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  • KNOCKHARDY PUBLISHING
  • 2008 SPECIFICATIONS
  • INTRODUCTION
  • This Powerpoint show is one of several produced to help students understand selected topics at AS and A2 level Chemistry. It is based on the requirements of the AQA and OCR specifications but is suitable for other examination boards.
  • Individual students may use the material at home for revision purposes or it may be used for classroom teaching if an interactive white board is available.
  • Accompanying notes on this, and the full range of AS and A2 topics, are available from the KNOCKHARDY SCIENCE WEBSITE at...
  • www.knockhardy.org.uk/sci.htm
  • Navigation is achieved by...
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  • KNOCKHARDY PUBLISHING
  • THE CHEMISTRY OF HALOGENOALKANES
  • CONTENTS
  • Structure of halogenoalkanes
  • Physical properties of halogenoalkanes
  • Nucleophilic substitution - theory
  • Nucleophilic substitution - examples
  • Substitution v. Elimination
  • Elimination reactions
  • Uses of haloalkanes
  • CFC’s
  • Revision check list
  • THE CHEMISTRY OF HALOGENOALKANES
  • Before you start it would be helpful to…
  • Recall the definition of a covalent bond
  • Be able to balance simple equations
  • Be able to write out structures for hydrocarbons and their derivatives
  • Understand the different types of bond fission
  • Recall the chemical properties of alkanes, alkenes and alcohols
  • THE CHEMISTRY OF HALOGENOALKANES
  • STRUCTURE OF HALOGENOALKANES
  • Format Contain the functional group C-X where X is a halogen (F,Cl,Br or I)
  • Halogenoalkanes - halogen is attached to an aliphatic skeleton - alkyl group
  • Haloarenes - halogen is attached directly to a benzene (aromatic) ring
  • STRUCTURE OF HALOGENOALKANES
  • Format Contain the functional group C-X where X is a halogen (F,Cl,Br or I)
  • Halogenoalkanes - halogen is attached to an aliphatic skeleton - alkyl group
  • Haloarenes - halogen is attached directly to a benzene (aromatic) ring
  • Structural
  • difference Halogenoalkanes are classified according to the environment of the halogen
  • PRIMARY 1° SECONDARY 2° TERTIARY 3°
  • STRUCTURE OF HALOGENOALKANES
  • Format Contain the functional group C-X where X is a halogen (F,Cl,Br or I)
  • Halogenoalkanes - halogen is attached to an aliphatic skeleton - alkyl group
  • Haloarenes - halogen is attached directly to a benzene (aromatic) ring
  • Structural
  • difference Halogenoalkanes are classified according to the environment of the halogen
  • Names Based on original alkane with a prefix indicating halogens and position.
  • CH3CH2CH2Cl 1-chloropropane CH3CHClCH3 2-chloropropane
  • CH2ClCHClCH3 1,2-dichloropropane CH3CBr(CH3)CH3 2-bromo-2-methylpropane
  • PRIMARY 1° SECONDARY 2° TERTIARY 3°
  • STRUCTURAL ISOMERISM IN HALOGENOALKANES
  • Different structures are possible due to...
  • Different positions for the halogen and branching of the carbon chain
  • 2-chlorobutane
  • 2-chloro-2-methylpropane
  • 1-chlorobutane
  • 1-chloro-2-methylpropane
  • PHYSICAL PROPERTIES
  • Boiling point Increases with molecular size due to increased van der Waals’ forces
  • Mr bp / °C
  • chloroethane 64.5 13
  • 1- chloropropane 78.5 47
  • 1-bromopropane 124 71
  • Boiling point also increases for “straight” chain isomers.
  • Greater branching = lower inter-molecular forces
  • bp / °C
  • 1-bromobutane CH3CH2CH2CH2Br 101
  • 2-bromobutane CH3CH2CHBrCH3 91
  • 2-bromo -2-methylpropane (CH3)3CBr 73
  • Solubility Halogenoalkanes are soluble in organic solvents but insoluble in water
  • Theory • halogens have a greater electronegativity than carbon
  • • electronegativity is the ability to attract the shared pair in a covalent bond
  • • a dipole is induced in the C-X bond and it becomes polar
  • • the carbon is thus open to attack by nucleophiles
  • • nucleophile means ‘liking positive’
  • the greater electronegativity of the halogen attracts the
  • shared pair of electrons so it becomes slightly negative;
  • the bond is now polar.
