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Types of catalysts

What is a catalyst? Includes examples of enzymes, acid-base catalysis, and heterogeneous (or
surface) catalysis.
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Key points
 A catalyst is a substance that can be added to a reaction to increase the
reaction rate without getting consumed in the process.

 Catalysts typically speed up a reaction by reducing the activation energy or


changing the reaction mechanism.

 Enzymes are proteins that act as catalysts in biochemical reactions.

 Common types of catalysts include enzymes, acid-base catalysts,


and heterogeneous (or surface) catalysts.

Introduction: A kinetics thought experiment


Your brain is powered by the oxidation of glucose. The oxidation of
glucose can be represented as the following balanced chemical reaction:
\text C_6 \text H_{12} \text O_6(s)+6\text O_2(g) \rightarrow
6\text C \text O_2(g) + 6\text H_2 \text O(l) +
heat\quad\quad{\Delta\text G^\circ \,\text {at }25\,^\circ \text
C=-2885\,\dfrac{\text{kJ}}{\text{mol}}}C6H12O6(s)+6O2
(g)→6CO2(g)+6H2O(l)+heatΔG∘at 25∘C=−2885molkJC, start
subscript, 6, end subscript, H, start subscript, 12, end subscript, O, start
subscript, 6, end subscript, left parenthesis, s, right parenthesis, plus, 6, O,
start subscript, 2, end subscript, left parenthesis, g, right parenthesis, right
arrow, 6, C, O, start subscript, 2, end subscript, left parenthesis, g, right
parenthesis, plus, 6, H, start subscript, 2, end subscript, O, left parenthesis,
l, right parenthesis, plus, h, e, a, t, space, space, delta, G, degree, space, a,
t, space, 25, space, degree, C, equals, minus, 2885, space, start fraction, k,
J, divided by, m, o, l, end fraction

Without this reaction, learning chemistry would be much harder. Luckily,


the oxidation reaction is thermodynamically favored at 25\,^\circ \text
C25∘C25, space, degree, C since \Delta\text G^\circ<0ΔG∘<0delta, G,
degree, is less than, 0.

a slice of a dark grape, about 5 mm thin and seen against a window


Did you know that glucose was first isolated from raisins? Image from Wikimedia Commons, public
domain

Why don't we give it a try? Find some food that is nice and sugary, such as
a raisin. Add some oxygen gas (i.e. hold it out in the air). What happens?
Do you notice a release of heat energy? The formation of water and a nice
explosive poof of carbon dioxide gas?

Chances are, the raisin doesn't do much besides maybe dry out a little bit
more. Even though the oxidation of glucose is a thermodynamically
favorable reaction, it turns out that the reaction rate is really really really
slow.

The rate of a reaction depends on factors such as:

 Activation energy

 Temperature: if you heat up the raisin to a high enough temperature, it will


probably catch on fire and oxidize

These two factors are closely related: increasing the reaction temperature
of the reaction increases the kinetic energy of the reactant molecules. This
increases the likelihood that they will have enough energy to get over the
activation barrier.
How does your body solve this problem for the oxidation of glucose?
After all, your body temperature isn't much higher than 25\,^\circ \text
C25∘C25, space, degree, C, so how is this reaction happening continuously
in your body?

Biological systems use catalysts to increase the rate of the oxidation


reaction so that it can occur at a faster rate at lower temperatures. in this
article, we will talk more about what a catalyst is, and the different types
of catalysts.

What is a catalyst?
Catalysts are substances that can be added to a reaction to increase the
reaction rate without getting consumed in the process. They usually work
by

1. Lowering the energy of the transition state, thus lowering the activation
energy, and/or

2. Changing the mechanism of the reaction. This also changes the nature (and
energy) of the transition state.

Catalysts are everywhere! Many biochemical processes, such as the


oxidation of glucose, are heavily dependent on enzymes, proteins that
behave as catalysts.

Other common kinds of catalysts include acid-base


catalysts and heterogeneous (or surface) catalysts.

