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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:
( t 2−t3 )
( m2 +W ) =m1 Eq. 3
( t 3−t1 )
( t2 −t3 )
W =m1 −m2 Eq. 4
( t3 −t1 )
Where: m 1 = mass of hot water; m 2 = mass of cold water; t 1 = temperature of cold water; t 2 =
temperature of hot water; t 3 = temperature after mixing; and W = water equivalent of the calorimeter.
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 the4:“Select
Experiment the test” drop down option. Ammonium Chloride (NH 4Cl) was then selected from the
Thermochemistry
“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).
CASTILLO, CARLO J. 2
Fig. 1. Experimental set-up (Water Equivalent)
Experiment 4: Thermochemistry
CASTILLO, CARLO J. 3
Calculations
t 2−t 3
Using Eq. 1: W =(m 1 )( )−m2
t 3−t 1
1g
m 1=50 mL ( )=50 g
1 mL
1g
m 2=50 mL( )=50 g
1 mL
47 ℃−36 ℃
W =(50 g)( )−50 g=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
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.
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 )
mol 1 kJ
E=[ ]( )=13.73
5g 1000 mol
CASTILLO, CARLO J. 4
By substituting the known values as seen on Table 1 in Eq. 5, the Enthalpies of Dissolution for the
other samples were also obtained.
From the table, it can be inferred that the Enthalpy of Dissolution is affected by the mass of the
sample inversely. Since KCl and KNO 3 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, 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.
Experiment 4: Thermochemistry
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 = 1 7.01
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.
CASTILLO, CARLO J. 5
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].
CASTILLO, CARLO J. 6
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.
E.REFERENCES
Experiment 4: Thermochemistry
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CASTILLO, CARLO J. 7
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insulators-definition/
Experiment 4: Thermochemistry
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CASTILLO, CARLO J. 8
Experiment 4: Thermochemistry
CASTILLO, CARLO J. 9