11.

CHEMICAL KINETICS I: DIAZONIUM SALT

DECOMPOSITION – DETERMINATION OF THE
ACTIVATION ENERGY
Experiment Station: 4

PRE LABORATORY WORK

In your laboratory notebook write down the following (see Introduction, What You
Should Record):

• the experiment title and the date the experiment will be carried out

• a brief statement of the experiment to be performed

• a brief plan of the experimental procedure

Please submit the answers to the following questions as a Word document using the
‘upload’ facility on the web marks and absences site at:
https://mole2.chm.bris.ac.uk/lab2005-6/index.jsp before midnight on the day before
53
you are due to carry out this practical .

1. What is meant by: (a) STP and (b) SATP? Define these conditions.

2. Calculate the maximum volume of gas evolved in the decomposition of C6H5N2Cl

prepared in this experiment at (a) STP and (b) SATP. Assume that sodium nitrite
is the limiting reagent. Show working.

The data obtained in this experiment MUST be processed using spreadsheets, make
sure you read Appendix D before you carry out this experiment. If you are still
unsure, consult a Demonstrator.

SAFETY DATA
Hydrochloric acid CAUSES BURNS, REACTS Wear protective gloves.
(concentrated) VIOLENTLY WITH WATER Spillages to sink with
plenty of water.
Aniline TOXIC Wear protective gloves
Spillages to sink with
plenty of water.
Sodium nitrite TOXIC IF SWALLOWED, Spillages to sink with
IRRITANT plenty of water
Waste reaction mixtures TOXIC IF SWALLOWED, To sink with plenty of
IRRITANT water

INTRODUCTION
In this experiment you will determine the rate constant and activation energy of a
simple first-order reaction. This experiment illustrates the volumetric method of
following the rate of a chemical reaction in which one of the products is a gas.

53 See Introduction, Instructions for Submitting Files via the Web System.

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Eqn 11.1 describes the decomposition of phenyldiazonium chloride. It has been
found experimentally that the rate of reaction depends solely on the concentration of
the phenyldiazonium chloride in the reaction mixture.

C6H5N2Cl + H2O → C6H5OH + HCl + N2↑ 11.1

i.e. the rate law for the reaction is:

d[C 6 H5 Cl]
rate = − = k [C 6 H5 Cl] 11.2
dt

Upon integration, Eqn 11.2 becomes:

ln[C 6 H 5 Cl] = −kt + ln[C 6 H 5 Cl] 0 11.3

where [C6H5Cl]0 is the initial concentration of the diazonium salt. The reaction kinetics
are much more easily followed if we monitor the volume of N2 (Vt) evolved during the
course of reaction rather than the disappearance of the diazonium salt. If we write the
integratred rate equation (Eqn 11.3) in terms of the volume of gas evolved we get:

ln(V∞ − Vt ) = −kt + lnV∞ 11.4

The volume evolved has to be monitored under conditions of constant temperature

and pressure. A gas burette, whose contents can be maintained at atmosphenic
pressure, forms an essential part of the apparatus. Look at the apparatus and make
sure that you understand how the various parts function and fit together.

If we determine the temperature dependence of k, we can also calculate the

activation energy (Ea) of the reaction. To do this you will need to work as a small
team, each studying the reaction at a different temperature (35, 40 or 45ºC).

During this practical you will encounter:

• Kinetic data analysis

• The rate constant

• A gas burette

EXPERIMENTAL
You will only need to prepare ONE sample of phenyldiazonium chloride for the whole
team since you only need about 30 ml of solution for each set of apparatus. Make
sure you record the temperature of the thermostat bath two or three times during the
course of your experiment.

Preparation of Phenyldiazonium Chloride Solution

CARRY OUT THE FOLLOWING PROCEDURE IN A FUME HOOD.

Use a 10 ml measuring cylinder to measure 5.3 ml of concentrated hydrochloric acid

into a 250 ml stoppered volumetric flask, immersed in an ice bath. Add 1.6 ml of
aniline (dispenser in fume hood) to the flask.

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Prepare a solution of 1.2 g of sodium nitrite in 19 ml of deionised water. Also cool this
solution in an ice bath.

When both solutions have cooled, SLOWLY add, via a dropping funnel, the sodium
nitrite solution to the aniline/hydrochloric acid solution in the 250 ml volumetric flask.
Make the solution up to 250 ml with deionised water. Keep the flask in the ice bath
until you are ready to use the phenyldiazonium chloride.

Kinetic Run
Make sure that the reaction vessel is CLEAN and that there is sufficient grease on the
stirrer-guide joint to ensure a gas-tight seal when the reaction vessel is connected to
it. Use the plastic clip to hold the reaction vessel in place. Raise the level of liquid in
the gas burette to just below the two-way tap, which should be set to connect the
burette to the plastic tubing.

Add about 30 ml of the phenyldiazonium chloride solution to the reaction vessel and
insert the stirrer assembly. Lower the reaction vessel into the temperature bath and
switch on the stirrer. MAKE SURE THAT YOU DO NOT TURN THE SPEED CONTROL
PAST THE MAXIMUM SAFE SPEED INDICATED ON THE STIRRER MOTOR.

