Lecture 11 Hydrogenation and Its Thermodynamics

Hydrogenation
 Hydrogenation – to treat with hydrogen – is a

chemical reaction between molecular hydrogen (H 2 )
and another compound or element, usually in the
presence of
a catalyst such as nickel, palladium or platinum.
 The process is commonly employed to reduce or
saturate organic compounds.
 Hydrogenation typically constitutes the addition of pairs
of hydrogen atoms to a molecule, often an alkene.
 Catalysts are required for the reaction
 non-catalytic hydrogenation takes place only at very
high temperatures.
 Hydrogenation reduces double and triple
bonds in hydrocarbons
Hydrogenation
 Hydrogenation reaction is basically a reduction
reaction
 Various reduction reaction takes place. For example
reduction of alkenes, reduction of alkynes.
 In hydrogenation H2 is added as reducing agents in
one of three ways.
Reducing
Agents
• There are three types of reductions differing in how H 2
is added.
• The simplest reducing agent is H2. Reductions using H2
are
carried out with a metal catalyst.
• A second way is to add two protons and two electrons
to a substrate—that is, H2 = 2H+ + 2e-.
 Reductions of this sort use alkali metals as a
source of
electrons, and liquid ammonia as a source of protons.
 These are called dissolving metal reductions.
4
• The third way to add H2 is to add hydride (H¯) and a proton
(H+ ).
• The most common hydride reducing agents contain a
hydrogen atom bonded to boron or aluminum. Simple
examples include sodium borohydride (NaBH4) and lithium
aluminum hydride (LiAlH4).
• NaBH4 and LiAlH4 deliver H¯ to the substrate, and then a
proton is added from H 2 O or an alcohol.
5
Reduction of Alkenes—Catalytic
Hydrogenation
• Reduction takes place by addition of H2 as a reducing agent.

• The addition of H2 occurs only in the presence of a metal catalyst, and
thus it is called catalytic hydrogenation.
• The catalyst consists of a metal—usually Pd, Pt, or Ni, adsorbed onto a
finely divided inert solid, such as charcoal.
• H2 adds in
a syn fashion.
6
• The Ho of hydrogenation, also known as the heat of hydrogenation,
can be used as a measure of the relative stability of two different
alkenes that are hydrogenated to form the same alkane.
• When hydrogenation of two alkenes gives the same alkane, the more
stable alkene has the smaller heat of hydrogenation.
7
Mechanism of hydrogenation of alkenes
• The mechanism explains two facts about
hydrogenation:
9
Reduction of
Alkynes
• There are three different ways in which H2 can add to the triple
bond:
10
Reduction of an Alkyne to an
Alkane
Alkane formation:
1
Reduction of an Alkyne to a Cis
Alkene
• Palladium metal is too reactive to allow hydrogenation of an
alkyne to stop after one equivalent of H 2 adds.
• To stop at a cis alkene, a less active Pd catalyst is used—Pd
adsorbed onto CaCO3 with added lead(II) acetate and quinoline.
This is called Lindlar’s catalyst.
• Compared to Pd metal, the Lindlar catalyst is deactivated or
“poisoned”.
• With the Lindlar catalyst, one equivalent of H 2 adds to an alkyne
to form the cis product. The cis alkene product is unreactive to
further reduction.
1
• Reduction of an alkyne to a cis alkene is a stereoselective
reaction, because only one stereoisomer is formed.
1
Reduction of an Alkyne to a Trans
Alkene
• In a dissolving metal reduction (such as Na in NH3 ), the elements
of H 2 are added in an anti fashion to form a trans alkene.
14
1
Summary of Alkyne
Reductions
16
Thermodynamics and kinetics of
hydrogenation
Factors affect the hydrogenation reaction are;
• Temperature
• Pressure
• Catalyst surface
• Time
• Ratio of hydrogen to substance being
hydrogenated
Temperature effect
 For the most part, the temperature for hydrogenation
reactions is usually below 400°C, except in reactions
where pyrolytic decomposition occurs concurrently with
the hydrogenation reactions
 Temperature is one of the most important variables
affecting a reaction
 hydrogenation reaction can be reversed by increasing
temperature.
 So hydrogenation reaction necessary occurs at low
temperature, where the reaction is satisfactory
 Catalyst affect the speed and course of reaction, while
temperature affects the equilibrium, speed, path or
course of reaction.
Temperature effect
 increasing temperature adversely affects the equilibrium

