When I talked about 10 key concepts in carbonyl chemistry a few weeks ago, there was one subject that I

wanted to talk about in more depth but left out. That subject is acid catalysis, and any discussion of carbonyls
would be remiss without it. Lets get back to the subject by taking a really straightforward reaction that youve
probably done in your labs. Its called the Fischer esterification and it illustrates two of the key roles that acids
can play in assisting chemical reactions.
The Fischer esterification is the reaction between a carboxylic acid and an alcohol to give an ester. You
typically run the reaction by dissolving the carboxylic acid in the alcohol you want to make the ester with (e.g.
ethanol to make the ethyl ester). The reason you do this is that its an equilibrium reaction: your product is
water, so by using your alcohol as solvent, you effectively drown out the reverse reaction, which is hydrolysis of
the ester to give you back the acid. The final step of setting up the reaction is the addition of a strong acid (like
HCl or tosic acid) and commencing heating. After an hour or two at reflux, you strip off the solvent, and voila
you have your ester.

Heres observation #1. Without the acid catalyst, the reaction is painfully slow. You could let this heat for a
week and the reaction would barely go anywhere. How do we best explain this? Well, there are two reasons.
Lets look at the mechanism in detail:

Youll notice that the first step of the reaction is protonation of the carbonyl oxygen by the strong acid.
Mechanistically, it might be tempting to protonate the OH, because we know thats the group thats going to
leave. Actually, the carbonyl oxygen is protonated first because it is the most nucleophilic site. Now,
when the carbonyl is protonated, some of the electron density on oxygen that was available for donation to the
carbonyl carbon is taken up by the new O-H bond. The net effect of protonation is thus to weaken the carbon
oxygen bond. That leads us to this: Protonation of the carbonyl makes the carbonyl carbon a stronger
electrophile. [This is true for all carbonyls, by the way, not just carboxylic acids.] This means it will react more
quickly with whatever nucleophiles might be present in solution; in our case, the alcohol.
Note, though, that in our reaction, were using methanol, which is a pretty weak nucleophile. This is
important. For a reaction involving acid catalysis, its really important to use a nucleophile that will
protonate reversibly under the reaction conditions. For instance, if we tried using a Grignard or even an
amine in this reaction, the acid would (irreversibly) hit the juicy lone pairs of those nucleophiles instead of the
carbonyl oxygen and our nucleophile would be toast. Result: no reaction at the carbonyl. So if we want to take
advantage of acid catalysis, we have to keep this in mind.*
Lets look at the second factor which makes acid catalysis effective. In part 3 of the mechanism, after the
alcohol attacks, were left with 3 carbon-oxygen bonds. Now as you well know, Nature abhors the hydroxyl ion
OH as a leaving group under most circumstances. When an acid catalyst is present, however, that OH is
easily protonated to OH2 and our leaving group becomes water, which is a wonderful leaving group. So heres
the second principle: Acid greatly facilitates elimination of the leaving group. Lets put this in perspective:
the pKa of H2O is about 16. Thats the equilibrium between H2O and OH i.e., a good measure of OH as
a leaving group. Compare that to the pKa of H3O(+), which is -1.7. Essentially what Im saying is that water is a
better leaving group than OH by about 10 to the power of 17. [This is your cue to say Holy f*ck!]. Thats the
power of acid catalysis.

Without the addition of acid, the carboxylic acid and alcohol would just stare at each other in the reaction flask,
bump into one another by accident, and continue on with their lives unchanged. The acid catalyst is the special
ingredient that transforms a really lame party into something burned into your long-term memory. Inhibitions
suddenly disappear. Barriers are lowered. Suddenly, chemistry happens!

Sulfuric acid (alternative spelling sulphuric acid) is a highly corrosive strong mineral acid with the molecular
formulaH2SO4 and molecular weight 98.079 g/mol. It is a pungent-ethereal, colorless to slightly yellow viscous
liquid which is soluble in water at all concentrations.[6] Sometimes, it is dyed dark brown during production to
alert people to its hazards.[7] The historical name of this acid is oil of vitriol.[8]
Sulfuric acid is a diprotic acid and shows different properties depending upon its concentration. Its
corrosiveness on other materials, like metals, living tissues or even stones, can be mainly ascribed to its strong
acidic nature and, if concentrated, strong dehydrating and oxidizing properties. Sulfuric acid at a
high concentration can cause very serious damage upon contact, since not only does it cause chemical
burns via hydrolysis, but also secondary thermal burnsthrough dehydration.[9][10] It can lead to permanent
blindness if splashed onto eyes and irreversible damage if swallowed.[9] Accordingly, safety precautions should
be strictly observed when handling it. Moreover, it is hygroscopic, readily absorbing water vapour from the air.[6]
Sulfuric acid has a wide range of applications including domestic acidic drain cleaner,[11] electrolyte in lead-acid
batteries and various cleaning agents. It is also a central substance in the chemical industry. Principal uses
includemineral processing, fertilizer manufacturing, oil refining, wastewater processing, and chemical synthesis.
It is widely produced with different methods, such as contact process, wet sulfuric acid process and some other
methods.