Example: Carbonic anhydrase


The enzyme carbonic anhydrase catalyzes the reversible reaction of carbon
dioxide (\text{CO}_2)(CO2)left parenthesis, C, O, start subscript, 2, end
subscript, right parenthesis and water (\text H_2 \text O)(H2O)left
parenthesis, H, start subscript, 2, end subscript, O, right parenthesis to
form carbonic acid. When the concentration of \text{CO}_2CO2C, O, start
subscript, 2, end subscript in the body is too high, carbonic anhydrase
catalyzes the following reaction:
\text{CO}_2 + \text H_2 \text O \rightarrow \text H_2
\text{CO}_3CO2+H2O→H2CO3C, O, start subscript, 2, end
subscript, plus, H, start subscript, 2, end subscript, O, right arrow, H, start
subscript, 2, end subscript, C, O, start subscript, 3, end subscript

By regulating the concentration of carbonic acid in the blood and tissues,


the enzyme is able to keep the \text{pH}pHp, H balanced in the body.

Ribbon diagram of human carbonic anhydrase II. The zinc ion is visible at
the protein's center as a dark grey sphere.
A ribbon diagram of human carbonic anhydrase II. Isn't chemistry beautiful? The grey sphere in the center
of the protein is a zinc ion. Image from Wikimedia Commons, public domain

Carbonic anhydrase is one of the fastest known enzymes, with reaction


rates between 10^410410, start superscript, 4, end
superscript and 10^610610, start superscript, 6, end superscript reactions
per second. This is even more amazing compared to the uncatalyzed
reaction, which has a rate of ~0.20.20, point, 2 reactions per second. That
is a ~10^5-10^7105−10710, start superscript, 5, end superscript, minus, 10,
start superscript, 7, end superscript increase in rate!!

The following diagram shows an energy diagram for the reaction between
carbon dioxide and water to form carbonic acid. The reaction with catalyst
is indicated with a blue line, and the uncatalyzed reaction is indicated with
a red line.
Diagram of a catalytic reaction (specifically, that catalysed by carbonic
anhydrase in the presence of high carbon dioxide concentrations) showing
difference in activation energy in uncatalysed and catalysed reaction. The
starting materials and products have the same energy for the reactions with
and without enzyme, so the overall change in energy for the system does
not change.
Diagram of energy for reaction between carbon dioxide and water to form carbonic acid. The addition of
catalyst (blue line) lowers the energy of the transition state, but does not change \Delta \text
H_{\text{rxn}}ΔHrxndelta, H, start subscript, r, x, n, end subscript compared to the uncatalyzed reaction
(red line). Image from Wikimedia Commons, CC BY-SA 3.0

The catalyst lowers the energy of the transition state for the reaction. Since
the activation energy is the difference between the transition state energy
and the reactant energy, lowering the transition state energy also lowers
the activation energy.
[How is the reaction rate related to the activation energy?]

kk\text E_aE, start subscript, a, end subscript

k=Ae^{-\text E_a/\text{RT}}k, equals, A, e, start superscript, minus, E,


start subscript, a, end subscript, slash, R, T, end superscript

AA\text RR\text TT

Notice that the energies of the reactants and products are the same for the
catalyzed and uncatalyzed reaction. Therefore, the overall energy released
during the reaction, \Delta \text H_{\text{rxn}}ΔHrxndelta, H, start
subscript, r, x, n, end subscript, does not change when you add the
enzyme. This emphasizes a very important point: the kinetics of a reaction,
i.e. reaction rate, is not directly related to the thermodynamics of the
reaction.

Acid-base catalysis
In acid catalysis, the catalyst is usually a \text{H}^+H+H, start superscript,
plus, end superscript ion. In base catalysis, the catalyst is usually
an \text{OH}^-OH−O, H, start superscript, minus, end superscript ion.

