enthalpy change (ΔH). Such change is manifested either by the
liberation or the absorption of energy (most commonly in the form of heat).The heat
absorbed (or evolved) by the system is equal to the heat released (or absorbed) by the
surroundings or the environment.

When a system gives off or releases heat to the surroundings or environment, the
process is said to be exothermic and ΔH is shown with a negative sign. In this case,
the system will have less energy than before, while the surroundings or environment
will gain the energy. On the other hand, processes wherein heat is absorbed by the
system from the surroundings or environment, the process is called endothermic and
ΔH is shown with a positive sign.

The sign conventions for heat flow and enthalpy changes are summarized in the
following table.

Reaction Type Heat(q) ΔHrxn

Exothermic Less than 0 <0
Endothermic Greater than 0 >0

Important in the determination of exothermic and endothermic processes is the

identification of the system and the environment. For example, when wood is burned in
the cooking of food, heat is released by the burning wood to the food being cooked. If
the food being cooked is the system and the burning wood and everything else outside
the food container is the environment, then the process is endothermic.

One way to monitor the flow of heat is to find the temperature change before and after
reaction. If a certain solid is dissolved in water and the resulting solution gets hot, this
means that the temperature after mixing is higher than the temperature before mixing.
Considering the solid to be the system and the water and the container as the
environment, the process is exothermic. The mixing process released heat to the
surrounding water molecules, thus the solution becomes hot. On the other hand, if the
resulting solution gets cold after mixing, the process is said to be endothermic, since
the surrounding water molecules have given off heat to the system.
The measurement of heat flow is calorimetry and the device used to measure heat flow
is a calorimeter. In a calorimeter, the change in temperature of the measuring part is
converted into the amount of heat. The measurement of heat transfer using this
approach requires the definition of a system and its surroundings. The system is the
substance or substances undergoing the chemical or physical change while the
surrounding is the other components of the measurement apparatus that serve to
either provide heat to the system or absorb heat from the system).

Figure 1. Calorimetric determination (http://cnx.org/contents/[email protected])

Imagine adding two aqueous solutions, each containing a reactant, to a coffee-cup

calorimeter. Once mixed, the reactants can react to form products. In this case there is
no physical boundary between the system and the surroundings. The reactants and
products of the reaction are the system, and the water in which they are dissolved is
part of the surroundings. (The calorimeter apparatus is also part of the surroundings.)
If we assume that the calorimeter is perfectly insulated, then any heat released or
absorbed by the reaction will raise or lower the temperature of the water in the
solution. Thus, we measure the temperature change of the solution and assume that
any changes are due to heat transferred from the reaction to the water (for an
exothermic process) or transferred from the water to the reaction (endothermic). In
other words, by monitoring the temperature of the solution, we are seeing the flow of
heat between the system (the reactants and products in the solution) and the
surroundings (the water that forms the bulk of the solution).

The thermal energy change accompanying a chemical reaction is responsible for the
change in temperature that takes place in a calorimeter. In a coffee-cup calorimeter, if
the reaction releases heat (q sys or qrxn < 0), then heat is absorbed by the water in
solution (qH2O > 0) and its temperature increases. Conversely, if the reaction absorbs
heat (qrxn > 0), then heat is transferred from the surrounding to the system (q surr or
qH2O < 0) and the temperature of water in solution decreases. In both cases, the
amount of heat absorbed or released by the water in solution is equal in magnitude
and opposite in sign to the amount of heat produced or consumed by the reaction. The
specific heat of solution or of the reaction mixture may be used to calculate the
amount of heat released or absorbed by the chemical reaction.

The heat capacity (C) of a body of matter is the quantity of heat (q) it absorbs or
releases when it experiences a temperature change (ΔT) of 1 degree Celsius or
equivalently, 1 kelvin. This capacity of the calorimeter or of the reaction mixture may
be used to calculate the amount of heat relationship is expressed in the equation
below.

Heat capacity is determined by both the type and amount of substance that absorbs or
releases heat. The heat capacity of an object depends on both its mass and its
composition. For example, doubling the mass of an object doubles its heat capacity.
Consequently, the amount of substance must be indicated when the heat capacity of
the substance is reported.

The specific heat capacity (c) of a substance, commonly called its specific heat, is the
quantity of heat required to raise the temperature of 1 gram of a substance by 1
degree Celsius or 1 kelvin.

Because ΔH is defined as the heat flow at constant pressure, measurements made

using a constant-pressure calorimeter give Δ H values directly. This device is particularly
well suited to studying reactions carried out in solution at a constant atmospheric
pressure. A version, called a coffee-cup calorimeter (Figure 2 ), is shown below..

Figure 2. Coffee cup calorimeter

Because the heat released or absorbed at constant pressure is equal to Δ H, the

relationship between heat and ΔH is

ΔHreaction = qsystem or qreaction =-qsurroundings or -qH2O = -mCΔT

Measuring Enthalpy (heat) of Reaction Experimentally

An expanded polystyrene foam cups can be used as a calorimeter as shown in the

Figure 2.

