Title : Heat of reaction

Date : 15/7/2020

Objectives :

1. To observe and investigate heat of reaction

2. To study and verify Hess’s Law by measuring, calculating and comparing the amount
of heat involved in a series of step.

Introduction :

There are usually change in heat in chemical changes. The reaction is said to be
endothermic if heat is being absorbed while exothermic reaction happens when heat is given
off. The change in temperature in a reaction can be measured by using the thermometer. The
heat effects are the result of bond forming and breaking. Energy in required to break a bond,
and energy is liberated during the formation of bond. The heat of reaction is the net heat effect
of the reaction and often be as the combination of several effects.

A statement of the law that bears Hess’s name, the founder of the study of
thermochemistry says : “ The enthalpy change for any reaction depends on the products and
reactants and is independent of the pathway or the number of steps between the reactant and
product”.

Heat and work are two most common ways of energy exchange for a system with its
surroundings. Calorimetry is used to determine the amount of heat that flows into or out of the
surroundings. A calorimeter consists of an insulted container, a thermometer, a mass of water
and the system to be studied. Insulted container is used to assume that no heat transferred
through the calorimeter walls. Then, an assumption can be made where the thermodynamics
universe consists of the system and the surroundings water only.

In Coffee cup experiment, three exothermic chemical reactions will be conduct and the quantity
of heat energy released will be determined and compared. For example, the acid-base
neutralization reaction between hydrochloric acid ( HCl ) and sodium hydroxide ( NaOH ) can
be conducted under two different conditions that give different molar heat of reaction ( qrxn ).

HCl (aq ) + NaOH ( aq ) NaCl ( aq ) + H2O ( l ) qrxn 1 = ?

HCl ( aq ) + NaOH ( s ) NaCl ( aq ) + H2O ( l ) qrxn 2 = ?

If solid sodium hydroxide is dissolved in water, molar heat of reaction generated is as follows:

NaOH ( s ) NaOH ( aq ) qrxn 3 = ?

According to Hess’s law, enthalpy change of an overall process is the sum of the enthalpy
changes of its individual steps. From the above , reaction 3 and 1 together can be considered
as alternative steps to reaction 2. Hence, when concentrations of NaOH and HCl are kept
constant, it is expected that :
 qrxn 1 + qrxn 3 = qrxn 2

The law of conservation of energy is used to calculate the heat of reaction ( assuming there is
no heat lost to the surrounding through the calorimeter ) :

qrxn + qsoln = 0

where qrxn is the heat generated by the reaction, qsoln is the heat absorbed by the solution which
is reflected by the temperature change.

qsoln can be calculated by using the following equation :

qsoln = msoln Csoln ∆T

where msoln is the mass of water with density 1.02 g/ml

Csoln is the specific heat of water : 4.18 J/goC

∆T is the change in temperature

( Assumption : The specific heat capacity of solution is approximately equal to that of water
and that the density of the solutions is equal to that of pure water )

The qrxn can be determine by

qrxn = -qsol

The heat released in each reaction will be divided by the number of moles of reactant used in
the reaction to find the Molar Heat of reaction.

In this experiment, the heat of reaction for neutralization reaction will be investigated where
the quantity of heat involved will be measured and compared.

Next, the bomb calorimeter is used to measure heat of combustion produced during a
combustion reaction. The thermal energy generated by the reaction is transferred to a
surrounding bath. The change in internal energy ∆U is equivalent to the heat measure by an
instrument. From the temperature change, ∆T and the heat capacity of the calorimeter, C cal ,
the heat can be determined. In bomb calorimeter, the heat capacity is usually large due to the
water and hardware ( strings, paddles, blades, the calorimeter and others ). Therefore, Ccal is
used to find qrxn of the system as follows :

qrxn = -Ccal ∆T

In this experiment, both Coffee cup and Bomb calorimetry concepts will be observed and
studied.
Material :

- computer
- simulation software

Apparatus :

- foam cups
- strings paddles
- stainless steel
- wiring walls
- graduated cylinder
- hot plate

Chemicals :

- Distilled water
- sodium hydroxide pellets
- 1.0M sodium hydroxide solution
- 1.0M hydrochloric acid solution
- benzoic acid
- naphthalene
- sucrose
- lactose
- citric acid

PROCEDURE :

Part I : Coffee cup calorimetry ( neutralization reaction )

Figure
The simulation software was opened through the given link and appeared as figure above.

Neutralization reaction

Caution : In real life, HCl and NaOH are corrosive. Avoid direct contact. If any touches skin,
wash off immediately with running water.

Dissolution of Solid NaOH in Water

1. In the glassware menu, a 50ml graduated cylinder and a foam cup has been taken out.
Scale was taken out from the instrument’s menu. From the chemical stockroom, the
distilled water and solid NaOH were moved on to the workbench.

2. 50 ml of distilled water was transferred into the 50ml graduated cylinder by dragging
the carboy of water on to the graduated cylinder. The temperature of the water was
measure and recorded as Ti.