position,
 so that the maximum ultimate yield is decreased;
 but it affects favorably the speed of a reaction, so that in
a given time a greater quantity of product can be
obtained.
 Fortunately in recent years knowledge of catalysis is
extended so satisfactory reactions are possible at
lower temperature. Where more satisfactory
equilibirium position is prevailed.
 In some cases increasing temperature has adverse effect
on catalyst,
 so the catalyst activity decreases and resultant rate of
reaction decreases.
 This type of case is known sintering of catalyst
Temperature effect
 In general, the noble-metal catalysts, such as platinum

or palladium, are used from room temperatures to
150°C
 catalysts of the nickel and copper type, from
150- 250°C
 various combinations of metals and metal oxides, from
250-400°C.
Pressure effect
 Pressure, like temperature, can affect the rate of

reaction.
 The rate of reaction is generally increased by
increasing pressure, because a gas phase is
usually present, and increased pressure gives
increased concentration.
 Pressure increases the equilibrium yield in a
hydrogenation reaction when there is a decrease in
the volume of the reaction as it proceeds.
 This is the simple application of the mass-action law,
or Le Chatelier's principle.
Pressure effect
 In general, however, increased pressure will result in

an increased reaction rate.
 Thus, Brochet observed that phenol is
hydrogenated very slowly at 150°C at atmospheric
pressure using a nickel catalyst but that at 15 atm
at the same temperature the reaction was complete
and rapid.
 Armstrong reported hydrogenation of acetone to
isopropyl alcohol with identical batches of a copper
chromite catalyst and observed the following as
shown in table.
Catalyst surface
 For the most part, hydrogenation catalysts are
solids consisting of metals and metal oxides
 . The hydrogenation is effected at the surface of
the catalyst; so a highly extended surface is
essential.
 Taking a piece of bar nickel or copper and
subdividing it mechanically to pass, say, a 50-mesh
sieve would not produce an active nickel or copper
catalyst.
 Usually, the preparation of a catalyst is associated with
some chemical reaction whereby a highly extended,
porous, and honeycombed surface is produced so that
the density of the surface metal is far less than that
of the bulk metal.
Catalyst surface
 Certain surface atoms may become so removed from other
adjoining ones that they may approach a gasified state, at
conditions far removed from the normal vaporization of
the metal.
 These surface atoms, having varying degrees of unsaturation
compared with the bulk metal or metal oxide, will
strongly adsorb other substances with which they may
come in contact, and active catalysts usually have high
absorptive powers.
 Although absorption is closely related to the
successful performance of a catalyst
 Thus speed of a hydrogenation will depend on the type
and amount of active surface available. Increasing the
ratio of catalyst to the substance undergoing
hydrogenation usually increases the speed of the
hydrogenation
Time
 The time necessary for a hydrogenation reaction may

vary from a few seconds to several hours, depending
on the materials being hydrogenated, the catalyst,
the temperature, and the pressure.
 In general, the more reactive the compound, the
faster the hydrogenation reaction.
 Thus, simple aldehydes are hydrogenated very readily,
whereas the reduction of aromatic rings to
saturated cyclic compounds is a or of esters to
alcohols is a slower reaction.
Ratio of Hydrogen to the Substances
Being Hydrogenated
 The ratio of hydrogen to the substance being

hydrogenated is conveniently expressed in terms
of partial pressures.
 It frequently happens that the speed or path of
a certain hydrogenation can be affected by the
proportion of hydrogen to the substance
 it has been found that ethyl lactate and malonate are
reduced to the corresponding alcohols in good yields
in a flow system at pressures of about 1,300 psig,
where practically the entire pressure is hydrogen and
the partial pressure of the esters is only a few
centimeters.
Ratio of Hydrogen to the Substances
Being Hydrogenated
In the examples previously cited, the higher total

pressure was lessened, and a higher ratio of hydrogen
pressure to the partial pressure of the substance being
hydrogenated was employed.
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you

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Hydrogenation

 Hydrogenation – to treat with hydrogen – is a

• Reduction takes place by addition of H2 as a reducing agent.

 increasing temperature adversely affects the equilibrium

 In general, the noble-metal catalysts, such as platinum

 Pressure, like temperature, can affect the rate of

 In general, however, increased pressure will result in

 The time necessary for a hydrogenation reaction may

 The ratio of hydrogen to the substance being

In the examples previously cited, the higher total

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