1. A known quantity of reactant is placed in a well-insulated vessel.

2. The initial temperature of this reactant is recorded, Ti.
3. A known quantity of the second reactant is added, the vessel is sealed with a lid
and the reaction mixture stirred.
4. The final temperature of the reaction mixture is recorded, Tf.
5. The heat released or absorbed (the heat change) q, in joules (J), for the reaction
is calculated as

q = m × cg × ΔT

The enthalpy change, ΔH, in kiloJoule per mole of a given reactant for the reaction is
calculated as:
ΔH = heat change/1000 ÷ moles
ΔH = q/1000 ÷ n
mass of compound
Where: n, mole of a compound =
molar mass of compound

There are common assumptions for reaction mixtures made up of aqueous solutions.
This includes:

1. The density of aqueous solutions is assumed to be the same as for water

which is, 1 g mL1 at 25°C.
For example, a 100-mL of aqueous solution is said to have a mass of 100
g.
2. The volumes of reactants in solution is additive.
For example, 100 mL of "reactant A (aq)" + 200 mL of "reactant B (aq)" =
300 mL of "aqueous solution"
3. The specific heat capacity of the reaction mixture assumed to be the same
as water, that is 4.184 J·K1g1 = 4.184 J·°C 1g1.

Procedure

Caution: Wear personal protective equipment (PPE) at all times while performing the
experiment.

I. Heat of Solution
1. Place 10.00 mL of water in a 25-mL graduated cylinder. Measure its
temperature.
2. Weigh 0.80 g of sodium hydroxide in a clean and dry watch glass. Transfer
the solid to the graduated cylinder with water. Stir the mixture to dissolve
the solid completely. Measure the temperature of the mixture.
Important notes: Sodium hydroxide is highly corrosive so perform the experiment
with care to avoid spillage and contact with the skin. Should there be spillage on the
balance pan, wipe them immediately with clean rag or tissue. Chemical in contact
with the skin should be washed immediately with running water for at least 15
minutes.

3. Add water to the mixture until the volume reaches 20.00 mL and stir.
4. Reserve the mixture for Part III.
5. Repeat procedures 1 to 3 using 1.10 g of ammonium chloride instead of
sodium hydroxide. Place this solution in a container labelled with “1M
NH4Cl” provided by the technician.

II. Heat of Dilution

1. Place 18.30 mL of water in a 50-mL beaker and measure its temperature.
2. Measure 1.70 mL of concentrated hydrochloric acid (12 M) and pour it slowly
to
the beaker with water.
Important notes: Always add acid to water, never water to acid. HCl is highly
corrosive so perform the experiment with care to avoid spillage and contact with the
skin. Chemical in contact with the skin should be washed immediately with running
water for at least 15 minutes.
3. Stir the mixture and measure its temperature.
4. Reserve the solution for Part III.

III. Heat of Neutralization

1. Prepare a calorimeter using nested coffee cups as shown in Figure 2.
2. Immerse the beaker containing sodium hydroxide (from Part I) and the
beaker with hydrochloric acid (from Part II) in a water bath for 5 minutes to
attain thermal equilibrium.
3. Check if the temperature in the beakers are the same. If not, continue the
equilibration for another 5 minutes.
4. Transfer the hydrochloric acid solution to the previously prepared
calorimeter. Pour the sodium hydroxide solution to the calorimeter
containing the acid and cover. Gently swirl the mixture and measure its
temperature.

Reference

Brown, T. L., LeMay, H. E., Bursten, B. E., Murphy, C. J., & Woodward, P. M. (2012).
Chemistry: The Central Science. (12 ed.) Pearson Prentice Hall.

Beran, JA. 2014. Laboratory Manual for Principles of General Chemistry, 10 th

Edition. John Wiley & Sons, Inc.
Fazal-ur-Rahman M, et al. 2017. Specific Heat of Solution of HCl-NaOH Reaction by a
Simple Handmade Calorimeter. Journal of Physical Chemistry & Biophysics.

Activity 5
HEATS OF REACTIONS

I. Heat of Solution
Beaker Initial Substanc Temp. of Type of Reaction
Temp. of e Added Mixture (Endothermic/Exothermic)
water (°C)
(°C)
1 25.0 NaOH 29.0 Exothermic
2 25.0 NH4Cl 20.0 Endothermic

II. Heat of Dilution

Initial Temp. of Temp. of Solution Type of Reaction
water (°C) (°C) (Endothermic/Exothermic)
25.0 31.0 Exothermic

III. Heat of Neutralization

Solution Initial Temp. of qrxn (kJ)* ΔHrxn Type of
Temp. Mixture (kJ/mol)* Reaction
(°C) (°C) (Endothermic
/Exothermic)
20.00 mL of 1 M 25.0 1171.52 117.152KJ/
NaOH KJ mol
20.00 mL of 1 M 25.0
32.0 Endothermic
HCl 1171.52 117.152KJ/
KJ mol

* Assume that the solution is close enough to being like water that the specific heat and density are 4.184 J/g-°C and 1.00

g/mL, respectively. Show calculations below.