Faculty of Natural and Agricultural Sciences

Chemistry Department

CMY 117 2025

Practical 4 Thermochemistry

Remember to bring your LAB COAT & SAFETY GLASSES, a marker pen. Remember the correct
Dress code!

Preparation before the practical session:

• Lab preparation: Read through this document thoroughly. Study the experimental
procedures and make a flow diagram for EACH EXPERIMENT in your LAB BOOK.
• Reading: Indicated sections from Kotz & Treichel (11th Ed).

You will be working pairs for these experiments.

Required self-study: Kotz & Treichel and Townsend

Chapter Sections Pages
Chapter 5: Principles of Chemical Reactivity : Energy and Chemical Reactions 5.1 , 5.2, 5.6 255-262,
and 5.7 274- 284

Introduction to Calorimetry and Enthalpy Change

Chemical reactions either absorb or release energy in the form of heat. Sometimes, this can be sensed qualitatively, if
the reaction vessel feels warm, the process is exothermic; if it feels cold, the reaction is endothermic. However, to
quantify the heat transferred during a chemical reaction, we use a device called a calorimeter.

In this practical, we focus on coffee-cup calorimetry, a method well-suited for reactions in solution involving liquids
and solids. The basic principle is that any heat absorbed or released by the chemical system is exchanged with the
surrounding water, whose temperature change we can measure. Water’s high specific heat capacity and ability to mix
easily make it ideal for detecting these temperature changes.

There are two common types of calorimeters:

1. Coffee-Cup Calorimetry

This simple calorimeter consists of a polystyrene (Styrofoam®) cup,

often with a lid to reduce heat loss containing the reaction mixture
and a thermometer. It operates at constant pressure, meaning the
heat measured corresponds to the enthalpy change (ΔH) of the
reaction.

2. Bomb Calorimetry (for comparison)

For high-temperature or gas-evolving reactions, a bomb calorimeter is used. In this setup, the reaction occurs
inside a sealed metal container (the "bomb") immersed in water. Because the volume remains constant, this
setup measures the change in internal energy (ΔU) rather than ΔH. The calorimeter is pre-calibrated with a
known heat capacity to account for heat absorbed by all its components, which is not negligible. We will not
look at this concept in this practical.

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 Theoretical Background
The First Law of Thermodynamics is the application of the conservation of energy principle for processes involving
heat and work. It states that the change in internal energy (∆U) of a system is equal to the sum of the heat (q) added or
lost by the system and the work (w) done by or on the system:

ΔU = w + q

Where:

• ΔU = change in internal energy,

• w = heat added to the system,
• q = work done by the system.

During chemical reactions work is done by the reaction when gaseous products expand:

w = –p∆V

where ∆V is Vfinal – Vinitial. When energy is transferred in the form of heat at constant pressure conditions (qp) we call this
heat the change in enthalpy

qp =∆H and ∆U = ∆H – p∆V

which is what we are investigating in this practical through Coffee-Cup Calorimetry.

Note: A coffee cup calorimeter is suitable for the determination of heat transfer during processes involving solids and
liquids. Under these conditions no significant volume changes occur, ∆V = 0, and so – p∆V = w = 0. The heat transfer
determined here at constant pressure will represent the change in enthalpy (∆H) which is equal to the change in internal
energy (∆U). During reactions which produce gases work is done as the gases expand (∆U = ∆H + w) and some of the
energy will be lost as the gases escape from the cup. The coffee cup calorimeter cannot be used for high temperature
reactions or very exothermic reactions either, since these would melt the cup. For measurements in a coffee-cup
calorimeter the energy absorbed (or lost) by the polystyrene cups, lids and the thermometer are regarded as negligible.

Energy Transfer in the Form of Heat

In any chemical reaction, energy is either absorbed from or released to the surroundings, often as heat. The total energy
of the system and surroundings is conserved. This is exactly the same case in a Coffee-Cup Calorimeter, and this
relationship is captured by:

qr + qsurroundings = 0

In a coffee-cup calorimeter, the reaction (the system) typically takes place in a solution, and the water (or dilute
solution) acts as the surroundings. Therefore, we can rewrite our equation as:

qr + qsolution = 0 or qr = –qsolution

where qsolution can be quantitatively calculated using the heat capacity,

qsolution = msolutionCsolution∆Tsolution ∴ qr = –(mC∆T)solution

and where:

• m is the mass of the solution (in grams),

• C is the specific heat capacity of the solution (assumed to be 4.184 J⋅g–1⋅K–1 the same as water),

• ΔT is the temperature change of the solution in °C or K (why?).

Note: For dilute solutions, we approximate the density as 1.00 g⋅mL–1 (i.e. 1 mL = 1 g). Thus, if 50 mL of solution is
used, its mass is assumed to be 50 g. If a solute is added (like KCl), its mass must also be included in the total
solution mass for accurate heat calculations.

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 Enthalpy Change
The enthalpy change of a reaction, denoted as ΔH, refers to the heat exchanged with the surroundings at constant
pressure. It is calculated from the heat of the reaction and expressed in units of kJ·mol-rxn–1, meaning "kilojoules per
mole of reaction as written in the balanced chemical equation." It can be calculated from the heat of the heat of the
reaction we obtained before (qr) and the number of mol of compound reacted (n)
qr
ΔH =
n

Where:

• qr is the heat released or absorbed (in kJ),

• n is the number of moles of the limiting reactant involved in the reaction.

