University of Santo Tomas CHE 2112L:

Faculty of Engineering PHYSICAL CHEMISTRY FOR

ENGINEERS 2 LABORATORY
Department of Chemical Engineering Post-Lab Written Report
Date Performed: 10/23/2020
Name: CASTILLO, Carlo J.
Date Submitted: 11/04/2020
Section: 3CHEA Group No: 4 Instructor: Engr. Rose Mardie Pacia

Experiment No.: THERMOCHEMISTRY

I. INTRODUCTION
Thermochemistry is a branch of chemistry that deals with a quantitative study and measurement of
changes in heat and enthalpy. It describes energy changes in chemical reactions as well as whether the
heat is released or absorbed. From the field of biochemistry to chemical engineering, thermochemistry has
a lot of applications such as understanding bioenergetics and designing manufacturing plants. This branch
of thermodynamics is widely used by scientists and engineers since it helps in determining particular
reactions that will occur. By determining how much a reaction will release or absorb, specific chemical
process will be determined if it’s viable economically or not. However, it is important to know that
thermochemistry does not predict how fast the reaction will occur [1,2,3,4].

Calorimetry plays a big role in thermochemistry. It is the process of measuring how much heat is
released or absorbed in the chemical reaction. Upon knowing the heat changes, the reaction can be
determined if it’s exothermic, where heat is released; and endothermic, when heat is absorbed. Calorimetry
deals with the relationship of the state of a body with the thermal aspects so physical and chemical changes
can be examined. Physical changes include melting and evaporation while chemical changes are burning,
acid-base neutralization and the likes [5,6]. In the measurement of heat changes, a calorimeter is needed.
It is a device that measures the amount of heat involved in the chemical reaction. To calculate the amount
of heat involved, the following are accounted: temperature change, specific heat, and mass of the solution
[7].

The calorimeter also absorbs heat during the measurement of heat changes. Thus, the calorimeter
constant or water equivalent of calorimeter must be determined. Due to conservation of energy, the heat
taken by the calorimeter and cold water are equal to the heat given by hot water [8]. The equation is as
follows:

𝑞𝑏𝑦 ℎ𝑜𝑡 𝑤𝑎𝑡𝑒𝑟 = 𝑞𝑏𝑦 𝑐𝑎𝑙𝑜𝑟𝑖𝑚𝑒𝑡𝑒𝑟 𝑎𝑛𝑑 𝑐𝑜𝑙𝑑 𝑤𝑎𝑡𝑒𝑟 Eq. 1

𝑚1 (𝑡2 − 𝑡3 ) = (𝑚2 + 𝑊)(𝑡3 − 𝑡1 ) Eq. 2
(𝑡2 −𝑡3 )
(𝑚2 + 𝑊) = 𝑚1 Eq. 3
(𝑡3 −𝑡1 )

(𝑡 −𝑡3 )
𝑊 = 𝑚1 (𝑡2 − 𝑚2 Eq. 4
3 −𝑡1 )

Where: 𝑚1 = mass of hot water; 𝑚2 = mass of cold water; 𝑡1 = temperature of cold water; 𝑡2 =
temperature of hot water; 𝑡3 = temperature after mixing; and 𝑊= water equivalent of the calorimeter.
Experiment 4: Thermochemistry

From the given equations, the enthalpy of dissolution can also be calculated. When dissolution of a
solute occurs, heat may be absorbed or evolved. Enthalpy change (∆H) of the system accompanies
dissolution. Thus, ∆H is positive when heat is absorbed and ∆H is negative when heat is evolved [8].

The aim of this is experiment is to determine the water equivalent of the calorimeter and to apply
its concept in determining the enthalpies of dissolution of salts.

II. METHODOLOGY
The virtual laboratory experiment was performed using the simulator tab in the site:
http://amrita.olabs.edu.in/?sub=73&brch=8&sim=145&cnt=1. The “Cross Section” tab was clicked to see
what’s happening in the calorimeter. Afterwards, 50 mL cold water was poured from the beaker into the
calorimeter. 50 mL hot water was then poured next. The system was stirred and the thermometer was
observed. The final temperature was recorded when the reading became constant. Lastly, the water
equivalent of the calorimeter was calculated.

For the determination of the enthalpies of dissolution, the “Enthalpy of Dissolution” was clicked from
the “Select the test” drop down option. Ammonium Chloride (NH4Cl) was then selected from the “Select the
Sample” drop down option. 50 mL cold water from the beaker was poured into the calorimeter. The selected
sample was then poured from the watch glass into the calorimeter. The system was stirred, the temperature
was observed, and the final temperature was recorded. Afterwards, the enthalpy was calculated. The same
steps aforementioned were performed for the following samples: Potassium Chloride (KCl), Potassium
Nitrate (KNO3), and Copper (II) Sulphate Pentahydrate (CuSO4∙ 5H2O).

