Introduction to Calorimetry

January 25th, 2018

Manish Selliah

20731825

Partner: Saad Chaudhry

TA: Fernando Rosales

Section: 008
 Introduction

Calorimetry is one of the greatest processes in science, it is the process of heat transfer, and the

piece of equipment that is used for this study is called a calorimeter (Gaisford, 2016). To attain

the heat transfer values within a reaction, substances are put inside of the calorimeter to allow for

the reaction to occur and the change in temperature should be observed allowing for the

calculation of heat transfer for the specific reaction to exist. To determine the heat transfer, q, of

this experiment, the equation, q=ms∆T is used. In addition to the change in temperature, one

must know the mass of the substance and also the specific heat of the substance. Specific heat is

a unique value given to every substance and is the measure of the amount of heat per unit mass

required to raise the temperature of the substance by one-degree Celsius (Gaisford, 2016). In

addition to the heat transfer equation, the equation qsystem=0 is used. This equation represents

the heat transfer within the system and the fact that it will add up to 0. Meaning, all the heat

produced by the reaction being studied will be either absorbed by the water or by the water and

calorimeter combined. The calorimeter specifically used for this experiment is made out of

Styrofoam. Styrofoam is a good insulation material but it has the inability to isolate the system

from its surroundings completely. Due to this, the pressure of the calorimeter inside is equal to

the barometric pressure on the outside of the calorimeter. Since there is an equal pressure

between the system and its surroundings, it is determined that the heat of the reaction is the same

as its enthalpy change, ∆H=qreaction (Gaisford, 2016). This equation will then allow for the

determination of the molar enthalpy for the reaction.

 Table #1: Temperature Change of Water when
Experimental Observations: combined with NaOH in a Calorimeter
Time Elapsed since Temperature of Water
Results Part A: reaction began (s) (ºC)
10 19.5
20 20
Mass of Empty Calorimeter: 51.47 g
30 21.5
Mass of NaOH used: 10.07 g
40 21.7
Initial temperature of H2O: 19.5 ºC
50 22
60 22

Table #2: Temperature Change of Water when combined with NaOH in a Calorimeter
Time Elapsed since Temperature of Time Elapsed (m) Temperature of
reaction began (m) Water (ºC) Water (ºC)
2 23 13 28.3
3 26.2 14 28.2
4 28 15 28.1
5 29 16 27.9
6 29 17 27.9
7 29.3 18 27.8
8 29.5 19 27.8
9 28.5 20 27.8
10 28.8 21 27.6
11 28.8 22 27.5
12 28.5 23 27.4
Results Part B:

Mass of Calorimeter (with 125 mL heated water): 122.52 g

Mass of Calorimeter (with 250 mL water after reaction): 253.43 g
Initial temperature of cool H2O: 20.01°C

Table #3: Temperature Change of Heated Water prior to mixing with Cool Water
Time Elapsed since Temperature of Time Elapsed (m) Temperature of
reaction began (m) Water (ºC) Water (ºC)
-6 50 -3 49.8
-5 50 -2 49
-4 50 -149.8 48

Table #4: Temperature Change of Mixture of Heated and Cool water

Time Elapsed Temperature of Water
since reaction (ºC)
began (m)
0 31
1 30
2 29.8
3 29.5
4 29.4
5 29.3
Time Elapsed (m) Temperature of Water
(ºC)
6 29.3
7 29.3
8 29.2
9 29.1
10 29
Results Part C:

Concentration of HCL: 1.0764 M

Temperature of HCl before mixing: 13 ºC
Temperature of NaOH before mixing: 13.5 ºC

Table #5: Temperature Change of combined HCl and NaOH Substance

Time Elapsed Temperature of Acid Time Elapsed (s) Temperature of
since reaction & Base Mixture (ºC) Acid & Base
began (s) Mixture (ºC)
0 15 35 18.5
5 18 40 18.5
10 20 45 18.5
15 19 50 18.5
20 19 55 18.5
25 19 60 18.5
30 19

Table #6: Temperature Change of combined HCl and NaOH Substance

Time Elapsed Temperature of Acid Time Elapsed (s) Temperature of
since reaction & Base Mixture (ºC) Acid & Base
began (s) Mixture (ºC)
90 18.5 360 18.5
120 18.5 390 18.7
150 18.5 420 18.8
180 18.5 450 18.8
210 18.5 480 18.7
240 18.5 510 18.7
270 18.5 540 18.7
300 18.5 570 18.5
330 18.5 600 18.7
 Cooling Curve of Temperature when NaOH and H2O are
combined
31