An example of a reaction that can be catalyzed by acid is the hydrolysis of


sucrose, also known as table sugar. Sucrose is a combination of two
simpler sugars (or monosaccharides), glucose and fructose. With the
addition of acid or an enzyme such as sucrase, sucrose can be broken
down into glucose and fructose as shown by the following series of
reactions:

Sucrose reversibly reacts with a hydrogen proton, H+, to form protonated


sucrose where the oxygen that connects the glucose and fructose molecules
gets protonated. The protonated sucrose reversibly reacts with water to
form one molecule of glucose, one molecule of fructose, and H+.
The acid-catalyzed reaction to form glucose and fructose from sucrose, which is also known as table sugar

In the first step, sucrose reversibly reacts with \text H^+H+H, start
superscript, plus, end superscript (in red), to form protonated sucrose. The
protonated sucrose reversibly reacts with water (in blue) to give \text
H^+H+H, start superscript, plus, end superscript, one molecule of glucose,
and one molecule of fructose. The overall reaction can be written as:
\text{Sucrose} + \text H_2 \text O \xrightarrow{\text{acid
catalyst}} \text{Glucose} + \text{Fructose}Sucrose+H2
Oacid catalystGlucose+Fructose
Since the \text H^+H+H, start superscript, plus, end superscript appears as
both a reactant and a product in equal amounts, it is not consumed during
the course of the reaction. Therefore, the catalyst does not appear on the
reactant or product side of the overall reaction.
Heterogeneous and surface catalysis
Heterogeneous catalysts are catalysts that are in a different phase than the
reactants. For example, the catalyst might be in the solid phase while the
reactants are in a liquid or gas phase.
[What do you call a catalyst in the same phase as the reactants?]

One example of a heterogeneous catalyst is the catalytic converter in


gasoline or diesel-fueled cars. Catalytic converters contain transition metal
catalysts embedded on a solid phase support. The solid-phase catalyst
comes into contact with gases from the car's exhaust stream, increasing the
rate of reactions to form less toxic products from pollutants in the exhaust
stream such as carbon monoxide and unburnt fuel.

Cross section of metal tube showing solid tan honey-comb like porous
material, the solid-state catalyst.
The solid phase catalyst inside a catalytic converter reduces emissions of toxic gases, unburned fuel, and
particulate matter. The solid support is designed to have a high surface area to increase the surface area
of catalyst available to react with the exhaust stream. Image from Oak Ridge National Laboratory on
flickr, CC BY-NC-ND 2.0

The catalytic converter is also an example of surface catalysis, where the


reactant molecules are adsorbed onto a solid surface before they react with
the catalyst to form the product. The rate of a surface-catalyzed reaction
increases with the surface area of catalyst in contact with the reactants.
Therefore, the solid support inside of a catalytic converter is designed to
have a very high surface area, hence the porous, honeycomb-like
appearance.

Another example of heterogeneous and surface catalysis is the process


used to make common plastics (or polymers) such as polyethylene. These
catalysts are called Ziegler-Natta catalysts, and they are used to make
everything from plastic wrap to yogurt cups. Transition metal catalysts are
embedded on a solid support before reacting them with the starting
materials (also called monomers) in the gas or solution phase.

X-ray showing a right hip (left of image) has been replaced, with the ball
of the ball-and-socket joint replaced by a metal head that is set in the femur
and the socket replaced by a white plastic cup (clear in this X-ray).
Polyethylene is also used for artificial joints! The metal ball-joint in this artificial hip fits into a
polyethylene socket, which appears clear in the X-ray.Image from Wikimedia Commons, public domain

Even though the reactants are in the gas phase, the product polymer is
usually a solid. I imagine this reaction being analogous to making
popcorn: the unpopped corn kernel is the catalyst on the solid support. The
gaseous monomers react to form layers of solid product polymer that build
up on the surface of the catalyst, which eventually becomes a polymer
"popcorn" bead. Chemistry-−minusit's like magic!

Summary
 A catalyst is a substance that can be added to a reaction to increase the
reaction rate without getting consumed in the process.
 Catalysts typically speed up a reaction by reducing the activation energy or
changing the reaction mechanism.

 Enzymes are proteins that act as catalysts in biochemical reactions.

 Common types of catalysts include enzymes, acid-base catalysts, and


heterogeneous (or surface) catalysts.

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