  • NUCLEOPHILIC SUBSTITUTION
  • Theory • halogens have a greater electronegativity than carbon
  • • electronegativity is the ability to attract the shared pair in a covalent bond
  • • a dipole is induced in the C-X bond and it becomes polar
  • • the carbon is thus open to attack by nucleophiles
  • • nucleophile means ‘liking positive’
  • the greater electronegativity of the halogen attracts the
  • shared pair of electrons so it becomes slightly negative;
  • the bond is now polar.
  • NUCLEOPHILES • ELECTRON PAIR DONORS
  • • possess at least one LONE PAIR of electrons
  • • don’t have to possess a negative charge
  • • are attracted to the slightly positive (electron deficient) carbon
  • • examples are OH¯, CN¯, NH3 and H2O (water is a poor nucleophile)
  • OH¯ CN¯ NH3 H2O
  • the nucleophile uses its lone pair to provide the electrons for a new bond
  • the halogen is displaced - carbon can only have 8 electrons in its outer shell
  • the result is substitution following attack by a nucleophile
  • the mechanism is therefore known as - NUCLEOPHILIC SUBSTITUTION
  • NUCLEOPHILIC SUBSTITUTION - MECHANISM
  • the nucleophile uses its lone pair to provide the electrons for a new bond
  • the halogen is displaced - carbon can only have 8 electrons in its outer shell
  • the result is substitution following attack by a nucleophile
  • the mechanism is therefore known as - NUCLEOPHILIC SUBSTITUTION
  • Points the nucleophile has a lone pair of electrons
  • the carbon-halogen bond is polar
  • a ‘curly arrow’ is drawn from the lone pair to the slightly positive carbon atom
  • a ‘curly arrow’ is used to show the movement of a pair of electrons
  • carbon is restricted to 8 electrons in its outer shell - a bond must be broken
  • the polar carbon-halogen bond breaks heterolytically (unevenly)
  • the second ‘curly arrow’ shows the shared pair moving onto the halogen
  • the halogen now has its own electron back plus that from the carbon atom
  • it now becomes a negatively charged halide ion
  • a halide ion (the leaving group) is displaced
  • NUCLEOPHILIC SUBSTITUTION - MECHANISM
  • the nucleophile uses its lone pair to provide the electrons for a new bond
  • the halogen is displaced - carbon can only have 8 electrons in its outer shell
  • the result is substitution following attack by a nucleophile
  • the mechanism is therefore known as - NUCLEOPHILIC SUBSTITUTION
  • ANIMATION SHOWING THE SN2 MECHANISM
  • NUCLEOPHILIC SUBSTITUTION - MECHANISM
  • the nucleophile uses its lone pair to provide the electrons for a new bond
  • the halogen is displaced - carbon can only have 8 electrons in its outer shell
  • the result is substitution following attack by a nucleophile
  • the mechanism is therefore known as - NUCLEOPHILIC SUBSTITUTION
  • ANIMATION SHOWING THE SN2 MECHANISM
  • NUCLEOPHILIC SUBSTITUTION - RATE OF REACTION
  • Basics An important reaction step is the breaking of the carbon-halogen (C-X) bond
  • The rate of reaction depends on the strength of the C-X bond
  • C-I 238 kJmol-1 weakest - easiest to break
  • C-Br 276 kJmol-1
  • C-Cl 338 kJmol-1
  • C-F 484 kJmol-1 strongest - hardest to break
  • NUCLEOPHILIC SUBSTITUTION - RATE OF REACTION
  • Basics An important reaction step is the breaking of the carbon-halogen (C-X) bond
  • The rate of reaction depends on the strength of the C-X bond
  • C-I 238 kJmol-1 weakest - easiest to break
  • C-Br 276 kJmol-1
  • C-Cl 338 kJmol-1
  • C-F 484 kJmol-1 strongest - hardest to break
  • Experiment Water is a poor nucleophile but it can slowly displace halide ions
  • C2H5Br(l) + H2O(l) ——> C2H5OH(l) + H+ (aq) + Br¯(aq)
  • If aqueous silver nitrate is shaken with a halogenoalkane (they are immiscible) the displaced halide combines with a silver ion to form a precipitate of a silver
  • halide. The weaker the C-X bond the quicker the precipitate appears.
