Bicol University

College of Engineering
East Campus, EM’s Barrio, Legazpi City

Laboratory Report No. 2: Thermodynamics Experiment

The Enthalpy of H2O2 Decomposition in Aqueous Solution

Chem 41L-Physical Chemistry 1 (Lab)
Engr. Michelle Canaria
Professor
September 26, 2016
Llorando, Patrick John L.
Miralpis, Frank Arven B.
Reonal, Samantha S.
LloReMi, BS Chemical Engineering III

Conceptual Overview
This experiment uses a calorimeter comprising a dewar vessel fitted with an electrically driven stirrer and a mercury
thermometer. The calorimeter is well-insulated from the surroundings. When an exothermic reaction is carried out inside
the calorimeter, the temperature rises. Provided the reaction and associated temperature rise are rapid then correction for
heat exchange between the calorimeter and the surroundings is unnecessary.
In a typical experiment the temperature inside the calorimeter is monitored for a period of five minutes. The reaction
is then initiated, causing a temperature rise. The temperature inside the calorimeter is then monitored for a further five
minutes.
A schematic temperature vs time graph is shown below. The readings are divided into two periods: pre-reaction and
post-reaction. Ideally, during the pre-reaction and post-reaction periods the temperature should remain constant, but in
practice there is often a slight drift owing to heat generated by the stirring and temperature equilibration between the
calorimeter and its contents.
The pre- and post-reaction period readings should be linearly extrapolated to five and a half minutes. The difference
Tf – Ti then gives the correct temperature rise.
In this experiment a reaction of known
molar enthalpy change is carried out inside
the calorimeter. Measurement of the
temperature rise enables determination of
the heat capacity of the calorimeter. Then,
A reaction of unknown molar enthalpy
change is carried out inside the calorimeter.
From the measured temperature rise and
the known heat capacity of the calorimeter
the unknown molar enthalpy may be
calculated.

When an exothermic reaction is carried out in the calorimeter, the heat liberated by the reaction is not
transferred from the calorimeter to the surroundings, but instead is used to heat up the calorimeter and its contents.
If the temperature increase is ∆T and ∆T = Tf – Ti, then the heat, q, required to heat the system by ∆T is:
q = Cp ∆T
where Cp is the isobaric heat capacity of the whole system. This heat comes from the enthalpy change of the
reaction:
 q = –∆rH
(Note: remember the reaction is exothermic i.e. ∆H is negative)
We therefore have:
–∆rH = Cp∆T
We use a reaction of known ∆rH to calibrate the calorimeter (i.e. determine Cp).We use the equation:
Cp = –∆rH / ∆T
In this experiment, ∆rH is negative because the reaction is exothermic, and so Cp is positive. The calorimeter
is then used to measure the molar enthalpy change for the unknown reaction, we reapply the equation:
–∆rH = Cp ∆T
where ∆T is the rise in temperature for the unknown reaction.
Objectives
The objectives of this experiment are to illustrate the use of calorimetry in the experimental measurement of
thermodynamic data and to illustrate the use of thermodynamics and specifically Hess’ Law calculation of enthalpies of
reaction, using H2O2 decomposition as a model system.
Equipments and Reagents
A.
Equipments Specification Quantity

Isobaric calorimeter with stirrer and precision thermometer 1

Volumetric flask 100 mL 1

Measuring cylinder 750 mL 1
Pipette 10 mL 1
Chronometer 1
Pipette filler 1
Wash bottle 1
Spatula 3
Weighing boats 3

Table 1: List of equipments needed for the experiment

B.
Reagents Specification Quantity

Sodium nitrite Solid 11.30g

Sulphamic acid Solid 5g

100 volume hydrogen peroxide solution Liquid 10 mL

Manganese dioxide Solid 6g
Distilled water liquid 1200 mL

Table 2: List of reagents needed for the experiment

Procedure

Calibration: Measurement of the Heat Capacity of the Calorimeter

The reaction between sulphamic acid and sodium nitrite in aqueous solution is used:

