Core Practical 5: Investigation of the rates of hydrolysis of some
halogenoalkanes
Objective
● To investigate the relative rates of hydrolysis of primary, secondary and tertiary
halogenoalkanes and of chloro-, bromo- and iodoalkanes
Safety
● Wear eye protection.
● Avoid skin contact with the reactants.
● There must be no naked flames in the vicinity as ethanol and halogenoalkanes are highly
flammable.
● The laboratory needs to be well ventilated to prevent the inhalation of fumes.
Maths skills
● Use ratios to construct and balance equations.
Equipment
● 250 cm3 beaker ● 0.05 mol dm–3 silver nitrate solution
● 12 test tubes with bungs ● 15 cm3 ethanol
● 1-chlorobutane ● dropping pipettes
● 1-bromobutane ● two 10 cm3 measuring cylinder
● 1-iodobutane ● stop clock
● 2-bromobutane ● labels for test tubes
● 2-bromo-2-methylpropane ● kettle
Procedure
Part 1
1. Set up a water bath by filling the 250 cm3 beaker up to the three-quarters mark with
water at around 50 °C.
2. Take three test tubes and add 5 cm3 of ethanol to each one.
3. Add four drops of 1-iodobutane to the first tube, four drops of 1-bromobutane to the
second tube and four drops of 1-chlorobutane to the third tube. Label the tubes.
4. Loosely place a bung in each test tube and place the test tubes in the water bath.
5. Take three clean test tubes and pour 5 cm3 of silver nitrate solution into each one.
Then place the test tubes in the water bath.
6. When the halogenoalkane–ethanol solutions have reached the temperature of the
water bath, add one test tube of silver nitrate solution to one of the halogenoalkane–
ethanol solutions and replace the bung. At the same time, start the stop clock.
7. Measure the time taken for a precipitate to appear. As soon as the solution becomes
cloudy, stop the stop clock.
8. Repeat steps 6 and 7 for the other two halogenoalkanes.
Part 2
9. Repeat Part 1 using 1-bromobutane, 2-bromobutane and 2-bromo-2-methylpropane
instead of the other halogenoalkanes.
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Practical activities have been safety checked but not trialled. Users may need to adapt the risk assessment
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Analysis of results
1. Describe the pattern shown in your results for Part 1.
2. Describe the pattern shown in your results for Part 2.
Learning tips
● The hydrolysis of halogenoalkanes is a nucleophilic substitution reaction.
● In this investigation, the nucleophile is water.
● NaOH can be used instead of water to hydrolyse the halogenoalkanes but then any excess
NaOH must be neutralised by HNO3 before the AgNO3 is added. Otherwise a precipitate of
Ag2O will form.
Questions
1. Write an equation for the reaction of 1-bromobutane with water.
2. In these reactions, a precipitate forms. Identify the precipitate formed when the
halogenoalkane is 1-iodobutane.
3. Explain why ethanol is used in these reactions.
4. Explain why water is able to act as a nucleophile.
5. Explain why water is used as the nucleophile rather than hydroxide ions.
6. Draw skeletal formulae for each of the halogenoalkanes used in this investigation
(there are five of them). Classify each halogenoalkane as primary, secondary or
tertiary.
© Pearson Education Ltd 2018. Copying permitted for purchasing institution only. This material is not copyright free.
Practical activities have been safety checked but not trialled. Users may need to adapt the risk assessment
information to local circumstances. 2
Exam-style questions
1. A student dissolves 0.005 mol of 2-chloropropane, 2-bromopropane and
2-iodopropane in 10 cm3 of ethanol, in three separate test tubes.
He stands the tubes in a 50 °C water bath.
He then adds 5 cm3 of aqueous silver nitrate solution to each test tube and times how
long it takes for the precipitate to form.
His results are shown in the table:
Halogenoalkane Time taken for a
precipitate to form/s
2-iodopropane 31
2-bromopropane 74
2-chloropropane 241
The mechanism for the reaction is:
(a) Using equal numbers of moles of each halogenoalkane ensures that this is a fair
test. Explain why.
(2)
The following table provides information on the electronegativities of the halogens and
C–Halogen bond strengths:
Halogen Electronegativity Mean C–Halogen bond strength/kJ mol–1
chlorine 3.2 339
bromine 3.0 284
iodine 2.7 218
(b) Explain how the student’s results (in the first table) show that it is not the
electronegativity of the halogen that determines the relative rate of the
nucleophilic substitution reaction.
(4)
(c) Use the data in the tables to explain the relative rates of the nucleophilic
substitution reaction for these halogenoalkanes.
(3)
© Pearson Education Ltd 2018. Copying permitted for purchasing institution only. This material is not copyright free.
Practical activities have been safety checked but not trialled. Users may need to adapt the risk assessment
information to local circumstances. 3
