Starter
1. What trends can you recall for the group 7 elements?
2. Write the equation for silver nitrate solution reacting with sodium
chloride solution.
3. Show the displayed formula for 1-chlorobutane
4. Breaden bonus: Name this molecule:
Haloalkanes & their reactions
Describe the structure & Construct the Relate the rates of primary
general formula for mechanism for the HALOALKANE hydrolysis to
haloalkanes. nucleophilic values of relative bond
D/C substitution of enthalpies for carbon–
haloalkanes. halogen bonds.
B/A
C
Haloalkanes
• Haloalkanes are compounds in which one or more hydrogen
atoms in an alkane have been replaced by halogen atoms
(fluorine, chlorine, bromine or iodine).
• Formerly used as refrigerants, aerosol propellants & dry-
cleaning solvents. These uses banned since understanding of
their impact on the ______________ _________.
• Now used in organic synthesis. Still used in fire fighting
applications for aviation & military.
• General formula for haloalkanes = , where
X is the halogen.
CFC - chlorofluorocarbon
E.g. ?
The haloalkanes
• In a primary (1°) HALOALKANE, the carbon which carries the
halogen atom is only attached to one other alkyl group.
• In a secondary (2°) HALOALKANE, the carbon with the halogen
attached is joined directly to two other alkyl groups, which may
be the same or different.
• In a tertiary (3°) HALOALKANE, the carbon atom holding the
halogen is attached directly to three alkyl groups, which may be
any combination of same or different.
Naming haloalkanes
• Haloalkanes are _____________ compounds & their names are
based on the alkane homologous series. This determines the
prefix.
• Indicate the position of the halogen(s) on the chain.
• If more than one halogen, then list them alphabetically.
Naming haloalkanes – name & classify these:
Reactivity of haloalkanes
Prediction: polar or non-polar?
Explain your answer
Key definition – a reminder!
Electronegativity is …………………………………………..
…………………………………………………………………………
…………………………………………………………………………
………………………………………………………………………….
A difference in electronegativity between
bonded atoms results in __________.
Reactivity of haloalkanes
Electronegativity of the halogens _____________ down
the group, resulting in a ___________ in the polarity of
the carbon-halogen, C-X, bond from fluorine to iodine.
Reactivity of haloalkanes
• The electron-deficient carbon atom in haloalkanes attracts ______________
such as H2O, OH- & NH3.
• Haloalkanes react with nucleophiles in _____________ reactions.
• The _______________ replaces the halogen atom in the haloalkane, forming a
compound containing a different _____________ ________.
Reactivity of haloalkanes
Polarity decreases ________the group because
in the halogen electronegativity ___________
as:
• Atomic radius ____________
• Electron shielding ____________
• Ability to gain an electron ____________
The outer electrons are _______ strongly attracted by the
positive nucleus, as would be any electrons shared to form a
covalent bond.
Mechanism for nucleophilic substitution
Mechanism for nucleophilic substitution
1. The nucleophile Nu- approaches the carbon atom attached to the halogen on the
opposite side of the molecule from the halogen atom. This minimises repulsion
between the negative charge on the nucleophile & the 𝛿- charge on the halogen
atom.
2. The lone pair on the nucleophile is attracted & donated to the 𝛿+ carbon atom.
3. A new bond is formed between the nucleophile & the carbon atom.
4. The carbon-halogen bond breaks by ______________fission.
5. A new organic product is formed & a halide ion is also formed.
Key definition
Hydrolysis is a reaction with water or
____________ __________________ ______
that breaks a chemical compound into two
compounds.
Nucleophilic substitution of primary haloalkanes –
hydrolysis
E.g. hydrolysis of 1-chloropropane
CH3CH2CH2Cl(aq) + OH-(aq) CH3CH2CH2OH(aq) + Cl-(aq)
1-chloropropane propan-1-ol
- A very slow reaction at room temperature
- Heat under ________ to obtain a good yield of product
Mechanism for nucleophilic substitution –
hydrolysis
E.g. hydrolysis of 1-iodopropane
Mechanism for nucleophilic substitution–
hydrolysis
Hydrolysis with aqueous sodium or potassium
hydroxide
Complete
The haloalkanes are attacked by_____________
undergoing _____________ reactions.
The attacking species all have a __________pair of
___________which form a bond with the __________
atom next to the halogen.
The reaction with OH- (aq) will give an _____________.
Hydrolysis with water
Rate of hydrolysis for different haloalkanes
• The rates of hydrolysis for different haloalkanes can be determined
by heating the HALOALKANE with ___________ __________
_________ , with __________ added.
• Water in the silver nitrate solution behaves as the _____________.
• The ethanol acts as a common __________, ensuring that the
HALOALKANE and aqueous silver nitrate mix together and react.
• As the hydrolysis reaction occurs, ___________ _______ form. The
aqueous silver nitrate reacts with any halide ion present, forming a
precipitate of the silver halide.
The hydrolysis of 1-chlorobutane
• Water in the silver nitrate solution behaves as the nucleophile.
CH3CH2CH2CH2Cl(aq) + H20(l) CH3CH2CH2CH2OH(aq) + H+(aq) + Cl-(aq)
The aqueous silver nitrate reacts with any halide ion present, forming a precipitate
of the silver halide.
Ag+(aq) + Cl-(aq) AgCl(s)
Rate of hydrolysis for different haloalkanes
• The rate of hydrolysis can be found by measuring how long it takes
for the precipitate to form for each HALOALKANE.
Procedure:
• A test tube of each HALOALKANE is placed in the water bath at
60oC.
• A test tube containing a solution of aqueous silver nitrate, water
and ethanol is placed in the same water bath.
• Once all the tubes have reached the same temperature, equal
volumes of the silver nitrate/ethanol mixture are added to each
HALOALKANE. You can then measure the time taken to form the
precipitate for each HALOALKANE.
• Rate can be found by calculating 1/time for each HALOALKANE
Explanation
1. As the hydrolysis takes place, halide ions form:
R-X (aq) + OH- (aq) R-OH(aq) + X- (aq)
2. The AgNO3 (aq) reacts with any halide ions
present, forming a precipitate of the silver
halide.
X- (aq) + Ag+ (aq) AgX(s)
3. The time for the precipitate to appear is
recorded.
The faster the hydrolysis, the faster the relative
rate of precipitation.
Comparing the rate of hydrolysis of primary
haloalkanes
Independent variable:
Dependent variable:
Control variables:
Your prediction (+ explanation):
Results
Explaining the results
• Polarity ___________ as we descend
the group.
• On the basis of polarity alone we
would expect that __________
would undergo hydrolysis the
quickest, with a ___________ rate of
reaction as we go down the group.
Explaining the results
• But …. ___________ ____________
is more important in determining
rate of reaction, than bond polarity.
Explaining the results
Bond Bond enthalpy
/kJ mol-1
C-F +467
C-Cl +340
C-Br +280
C-I +240
Explaining the results
Bond Bond enthalpy
/kJ mol-1
C-F +467
C-Cl +340
C-Br +280
C-I +240
The rate of reaction _____________ from the fluoroalkanes to the
iodoalkanes as the carbon-halogen bond enthalpy ____________.
Describe and explain the order of the rate of
hydrolysis
Halogen bond enthalpies
Halogen bond energies (kJ/mol)
X X2 HX BX3 AlX3 CX4
F 159 574 645 582 456
Cl 243 428 444 427 327
Br 193 363 368 360 272
I 151 294 272 285 239
