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Cristina Silva
Calorimetry Neptun code: GNOWHO
Date of measurement:
28.10.2021 Group: 1
2. Theoretical background
Among the numerous amount of types of calorimeters, which can be classified in various forms,
there are three main types of calorimeters which differ from each other based on their operation
principle:
1) Adiabatic calorimeters
2) Isotherm calorimeters
3) Heat transfer calorimeters
Adiabatic calorimeters: Based on the term “adiabat”, it can be stated that we do not experience
any heat transfer process between ambience and thermodynamic systems inside a calorimeter
device. One can imagine two systems: System I and System II. System I can absorb or produce the
heat and it transfers to (or from) the System II with heat capacity C. This leads to the change in the
temperature of System II which can be measured based on a simple energy balance:
Q=−C∗T (1)
It is valid only in case no heat flux is present or its magnitude can be neglected. If such systems
(I and II) are part of the adiabatic calorimeter, it needs to be isolated from the outer space in a
thermal way or kept under a secondary environment.
In addition, when it comes to the measurements done with adiabatic calorimeter, one should
know how large the temperature difference of the measurement needs to be. As the heat capacity is a
temperature function, one has to keep T value in a lower range. If not, the accuracy of the
measured heat capacity would not be promising. Nonetheless, too small T values would be
challenging for a precise measurement and so the measurement would not be that precise either.
Compared to adiabatic calorimeters, in isotherm calorimeters one does not have to deal with the
points mentioned above. In this type of calorimeter device, System I’s heat has a relation either with
the electric energy absorption or with the System II release so that we can observe a constant
temperature in the calorimeter. Compensating energy amount measurement takes place in this
method. It also needs to be considered that one expels fluxes of the heat from (or to) the ambience in
a manner which has a use with adiabatic calorimeters.
The third calorimeter type is heat transfer calorimeters. It is first to mention that one can apply
them in the specific heat measurement. Unlike the first two calorimeter types, we can take note of
the heat transfer from (or to) the outer environment. There is a process of equalizing of the
temperature which occurs between the environment and the calorimeter material and afterwards one
can measure the process rate. An Ohmic law is to be used when there is a heat transfer happening:
( C +c∗p∗V )∗dT
IQ= =−k∗(T −Tenviron ment ) (2)
dt
where C: calorimeter heat capacity
c: specific heat
p: density of the material which is under research
V: volume
k: heat transfer coefficient
Note that IQ is directly proportional to its driving force and the temperature difference equation is
illustrated above.
If Tenvironment is constant:
dT =d (T −Tenvironment)
and Equation (2) can be modified:
( ln ( T −Tenvironment
dt
)
)=
−k
C+ c∗p∗V
=p
If k and (C + c*p*V) temperature dependences equalize each other, the temperature difference
logarithm plot between ambience and material against time must be linear. The line’s ‘p’ slope is
constant in that case. One is familiar with two constant parameters which are unknown: C and k.
The constancy of k needs to be assured by the calorimeter construction. Therefore, we can perform
calibration with two liquids of known density and specific heat.
3. Equipment
In the lab experiment, two types of calorimeters (namely: adiabatic and heat transfer) are used.
The adiabatic calorimeter (see Fig.1) consists of a vessel named Dewar (1). Styrofoam (3) isolates
lid (2) of the vessel thermally. A thermometer (4), a heating rod/calorifier (5) and a metering
pipette (6) are held by the vessel lid. To make sure that there is a homogeneity in the calorimeter
device, a magnetic stirrer (7) is used as well. Also, there is a supply of power for the calorifier with
separate ammeter (A) and voltage (V) parts. We use measuring cylinders and burettes to measure
the necessary liquid amounts. Time is measured by the stopwatches provided in the lab.
In the Figure 2, one can see the heat transfer calorimeter which is a plastic cylinder (1) inside a
vessel (2). To have a constant distance between the vessel and the cylinder, some silicon rings (3)
are present. Transfer through the air between the outside vessel and the cylinder is called heat
transfer’s rate limiting step. Hence, there is an independent relation between the heat transfer
coefficient (k) and the material measured. To ensure homogeneity inside the plastic cylinder, a
magnetic stirrer (4) is used. Thermocouple notes the difference in the temperature. There is a
junction (5) immerged in the thermostating liquid whereas another junction (6) is immersed in the
liquid that is going to be measured. An amplifier (7) enlarges the thermoelectric voltage and it is
measured by a digital multimeter (8). The value measured up to that is noted down to make a plot
against time using a computer connected to the digital multimeter based on a serial interface.
4.1. Specific heat determination of an organic liquid with heat transfer calorimeter
1) Firstly, we waited until the heat transfer calorimeter thermostat reached 50C.
2) One measured 15 cm3 of distilled water into the 50 ml plastic cylinder. Then, the device (see
Figure 2) was assembled; it is needed to make sure that a proper and operable magnetic stirrer is
used to ensure the homogeneity inside the vessel. The plastic stirrer content is poured into the
thermostated vessel with the magnetic stirrer inside. A stirring was started and T was registered on
a computer. After finishing with the first T measurement, the thermostated vessel content was
poured out to a residue beaker and was cleaned with a piece of tissue paper. The plastic cylinder and
the magnetic stirrer were also cleaned with the paper.
3) We repeated the procedure 2 with same volumes of ethanol and 1-propanol (15 ml each).
