Core Practical 5 (Topic 10)

Hydrolysis of Halogenoalkanes
 Objectives

Experimental Objective
• To investigate the relative rates of hydrolysis of primary, secondary, tertiary halogenoalkanes
and of chloro-, bromo- and iodoalkanes
• Specification point link: 10.6, 10.8, 10.10 and 10.11
Background
• Primary halogenoalkanes have one alkyl group attached (RX), secondary have two alkyl
groups (R2CHX) and tertiary have three alkyl groups (R3CX)
• Each halogenoalkane wil form a precipitate with silver nitrate and each wil have a different
rate of the formation of precipitate

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 Safety and Apparatus
Safety
• Apparatus • Wear eye protection and suitable
chemical resistant gloves
• 250 cm3 conical flask
• 12 test tubes and bungs • Avoid skin contact with reactants 1-
• 1-chlorobutane bromobutane and products
• •1-iodobutane
• 2-bromobutane • There must be no naked flames in
• 2-bromo-2-methylpropane the vicinity as halogenoalkanes and
• 0.05 mol dm-3 silver nitrate solution ethanol are flammable
• 15 cm3 ethanol
• Dropping pipettes • The lab needs to be well ventilated
• 10 cm' measuring cylinder
• Stop clock
• Kettle

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 Method

1. Set up a water bath using a 250 cm3 beaker with water 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 test tube, 1-bromobutane to the second test tube and 1-
chlorobutane to the third test tube
4 Loosely place bungs in the test tubes and place them in a water bath
5.Take three clean test tubes and pour 5 cm? of silver nitrate solution into each one and also place in the
water bath
6. When the halogenoalkane-ethanol solutions have reached the temp of the water bath, add a silver nitrate
to each test tube and measure the time taken for the precipitate to form
7 Repeat step 6 using the primary, secondary and tertiary halogenoalkanes

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 Key Points

• •This is a nucleophilic substitution reaction where water acts as the nucleophile - ti is also
known as hydrolysis
• The equation for the formation of the precipitation is:
• RX+H O →ROH + H + X
2
+ -

• X (aq) + Ag (aq) →AgX(s)

- +

• The variables that are independently controlled are the nature of the halide (chloro-, bromo-
or iodo-) or the type of alkane (primary, secondary or tertiary)

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 Expected Results

Haloalkane Result
Chloroalkane White precipitate forms slowly.
Cream precipitate forms faster than chloro but slower than
Bromoalkane iodo.

Iodoalkane Yellow precipitate forms quickly.

• This is due to the relative strength of the C-X bond

• C-I is the weakest bond so it is the easiest one to break therefore the precipitate forms the
quickest.
• C-Cl si the strongest bond so it is the hardest one to break therefor the precipitate forms the
slowest.

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 Expected Results

• When different structural isomers are tested, the pattern is tertiary is the quickest, followed
by secondary and lastly primary
• The reasons behind this trend are not needed in this topic as ti requires a deeper
understanding of the reaction mechanism. This will be covered in Topic 11 in IAL.

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 Errors

• Ensure that the water bath is at the correct temperature to control the temperature of the
halogenoalkane
• Use lower temperatures to reduce the rates of reaction as ti makes the time difference
between the halogenoalkanes larger, giving a lower uncertainty

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 Core Practical 6 (Topic 10)
Chlorination of 2-methy|propan-2-ol
 Objective

• Experimental Objective: To produce and purify a sample of 2-chloro-2-methylpropane

• Specification point link: 10.8, 10.9 and 10.14
Background
• Halogenoalkanes can be formed from alcohols by replacing the OH group with a halogen
• Primary and secondary alcohols form chloroalkanes when reacted with phosphorus(V) chloride
whereas tertiary alcohols react with concentrated hydrochloric acid
• Any organic compound formed should then be purified, usually using a separating funnel,
distillation and a drying agent

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 Apparatus

• 2-methylpropan-2-ol
• 250 cm 3
conical flask with bung
• 100 cm 3
separating funnel with bung 250 cm 3 • 0.1 mol dm-3 sodium
beaker
• hydrogencarbonate solution
• Filter funnel
• Distillation apparatus - 50 cm 3
pear shaped flask • 6 g powdered anhydrous calcium chloride
and thermometer
• 25 cm and 100 cm measuring cylinders
3 3 • Anhydrous sodium sulfate
• Conical Flask with tubing • 0.05 mol dm-3 silver nitrate solution
• Test tubes and sample tube
• Spatula • 0.5 mol dm-3sodium hydroxide solution
• Bunsen burner • 0.1 mol dm-3nitric acid
• Water bath
• 70 cm3 concentration hydrochloric acid
• 5 cm3 ethanol
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 Safety

• This procedure requires the use of a working fume cupboard

• Wear eye protection - goggles are preferred
• Avoid skin contact with the reactants and products - wear gloves Avoid inhaling vapours
• The product of the distillation process is flammable
• The fumes from the concentrated hydrochloric acid are toxic and corrosive and must not be
inhaled, especially by anyone with a respiratory problem

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 Method

1 Pour 10 cm of 2-methy|propane-2-ol and 35 cm of concentrated hydrochloric acid in to a

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large conical flask and swirl

2. Place the bung in the mouth of the flask and swirl again. Remove the bung to release the
pressure.
3. Continue this for approx. 20 minutes until two layers begin to appear
4 Add approx. 6 g of anhydrous calcium chloride and swirl until dissolved - this will ensure
all unreacted alcohol goes in to the bottom aqueous layer and not the top organic layer
(desired product)
5. Transfer the reaction to a separating funnel and allow it to settle in to two layers. Run off
and discard the lower layer but keep the upper layer (aqueous layer)
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 Method

6. Add approx. 10 cm sodium hydrogencarbonate solution to the separating funnel and swirl whilst
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releasing the pressure. Run off and discard the lower aqueous layer and repeat.
7 Run of the organic layer ni to a small conical flask and add a spatula of anhydrous sodium sulfate. Swirl
and leave until the mixture looks completely clear (washing)
8. Decant the organic liquid in to a 50 cm 3 pear-shaped flask and set up for distillation
9. Collect the fraction boiling between 50 °C and 52 C°
10. Analyse the sample by adding 5 cm ethanol and 1 cm sodium hydroxide and warm in a water bath
3 3

11. Add excess nitric acid and a few drops of silver nitrate and record observations (Test for Halides
AgCl)

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• Diagram, Key Points and Errors

• • A weaker base is used to prevent to hydrolysis of the

Halgenalkane
• If sodium hydroxide was used, it could react with the
product via nucleophilic substitution

• The equation for this reaction is:

• (CН3)3 СОН + НСl →(СНз)ССl + Н20
• Be aware that some product may be lost when transferring
liquid between the different vessels used

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