Tf = 30 °C
30

29

28

27

26
Temperature (°C)

25

24

23

22

21

20
Ti = 19.5 °C ΔT:
10.5 °C

19 Time (s)
0 200 400 600 800 1000 1200 1400 1600
PART A:

Calculating Molar Enthalpy for NaOH:

Without Heat Lost

qrxn = (Ccal + msoln*ssoln)(ΔT)
qrxn = (0 + 250 g*4.184 J deg-1 g-1)(10.5 ºC)
qrxn = 10,983 J

ΔHsoln = qrxn / n
ΔHsoln = 10,983 J / 0.2518 mol
ΔHsoln = 43,617.95 J/mol

With Heat Lost

qrxn = (Ccal + msolnssoln)(ΔT)

qrxn = (62.93 J/ºC + 250 g*4.184 J deg-1 g-1)(10.5 ºC)
qrxn = 13,747.60 J

ΔHsoln = qrxn / n
ΔHsoln = 13,332.69 J / 0.2518 mol
ΔHsoln = 54,593.31 J/mol
 Temperature of Water before and after the addition of Cold
Water
52

50

Ti heated water: 50 °C
48

46

44

42
Temperature (ºC)

40

38

ΔT heated water: -21 36

°C

34

32

Tf hot & cold water: 30

29 °C

28

26
ΔT cool water: 8.99 °C
Ti cool water: 20.01 °C

24
-8 -6 -4 -2 0 2 4 6 8 10 12
Time (m)
PART B:

Calculating the Heat Capacity of the Calorimeter:

ΔTcal = ΔTcold water = 8.99 °C

ΔThot water = -21.01 °C
mcold water = mcal with hot & cold – mcal with hot water = 253.43 g – 122.52 g = 130.91 g
mhot water = mcal with hot water – mcal = 122.52 g – 51.47 g = 71.05 g
s = specific heat of water = 4.184 J deg-1 g-1

qcal = -qhot water – qcold water

Ccal *ΔTcal = - (m*s* ΔT)hot water - (m*s*ΔT)cold water
Ccal * 21 ºC = - (71.05 g *4.184 J deg g*-21.01 ºC)hw- (130.91 g*4.184 J deg g*8.99 ºC)cw
Ccal * 21 ºC = (6245.7 J)hw - (4924.18 J)cw
Ccal * 21 ºC = 1321.51 J
Ccal = 1321 J / 21 ºC
Ccal = 62.92 J/ºC = 0.063 kJ/ºC

Therefore, the calorimeter constant is -0.063 kJ/ºC.

Calculating the Specific Heat of the Calorimeter:

Specific heat calorimeter = heat gained calorimeter * ΔTcal -1 * mass calorimeter-1

Specific heat calorimeter = 1321.51 J * 8.99 °C -1 * 51.47 g -1
Specific heat calorimeter = 2.856 J ºC -1 g -1

Therefore, the specific heat of the calorimeter is 2.856 J ºC -1 g -1.

 Figure #3: Temperature Change of HCl when NaOH is
added
21
20.8
20.6
20.4
20.2
20
19.8
19.6
19.4
19.2
19
18.8
18.6
18.4
18.2
Temperature (ºC)

18
17.8
17.6
17.4
ΔT = 4 ºC Tf: 19 °C
17.2
17
16.8
16.6
16.4
16.2
16
15.8
15.6
15.4 Ti =15 °C
15.2
15
14.8
14.6
14.4
14.2
14
0 50 100 150 200 250 300 350 400 450 500 550 600 650

Time (s)
Calculating the Molar Concentration of NaOH:

nNaOH = mNaOH / MNaOH

nNaOH = 10.07 g / 39.99 g/mol
nNaOH = 0.252 mol
Using the mass of NaOH and volume of water
CNaOH = nNaOH / Vwater
CNaOH = 0.252 mol / 0.250 L
CNaOH = 1.008 mol/L

The concentration of NaOH is 1.008 mol/L.