Wait for about 5 minutes (to ensure that the reaction mixture has reached
temperature equilibrium with the bath) and then connect the plastic tubing to the
reaction vessel. Record the level of liquid in the burette (V0) and start the stopwatch.
You should record the level of liquid (V) in the gas burette periodically, AFTER you
have levelled the heights of the liquid in the two columns. This is done to ensure that
the gas in the burette is at atmospheric pressure. Obviously, if your thermostat is set
at 45ºC then you will need to take measurements at more frequent intervals than at
35ºC. Take measurements for a period of about 45 mins (45ºC) to about 1½ hr
(35ºC).

IT IS ESSENTIAL TO DO A ROUGHT PLOT OF Vt = V – V0 AGAINST t IN YOUR LAB

NOTEBOOK AS YOU CARRY OUT THE EXPERIMENT, TO ENSURE THAT THERE ARE
NO LEAKS OR OTHER PROBLEMS WITH THE EXPERIMENTAL SET-UP.

Determination of the Final Volume

Rather than wait for all the N2 to be evolved, it is more convenient to drive the
reaction to completion by raising the temperature to ~60ºC. This is done by heating a
beaker of water to this temperature and then lifting the whole reaction assembly out
of the thermostat bath and immersing it in the beaker. When no more N2 is seen to
evolve return the reaction vessel to the thermostat bath and record the final burette
reading, V∞, once temperature equilibrium has been re-established.

The Temperature Dependence of Reaction Rates

Most chemical reactions are found to go faster if the temperature is increased. The
Arrhenius equation relates the rate constant to the reaction temperature. This
equation can be written as follows:

Ea
ln k = ln A − 11.5
RT
This equation also has the form y = mx + c and so a plot of ln k against 1/T is linear
with a slope of –Ea/R and an intercept of ln A (R is the ideal gas constant and Ea has
units of J mol-1).

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DATA ANALYSIS
Calculate the rate constant, k. This is obtained from a plot of ln(V∞ – Vt) vs time (in
seconds); the slope will be equal to –k. USE ‘LEAST’ TO DO THIS. REMEMBER TO
QUOTE AN ERROR ON YOUR VALUE.

Calculate the activation energy. To work this out you will need values for the rate
constant at three or four different temperatures, get these from the other members of
your team. USE ‘LEAST’ TO DO THIS. REMEMBER TO QUOTE AN ERROR ON YOUR
VALUE.

REPORT
54
Short report format , include the following:
1. A table and plot of your data including proper figure/table legends etc.
55
2. Values of k and Ea compared to literature values – quote your source (i.e
Crossley et al).

3. Any physical variable giving an accurate estimation of how far the reaction has
gone can be used to obtain the rate data. How else could you follow the reaction?

4. What would be the effect on the rate of reaction if you forgot to adjust for
pressure during the experiment?

SOURCES OF INFORMATION
http://www.bris.ac.uk/is/selfhelp/faqs/librarycollections/findjournalarticle.html
P. W. Atkins and J. de Paula, Atkins’ Physical Chemistry, 7th ed., Oxford University
Press, Oxford (2002) pp.862-872, 879-881.
P. W. Atkins, Elements of Physical Chemistry, 3rd ed., Oxford University Press,
Oxford (2000) pp.215-231.
B. P. Levitt, Findlay's Practical Physical Chemistry, Longman, London (1973) pp.341-
343.
C. W. Garland, J. W. Nibbler and D. P. Shoemaker, Experiments in Physical
Chemistry, 7th ed., McGraw-Hill, New York (2003) pp.276-280.
M. L. Crossley, R. H. Kienle and C. H. Benbrook, J. Am. Chem. Soc., 62, (1940)
1400.

54 See Introduction p.11 and Appendix F. Please submit as a Word document using the
‘upload’ facility on the web marks and absences site.
55 To obtain literature data you’ll need to check the data on p.1400 of Crossley et al. To do
this go to the URL above and under section 2, click on the ‘electronic journals’ link. Once
you’ve found the journal click on ‘search the journals’. Under ‘Citation Find’ select the journal
and enter the volume and first page numbers (62 and 1400) then click the ‘Citation Find’
button. Finally you’ll see options: ‘First page’ or ‘Full pdf’ – the information you want is on the
first page so click on that. To work out the literature Ea you’ll need to plot lnk against 1/T
(where T is in K).

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SAFETY INFORMATION SHEET
CHEMICAL KINETICS I – DIAZONIUM SALT DECOMPOSITION
This information must be read before the experiment is attempted. You are required
to sign the declaration at the bottom of the page and have this countersigned by a
demonstrator before commencing the practical. Do not sign this form until you are
satisfied that you appreciate the risks associated with all aspects of the experiment.

Hydrochloric acid CAUSES BURNS, REACTS Wear protective gloves.

(concentrated) VIOLENTLY WITH WATER Spillages to sink with
plenty of water.
Aniline TOXIC Wear protective gloves
Spillages to sink with
plenty of water.
Sodium nitrite TOXIC IF SWALLOWED, Spillages to sink with
IRRITANT plenty of water
Waste reaction mixtures TOXIC IF SWALLOWED, To sink with plenty of
IRRITANT water

I have read the risk assessment and will comply with these procedures.

Name Group Date

(Please print)

Signature Demonstrator's
Signature

CAREFULLY TEAR THIS SHEET FROM YOUR LABORATORY MANUAL

AND HAND IT TO A DEMONSTRATOR

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