Calorimetry

Introduction

Thermochemistry is the study of the relationships between chemistry and energy [1]. The

purpose of this experiment was to take measurements of heat changes over a span of 2-3 minute

intervals during chemical reactions and to validate the accuracy of these quantities whilst using

the knowledge of thermodynamics. Energy is the ability to do work. The law of conservation of

energy states that energy can neither be created nor destroyed but rather transferred from one

object to another [1]. One of the ways energy can be transferred is through heat (q), the flow of

energy caused by a temperature difference [1]. The S.I. unit of heat is the joule (J). One of the

most important fields of thermochemistry is heat transfer. The concept of heat transfer is used in

a wide range of systems as small as radiators and heaters to massive nuclear power plants.

Thermochemistry is a very important field of study as it helps to determine if a particular

reaction will occur and if it will release or absorb energy as it occurs. It is also possible to

calculate how much energy a reaction will release or absorb and this information can be used to

determine if it is economically practicable to use a particular chemical process.

In this experiment, the focus is on the energy - heat - and its properties between the

neutralization reaction between a strong acid and a strong base, the hydration of a liquid and the

dissolving of a solid. The experimental procedure of calorimetry was used to measure the heat

evolved in these chemical reactions. A calorimeter, an insulated vessel used to contain a

chemical reaction and to prevent the gain from or the loss of heat to the surroundings, was used

to implement this procedure [1]. The two main types of calorimeters are coffee-cup calorimeters,

which was used in this experiment, and bomb calorimeters. A coffee-cup calorimeter consists of

two Styrofoam coffee cups, one inserted into the other, to provide insulation from the lab

environment and is equipped with a thermometer and a stirrer [1]. A bomb calorimeter consists

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of the reactant sample, oxygen, the stainless steel bomb, water, and is used in combustion

reactions with constant volumes unlike coffee-cup calorimetry where instead reactions occur at

constant pressure [2]. These reactions that occur inside a calorimeter can either be classified as

endothermic or exothermic. Endothermic reactions are any chemical reactions that absorb heat

form the surroundings whereas exothermic reactions are any chemical reactions that release heat

to its surroundings. In this calorimetric experiment, reactions will exhibit either exothermic or

endothermic properties.

When discussing the study of Thermodynamics or partaking in calorimetric experiments,

it is important to define Enthalpy or heat of reaction (∆H). Enthalpy is the amount of energy or

heat absorbed in a reaction [3]. With that being said, ∆H is positive for endothermic reactions

and negative for exothermic reactions. Enthalpy can be classified into more specific categories

which were dealt with in this experiment such as heat of solution, heat of hydration and heat of

neutralization. Heat of solution and hydration are concerned with changes in state of hydration or

molecules or ions, and heat of neutralization is the heat evolved when 1.0 mole of water is

produced by the reaction between acid and base [4]. Given this information, it is also required to

define the specific heat capacity of a material. The specific heat capacity (𝐶𝑠 ) is the amount of

energy required to raise the temperature of 1 gram of a substance by 1 degree Celsius [1]. It can

be used to quantify the relationship between the amount of head added to a given amount of the

substance and the corresponding temperature increase. To equation relating these quantities is as

follows:

𝑞 = 𝑚 × 𝐶𝑠 × ∆𝑇

where q is the heat in joules, m is the mass in grams, Cs is the specific heat capacity in Jg-1˚C-1

and ∆𝑇 is the temperature change in ˚C.

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 In this experiment, the reaction between the strong acid and strong base was done with

5.00 M hydrochloric acid (HCl) and 5.00 M sodium hydroxide (NaOH). The neutralization

reaction is as follows:

HCl(aq) + NaOH(aq)  NaCl(aq) + H2O(l) + heat

The heat of hydration reaction was done with water and concentrated sulphuric acid (0.144

moles of hydrogen sulphate). The reaction is as follows:

HSO4(aq) + H3O(aq)  H2SO4(aq) + H2O(l)

The heat of solution reaction was done with water and solid ammonium chloride. The reaction is

as follows:

NH4Cl(s) + H2O(l)H2O(l) + NH4+(aq) + Cl-(aq)

Procedure

To determine the heat capacity of the calorimeter, the following steps were taken. Fifty

millilitres of water were poured into a 125 mL Erlenmeyer flask using a graduated cylinder and

was heated on a hot plate. The temperature of the water was risen to about 20˚C above room

temperature then removed from the hot plate. The dry 2 cup assembly calorimeter was weighed

on a top-loading balance. Fifty millilitres of distilled water were then poured into the calorimeter

and re-weighed. The temperature of the water in the calorimeter was measured and recorded. The

temperature of the heated water was cooled to 15˚C above that in the calorimeter. This

temperature was recorded and the hot water was immediately poured into the calorimeter. The

cover was placed on and stirring commenced. Temperature readings were recorded every 5

seconds for 2 minutes. When this was completed, the calorimeter and its contents were weighed

to determine the mass of the hot water. The entire procedure was repeated for a second trial. [4]

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 To determine the heat of neutralization of a strong base with a strong acid, the following

steps were taken. The calorimeter was first dried with a Kimwipe. Fifty millilitres of 5.00 M HCl

was poured into the calorimeter using a graduated cylinder. Another graduated cylinder was used

to measure out 50 mL of 5.00 M NaOH. The temperature of this base solution was measured and

recorded. The solution was poured immediately into the calorimeter, the cover was placed and

stirring commenced. The temperature values were read and recorded every 5 seconds for 3

minutes. When time was up, the calorimeter and its contents were reweighed to find the mass of

the final solution. This procedure was repeated for a second trial. [4]

To determine the heat of hydration of concentrated sulphuric acid, the following steps

were taken. The calorimeter was rinsed with water and dried. Eighty-eight millilitres of water

were poured into the calorimeter using a graduated cylinder. The temperature of the water was

measured and recorded. Using a 10 mL graduated cylinder, 8.0 mL of concentrated sulphuric

acid was measured and poured quickly into the calorimeter. The cover was placed and stirring

commenced. The temperature values were read and recorded every 5 seconds for 3 minutes.

When time was up, the calorimeter and its contents were reweighed to find the mass of the final

solution. This procedure was repeated for a second trial. [4]

To determine the heat of solution of ammonium chloride, the following steps were taken.

The calorimeter was rinsed with water and dried. Eighty millilitres of water were poured into the

calorimeter using a graduated cylinder. The temperature of the water was read and recorded.

Twelve grams of ammonium chloride was weighed on a weigh boat and poured immediately into

the water in the calorimeter. The cover was placed and stirring commenced. The temperature

values were read and recorded every 5 seconds for 3 minutes. When time was up, the calorimeter

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and its contents were reweighed to find the mass of the final solution. This procedure was

repeated for a second trial. [4]

Results

N.B. The following temperature readings are shown up until 120 seconds showing the most

relevant data.

PART A: HEAT CAPACITY OF THE CALORIMETER

Time (s) Temperature (˚C) Time (s) Temperature (˚C)

TRIAL 1 TRIAL 2 TRIAL 1 TRIAL 2

5 31.5 33.4 65 31.6 31.8

10 31.6 32.5 70 31.6 31.8

15 31.7 32.2 75 31.6 31.8

20 31.7 32.0 80 31.6 31.7

25 31.7 31.9 85 31.6 31.7

30 31.7 31.9 90 31.6 31.7

35 31.6 31.8 95 31.6 31.7

40 31.6 31.8 100 31.5 31.7

45 31.6 31.8 105 31.5 31.7

50 31.6 31.8 110 31.5 31.7

55 31.6 31.8 115 31.5 31.7

60 31.6 31.8 120 31.5 31.7

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PART B: HEAT OF NEUTRALIZATION OF A STRONG ACID/BASE REACTION

Time (s) Temperature (˚C) Time (s) Temperature (˚C)

