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SULFURIC ACID

Concentrated sulfuric acid two very different


Dilute sulfuric acid reagents.
CONCENTRATED SULFURIC ACID
NO WATER PRESENT

O 18 M

H O S O H
O expanded octet
representation

There is no species other than H2SO4 present.


6M AQUEOUS SULFURIC ACID
~0M 55.6 M 12 M 6M
H2SO 4 + 2 H2O 2 H3O+ + SO4-2
excess
strong acid ionizes almost completely

Three predominant species are present :

H O
+ - -
H O H O O S O
H H O
water hydronium ion sulfate ion
ADDITION OF
SULFURIC ACID AND WATER
ADDITION OF WATER AND SULFURIC ACID TO ALKENES
THREE DIFFERENT REACTIONS
cold,
1) Alkyl hydrogen sulfates concentrated,
large amount
18M
(stoichiometric)
conc. OSO3H
0o C
C C + H2SO4
C C
H
2) Hydration to alcohol
2-6M
H2 SO4
OH
C C + H2O C C
H
NOTE DIFFERENT
CONDITIONS FOR dilute, aqueous
EACH REACTION
HERE AND ON THE
6M
NEXT SLIDE continued
warm,
concentrated, 18 M
smaller amount, small amt.
(not stoichiometric)
3) Polymerization
conc
H2SO4 H
C C
C C
C C
C C
excess n
OSO3H
polymer
monomer A
Alkene molecules add
together to make long
Sections 8.9 and 8.14
( discussed later … )
chains or polymers
A-A-A-A-A-A-A-A-A

REACTION CONDITIONS
ARE IMPORTANT !
CONCENTRATED SULFURIC

Formation of Alkyl Hydrogen Sulfates


ALKYL HYDROGEN SULFATES
bisulfate ion
Concentrated H2SO4 O ( or hydrogen sulfate)
-O S O H
O OSO3H
cold
C C C C C C
+
O H carbocation H
H O S O H
an alkyl hydrogen sulfate
O
discussed later

FOLLOWS THE OH add water


MARKOVNIKOFF room temp
RULE
C C alcohol
SAME MECHANISM
AS HCl ADDITION
H HYDROLYSIS
DILUTE SULFURIC ACID

Formation of Alcohols
sulfate is a
MECHANISM poor nucleophile
dilute higher conc.
H2SO4 ADDITION OF WATER than SO42-
(HYDRATION)

alkene H
H + O H
O H
O H
H2SO4 H
C C C C C C
H2O oxocation
+
H H (oxonium ion)
+
H O H
used the catalyst is
H not used up H
FOLLOWS THE O +
MARKOVNIKOFF C C + H O H
RULE
H H
SAME MECHANISM regenerated
AS HCl ADDITION alcohol
MARKOVNIKOFF ADDITION
( HYDRATION REACTIONS, H2SO4 + H2O )

CH3 CH3
H2SO4
+ H2O OH

CH2 CH3
H2SO4 OH
+ H2O

H2SO4
CH CH2 CH CH3
+ H2O OH
DIFFERENT WAYS OF WRITING REACTIONS
Reactants specifically shown with a “+” sign,
catalyst written over arrow.

H2SO4
+ H2O OH

Reactant(s) and catalyst both written over the arrow.

H2SO4
H2O OH

Solvent written over the arrow.

H2O
Chemists
+ HCl Cl use all of
these!
STEREOCHEMISTRY

HX and H2O

These additions are usually not stereospecific.

Some compounds*, under some conditions*,


may give stereoselective results.
* Stereoselective examples will not be discussed in
any detail here, you may assume these reactions
are not stereospecific most of the time.
STEREOCHEMISTRY OF HX AND H2O ADDITIONS
from H3O+ H2SO4 a
sp2
H+ catalyst
Ph +
C CH2
HX or H2O
C CH3 X
-
CH2CH3 CH3CH2
b
The carbocation is planar.
a b
In the second step, X or H2O 50/50
can add equally 50/50 to
either side (top or bottom). X Ph
CH3CH2 CH3
Ph C C
CH +
CH3CH2 3
X
AQUEOUS The resulting halides or alcohols are
SOLUTIONS ENANTIOMERS (racemic mixture)
ADDITION OCCURS TO BOTH SIDES OF AN OPEN CARBOCATION

H+ could add H
to either side O H
left or right

+
CH3 H2O CH3 CH3
H2SO4
H
H3C add to left
H
H+ side bottom O H

CH3 OH
CH3 CH3
+ + enantiomer

+ enantiomer OH CH3
H H
syn addition DIASTEREOMERS anti addition
EFFECT OF POLARITY OF THE SOLVENT

