Halogenoalkanes: Reactions and Environmental Effects

Our old friend silver nitrate returns to haunt us.

From the scheme

Candidates should be able to: (a) describe the hydrolysis of halogenoalkanes as a substitution reaction; (b) define the term nucleophile as an electron pair donor; (c) describe the mechanism of nucleophilic substitution in the hydrolysis of primary halogenoalkanes with hot aqueous alkali; (d) explain the rates of hydrolysis of primary halogenoalkanes in terms of the relative bond enthalpies of carbonhalogen bonds (CF, CCl, CBr and CI);

From the scheme

(e) outline the uses of chloroethene and tetrafluoroethene to produce the plastics PVC and PTFE; (f) explain that CFCs:
(i) were developed as aerosols, refrigerants, and in airconditioning because of their low reactivity, volatility and non-toxicity, (ii) have caused environmental damage to the ozone layer;

(g) outline the role of green chemistry in minimising damage to the environment by promoting biodegradable alternatives to CFCs, such as hydrocarbons and HCFCs; CO2 as a blowing agent for expanded polymers.

Something to draw...
1,1-dibromobutane 2-chlorohexan-2-ol 1-bromo-2-chloropent-2-ene 1-iodopropan-2-one 2,3-difluoroheptanal

Reactivity of the halogenoalkanes

Using the table on page 61 write out the halogens in order of electronegativity (greatest first). What is the electronegativity value for carbon? What does this all mean?

Reactivity of the halogenoalkanes

Nucleophiles
A nucleophile is a reactant which attacks an electron deficient atom, donating its electron pair. Nucleophiles include: OH-, NH3 and H2O Nucleophiles react with halogenoalkanes in substitution reactions the nucleophile replaces the halogen, resulting in a different functional group.

Hydrolysis
Heating with hot, aqueous hydroxide ions leads to nucleophilic substitution. The product is an alcohol. Conditions for reaction: reflux.

Mechanism

Remember: curly arrows ONLY EVER start from where the electrons are: in a bond or electrons shown on a negative ion/lone pair

How fast?
How can I measure the rate of hydrolysis of the halogenoalkanes? We have to look at what is produced....

Hydrolysis of primary halogenoalkanes

Halogenoalkane heated with:
Aqueous silver nitrate Ethanol (solvent) Water from the mixture acts as nucleophile

Controlling Variables
If we are comparing rates of hydrolysis between chloro, bromo and iodo alkanes what variables should be controlled to make this a fair test?

Control Variables
Equal amounts of each halogenoalkane Water bath to keep temperature constant (50oC) Use halogenoalkanes with the same chain length.

Factors affecting rate

The rate of hydrolysis is affected by two things
Polarity of the bond (C-F is most polar, C-I is least polar and so is least likely to react) Strength of the bond (C-F is strongest, C-I is weakest and should be broken most easily)

What is the problem?

Something to remember
In the hydrolysis of halogenoalkanes bond enthalpy is more important than bond polarity.

Exam Question
The rates of hydrolysis of chloroethane, bromoethane and iodoethane are different.
Describe how you would monitor the reaction rates. Explain why chloroethane, bromoethane and iodoethane react at different rates.

Use suitable equations in your answer.

[Total 6 marks]

Essential marks: Order : I>Br>Cl 1 reason for the order: C-I bond weakest/length (C-Cl bond strongest and mention/intermolc forces loses the mark) 1 an equationAg + X AgX (solid or ppt) or an equation for hydrolysis/using OH- or H O 1
+ 2

method of monitoring the reaction AgNO3 Ethanol & Waterbath temp 40 - 80C (not heat/not bunsen) relative rate of precipitation

1 1 1 [6]

Halogenoalkanes and the environment

Polymers containing halogens

A quick recap on polymers