Fig. 1. Experimental set-up (Water Equivalent)

CASTILLO, CARLO J. 2
 Experiment 4: Thermochemistry

Fig. 2. Experimental set-up (Enthalpy of Dissolution)

III. RESULTS AND DISCUSSION

A. DETERMINATION OF WATER EQUIVALENT OF CALORIMETER

Mass of hot water (m1) = 50 g

Mass of cold water (m2) = 50 g
Temperature of cold water (t1) = 47 ℃
Temperature of hot water (t2) = 27 ℃
Temperature after mixing (t3) = 36 ℃
Water equivalent of calorimeter (W) = 11.11 g

Calculations
𝑡2 − 𝑡3
Using Eq. 1: 𝑊 = (𝑚1 )( ) − 𝑚2
𝑡3 − 𝑡1

1𝑔
𝑚1 = 50 𝑚𝐿 ( ) = 50 𝑔
1 𝑚𝐿
1𝑔
𝑚2 = 50 𝑚𝐿 ( ) = 50 𝑔
1 𝑚𝐿
47 ℃ − 36 ℃
𝑊 = (50𝑔)( ) − 50𝑔 = 11.11 𝑔
36 ℃ − 27 ℃

As observed, the temperature after mixing is between 27 ℃ and 47 ℃. Theoretically, when equal
volumes of hot and cold water are mixed together, the final temperature is the average of the two [9].
Averaging the temperatures of the hot and cold water, the answer will arrive at 37 ℃, which is relatively
close to the observed final temperature at 36 ℃. However, the cold water is also in contact with the
thermometer, stirrer, and the calorimeter. Thus, a little bit of heat was absorbed by the objects in contact

CASTILLO, CARLO J. 3
 Experiment 4: Thermochemistry

with the cold water [10]. It can be inferred that the 1 ℃ discrepancy between the observed and averaged
final temperature were given off in the calorimeter. This further supports Eq. 1 in the introduction where the
heat absorbed by the hot water is equal to the heat absorbed by the cold water and the calorimeter.

B. DETERMINATION OF ENTHALPIES OF DISSOLUTION

Sample Calculations using Ammonium Chloride (NH4Cl)
From the online simulator for the experiment, the formula for Enthalpy of Dissolution was given:
(𝑊+𝑚1 )(𝑡1 −𝑡2 )(4.2)(𝑀)
𝐸=[ 𝑤
] Eq. 5
Where:
• Mass of cold water (m1)
• Mass of sample (w)
• Temperature of cold water (t1)
• Temperature after mixing (t2)
• Water equivalent of calorimeter
(W) = 11.11 g
• Molar mass of sample (M)
• Enthalpy of dissolution (E)
• Specific heat of H2O = 4.2 J/g℃
𝑔
(11.11 𝑔 + 50 𝑔)(27℃ − 22℃)(4.2 J/g ℃)(53.49 ) 1 𝑘𝐽
𝐸 = [ 𝑚𝑜𝑙 ]( ) = 13.73
5𝑔 1000 𝑚𝑜𝑙

By substituting the known values as seen on Table 1 in Eq. 5, the Enthalpies of Dissolution for the
other samples were also obtained.

Table 1. Calculated Enthalpy of Dissolution of each sample

Molar Temperature Temperature
Mass of Enthalpy of
Mass of the Mass of of cold after mixing
Sample cold Dissolution
Sample (g) Sample
water (g) water (℃) (℃) (kJ/mol)
(g/mol)
NH4Cl 5 53.49 50 27 22 13.73
KCl 4.5 74.55 50 27 23 17.01
KNO3 4.5 101.1 50 27 21 34.60
CuSO4∙ 5H2O 6 249.68 50 27 26 10.68

From the table, it can be inferred that the Enthalpy of Dissolution is affected by the mass of the
sample inversely. Since KCl and KNO3 have the lowest mass sample, they yielded higher Enthalpies of
Dissolution. But since, the molar mass of KNO3 is greater than KCl, it has higher Enthalpy of Dissolution.
Meanwhile, CuSO4∙ 5H2O yielded the lowest Enthalpy of Dissolution since it has the highest mass of the
sample. Another pertinent observation is that CuSO4∙ 5H2O has the lowest temperature change among
the samples. Lastly, from the table, it can be observed that the ∆T are all negative. Thus, the Enthalpies of
Dissolution are all positive. This means that the system loses energy as indicated by the negative ∆T. So,

CASTILLO, CARLO J. 4
Experiment 4: Thermochemistry

it needs absorb an equal amount of energy as well since it follows the conservation of energy [10]. It can
be said that the Enthalpy of Dissolution is endothermic.