3. 1 g NaOH ( s ) was weighed directly into the foam cup and its mass was recorded to the
nearest 0.01g. In order to do this, the foam cup was placed on the balance and the “Tare”
button was clicked. The NaOH bottle was dragged onto the foam cup and 1g of solid
NaOH was transferred into the foam cup. The balance then read the mass of solid NaOH
transferred.

4. The graduated cylinder containing 50 ml distilled water was then dragged onto the foam
cup containing the solid NaOH and the 50 ml of distilled water was poured into the
foam cup. The highest temperature reached was recorded as Tf .

Reaction of NaOH solution with HCl solution

1. Another graduated cylinder, a fresh foam cup, 1.0M HCl and the 1.0M NaOH were
taken out. 25 ml of 1.0 M HCl solution was measured and poured into the foam cup.
An equal volume of 1.0 M NaOH solution was poured into the clean graduated cylinder.

2. The temperature of each solution was recorded to the nearest 0.1 oC. The temperature
of HCl was recorded as Ti .

3. NaOH solution which was prepared earlier was added to the acid solution. The solution
was stirred with thermometer. The highest temperature obtained during the reaction
was recorded as Tf .

Reaction of solid NaOH with HCl solution

1. Steps 1 to 4 in the Dissolution of solid NaOH in water were repeated by replacing 50

ml of H2O with 25 ml of 1.0 M HCl solution.
Part II : Bomb calorimetry ( Combustion reaction )

The simulation software was opened through the given link.

1. 500 mg of benzoic acid was selected from the compound selection to combust.

2. Using the mass slider, the amount of water inside the calorimeter was set to 1000g.

3. The ignite button was then pressed to run the reaction.

4. The temperature change was observed and recorded.

5. The reset button was clicked to repeat the experiment from step 2 to step 4 by changing
the compound to naphthalene, sucrose, lactose and citric acid. The temperature change
of each compound was recorded.
 DATA :

PART I : Coffee cup calorimetry

Part I: Part II: Part III:

The Dissolution of The Reaction of The Reaction of Solid
Solid Sodium Sodium Hydroxide Sodium Hydroxide with
Hydroxide in Water Solution with Hydrochloric Acid
Hydrochloric Acid Solution
Solution

Mass of solid NaOH (g) 1.00 1.00

Volume of
1.0 M HCl ( ml ) 25.00 25.00

Number of moles, n
( mol) 0.025 0.025

Initial temperature,
Ti 25.00 25.00 25.00
(0C)

Final temperature,
Tf 30.30 31.67 48.94
0
( C)

Change in temperature,
ΔT 5.30 6.67 23.94
(0C)

qsoln ( J ) 1152.01 1421.91 2651.83

 PART II : Bomb calorimetry

Benzoic Naphthalene Sucrose Lactose Citric acid

acid

Initial temperature, 20.00 20.00 20.00 20.00 20.00

Ti (°C)

Final temperature, 22.80 24.30 21.70 21.70 21.10

Tf (°C)

Change in
temperature 2.80 4.30 1.70 1.70 1.10
∆T (°C)

qwater
( kJ ) 11.70 17.97 7.11 7.11 4.60

qcal
( kJ ) 1.18 1.81 0.71 0.71 0.46

qTotal ( kJ ) 12.88 19.78 7.82 7.82 5.06

DISCUSSION :

Part I : Coffee cup calorimetry

In coffee cup calorimetry, the heat measured is the heat absorbed by the solution or
the water. In this case, the formula of specific heat capacity is used :
𝑞𝑠𝑜𝑙𝑛
csoln = 𝑚
𝑠𝑜𝑙𝑛 ∆𝑇

where c is the specific heat capacity of the solution, qsoln is the heat absorbed by the solution,
msoln is the mass of the solution and ∆T is the temperature change. The definition of specific
heat capacity is the heat required to change the temperature of 1 g substance by 1K. In this
experiment, the temperature is measured in oC . Hence, specific heat capacity means the amount
of heat required to change the temperature of 1 g substance by 1oC.

To obtain the value of qsoln , assumptions were made where the density of the solution is equal
to that of water which is 1.02 g/ml . The specific heat capacity of the solution is also equal to
that of pure water. Hence, the specific heat capacity of solution is a constant with the value of
4.18 J/goC .

For example , qsoln for the reaction between 1.0 M HCl and 1.0 M NaOH is as below :
In part I, the heat of dissolution and heat of neutralization is studied. Heat of dissolution is
obtained when solid sodium hydroxide is dissolved in water while heat of neutralization is
measured when sodium hydroxide solution reacts with hydrochloric acid solution and also the
reaction between solid sodium hydroxide reacts with hydrochloric acid solution. In this
experiment, the heat measure is the heat absorbed by the solution, therefore, the value q soln is
positive. However, for the heat of reaction, the value of ∆Hrxn will be negative as heat is being
liberated from the system. This is verified by the law of conservation of energy :

qrxn + qsoln = 0
qrxn = - qsoln

By dividing the qrxn with the mole of reactants used, the ∆Hrxn can be calculated :
𝑞
∆Hrxn = − 𝑚𝑜𝑙𝑒 𝑜𝑓𝑠𝑜𝑙𝑛
𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡

Based on the data table, the overall reaction can be concluded to be exothermic reactions. Based
on the change in temperature, Tfinal of each reaction is higher than Tinitial. This means that heat
liberated by the system is absorbed by the solution. According to data table, the heat of solution
increases from Part I to Part III. This is because the heat of reaction depends on the reactants
and products. In part I, the heat of reaction is the least. This is because compared to the reaction
of part II and III only involves the dissolution of NaOH which released a lesser amount of heat
to form the bond between H2O molecules with Na+ ion and OH- ion. While in Part II and III,
the heat released is to form the bond between Na+ ion and Cl- ion and also between H+ ion and
OH- ion.

Hess’s law states that enthalpy change of an overall process is the sum of the enthalpy changes
of its individual steps. Therefore, when concentration of NaOH and HCl is constant, the
enthalpy change of the overall reaction is :

qrxn ( Part I ) + qrxn ( Part II ) = qrxn ( Part III )

Therefore, the heat of neutralization can be calculated by using the Hess’s law and at the same
time, Hess’s law can be verified.
Part II : Bomb calorimetry

In bomb calorimetry, the heat measured is the heat absorbed by the water and by the
calorimeter itself. In order to calculate heat absorbed by water, the same formula as in coffee
cup calorimetry is used. While bomb calorimetry can be obtained using the formula :
𝑞𝑐𝑎𝑙
Ccal = ∆𝑇

Ccal is the heat capacity of calorimeter. According to definition, heat capacity is the amount of
heat require to change the temperature by 1K. In this experiment, the temperature change
measured is in oC. Therefore, the heat capacity of calorimeter is measured by the change of
1oC. Usually, the heat capacity of calorimeter is too big, so the heat capacity of calorimeter is
kept constant in this experiment which 420 J/oC.

In bomb calorimetry, the overall heat of reaction is actually the heat of combustion when a
substance is burned with excess oxygen. Heat of combustion is the heat of the system while
the heat absorbed by the water and calorimeter is the heat of the surrounding. Therefore , the
total heat absorbed by water and the calorimeter is the heat released by the system. To find the
heat of reaction, the formula is derived as below :

qsystem = - qsurrounding

qrxn = - ( qTotal )

qrxn = - ( qcal + qwater )

From the data table , the combustion reaction can be concluded as exothermic as the final
temperature is higher than the initial temperature which means that heat is absorbed by the
surrounding. In this experiment, 5 different compounds are used to combust. Based on the data
table, different compound released different amount of heat. Heat of a reaction depends on its
reactants and products. Hence, the amount of heat of reaction is different for different reactant.

Reliability

The readings and measurements are 100% reliable as there are no errors made in the simulation.
This is because the reading is made by the software itself which is precise and accurate.
However, there were difficulties while conducting the simulation. Firstly, the balance used to
weigh the solid NaOH could not be tared even after trying for several time. Hence, the balance
needed to be removed and added into the workbench again and again. Next, there was also
difficulty in pouring the substances into the foam cup and graduated cylinder. The prompt
message that should appear to insert the amount desired to pour would not appear after
following the procedure. Hence, the procedure was repeated again and again until the prompt
message appeared.
QUESTIONS :
QUESTION 5

The cause of the difference is probably because of unwanted heat loss to the surrounding. It is
because the foam cup is not insulated enough to prevent heat loss through the wall of the foam
cup making the change in temperature to become lower. It is also because the mass of solution
is added with 1g of NaOH, if the mass of solution is not added with 1 g of NaOH, there will be
no difference between part I + part II and part III.

QUESTION 6

Basically, benzoic acid is used to calibrate the bomb calorimetry so that the calorimeter follows
the standard condition. Benzoic acid is selected because it is a crystalline solid that can be
obtained in high purity. Therefore , it is convenient to find the energy of combustion per unit
mass of benzoic under the standard bomb calorimeter conditions.
CONCLUSION :

In conclusion, the heat of reaction can be investigated using coffee cup and bomb
calorimeter and also by using the formula of heat capacity and specific heat capacity, the
amount of heat absorbed by the surrounding can be calculated. The law of conservation of
energy is also obeyed where qrxn + qsoln = 0 . Hess’s Law is also verified where the heat of
reaction depends on its reactants and products and independent of the pathway or the number
of steps between the reactant and product. Therefore, the hypothesis is accepted. As a summary,
different reaction and different reactants will result in different amount of heat. For instance,
heat of dissolution is lower than heat of neutralization. While in bomb calorimetry, different
compound such as benzoic acid, naphthalene and others has different change in temperature
which resulted in different heat absorbed by the calorimeter. In daily life, the concept of
calorimeter can be found in the kitchen, where a certain ingredient is added to a hot water, and
then the change in temperature can be measured. The temperature change can be used to
determine whether the reaction is exothermic or endothermic.

Link to simulation video :

https://utpmy-
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