  • Ag+ (aq) + X¯(aq) ——> AgX(s)
  • AgCl white ppt AgBr cream ppt AgI yellow ppt
  • NUCLEOPHILIC SUBSTITUTION - RATE OF REACTION
  • Basics An important reaction step is the breaking of the carbon-halogen (C-X) bond
  • The rate of reaction depends on the strength of the C-X bond
  • C-I 238 kJmol-1 weakest - easiest to break
  • C-Br 276 kJmol-1
  • C-Cl 338 kJmol-1
  • C-F 484 kJmol-1 strongest - hardest to break
  • Experiment Water is a poor nucleophile but it can slowly displace halide ions
  • C2H5Br(l) + H2O(l) ——> C2H5OH(l) + H+ (aq) + Br¯(aq)
  • If aqueous silver nitrate is shaken with a halogenoalkane (they are immiscible) the displaced halide combines with a silver ion to form a precipitate of a silver
  • halide. The weaker the C-X bond the quicker the precipitate appears.
  • Advanced This form of nucleophilic substitution is known as SN2; it is a bimolecular process.
  • work An alternative method involves the initial breaking of the C-X bond to form a carbocation,
  • or carbonium ion, (a unimolecular process - SN1 mechanism), which is then attacked by
  • the nucleophile. SN1 is favoured for tertiary haloalkanes where there is steric hindrance
  • to the attack and a more stable tertiary, 3°, carbocation intermediate is formed.
  • AQUEOUS SODIUM HYDROXIDE
  • Reagent Aqueous* sodium (or potassium) hydroxide
  • Conditions Reflux in aqueous solution (SOLVENT IS IMPORTANT)
  • Product Alcohol
  • Nucleophile hydroxide ion (OH¯)
  • Equation e.g. C2H5Br(l) + NaOH(aq) ——> C2H5OH(l) + NaBr(aq)
  • Mechanism
  • * WARNING It is important to quote the solvent when answering questions.
  • Elimination takes place when ethanol is the solvent - SEE LATER
  • The reaction (and the one with water) is known as HYDROLYSIS
  • NUCLEOPHILIC SUBSTITUTION
  • AQUEOUS SODIUM HYDROXIDE
  • ANIMATED MECHANISM
  • NUCLEOPHILIC SUBSTITUTION
  • POTASSIUM CYANIDE
  • Reagent Aqueous, alcoholic potassium (or sodium) cyanide
  • Conditions Reflux in aqueous , alcoholic solution
  • Product Nitrile (cyanide)
  • Nucleophile cyanide ion (CN¯)
  • Equation e.g. C2H5Br + KCN (aq/alc) ——> C2H5CN + KBr(aq)
  • Mechanism
  • NUCLEOPHILIC SUBSTITUTION
  • POTASSIUM CYANIDE
  • Reagent Aqueous, alcoholic potassium (or sodium) cyanide
  • Conditions Reflux in aqueous , alcoholic solution
  • Product Nitrile (cyanide)
  • Nucleophile cyanide ion (CN¯)
  • Equation e.g. C2H5Br + KCN (aq/alc) ——> C2H5CN + KBr(aq)
  • Mechanism
  • Importance extends the carbon chain by one carbon atom
  • the CN group can be converted to carboxylic acids or amines.
  • Hydrolysis C2H5CN + 2H2O ———> C2H5COOH + NH3
  • Reduction C2H5CN + 4[H] ———> C2H5CH2NH2
  • NUCLEOPHILIC SUBSTITUTION
  • POTASSIUM CYANIDE
  • ANIMATED MECHANISM
  • NUCLEOPHILIC SUBSTITUTION
  • NUCLEOPHILIC SUBSTITUTION
  • AMMONIA
  • Reagent Aqueous, alcoholic ammonia (in EXCESS)
  • Conditions Reflux in aqueous , alcoholic solution under pressure
  • Product Amine
  • Nucleophile Ammonia (NH3)
  • Equation e.g. C2H5Br + 2NH3 (aq / alc) ——> C2H5NH2 + NH4Br
  • (i) C2H5Br + NH3 (aq / alc) ——> C2H5NH2 + HBr
  • (ii) HBr + NH3 (aq / alc) ——> NH4Br
  • Mechanism
  • Notes The equation shows two ammonia molecules.
  • The second one ensures that a salt is not formed.
  • NUCLEOPHILIC SUBSTITUTION
  • AMMONIA
  • Why excess ammonia?
  • The second ammonia molecule ensures the removal of HBr which would lead to the formation of a salt. A large excess ammonia ensures that further substitution doesn’t take place - see below
  • Problem
  • Amines are also nucleophiles (lone pair on N) and can attack another molecule of halogenoalkane to produce a 2° amine. This too is a nucleophile and can react further producing a 3° amine and, eventually an ionic quarternary ammonium salt.