To further understand the reactions that occurred in the calorimeter, here are the following chemical
reaction of the salts dissolved in the solvent:
For Ammonium Chloride:
𝑘𝐽
NH4Cl(s) + H2O(l) → NH4+(aq) + Cl-(aq) ∆H = 13.73
𝑚𝑜𝑙

For Potassium Chloride:

𝑘𝐽
KCl(s) + H2O(l) → K+(aq) + Cl-(aq) ∆H = 17.01
𝑚𝑜𝑙

For Potassium Nitrate:

𝑘𝐽
KNO3(s) + H2O(l) → K+(aq) + NO3-(aq) ∆H = 34.60
𝑚𝑜𝑙

For Copper (II) Sulphate Pentahydrate:

𝑘𝐽
CuSO4∙ 5H2O(s) + H2O(l) → Cu2+(aq) + SO42-(aq) ∆H = 10.68
𝑚𝑜𝑙

As seen on the chemical reactions, the chemical bonds are broken. And, we all know that in
thermochemistry when chemical bonds are broken, heat is absorbed; and when chemical bonds are
formed, heat is released. In order to break bonds, higher energy is needed. Thus, the following Enthalpy
of Dissolutions are relatively high (positive) for the given salts to dissociate into ions.

C. ANSWERS TO QUESTIONS
1. What are the characteristics of a calorimeter? What is a good substitute for the used calorimeter in the
VLE?
- Basically, a calorimeter comprises of insulating walls so that no heat can transfer between the
calorimeter and the surroundings. To measure accurately the temperature change before and after
some change, a calorimeter is used [11]. The simplest calorimeter is called the coffee-cup
calorimeter. Not only it is easily accessible but it is also an example of a constant-pressure
calorimeter, perfect for measuring ∆H, since change in enthalpy is defined as the heat flow at constant
pressure. This means that we can get ∆H directly for the experiment. Other alternatives for the
wooden box calorimeter in the VLE are commercial calorimeters which operate at smaller volumes
of solution, have better insulation, and it can also detect the smallest temperature change as low as
10−6 °C [12].

2. Define thermo insulators and where are these commonly used?

- Thermo insulators are materials with very low thermal conductivity. Thus, they are poor conductors
of heat and good thermal insulators. Examples of these materials are the following: wool, fiberglass,
rock wool, polystyrene, polyurethane, and goose feather [13]. Thermal insulators are often used in
clothing. For example, wool functions by having a large number of gas-filled pockets so it would

CASTILLO, CARLO J. 5
Experiment 4: Thermochemistry

prevent convection. Another application of thermo insulators is in building insulations to minimize the
total heat transfer coefficient by adding materials with low thermal conductivity [14].

3. What is calibration? How is it applicable in the experiment?

- In a calorimeter, calibration is defined as the determination of how many moles of energy are required
to raise the temperature of the contents by 1 degree Celsius [15]. In real life, each calorimeter is not
ideal. Even if it’s well insulated, heat can also be transferred to the objects touching the solution such
as the calorimeter itself. Thus, to obtain reliable results, calibration of the calorimeter is needed to
know how much heat is exchanged with the calorimeter and/or the surroundings [16]. That’s why in
the VLE, the calorimeter constant or the water equivalent of the calorimeter was obtained. It serves
as the correction factor to obtain reliable results in the determination of Enthalpies of Dissolution of
salts. The calorimeter was calibrated by adding 50 mL cold water in the calorimeter and mixing it with
50 mL hot water.

4. Explain the importance of water equivalent calorimeter?

- The calorimeter constant or water equivalent of calorimeter is important to know how much heat is
generated by combustion of the sample [17]. As stated in the previous question, it serves as a
correction factor since some of the heat is exchanged in the calorimeter. By knowing this correction
factor or the heat capacity of the calorimeter, the calorimeter can now be used to calculate the specific
heat of an unknown substance [18].

5. What is heat of solution? What is the importance or application of evaluating heat of solution?
- The heat of dissolution or enthalpy of solution, also known as enthalpy of dissolution, is defined as
the enthalpy change from the dissolution of a solute in a solvent at constant pressure. This results in
infinite dilution [19]. Hot packs and cold packs are examples of application of heat of solution.
Because of the chemicals inside them, upon squeezing the bags, an inner pouch will burst allowing
the chemicals to dissolve in water. An endothermic reaction occurs in the cold pack and an
exothermic reaction happens in the hot pack [20].

D. CONCLUSION
Using Eq. 4 and Eq. 5, the water equivalent of the calorimeter and the Enthalpies of Dissolution of
salts were calculated. Thus, the objectives of the experiment were met. It was concluded that the ∆H for
the salts are all endothermic, meaning the system absorbs heat. The energy needed to break the bonds of
the given salts are relatively high (positive) so it could break down into simpler ions. It was also inferred
that the mass of the solute to be dissolved in the solvent is directly proportional to the Enthalpy of
Dissolution. Thus, CuSO4∙ 5H2O yielded the lowest ∆H and KNO3 yielded the highest ∆H.

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Experiment 4: Thermochemistry

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Experiment 4: Thermochemistry

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