TRIAL 1 TRIAL 2 TRIAL 1 TRIAL 2

5 49.5 51.9 65 62.1 62.1

10 56.1 57.0 70 62.1 62.0

15 60.2 60.2 75 62.0 61.9

20 61.6 61.5 80 61.9 61.8

25 62.1 62.2 85 61.8 61.8

30 62.3 62.4 90 61.8 61.7

35 62.5 62.5 95 61.7 61.6

40 62.5 62.5 100 61.6 61.6

45 62.4 62.4 105 61.6 61.5

50 62.3 62.4 110 61.5 61.4

55 62.3 62.3 115 61.4 61.3

60 62.2 62.2 120 61.4 61.3

PART C: HEAT OF HYDRATION OF CONCENTRATED SULPHURIC ACID

Time (s) Temperature (˚C) Time (s) Temperature (˚C)

TRIAL 1 TRIAL 2 TRIAL 1 TRIAL 2

5 39.0 37.9 65 46.0 46.4

10 40.4 42.6 70 46.0 46.4

15 43.8 44.9 75 45.9 46.3

20 45.1 45.8 80 45.9 46.3

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25 45.7 46.3 85 45.8 46.3

30 45.9 46.4 90 45.8 46.2

35 46.0 46.5 95 45.8 46.2

40 46.1 46.5 100 45.7 46.2

45 46.1 46.5 105 45.7 46.1

50 46.1 46.5 110 45.7 46.1

55 46.1 46.5 115 45.6 61.1

60 46.0 46.4 120 45.6 61.1

PART D: HEAT OF SOLUTION OF AMMONIUM CHLORIDE

Time (s) Temperature (˚C) Time (s) Temperature (˚C)

TRIAL 1 TRIAL 2 TRIAL 1 TRIAL 2

5 17.9 17.6 65 15.8 15.7

10 17.2 17.5 70 15.8 15.7

15 16.7 16.4 75 15.9 15.8

20 16.1 16.3 80 15.9 15.8

25 15.9 15.7 85 15.9 15.8

30 15.8 15.7 90 15.9 15.8

35 15.7 15.6 95 15.9 15.8

40 15.7 15.6 100 15.9 15.8

45 15.7 15.6 105 15.9 15.8

50 15.7 15.6 110 15.9 15.8

55 15.7 15.6 115 15.9 15.9

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 60 15.8 15.7 120 16.0 15.9

Discussion

1) The main sources of error in this experiment may be due to the calorimeter’s insulation,

error in thermometers, increased heat due to factors other than the elements in the

reaction as well as incorrect measurements taken and insufficient stirring due to human

error. Firstly, the Double-Styrofoam cup calorimeter was not an entirely closed system

since there were two holes at the top. These holes had a larger diameter than the

thermometer and stirrer so energy was able to transfer to the surroundings through it.

Heat was also able to transfer to the surroundings when the calorimeter was opened to

pour substances into it. Secondly, the thermometer may have had previous solution

residue on it before reading the next set of values leading to incorrect readings. Thirdly,

the rapid stirring may have caused the solution to become hotter than it actually was due

to increased kinetic energy. Insufficient stirring is another possible source of error as the

mixture may have not been uniform. Lastly, the calorimeter may not have been dried

properly before weighing it causing the weight of the calorimeter and volumes of

substances to be off, leading to inconsistent measurements between the two trials.

2) “Joule” (J) is the S.I. unit used to measure energy or work. It is derived from the
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definition of kinetic energy given by, 𝐾𝐸 = 2 𝑚𝑣 2 , where the unit of mass is kg and the

unit of velocity is ms-1. The SI unit of energy is therefore kg m2 s-2, named after the

English scientist James Joule [1].

1 kg m2 s-2 = 1 J

6.86 calories to joules:

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 1 calorie = 4.184 joules

4.184 𝐽
6.86 𝑐𝑎𝑙 × = 28.7 𝐽
1 𝑐𝑎𝑙

3) A weak acid/strong base neutralization will not have the same molar heat of

neutralization as the strong acid/strong base neutralization since strong acids and bases

dissociate almost completely in aqueous solution resulting in the molar enthalpy change

of neutralization to be always constant. For example, the reactions between HCl and

NaOH, and HNO3 and KOH:

HCl(aq) + NaOH(aq)  NaCl(aq) + H2O(l) + heat ∆H=-57.8

HNO3(aq) + KOH(aq)  KNO3(aq) + H2O(l) ∆H=-57.8

Since strong acid and strong bases completely ionize in aqueous solutions, the number of

H+ and OH- ions produced by 1 gram equivalent of strong acid and base is always the

same, hence enthalpy of neutralization between a strong and base is always constant.

