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Derived from Catalysis by OpenStax

Page by: OpenStax Chemistry: Atom First

Summary

A catalyst speeds up the rate of a reaction by lowering the activation energy; in addition, the catalyst is regenerated in the process. Several reactions that are energetically favorable in the absence of a catalyst only occur at a reasonable rate when a catalyst is present. One example is hydrogenation, a process used in food industries to convert unsaturated fats to saturated fats. A comparison of the reaction coordinate diagrams (also known as energy diagrams) for catalyzed and uncatalyzed hydrogenation of a simple hydrocarbon molecule is shown in Figure.

A graph is shown with the label, “Reaction coordinate,” on the x-axis and the label,“Energy,” on the y-axis. Approximately half-way up the y-axis, a short portion of a black concave down curve which has a horizontal line extended from it across the graph. The left end of this line is labeled “H subscript 2 C equals C H subscript 2 plus H subscript 2.” The black concave down curve extends upward to reach a maximum near the height of the y-axis. The peak of this curve is labeled, “Transition state.” A double sided arrow extends from the horizontal line to the peak of the curve. This arrow is labeled, “Activation energy of Uncatalyzed reation.” From the peak, the curve continues downward to a second horizontally flattened region well below the origin of the curve near the x-axis. This flattened region is shaded in blue and is labeled “H subscript 3 C dash C H subscript 3.” A double sided arrow is drawn from the lowers part of this curve at the far right of the graph to the line extending across the graph above it. This arrow is labeled, “capital delta H less than 0 : exothermic.” A second curve is drawn with the same flattened regions at the start and end of the curve. The height of this curve is about two-thirds the height of the first curve. A double sided arrow is drawn from the horizontal line that originates at the left side of the graph to the peak of this second curve. This arrow is labeled, “Activation energy of catalyzed reaction.”
This graph compares the reaction coordinates for catalyzed and uncatalyzed alkene hydrogenation.

Catalysts Do Not Affect Equilibrium

A catalyst can speed up the rate of a reaction. Though this increase in reaction rate may cause a system to reach equilibrium more quickly (by speeding up the forward and reverse reactions), a catalyst has no effect on the value of an equilibrium constant nor on equilibrium concentrations.

The interplay of changes in concentration or pressure, temperature, and the lack of an influence of a catalyst on a chemical equilibrium is illustrated in the industrial synthesis of ammonia from nitrogen and hydrogen according to the equation:

 

<span id="MathJax-Element-111-Frame" class="MathJax" style="font-style: normal;font-weight: normal;line-height: normal;font-size: 14px;text-indent: 0px;text-align: center;letter-spacing: normal;float: none;direction: ltr;max-width: none;max-height: none;min-width: 0px;min-height: 0px;border: 0px;padding: 0px;margin: 0px" role="presentation" data-mathml="N2(g)+3H2(g)⇌2NH3(g)N2(g)+3H2(g)⇌2NH3(g)“>N2(g) + 3H2(g) ⇌ 2NH3(g) 
<span id="MathJax-Element-111-Frame" class="MathJax" style="font-style: normal;font-weight: normal;line-height: normal;font-size: 14px;text-indent: 0px;text-align: center;letter-spacing: normal;float: none;direction: ltr;max-width: none;max-height: none;min-width: 0px;min-height: 0px;border: 0px;padding: 0px;margin: 0px" role="presentation" data-mathml="N2(g)+3H2(g)⇌2NH3(g)N2(g)+3H2(g)⇌2NH3(g)“>A large quantity of ammonia is manufactured by this reaction. Each year, ammonia is among the top 10 chemicals, by mass, manufactured in the world. About 2 billion pounds are manufactured in the United States each year. Ammonia plays a vital role in our global economy. It is used in the production of fertilizers and is, itself, an important fertilizer for the growth of corn, cotton and other crops. Large quantities of ammonia are converted to nitric acid, which plays an important role in the production of fertilizers, explosives, plastics, dyes, and fibers, and is also used in the steel industry.

Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps, as depicted in the reaction diagrams shown in Figure 2. This lower activation energy results in an increase in rate as described by the Arrhenius equation. Note that a catalyst decreases the activation energy for both the forward and the reverse reactions and hence accelerates both the forward and the reverse reactions. Consequently, the presence of a catalyst will permit a system to reach equilibrium more quickly, but it has no effect on the position of the equilibrium as reflected in the value of its equilibrium constant (see the chapter on chemical equilibrium).