100%
CAUTION anti
CH3 HBr (g) CH3 Br
The addition to + addition
pentane to top
both sides of
the C+ ion is H CH3 H CH3 side only
common in H2O conc. HBr
solutions, but The typical result in
(in H2O)
if you change a non-polar solvent.
to a non-polar
solvent, this
may not happen.
CH3 Br + CH3 CH3
anti + syn
This will be addition to
explained later H CH3 H Br
both sides
50/50
A “bridged” rather The typical result in a
than an “open” cation
polar solvent like H2O.
is involved.
ADDITION POLYMERS
ADDITION POLYMERS
A + A + A + A A A A A
monomers polymer

+ + +

ethylene (ethene) polyethylene linear

+ + +

propylene (propene) polypropylene branched

many (n) nA (A)n polymer


monomers
SOME NOMENCLATURE

A Monomer (The alkene that is polymerized)

A-A A Dimer (Two units)


A-A-A A Trimer (Three units)

A-A-A-A A Tetramer (Four units)

A-(A)n-A A Polymer (Many units)

Depending on the reaction conditions and stoichiometry


the chains formed can have lengths that vary from two
units (dimer) to thousands of units (polymer).
PREPARATION OF ADDITION POLYMERS
CATIONIC MECHANISM
POLYMERIZATION
( lots of alkene, smaller amount of H2SO4 )

concentrated,
smaller amount,
not cold
Polymerization
conc
H2SO4 H
C C
C C
C C
C C
excess n
OSO3H
repeating
unit polymer

A cationic polymerization catalyst (Ziegler Catalyst)


can be used instead of H2SO4.
CATIONIC MECHANISM
styrene
+ small H
H amount

+
resonance
stabilized
(Markovnikoff)
H2SO4 (+) (+)

(+)
H H

+ + etc.
Polystyrene

another alkene adds there is no other nucleophile


to the carbocation in this solution
H HOW DOES THE CHAIN END?
+

The simplest way


is to have a nucleophile
add to the carbocation
site
etc. etc. ..
O
- :O
.. S OH
H H O

+ Another way is to
lose a hydrogen
and form a double
bond (ghosted).
This method will be
discussed in the
next chapter.
POLYSTYRENE
starting
proton
addition of OSO3H-
completes the end
H
of the chain
OSO3H

CH2 CH
repeating
unit
=

The repeating units of some other


polymers are shown on the next
two slides.
SOME COMMON ADDITION POLYMERS
example monomer polymer uses
most common polymer
polyethylene CH2 CH2 CH2 CH2
bags, wire insulation,
squeeze bottles
polypropylene CH2 CH CH2 CH
fibers, bottles,
CH3 CH3 indoor-outdoor carpet

polystyrene CH2 CH CH2 CH


styrofoam,
inexpensive molded
objects: household items,
toys

polyvinyl chloride CH2 CH CH2 CH synthetic leather, clear


(PVC) Cl bottles, floor coverings,
Cl
water pipe
Teflon CF 2 CF 2 CF2 CF2 non-stick surfaces,
chemically resistant items
polyacrylonitrile CH2 CH CH2 CH fiber used in sweaters,
(Orlon, Acrilan) C N C N blankets, carpets
COMMON ADDITION POLYMERS (cont)
example monomer polymer uses
CH3 CH3
poly(methyl unbreakable glass,
methacrylate) CH2 C CH2 C latex paint
(Lucite, Plexiglass) CO2CH3 CO2CH3

poly(vinyl acetate) CH2 CH CH2 CH adhesives,


latex paints,
(PVA) O C CH3 O C CH3 textile coatings
O O chewing gum

natural rubber CH3 the polymer is cross-


CH2 C CH CH2 CH3 linked with sulfur
(vulcanization)
CH2 C CH CH2

neoprene rubber Cl cross-linked with ZnO,


CH2 C CH CH2 Cl resistant to gasoline
and oil
CH2 C CH CH2
SUMMARY
REACTION WITH SULFURIC ACID DEPENDS ON CONDITIONS

1. Cold Concentrated Stoichiometric Sulfuric acid (18M)


Only H2SO4 is present, therefore HOSO3-
Formed
from
is the most abundant nucleophile. H2SO4
O
-O
HOSO3- adds to S O H
the carbocation O
C C
+
H
2. Hydration - Dilute Aqueous Sulfuric Acid (3-6M)
Water is the most abundant nucleophile (55.6 M)
H
H2O adds to O H
the carbocation
C C
+
H
3. Polymerization - Small Amount of Concentrated H2SO4
The alkene itself is the most abundant nucleophile.

Another alkene molecule adds to the carbocation

C C
There is only a small
amount of HOSO - 3
and a large amount
C C of alkene.
+
H

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