NH2SO3H (aq) + NaNO2 (aq) → N2 (g) + H2O (l) + NaHSO4 (aq)

 For this reaction at 25 °C, ∆rHm = –420.5 kJ mol–1.
1. Accurately weigh out 11.30 g of NaNO2, dissolve in distilled water and make up to 100 mL in a 100 mL
volumetric flask. Mix thoroughly.
2. Transfer 600 mL of distilled water to the calorimeter, add approximately 5 g of sulphamic acid, and put the lid
on. Attach the stirrer cable.
3. Switch on the stirrer and allow ten minutes for the sulphamic acid to dissolve completely and for an
equilibrium rate of temperature rise to be established.
4. Start the chronometer and take temperature readings at one minute intervals for five minutes to define the slope
of the pre-reaction period.
5. On five minutes, pipette 10 mL of the NaNO2 solution into the calorimeter through the open glass tube in the
lid. The temperature rises rapidly. By six minutes the actual reaction should be complete. Continue taking
readings at one minute intervals from six minutes to ten minutes to establish the slope of the post-reaction period.
6. Empty, clean and dry the calorimeter.

Measurement of the Enthalpy of Decomposition of Hydrogen Peroxide

The decomposition of hydrogen peroxide is:

H2O2 (aq) → H2O (l) + ½ O2 (g)

1. Transfer 600 mL of distilled water to the calorimeter and put the lid on. Attach the stirrer cable. Pipette 10 mL
of the hydrogen peroxide solution into the calorimeter.
2. Switch on the stirrer and allow ten minutes for an equilibrium rate of temperature rise to be established.
3. Weigh out roughly 6 g of manganese dioxide.
4. Start the chronometer and take temperature readings at one minute intervals for five minutes to define the slope
of the pre-reaction period.
5. On five minutes, add the manganese dioxide through the open glass tube in the lid to catalyse the
decomposition. The temperature rises rapidly. By six minutes the actual reaction should be complete. Continue
taking readings at one minute intervals from six minutes to ten minutes to establish the slope of the post-reaction
period.
6. Empty, clean and dry the calorimeter.
Results and Discussion
A. Calibration: Measurement of the Heat Capacity of the Calorimeter

Calibration of Isobaric Calorimeter

time/min temperature/˚C temperature/˚C
0 19.18
1 19.21
2 19.24
3 19.28
4 19.31
5 19.35
6 21.17
7 21.2
8 21.23
9 21.26
10 21.28
By extrapolation(using calculator)
time/min Ti(˚C) Tf(˚C)
 5.499999 19.3637
5.500001 21.158

Table 3: Temperature record for calibration of Calorimeter within 10 minutes

The recorded temperature of the solution inside the calorimeter with1-minute interval for 10 minutes is shown
in the table above. For 5 minutes, sulphamic acid (NH2SO3H) was continuously stirred and the temperature change
was very minimal. To establish a reaction with known molar enthalpy change, 10 mL of Sodium nitrite solution
(NaNO2) was added to the sulphamic acid solution in order to determine the isobaric heat capacity of the
calorimeter. It released heat because it is an exothermic reaction. The temperature changes abruptly until the 6th-
minute mark. The temperature
increases gradually after 6 minutes
Temperature vs Time plot
until 10 minutes. The pre-reaction
(Calorimeter calibration)
and post-reaction period readings
were linearly extrapolated to 5 and a 21.5
TEMPERATURE (˚C)

half minute. The temperatures 21

obtained were 19.3637 ˚C and 20.5

21.158 ˚C, respectively. 20
19.5
19
Figure 2: Temperature vs Time 0 1 2 3 4 5 6 7 8 9 10 11
plot for calorimeter calibration Time (minutes)

Pre-reaction Post-reaction
Linear (Pre-reaction) Linear (Post-reaction)
The graph above shows the
Temperature change with respect to
time. Minimal change in temperature was observed between 0-5 minutes and 6-10 minutes as stated in the earlier
paragraph. Temperature increases drastically between 5 to 6 minutes. To determine the ∆T, pre and post-reaction
readings were extrapolated at 5 and a half minutes. The 2 extrapolated values of temperature were connected by
a straight line. This implies the change in temperature which is equal to the diference of Ti from Tf. ∆T is 1.7943
˚C or 1.7943 K.