Sulphuric Acid
A molecule of Sulphuric Acid, H2SO4, consists of two atoms of hydrogen, one atom
of sulphur and four atoms of oxygen
Sulphuric acid is a colourless viscous corrosive oily liquid, which has
Melting Point : 10.3 degC

 Boiling Point : 338 degC

Formula weight 98.08
Specific gravity or density 1.94
Flash point none
Sulphuric acid is the strong acid produced by dissolving sulphur trioxide in water.
SO3

H2O

==>

H2SO4

The Strength of Acids is determined by the degree to which they are ionised in
aqueous solution.
For example, Sulphuric Acid, H2SO4, which is a strong acid is fully dissociated, and
all the displaceable hydrogen in the acid is present in solution as Hydrogen Ion, H(+).
H2SO4

==>

H(+)
+
SO4
100% as H(+)

In contrast, the weak acids ethanoic acid, CH3COOH, is partially ionised in solution,
and only approximately 5% of the displaceable Hydrogen in the acid is present in
solution as hydrogen ion, H(+).
CH3COOH

==>

H(+)
+
5% as H(+)

CH3COO(-)

Properties of Sulphuric Acid

Sulphuric acid is a powerful protonating agent.
It is also a moderately strong oxidizing agent.
Sulphuric acid is also a powerful dehydrating agent and is used to remove a
molecule of water from many organic compounds.
In dilute solution, sulphuric acid is a strong dibasic acid forming two series of
salts.
A Dibasic Acid has two acidic hydrogen atoms in its molecules which can be ionised.
Sulphuric Acid, H2SO4, is a dibasic acid, because it contains two hydrogens atoms
which ionise in aqueous solution to become Hydrogen Ions, H(+).

H2SO4

==>

2 H(+)

SO4(2 -)

Sulphuric acid is an important industrial chemical and it has many uses as a strong
oxidising agent and a powerful dehydrating agent.
Commercially available sulphuric acid is as a 96-98% solution of the acid in water.
It is a powerful protonating agent.
It is also a powerful dehydrating agent and is used to remove a molecule of Water,
HO2, from many organic compounds.
The Dehydration Reactions of Alcohols results in their converted into an alkene, and
involves the elimination of a molecule of water. Dehydration requires the presence of
an acid and the application of heat.

Preparation of Sulphuric Acid

Combustion of Sulphur
When a small amount of Sulphur, S, is kindled on a deflagrating spoon, it burns with a
bright blue flame when introduced into a gas jar containing Oxygen, O2. A gas,
Sulphur Dioxide, SO2, is the main product of the combustion. However, a little
Sulphur Trioxide, SO3, is also formed, which makes the gas slightly cloudy.
S
2S

O2
+

==>

3O2

SO2
Sulphur Dioxide

==>

2SO3
Sulphur Trioxide

When shaken with water, the products of combustion dissolve, forming an acidic
solution which turns litmus red.
SO2
+
Sulphur
Dioxide

H2O

==>

SO2
+
Sulphur
Trioxide

H2O

==>

H2SO3
Sulphurous
Acid
H2SO4
Sulphuric
Acid

Manufacture of Sulphuric Acid

Sulphuric acid was manufactured by the lead-chamber process until the mid-1930s,
but this process has now been replaced by the contact process, involving the catalytic
oxidation of sulphur dioxide.

Properties of Sulphuric Acid

The Contact Process is used for manufacturing sulphuric acid and fuming sulphuric
acid from sulphur dioxide, which is made by burning sulphur or by roasting sulphide
ores and oxygen (in the form of air) which combine to form sulphur trioxide in the
presence of a catalyst. The reaction is exothermic and the conditions are controlled to
keep the temperature at 450 degC. The catalyst used is valadium oxide (V2O5). The
sulphur trioxide is dissolved in sulphuric acid to form fuming sulphuric acid, this is
called oleum.
S(s)

O2(g)

==>

SO2(g)
Sulphur
Dioxide

2SO2(g) +

O2(g)

==>

2SO3(g)
Sulphur
Trioxide

SO3(g) +

H2SO4(l)==>

H2S2O7(l)
Oleum

This Oleum, H2S2O7, is then diluted with Water, H2O, to produce concentrated
Sulphuric Acid, H2SO4.
H2S2O7(l)+
Oleum

H2O (l) ==>

2 H2SO4(l)
Sulphuric
Acid

Reactions of Sulphuric acid

Electrolysis of a Solution of dilute Sulphuric Acid
The Electrolysis of an Aqueous Solution of dilute Sulphuric Acid is often carried out
in a Hofmann Voltammeter, an apparatus in which the gases evolved at the anode and
cathode can be collected in separate graduated tubes. When the solution is
electrolyzed hydrogen is produced at the cathode and oxygen at the anode. These

gases can be shown to be present in a 2 to 1 ratio and result from the electrolysis of
water under acidic conditions.
Sulphuric acid is a strong electrolyte is fully dissociated in aqueous solution.
H2SO4

==>

2 H(+)

SO4(2 -)

Water is a weak electrolyte and is only slightly dissociated

H2O

==>

H(+)

OH(-)

During electrolysis, the Hydrogen Ions, H(+), migrates towards the cathode, and are
discharged there (i.e. they gain an electron and are converted to hydrogen gas).
2 H(+)

2 e(-)

==>

H2-

At the anode the concentration of Hydroxyl Ions, HO(-),is too low to maintain a
reaction and the Sulphate Ions, SO4(2 -) are not oxidized but remain on in solution at
the end. Water molecules must be the species reacting at the anode.