This is the opposite compared to weak acid/strong base neutralization because the acids

don’t dissociate completely, therefore the heat released during neutralization is absorbed

in the dissociation of the acid.

4) The measured value of ∆H for the strong acid/strong base neutralization was calculated to

be -62.2 kJ/mole. Compared to the lit value of -60.2 kJ/mole, it can be said that these

values are fairly close in numerical value giving a % relative error of:

|𝑚𝑒𝑎𝑠𝑢𝑟𝑒𝑑 − 𝑙𝑖𝑡|
% 𝑟𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑒𝑟𝑟𝑜𝑟 = × 100
𝑙𝑖𝑡

|−62.2 − (−60.2)|
= × 100 = 3.32%
−60.2

5) It is expected to get a larger temperature change since the initial amounts of water and

solid increased.

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 6) An acid and base reaction produces a salt as one of its products. This salt participates in

the heat transferring process which in turn depends on its conductivity for transferring

heat. This is why the heat capacity of the 2.5 M NaCl salt solution was used for the

calculation rather than the original acid and base solution.

7) The dissolving of ammonium chloride is endothermic because its lattice energy, the

energy required to beak the ionic bonds of the crystal lattice [1], is larger than its

hydration energy, which is when the freed ions become hydrated due to electrostatic

attraction to the water molecules. The heat is absorbed by ammonium chloride and is

used to break the bonds of the salt crystal hence being endothermic. One would not get

similar results for dissolving all salts. For example, dissolving calcium chloride in water

results in an exothermic reaction:

CaCl2(s) + 2H2O(l)  Ca(OH)2(aq) + 2HCl(aq) + heat

More energy is released into the solution required to pull apart the ions, therefore

dissolving calcium chloride in water in exothermic.

8) If the calorimeter was made of a heat-conducting material such as metal rather than

Styrofoam, the measured calorimeter constant would be larger because metal conducts

heat and will absorb heat better than a Styrofoam which is an insulator, not a conductor.

Conclusion

This experiment was done to determine the heat of neutralization of a strong acid/strong

base reaction, to determine the heat of hydration of concentrated sulphuric acid and determine

the heat of solution of ammonium chloride, by overall measuring the amount of heat released or

absorbed in a reaction. The average molar heat of neutralization was determined to be -62.2 ± 0.2

kJ/mole which meant that this was the amount of heat evolved when 1.0 mole of water is

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produced by an acid and base reaction. The heat of hydration was determined to be -65.9 ± 0.1

kJ/mole which meant that this was the amount of heat released when a mole of the ion dissolves

in a large amount of water forming an infinite dilute solution in the process [5]. Lastly, the heat

of solution was determined to be 15.7 ± 0.2 kJ/mole which meant that this was the amount of

heat that was absorbed during the dissolving process [5].

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References

[1] Tro, N.J., Fridgen, T.D., Shaw, L.E. (2017). Chemistry: A Molecular Approach, Second

Canadian Edition. Chapter 6, 197-229.

[2] Bomb calorimetry. Retrieved from: http://www.chem.hope.edu/~polik/Chem345-

2000/bombcalorimetry.htm

[3] Enthalpies of Reactions. Retrieved from:

http://www.science.uwaterloo.ca/~cchieh/cact/c120/heatreac.html

[4] CHY211 General Chemistry Laboratory Manual. Calorimetry. p 64-72.

[5] Stephen Lower (2017). Hydration. Retrieved from

https://chem.libretexts.org/Core/Physical_and_Theoretical_Chemistry/Thermodynamics/Ener

gies_and_Potentials/Enthalpy/Hydration#What_is_the_Enthalpy_of_Hydration.3F

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