Chemical Calculations
mass NaNO2 11.30 grams
MM NaNO2 69.01 grams/mol
moles of NaNO2 0.163744385 moles

Vol of H2O 0.1 dm3

M of NaNO2 1.637443849 mol/dm3
V of NaNO2 used 0.01 dm3
mol NaNO2 used 0.016374438 mol
Table 4: Chemical calculations for Calorimeter calibration reaction
Chemical Equation
NH2SO3H (aq) + NaNO2 (aq) → N2 (g) + H2O (l) + NaHSO4 (aq)
We will only deal with the NaNO2 calculations since it is the limiting reagent and having the Sulphamc
acid used as excess. We can now compute for the moles of NaNO2 used assuming that all of it gone to completion
during the exothermic reaction between sulphamic acid.
 (11.30𝑔)
𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑚𝑜𝑙 𝑁𝑎𝑁𝑂2 = 𝑔 = 0.163744385
(69.01 )
𝑚𝑜𝑙
This initial amount of NanO2 was dissolved in 100 mL water and only 10 ml was used to react with
sulphamic acid. Computing for the moles of NaNO2 used in the reaction, we will have
0.163744385 mol
𝑚𝑜𝑙 𝑁𝑎𝑁𝑂2 𝑢𝑠𝑒𝑑 = ( ) (0.01 𝑑𝑚3) ≈ 0.01637 𝑚𝑜𝑙
0.1 𝑑𝑚3
The amount of NaNO2 used for this reaction is approximately 0.01637 mol.

Thermodynamic Calculations
Isobaric heat capacity Cp= qp / ∆T
Cp= -∆rH/ ∆T
Molar enthalpy change ∆rHm
Enthalphy change -∆rH= -(∆rHm)(mol)
∆rHm -420.5 kJ/mol
-∆rH 6.885451384 kJ
∆T =Tf-Ti 1.7943 K
Cp 3.837402544 kJ/K
Table 5: Thermodynamic calculations for Calibration reaction
Table 4 summarizes the thermodynamic calculations performed in MS Excel for the calibration reaction.
To compute for the isobaric heat capacity of the calorimeter, we will use the equation below.
𝑞𝑃 −∆rH
𝐶𝑝 = =
∆T ∆T
Given that the ∆rHm for this exothermic reaction is -420.5 kJ/mol and the moles of NaNO2 calculated
above which is 0.01637 mol, the value of Cp can be calculated as follows:
−(−420.5𝑘𝐽𝑚𝑜𝑙 −1 )(0.01637 𝑚𝑜𝑙
𝐶𝑝 = ( ) ≈ 3.837 kJ/mol
1.7943 K

B. Measurement of the Enthalpy of Decomposition of Hydrogen Peroxide

Decomposition of Hydrogen Peroxide

time/min temperature/˚C temperature/˚C
0 19.43
1 19.45
2 19.47
3 19.5
4 19.52
5 19.54
6 21.67
7 21.7
8 21.74
9 21.78
10 21.82
By extrapolation(using calculator)
 time/min Ti(˚C) Tf(˚C)
5.499999 19.5527
5.500001 21.647
Table 6: Temperature record Decomposition of H2O2 within 10 minutes
The table above shows the
recorded temperature of solution Temperature vs Time plot
inside the calorimeter with 1-minute (Decomposition of H2O2)
interval for 10 minutes. The H2O2 22
solution was continuously stirred 21.5

Teperauture (˚C)
for 5 minutes. Gradual increase in 21
temperature was observed.6 g of 20.5
Manganese sulfate (MnSO4) was 20
added to the solution after 5 minutes 19.5
which catalyze the decomposition 19
0 1 2 3 4 5 6 7 8 9 10 11
of H2O2. The temperature changes
Time (min)
rapidly until the 6th-minute mark.
After 6 minutes, the temperature Pre-reaction Post-reaction
change was very minimal again. Linear (Pre-reaction) Linear (Post-reaction)
The pre-reaction and post-reaction
period readings were linearly extrapolated to 5 and a half minutes . The temperatures obtained were 19.5527 ˚C
and 21.647 ˚C, respectively.