2 H2O

==>

O2

4 H(+)

4 e(-)

The overall reaction is

Cathode Reaction :
2 H(+)
4 H(+)

+
+

2e(-)
4e(-)

2 H2O

==>

O2

==>
==>

H2
2H2

Anode Reaction :
+

4 H(+)

4 e(-)

Overall Cell Reaction:

4 H(+)

2 H2O

==>

2 H2

O2

4 H(+)

For every Hydrogen Ions, H(+), discharged at the anode, another hydrogen ion is
formed at the cathode. The net result is that the concentration of the Sulphuric Acid,
H2SO4, remains constant and this electrolysis consists of the decomposition of water
with the overall reaction
2H2O

==>

2H2-

O2-

Ferrous Sulphate, Fe(II)SO4, is the salt formed when Iron, Fe, is dissolved in
Sulphuric Acid, H2SO4.
Hydrogen Chloride, HCl, may be prepared in the laboratory by heating Concentrated
Sulphuric Acid, H2SO4, with Sodium Chloride, NaCl.
NaCl

H2SO4

==>

NaHSO4

HCl

Many Metallic Chlorides liberate Chlorine, Cl2, when treated with Sulphuric Acid,
H2SO4, and Manganese Dioxide, MnO2).
Many Metallic Chlorides liberate Hydrogen Chloride gas, HCl, when warmed with
concentrated Sulphuric Acid, H2SO4.
Sulphur Trioxide, SO3, is prepared by heating concentrated Sulphuric Acid, H2SO4,
with a large excess of Phosphorus Pentoxide, P2O5.
H2SO4

P2O5

==>

SO3

2 HPO3

Sulphur Dioxide, SO2, is usually made in the laboratory by heating concentrated

Sulphuric Acid, H2SO4, with Copper turnings, Cu.
Cu

2 H2SO4

==>

CuSO4

SO2

2 H2O

Hydrogen Fluoride, HF, can be prepared in the laboratory by heating Concentrated

Sulphuric Acid, H2SO4, with Calcium Fluoride, CaF2.
H2SO4

CaF2

==>

2 HF

CaSO4

Hydrogen Iodide, HI, can be prepared by direct combination of the elements using a
platinum catalyst. In the laboratory it is prepared by heating Concentrated Sulphuric
Acid, H2SO4, with Sodium Iodide, NaI.
H2SO4

2 NaI

==>

2 HI

Na2SO4

Methanol, CH3OH, does not undergo dehydration reactions. Instead, in reaction with
Sulphuric Acid, H2SO4, the ester, Dimethyl Sulphate, (CH3)2SO4, is formed.

2CH3OH
Methanol

concentrated
H2SO4
==>
(CH3)2SO4
Dimethyl
Sulphate

H2O
Water

Sulphuric Acid, H2SO4, absorbs Ethylene, C2H4, at room temperature to form Ethyl
Hydrogen Sulphate, C2H5.HSO4, with much evolution of heat.

C2H4

H2SO4

==>

C2H5.HSO4

If this is treated with Water, H2O and warmed, Ethanol, C2H5OH, is formed.

C2H5.HSO4

H2O

==>

C2H5OH + H2SO4

heat

Uses of Sulphuric Acid

The Daniell Cell, which is a primary voltaic cell having a positive electrode of
Copper, Cu, and a negative electrode of Zinc Amalgam, Zn (in alloy with Hg), was
invented by the British chemist John Daniel in 1836AD.
The Zinc Amalgam electrode is placed in an electrolyte of dilute Sulphuric Acid
solution, H2SO4, or Zinc Sulphate solution, ZnSO4, in a porous earthenware pot. This
porous pot stands in a solution of Copper Sulphate, CuSO4, in which the Copper
electrode is immersed.

The Zinc electrode, Zn, acts as a source of electrons, which flow through an external
wire which connects the two electrodes, while the Zinc Ions, Zn(2 +), from the
electrode go into solution.
Cathode reaction : Zn

==>

Zn(++)

2 e(-)

On reaching the Copper Electrode, these electrons combine with Copper Ions, Cu(2
+), in solution and the discharged copper ions are deposited on the copper electrode as
Copper metal, Cu.
Anode reaction : Cu(++)

2 e(-)

==>

Cu

An equation for the overall chemical process is obtained by adding together the two
half-cell reactions in such a way that the electrons "cancel out".
Zn

Cu(++)

==>

Zn(++)

Cu

While the reaction takes place ions move through the porous pot, but when it is not in
use the cell should be dismantled to prevent the diffusion of one electrolyte into the
other.
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