qrxn = - (Ccal + msoln*ssoln)(ΔT)

qrxn = - (0 + 250 g*4.184 J deg-1 g-1)(4 °C)
qrxn = - 4184 J Ccal is 0 as no heat was lost to the calorimeter

qneut = -55.90 kJ/mol

nNaOH = -4184 J / (-55.90 kJ/mol)
nNaOH = 0.0748 mol

CNaOH = nNaOH / Vwater

CNaOH = 0.0748 mol / 0.1 L
CNaOH = 0.7484 mol/L

The concentration of NaOH is 0.748 mol/L.

qrxn = - (Ccal + msoln*ssoln)(ΔT)

qrxn = - (57.44 J/ºC + 250 g*4.184 J deg-1 g-1)(4 ºC)
qrxn = - 5145.32 J

qneut = -55.90 kJ/mol

nNaOH = -5145.32 kJ / (-55.90 kJ/mol)
nNaOH = 0.0920 mol

CNaOH = nNaOH / Vwater

CNaOH = 0.0920 mol / 0.1 L
CNaOH = 0.9204 mol/L

Therefore, the concentration of NaOH is 0.9204 mol/L.

Discussion

The results aquired for the molar enthalpy of NaOH, incorporating the heat lost to the calorimeter,

it was quite close to the expected result of – 44.51 kJ/mol (Petrucci, 2011). This emphasizes the

fact that the heat lost to the calorimeter must be added into calculations to make sure that the most

accurate results occur. Some assumptions that were made in this experiment was that the solutions

in Part C were very similar to water, proving that 1 mL of each solution was equal to 1 g. The

evidence of this assumption is strong since the theoretical density of 1.0M NaOH is 1.0411 g/mL

which is close enough to make this assumption true (Petrucci, 2011). The same assumption is

valid for HCl which has a theoretical density of 1.0 – 1.1 g/mL which is close enough to make this

assumption true(Petrucci, 2011). The calorimeter used in this experiment allowed for the reactions

to occur, but an observation during the experiment, it usually leaks, so this may have led to a

decrease in accuracy of the results obtained. Methods of aquring accurate results for the

measurements of the mass of the calorimeter and contents may have also caused the decrease in

the accuracy of results as the top loading balances were used and those did not give as accurate of
a mass as an analytical balance could have given. This would have affected the final masses and

inevitably changing the calorimetric calculations done. The method used to calculate the

concentration of the NaOH using the mass of the NaOH and volume of water gave a result closest

to the approximate concentration from in the lab book, 1.008M vs 1.00M, compared to the method

using the calorimetric data to calculate the concentration which gave a result that was lower than

then expected, 0.92M vs 1.00M. This may be due to the fact that the first result was a theoretical

calculation whereas the other two were experimental calculations where error can be present and

the result is going to be different than what is expected.

Conclusion

The purpose of this experiment was to determine the molar concentration of NaOH using a

neutralization reaction in a calorimeter. This was done by calorimetric calculations, through

obtaining the molar enthalpy of NaOH, using the calorimetric constant to ensure the heat lost to

the calorimeter, and taking the heat released by NaOH in the neutralization reaction and dividing

it by the the theoretical kJ/mol figure of H O to determine the molar concentration of NaOH. These
2

objectives were all achieved, the findings being 43,617.95 J/mol for the molar enthalpy of NaOH

without heat lost to the calorimeter, 54,593.31 J/mol for the molar enthalpy with heat lost to the

calorimeter, 0.063 kJ/ºC for the calorimeter constant, 2.856 J ºC g for the specific heat of the
-1

calorimeter, 1.008 mol/L for the molar concentration of NaOH using mass of NaOH and volume

of water, 0.748 mol/L for the molar concentration of NaOH using calorimetric calculations without

heat lost to the calorimeter, and 0.9204 mol/L for the molar concentration of NaOH using

calorimetric calculations with heat lost to the calorimeter. The molar concentrations of NaOH

calculated and are not as close to the expected molar concentration as would’ve been wanted,

allowing the conclusion of the experiment to be a failure.

References:

Gaisford, S. (2016). Principles of Thermal Analysis and Calorimetry: 2nd Edition.

Department of Chemistry. Chem120L Laboratory Manual, University of Waterloo: Waterloo,

2018.

Petrucci, R. et al., General Chemistry: Principles and Modern Applications, 10th ed. ; Pearson
Canada Inc., Ontario, 2011.