Figure 3: Temperature vs Time plot for H2O2 decomposition

The graph above shows the Temperature change varying with time, similar to Figure 2. Likewise, gradual
change in temperature was observed between 0-5 minutes and 6-10 minutes. Temperature increases rapidly
between 5 to 6 minutes. In order to determine the change in temperature, linear extrapolation of the before and
after reaction readings was performed at 5 and a half minutes. A straight line connects the 2 extrapolated values
of temperature. This indicates the ∆T which is equal to Tf minus Ti. ∆T is 2.0943˚C or also equal to 2.0943K.
The calorimeter contains the same volume of solution (6oomL) in both calibration and decomposition
experiments so we can assume the same heat capacity of 3.837 kJ/mol. Calculating for enthalpy change ∆H:
∆H = -∆Cp∆T = (-3.837 kJ/mol)( 2.0943K) = -8.0367 kJ
The hydrogen peroxide used was 100 volume, meaning it releases 100 times its own volume of oxygen gas
upon decomposition. Its concentration was determined, by titration against standard potassium permanganate
solution, as 8.920 mol dm–3. We used 10 mL of H2O2 which is equal to 0.01 dm3 Given this concentration, we
can now compute for the amount of H2O2 added to the calorimeter and the molar enthalpy change for
decomposition.
𝑚𝑜𝑙 𝐻2𝑂2 = (8.920 𝑚𝑜𝑙 𝑑𝑚−3 )(0.01𝑑𝑚3 ) = 0.0892 𝑚𝑜𝑙 𝐻2𝑂2
∆rHm= ∆H/mol = -8.0367 kJ/ 0.0892 mol = -90.10 kJ/mol
 Hess’ law states that the standard enthalpy of an overall reaction is the sum of the standard enthalpies of the
individual reactions into which a reaction may be divided. Applying this law, we can determine ∆rHm for
decomposition of liquid H2O2.
H2O2 (aq) → H2O (l) + ½ O2 (g) ∆rHm = –90.10 kJ/mol
H2O2 (l) → H2O2 (aq) ∆rHm = –2.1 kJ/mol

H2O2(l) → H2O(l) + ½ O2 (g) ∆rHm= –90.10 kJ/mol –2.1 kJ/mol

∆rHm= –92.2 kJ/mol
The molar enthalphy change ∆rHm for is -92.2 kJ/mol. The table below summarizes the calculations
performed in MS Excel for the decomposition of H2O2.

Chemical Equation
H2O2 (aq) → H2O (l) + ½O2 (g) reaction 1
H2O2 (l) → H2O2 (aq) reaction 2
H2O2 (l) → H2O (l) + ½O2 (g) reaction 3

By Hess' Law
∆r3Hm=∆r1Hm+∆r2Hm

Chemical Calculations
V of H2O2 0.01 dm3
M of h2O2 8.92 mol/dm3
mol of H2O2 0.0892 mol

Thermodynamic Calculations
Enthalphy change ∆rH=-Cp∆T
∆T =Tf-Ti 2.0943 K
∆r1H -8.036672147 kJ
∆r1Hm (molar ∆H of rxn1) -90.09722138 kJ/mol
∆r2Hm (molar ∆H of rxn2) -2.1 kJ/mol
∆r3Hm molar (∆H of rxn1) -92.19722138 kJ/mol
Table 7: Summary of Thermdynamic calculations for H2O2 decomposition

Conclusion

The application of calorimetry and thermodynamics that was used in order to compute for the values
needed to complete the experimental data in the virtual experiment.
References

Physical Chemistry, Atkins, Peter and Julio de Paula, 8th edition