What does the Sign of ΔH Mean?

Because enthalpy is the heat at constant pressure, we can relate it to the ideas of exothermicity. An Exothermic
reaction is where the system releases heat to the surroundings. The solution warms up, and qr is negative and
so ΔH < 0.

An Endothermic reaction is where the system absorbs heat from the surroundings. The solution cools down, qr
is positive, and ΔH > 0.

In this practical, you will observe both types:

• The dissolution of KCl is endothermic (temperature decreases).

• The neutralisation of HCl and NaOH is exothermic (temperature increases).

Overview of the experiments

Exp Descriptions
4.1 Determine the enthalpy change (ΔH) per mole for the dissolution of KCl in water

4.2 Determine the enthalpy change (ΔH) for the reaction between HCl and NaOH per mole of reaction.

Experiment 4.1 | The Enthalpy of Solution of an Endothermic Process

Objective: Determine the enthalpy change (ΔH) per mole for the dissolution of KCl in water.

General Apparatus, Equipment and Chemicals used for the Experiment

Apparatus and equipment Chemicals
- 2x Polystyrene (Styrofoam®) coffee cups - Potassium chloride
- 1x Thermometer - Distilled water
- 1x 50mℓ Measuring cylinder
- 1x Mass balance
- 1x Glass rod

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 Experimental Procedure
1. Measure 50 mL of distilled water in a dry measuring cylinder. Transfer it to the coffee-cup calorimeter. Measure
the temperature of the water. This is the initial temperature, Ti.
2. Carefully weigh about 5 g of potassium chloride. Record your exact mass. Add it to the water in the calorimeter
and stir gently with the thermometer until the salt dissolves in the water. The temperature of the water will drop.
Note the minimum temperature reached. This is the final temperature, Tf.
3. Calculate the change in temperature, ∆T = Tf – Ti.

4. Repeat Steps 1–3 and obtain another value for ∆T, using the same thermometer, i.e. that you did it in duplicate
fashion (having 2 data points)
5. Assuming that all the heat comes from the solution in the calorimeter, calculate qr using the following data:

• Specific heat capacity of the solution: 4.184 J⋅g–1⋅K–1

• Density of the solution: 1.0 g⋅mL–1
6. Calculate the enthalpy of solution per mole of potassium chloride for each of your runs, and calculate the
average enthalpy change from your two values in kJ⋅mol–1.

Experiment 4.2 | The Enthalpy Change of a Neutralization Reaction

Objective: Determine the enthalpy change (ΔH) for the reaction between HCl and NaOH per mole of reaction.

CAUTION: Hydrochloric acid solutions can cause chemical burns. Avoid contact with skin, do not swallow and
do not spill. If you spill one of these solutions on you, wash the contaminated area thoroughly and report the
incident to your tutor. You may require further treatment. Ensure you wear eye protection and your laboratory
overcoat!

General Apparatus, Equipment and Chemicals used for the Experiment

Apparatus and equipment Chemicals
- 2x Polystyrene (Styrofoam®) coffee cups - Hydrochloric acids (1.0M)
- 1x Thermometer - Sodium Hydroxide (1.0M)
- 2x 100mℓ Glass beaker
- 1x Mass balance
- 1x Plastic container (water bath)
- 1 Stopwatch of timer (smartphone may be used at your own risk)

Experimental Procedure
1. Measure 25 mL of a 1.0 M solution of HCl in a clean, dry measuring cylinder and pour the solution into a small
beaker.
2. Measure 25 mL of a 1.0 M solution of NaOH in another clean, dry measuring cylinder and pour the solution into
a separate small beaker.
3. Place the two beakers in a water bath (tap water) for about 5 minutes and measure the temperature of each of
these solutions, using the same thermometer. Rinse and dry the thermometer after every measurement
(remember, if you do not do this it will lead to contamination and reaction!).
The temperature should agree to within ±0.2 oC. Record the mean temperature. This is the initial temperature,
Ti.
4. Pour the acid into the coffee-cup calorimeter. (Make sure you add all the acid). Place the clean and dried
thermometer in the acid.
5. Add the base to the calorimeter and start stirring immediately. The temperature will rise. Closely monitor the
temperature for about 3 minutes and record the maximum temperature reached (before it starts cooling again).
This is the final temperature, Tf.
6. Calculate the change in temperature, ∆T = Tf – Ti.
7. Repeat Steps 1–6 and obtain another value for ∆T, using the same thermometer.
8. Calculate qr using the following data:
• Specific heat capacity of the solution: 4.184 J⋅g–1⋅K–1 and that the density of the solution: 1.0 g⋅mL–1
9. Calculate the enthalpy change ∆H in kJ⋅mol-rxn–1 and calculate the average enthalpy change from your two
values in kJ⋅mol-rxn–1.
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 Disposal of chemical waste
Exp 4.1 The waste solution can be washed down the drain with lots of water.

Exp 4.2 Bring the final solution to the tutor where they will neutralise it and dispose of it
properly.

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