6. Calculations
6.1. Adiabatic calorimeter calculations
First, I put the obtained temperature values with corresponding time in a table:
Time
T [ᵒC]
[min]
0 24.22
1 24.2
2 24.19
3 24.19
4 24.18
5 24.18
6 24.19
7 24.18
8 24.19
9 24.19
10 24.19
11 25.98
12 25.98
13 25.97
14 25.95
15 25.95
16 25.94
17 25.95
18 25.94
19 25.94
20 25.93
21 26.38
22 26.83
23 27.51
24 28.02
25 28.26
26 28.23
27 28.23
28 28.2
29 28.2
30 28.19
31 28.17
32 28.17
33 28.15
34 28.14
Table 1. Time – measured temperature values.
Then, I made a plot based on the table above:
26
f(x) = − 0.00539393939393931 x + 26.0366060606061
25
24 f(x) = − 0.00181818181818165 x + 24.2
23
22
0 5 10 15 20 25 30 35 40
Time [min]
IMPORTANT NOTES:
(1) Time when acetic acid was added into the calorimeter: 10 mins and 2 secs.
(2) Time when the heating was turned on: 20 mins and 5 secs.
(3) Time when the heating was turned off: 24 mins exactly.
(4) Value of measured current (I): 0.58 A
(5) Value of measured voltage (U): 26.68 V
1) y = -0.0018x + 24.2 (BROWN LINE)
2) y = -0.0054x + 26.037 (GREY LINE)
3) y = -0.0124x + 28.559 (YELLOW LINE)
Keeping in mind the time of adding the acetic acid (10 mins 2 secs = 10.0333 mins):
- Calculating the specific temperature before adding the acid:
Based on these => ΔT1 = Tafter – Tbefore = (25.98282 – 24.18194) C = 1.80088 C = 1.801C
Keeping in mind heating (on/off) times (20 mins 5 secs (or 20.0833 mins) and 24 mins):
- Average time of heating activity (tavg.heat):
tavg.heat = (20.0833 + 24) mins / 2 = 22.042 mins
Having considered that there is a proportionality between ∆U and ∆T, let’s plot “ln ∆T vs time”
graphs of water, ethanol and 1-propanol:
4.6
f(x) = − 0.000874394781741355 x + 4.58550078952961
4.5
4.4
ln ∆T [-]
4.3
4.2
4.1
4
0.00 50.00 100.00 150.00 200.00 250.00 300.00 350.00 400.00 450.00 500.00
Time [s]
4.2
4.1
4
3.9
3.8
3.7
3.6
0 50 100 150 200 250 300 350 400 450 500
Time [s]
4.2
4.1
4
3.9
3.8
3.7
3.6
0 50 100 150 200 250 300 350 400 450 500
Time [s]
[kg/m3] c [J/kgK]
Water 994.2 4178
Ethanol 776 2558
Propanol 792 ?
Table 2. Density and specific heat values of water, ethanol and propanol.
Considering that V = 15 cm3 = 1.5 * 10-5 m3, let’s calculate cpropanol:
−k
p=
C+ c ⋅ ρ⋅V
−k
pwater=−0.000874=
J kg
C +4178 ⋅ 994.2 3 ⋅1.5 ⋅10−5 m3
kgK m
−k
pethanol=−0.0 0 1275=
J kg
C+2558 ⋅776 3 ⋅1.5 ⋅10−5 m3
kgK m
By solving this equation system (two equations and two unknowns), we get:
C = 1.389 and k = 0.0557
−K−C ⋅ p −0.0557−1.389 ⋅(−0.001 238) J
cpropanol= = −5
=3670.28
p ⋅ ρ ⋅V −0.0 01238 ⋅792 ⋅1.5⋅10 kgK
7. Conclusion
Regarding the adiabatic calorimeter, the calculated reaction molar enthalpy change (∆ Hm ) is -
55.315 kJ/mol. The value is lower than the one in the literature (Internet sources).
Some reasons have been noted down to explain the difference in the values:
1) NOT HOMOGENEOUS STIRRING: The stirring inside the adiabatic calorimeter might not have
resulted in a good homogeneity of the solution.
2) CORRECT TIMING: The time measurement for turning (on/off) the heating and adding acetic
acid using the metering pipette was not accurate at all. I was doing the adiabatic calorimeter part
with one more person and we could not manage to note down the exact times (although we were
told by the lab instructor that it is crucial to write down the exact time). I believe probably this was
one of the main reasons why the calculated value differs from the literature value quite a lot.
3) MEASURING THE SOLUTIONS: Another possible reason is that measuring the exact amount of
solutions (e.g. NaOH, CH3COOH) was not so precise because of using measuring cylinders (which
might have caused the systematic errors of the measurement). Instead, it would be better to use a
burette and electronic pipettes to measure all the solutions to ensure the preciseness of their
amounts.
On the other hand, considering the heat transfer calorimeter, it can be seen that, based on the txt
files which were got from the lab computer, “ln T vs time” plots were obtained for water, ethanol
and propanol (so in total = 3 graphs) to afterwards get the slope values of each linear equation.
Having considered those slope values, the table and the equations provided in the lab recipe, the
specific heat of propanol was calculated (Cpropanol = 3670.28 J/kgK) which, as it was compared with
the literature values (Internet sources), is quite higher than those.
Aside from the reasons mentioned above, in general, it can be said that the experiment was
conducted quite well.