Thermodynamics Lab Guide PDF

Thermodynamics Experiment
The Enthalpy of H2O2 Decomposition in Aqueous Solution

OBJECTIVES
1. To illustrate the use of calorimetry in the experimental measurement of thermodynamic data.
2. To illustrate the use of thermodynamics and specifically Hess’ Law calculation of enthalpies of
reaction, using H2O2 decomposition as a model system.
INTRODUCTION
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.
Figure 1: A schematic temperature vs time graph.
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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 = Tf – Ti, then the heat, q, required to heat the
system by T is:
q = Cp T [1]
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 [2]
We use a reaction of known rH to calibrate the calorimeter (i.e. determine Cp). We use the equation:
Cp = –rH / T [3]
N.B. 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 [2]
where T is the rise in temperature for the unknown reaction.
EXPERIMENTAL PROCEDURE
Equipment:
Isobaric calorimeter with stirrer and precision thermometer
100 mL volumetric flask
250 mL measuring cylinder
10 mL pipette
Chronometer
Pipette filler
Wash bottle
Spatula
Weighing boats
Chemicals:
Sodium nitrite NaNO2
Sulphamic acid NH2SO3H
100 volume hydrogen peroxide solution H2O2

Manganese dioxide MnO2
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.
 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.
 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.
 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.
 Start the chronometer and take temperature readings at one minute intervals for five minutes to
define the slope of the pre-reaction period.
 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.
 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)
 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.
 Switch on the stirrer and allow ten minutes for an equilibrium rate of temperature rise to be
established.
 Weigh out roughly 6 g of manganese dioxide.
 Start the chronometer and take temperature readings at one minute intervals for five minutes to
define the slope of the pre-reaction period.
 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.
 Empty, clean and dry the calorimeter.
DATA TREATMENT
For each reaction in turn type your values into Microsoft Excel, or any other suitable spreadsheet
package or draw your own table. Put your times from 0 to 10 minutes in the first column, your pre-
reaction temperatures in the second column and your post-reaction temperatures in the third column
as shown in figure 2.

Figure 2: Schematic data layout.
Drag a box around the complete set of data and insert or draw a scatter graph (do not connect the
points). Add a linear trendline to each of the two data sets, for the pre-reaction temperatures forecast
the line forwards and for the post-reaction temperatures forecast the line backwards. Draw a vertical
line at five and a half minutes and where this line intersects your extrapolations will give you Ti and Tf.
Your graph should resemble figure 1. T is simply then Tf – Ti.
Calorimeter calibration
(i) The sulphamic acid was used in excess, hence the number of moles of reaction is equal to the
number of moles of NaNO2 reacting. Calculate the quantity of NaNO2 added to the calorimeter
in moles.
(ii) Given that rHm for the calibration reaction is –420.5 kJ mol–1, calculate rH using your quantity
of sodium nitrate and hence determine Cp using equation [3]. Hint: bear in mind the units, 1 kJ
= 1000 J.
Enthalpy of decomposition of H2O2
(i) The calorimeter contains the same volume of solution in both calibration and decomposition
experiments so we can assume the same heat capacity. From the observed temperature rise
and Cp, calculate rH for the H2O2 decomposed in the calorimeter using equation [2].
(ii) 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. Given this concentration,
calculate the quantity of H2O2 added to the calorimeter in moles.
(iii) From the number of moles of H2O2 added to the calorimeter, calculate rHm, in units of kJ mol–1,
for the decomposition.

(iv) The experiment measures the enthalpy of decomposition of H2O2 in aqueous solution, i.e. rH
for the reaction:
H2O2 (aq) → H2O (l) + ½ O2 (g)
For the dissolution of pure liquid H2O2 in a large excess of water:
H2O2 (l) + water  H2O2 (aq) rH = –2.1 kJ mol–1
Use Hess’ Law to calculate the enthalpy for the decomposition of liquid H2O2.
H2O2 (l)  H2O (l) + ½ O2 (g)
Calculation of the O–O bond dissociation energy in H2O2
(i) Write out the equation for the decomposition of pure H2O2 (l). Above the arrow, write in the value
you obtained for the reaction enthalpy in the previous part. Leave a little space and then
underneath the equation write elements in their standard states. Draw an arrow from there up to
each substance. The arrows represent the enthalpies of formation of the species. Bearing in
mind the enthalpy of formation of O2 (g) is zero and given the enthalpy of formation of liquid water
is –285.8 kJ mol–1 it is now possible to determine the enthalpy of formation of liquid hydrogen
peroxide using a Hess’ Law cycle.
(ii) The enthalpy of vaporisation of H2O2, vapH, is rH for the process:
H2O2 (l) → H2O2 (g)
Given the value of vapH is +48.5 kJ mol–1, once again write elements in their standard states
under this equation, draw arrows and using Hess’ Law calculate the enthalpy of formation of
gaseous hydrogen peroxide.
(iii) The dissociation energy of the (O–O) bond in hydrogen peroxide, written D(HO–OH), is rH for
the process
H2O2 (g) = 2HO· (g)
Given the value of fH for OH· (g) is +33.9 kJ mol–1, once more, write elements in the standard
states under this equation, draw arrows and using Hess’ Law calculate D(HO–OH)
Finally, the dissociation energy of the O–O bond in the oxygen molecule, D(O2), is 498.3 kJ mol–1.
This should be significantly higher than the value you have just calculated for the dissociation energy
of the O–O bond in H2O2, D(HO–OH). Whilst there is no extra credit for doing so, can you think of a
reason why this might be?
You will be assessed on your calculated values for the enthalpy of decomposition of liquid hydrogen
peroxide and, D(HO–OH), the bond dissociation energy of hydrogen peroxide.


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Thermodynamics Experiment

The Enthalpy of H2O2 Decomposition in Aqueous Solution

Figure 1: A schematic temperature vs time graph.

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Measurement of the Enthalpy of Decomposition of Hydrogen Peroxide

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