Acid catalysis

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In acid-catalyzed Fischer esterification, the proton binds to oxygens and functions as a Lewis acid to activate the ester carbonyl (top row) as an electrophile, and converts the hydroxyl into the good leaving group water (bottom left). Both lower the kinetic barrier and speed up the attainment of chemical equilibrium.

In acid catalysis and base catalysis a chemical reaction is catalyzed by an acid or a base. The acid is the proton donor and the base is the proton acceptor. Typical reactions catalyzed by proton transfer are esterfications and aldol reactions. In these reactions the conjugate acid of the carbonyl group is a better electrophile than the neutral carbonyl group itself. Catalysis by either acid or base can occur in two different ways: specific catalysis and general catalysis.

Use in synthesis[edit]

Nature of the acid[edit]

Classical Bronsted acids[edit]

Acid catalysis is mainly used for organic chemical reactions. Many acids can function as sources for the protons. Acid used for acid catalysis include hydrofluoric acid (in the alkylation process), phosphoric acid, toluenesulfonic acid, polystyrene sulfonate, heteropoly acids, zeolites.

Solid acid catalysts[edit]

In industrial scale chemistry, many processes are catalysed by "solid acids." As heterogeneous catalysts, solid acids do not dissolve in the reaction medium. Well known examples include these oxides, which function as Lewis acids: silico-aluminates (zeolites, alumina, silico-alumino-phosphate), sulfated zirconia, and many transition metal oxides ( titania, zirconia, niobia, and more). Such acids are used in cracking. Many solid Bronsted acids are also employed industrially, including sulfonated polystyrene, solid phosphoric acid, niobic acid, and heteropolyoxometallates[1]

A particularly large scale application is alkylation, e.g., the combination of benzene and ethylene to give ethylbenzene. Another major application is the rearrangement of cyclohexanone oxime to caprolactam.[2] Many alkylamines are prepared by amination of alcohols, catalyzed by solid acids.

Zeolite, ZSM-5 is widely used as a solid acid catalyst.

Enzymatic catalysis[edit]

Many enzymes operate by acid-catalysis.

Applications[edit]

In one role, acids enhance the ability of leaving groups. For example, hydroxyl (OH-) is a poor leaving group, but water is a good one. Thus acids are used to convert alcohols into other classes of compounds, such as thiols and amines.

For the hydrolysis of esters, strong acids protonate the carbonyl oxygen, making the carbonyl carbon more electrophilic and susceptible to hydration. In this way, acids enable the hydrolysis of esters. Similarly they also catalyze the transesterification, where instead of water as the nucleophile, alcohol attacks the carbocation.

Mechanism[edit]

The kinds of acid catalysis are recognized, specific acid catalysis and general acid catalysis.[3]

Specific catalysis[edit]

In specific acid catalysis, protonated solvent is the catalyst. The reaction rate is proportional to the concentration of the protonated solvent molecules SH+.[4] The acid catalyst itself (AH) only contributes to the rate acceleration by shifting the chemical equilibrium between solvent S and AH in favor of the SH+ species. This kind of catalysis is common for strong acids in polar solvents, such as water.

S + AH → SH+ + A

For example, in an aqueous buffer solution the reaction rate for reactants R depends on the pH of the system but not on the concentrations of different acids.

This type of chemical kinetics is observed when reactant R1 is in a fast equilibrium with its conjugate acid R1H+ which proceeds to react slowly with R2 to the reaction product; for example, in the acid catalysed aldol reaction.

General catalysis[edit]

In general acid catalysis all species capable of donating protons contribute to reaction rate acceleration.[5] The strongest acids are most effective. Reactions in which proton transfer is rate-determining exhibit general acid catalysis, for example diazonium coupling reactions.

When keeping the pH at a constant level but changing the buffer concentration a change in rate signals a general acid catalysis. A constant rate is evidence for a specific acid catalyst. When reactions are conducted in nonpolar media, this kind of catalysis is important because the acid is often not ionized.

References[edit]

  1. ^ Busca, Guido "Acid Catalysts in Industrial Hydrocarbon Chemistry" Chemical Reviews 2007, volume 107, 5366-5410. doi:10.1021/cr068042e
  2. ^ Michael Röper, Eugen Gehrer, Thomas Narbeshuber, Wolfgang Siegel "Acylation and Alkylation" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2000. doi:10.1002/14356007.a01_185
  3. ^ Lowry, T. H.; Richardson, K. S., "Mechanism and Theory in Organic Chemistry," Harper and Row: 1981. ISBN 0-06-044083-X
  4. ^ "IUPAC Compendium of Chemical Terminology, 2nd Edition (1997)". www.iupac.org. Retrieved 2009-11-22. 
  5. ^ "IUPAC Compendium of Chemical Terminology, 2nd Edition (1997)". www.iupac.org. Retrieved 2009-11-22.