  • C2H5NH2 + C2H5Br ——> HBr + (C2H5)2NH diethylamine, a 2° amine
  • (C2H5)2NH + C2H5Br ——> HBr + (C2H5)3N triethylamine, a 3° amine
  • (C2H5)3N + C2H5Br ——> (C2H5)4N+ Br¯ tetraethylammonium bromide
  • a quaternary (4°) salt
  • NUCLEOPHILIC SUBSTITUTION
  • WATER
  • Details A similar reaction to that with OH¯ takes place with water.
  • It is slower as water is a poor nucleophile.
  • Equation C2H5Br(l) + H2O(l) ——> C2H5OH(l) + HBr(aq)
  • ELIMINATION v. SUBSTITUTION
  • The products of reactions between haloalkanes and OH¯ are influenced by the solvent
  • SOLVENT
  • ROLE OF OH–
  • MECHANISM
  • PRODUCT
  • WATER
  • NUCLEOPHILE
  • SUBSTITUTION
  • ALCOHOL
  • ALCOHOL
  • BASE
  • ELIMINATION
  • ALKENE
  • Modes of attack
  • Aqueous soln OH¯ attacks the slightly positive carbon bonded to the halogen.
  • OH¯ acts as a nucleophile
  • Alcoholic soln OH¯ attacks one of the hydrogen atoms on a carbon atom adjacent
  • the carbon bonded to the halogen.
  • OH¯ acts as a base (A BASE IS A PROTON ACCEPTOR)
  • Both reactions take place at the same time but by varying
  • the solvent you can influence which mechanism dominates.
  • ELIMINATION
  • Reagent Alcoholic sodium (or potassium) hydroxide
  • Conditions Reflux in alcoholic solution
  • Product Alkene
  • Mechanism Elimination
  • Equation C3H7Br + NaOH(alc) ——> C3H6 + H2O + NaBr
  • Mechanism
  • the OH¯ ion acts as a base and picks up a proton
  • the proton comes from a carbon atom next to that bonded to the halogen
  • the electron pair left moves to form a second bond between the carbon atoms
  • the halogen is displaced
  • overall there is ELIMINATION of HBr.
  • Complication With unsymmetrical halogenoalkanes, you can get mixture of products
  • ELIMINATION
  • ANIMATED MECHANISM
  • ELIMINATION
  • Complication
  • The OH¯ removes a proton from a carbon atom adjacent the C bearing the halogen. If there had been another carbon atom on the other side of the C-Halogen bond, its hydrogen(s) would also be open to attack. If the haloalkane is unsymmetrical (e.g. 2-bromobutane) a mixture of isomeric alkene products is obtained.
  • but-1-ene
  • but-2-ene
  • can exist as cis and trans isomers
  • USES OF HALOGENOALKANES
  • Synthetic The reactivity of the C-X bond means that halogenoalkanes play an
  • important part in synthetic organic chemistry. The halogen can be replaced by a variety of groups via nucleophilic substitution.
  • USES OF HALOGENOALKANES
  • Synthetic The reactivity of the C-X bond means that halogenoalkanes play an
  • important part in synthetic organic chemistry. The halogen can be replaced by a variety of groups via nucleophilic substitution.
  • Polymers Many useful polymers are formed from halogeno hydrocarbons
  • Monomer Polymer Repeating unit
  • chloroethene poly(chloroethene) PVC - (CH2 - CHCl)n –
  • USED FOR PACKAGING
  • tetrafluoroethene poly(tetrafluoroethene) PTFE - (CF2 - CF2)n -
  • USED FOR NON-STICK SURFACES
  • USES OF HALOGENOALKANES
  • Synthetic The reactivity of the C-X bond means that halogenoalkanes play an
  • important part in synthetic organic chemistry. The halogen can be replaced by a variety of groups via nucleophilic substitution.
  • Polymers Many useful polymers are formed from halogeno hydrocarbons
  • Monomer Polymer Repeating unit
  • chloroethene poly(chloroethene) PVC - (CH2 - CHCl)n –
  • USED FOR PACKAGING
  • tetrafluoroethene poly(tetrafluoroethene) PTFE - (CF2 - CF2)n -
  • USED FOR NON-STICK SURFACES
  • Chlorofluorocarbons - CFC’s
  • dichlorofluoromethane CHFCl2 refrigerant
  • trichlorofluoromethane CF3Cl aerosol propellant, blowing agent
  • bromochlorodifluoromethane CBrClF2 fire extinguishers
  • CCl2FCClF2 dry cleaning solvent, degreasing agent
  • All are/were chosen because of their LOW REACTIVITY, VOLATILITY, NON-TOXICITY
  • USES OF HALOGENOALKANES
  • Synthetic The reactivity of the C-X bond means that halogenoalkanes play an
  • important part in synthetic organic chemistry. The halogen can be replaced by a variety of groups via nucleophilic substitution.
  • Polymers Many useful polymers are formed from halogeno hydrocarbons
  • Monomer Polymer Repeating unit
  • chloroethene poly(chloroethene) PVC - (CH2 - CHCl)n –
  • USED FOR PACKAGING
  • tetrafluoroethene poly(tetrafluoroethene) PTFE - (CF2 - CF2)n -
  • USED FOR NON-STICK SURFACES
  • Chlorofluorocarbons - CFC’s
  • dichlorofluoromethane CHFCl2 refrigerant
  • trichlorofluoromethane CF3Cl aerosol propellant, blowing agent
  • bromochlorodifluoromethane CBrClF2 fire extinguishers
  • CCl2FCClF2 dry cleaning solvent, degreasing agent
  • All are/were chosen because of their LOW REACTIVITY, VOLATILITY, NON-TOXICITY
  • CFC’s have been blamed for damage to the environment by thinning the ozone layer
  • Ozone absorbs a lot of harmful UV radiation
  • However it breaks down more easily in the presence of CFC's
  • CFC’s break up in the atmosphere to form radicals CF2Cl2 ——> CF2Cl• + Cl•
  • Free radicals catalyse the breaking up of ozone 2O3 ——> 3O2
  • PROBLEMS WITH CFC’s AND THE OZONE LAYER
  • CFC’s have been blamed for damage to the environment by thinning the ozone layer
  • Ozone absorbs a lot of harmful UV radiation
  • However it breaks down more easily in the presence of CFC's
  • CFC’s break up in the atmosphere to form radicals CF2Cl2 ——> CF2Cl• + Cl•
  • Free radicals catalyse the breaking up of ozone 2O3 ——> 3O2
  • CFC’s were designed by chemists to help people
  • Chemists are now having to synthesise alternatives to CFC’s to protect the environment
  • - Hydrocarbons and HCFC’s are used for propellants
  • - CO2 can be used as a blowing agent for making expanded polystyrene
  • This will allow the reversal of the ozone layer problem
  • PROBLEMS WITH CFC’s AND THE OZONE LAYER
  • CFC’s have been blamed for damage to the environment by thinning the ozone layer
  • Ozone absorbs a lot of harmful UV radiation
  • However it breaks down more easily in the presence of CFC's
  • CFC’s break up in the atmosphere to form radicals CF2Cl2 ——> CF2Cl• + Cl•
  • Free radicals catalyse the breaking up of ozone 2O3 ——> 3O2
  • CFC’s were designed by chemists to help people
  • Chemists are now having to synthesise alternatives to CFC’s to protect the environment
  • - Hydrocarbons and HCFC’s are used for propellants
  • - CO2 can be used as a blowing agent for making expanded polystyrene
  • This will allow the reversal of the ozone layer problem
  • PROBLEMS WITH CFC’s AND THE OZONE LAYER
  • There is a series of complex reactions but the basic process is :-
  • ozone in the atmosphere breaks down naturally O3 ——> O + O2
  • CFC's break down in UV light to form radicals CCl2F2 ——> Cl• + CClF2•
  • chlorine radicals then react with ozone O3 + Cl• ——> ClO• + O2
  • chlorine radicals are regenerated ClO• + O ——> O2 + Cl•
  • Overall, chlorine radicals are not used up so a small amount of CFC's can destroy
  • thousands of ozone molecules before they take part in a termination stage.
  • PROBLEMS WITH CFC’s AND THE OZONE LAYER
  • REVISION CHECK
  • What should you be able to do?
  • Recall and explain the physical properties of halogenoalkanes
  • Recall and explain the chemical properties of halogenoalkanes based on their structure
  • Recall and explain the properties of nucleophiles
  • Write balanced equations for reactions involving substitution and elimination
  • Understand how the properties of a hydroxide ion are influenced by the choice of solvent
  • Recall the effect of CFC’s on the ozone layer
  • CAN YOU DO ALL OF THESE? YES NO
  • You need to go over the relevant topic(s) again
  • Click on the button to
  • return to the menu
  • WELL DONE!
  • Try some past paper questions
  • © 2009 JONATHAN HOPTON & KNOCKHARDY PUBLISHING
  • THE END
  • AN INTRODUCTION TO
  • THE CHEMISTRY
  • OF HALOGENOALKANES


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