A graph is shown with the label, “Extent of reaction,” appearing in a right pointing arrow below the x-axis and the label, “Energy,” in an upward pointing arrow just left of the y-axis. Approximately one-fifth of the way up the y-axis, a very short, somewhat flattened portion of both a red and a blue curve are shown. This region is labeled “Reactants.” A red concave down curve extends upward to reach a maximum near the height of the y-axis. This curve is labeled, “Uncatalyzed pathway.” From the peak, the curve continues downward to a second horizontally flattened region at a height of about one-third the height of the y-axis. This flattened region is labeled, “Products.” A second curve is drawn in blue with the same flattened regions at the start and end of the curve. The height of this curve is about two-thirds the height of the first curve and just right of its maximum, the curve dips low, then rises back and continues a downward trend at a lower height, but similar to that of the red curve. This blue curve is labeled, “Catalyzed pathway.”
This potential energy diagram shows the effect of a catalyst on the activation energy. The catalyst provides a different reaction path with a lower activation energy. As shown, the catalyzed pathway involves a two-step mechanism (note the presence of two transition states) and an intermediate species (represented by the valley between the two transitions states).
Using Reaction Diagrams to Compare Catalyzed ReactionsThe two reaction diagrams here represent the same reaction: one without a catalyst and one with a catalyst. Identify which diagram suggests the presence of a catalyst, and determine the activation energy for the catalyzed reaction: 

In this figure, two graphs are shown. The x-axes are labeled, “Extent of reaction,” and the y-axes are labeled, “Energy ( k J ).” The y-axes are marked off from 0 to 50 in intervals of five. In a, a blue curve is shown. It begins with a horizontal segment at about 6. The curve then rises sharply near the middle to reach a maximum of about 32 and similarly falls to another horizontal segment at about 10. In b, the curve begins and ends similarly, but the maximum reached near the center of the graph is only 20.

Solution:

A catalyst does not affect the energy of reactant or product, so those aspects of the diagrams can be ignored; they are, as we would expect, identical in that respect. There is, however, a noticeable difference in the transition state, which is distinctly lower in diagram (b) than it is in (a). This indicates the use of a catalyst in diagram (b). The activation energy is the difference between the energy of the starting reagents and the transition state—a maximum on the reaction coordinate diagram. The reagents are at 6 kJ and the transition state is at 20 kJ, so the activation energy can be calculated as follows, Ea=20kJ−6kJ=14kJ.

Check Your Learning

Determine which of the two diagrams here (both for the same reaction) involves a catalyst, and identify the activation energy for the catalyzed reaction:

In this figure, two graphs are shown. The x-axes are labeled, “Extent of reaction,” and the y-axes are labeledc “Energy (k J).” The y-axes are marked off from 0 to 100 at intervals of 10. In a, a blue curve is shown. It begins with a horizontal segment at about 10. The curve then rises sharply near the middle to reach a maximum of about 91, then sharply falls to about 52, again rises sharply to about 73 and falls to another horizontal segment at about 5. In b, the curve begins and ends similarly, but the first peak reaches about 81, drops to about 55, then rises to about 77 before falling to the horizontal region at about 5.

ANSWER:

Diagram (b) is a catalyzed reaction with an activation energy of about 70 kJ.

Key Concepts and Summary

Catalysts affect the rate of a chemical reaction by altering its mechanism to provide a lower activation energy, but they do not affect equilibrium.

Chemistry End of Chapter Exercises

  1. Water gas is a 1:1 mixture of carbon monoxide and hydrogen gas and is called water gas because it is formed from steam and hot carbon in the following reaction: <span id="MathJax-Element-134-Frame" class="MathJax" style="font-style: normal;font-weight: normal;line-height: normal;font-size: 14px;text-indent: 0px;text-align: left;letter-spacing: normal;float: none;direction: ltr;max-width: none;max-height: none;min-width: 0px;min-height: 0px;border: 0px;padding: 0px;margin: 0px" role="presentation" data-mathml="H2O(g)+C(s)⇌H2(g)+CO(g).H2O(g)+C(s)⇌H2(g)+CO(g).“>H2O(g)+C(s)⇌H2(g)+CO(g).H2O(g)+C(s)⇌H2(g)+CO(g). Methanol, a liquid fuel that could possibly replace gasoline, can be prepared from water gas and hydrogen at high temperature and pressure in the presence of a suitable catalyst. What will happen to the concentrations of H2, CO, and CH3OH at equilibrium if more catalyst is added?

2. Nitrogen and oxygen react at high temperatures. What will happen to the concentrations of N2, O2 and NO at equilibrium if a catalyst is added?

3. For each of the following pairs of reaction diagrams, identify which of the pair is catalyzed:

(a)

In this figure, two graphs are shown. The x-axes are labeled, “Extent of reaction,” and the y-axes are labeled, “Energy (k J).” The y-axis of the first graph is marked off from 0 to 30 in intervals of 5. The y-axis of the second graph is marked off from 0 to 25 by intervals of 5. In a, a blue curve is shown. It begins with a horizontal region at about 12. The curve then rises sharply near the middle to reach a maximum of about 24 and similarly falls to another horizontal segment at 5. In b, the curve begins and ends similarly, but the maximum reached near the center of the graph is only 20.

(b)

In this figure, two graphs are shown. The x-axes are labeled, “Extent of reaction,” and the y-axes are labeled, “Energy.” The y-axes are marked off from 0 to 50 in intervals of 5. In a, a blue curve is shown. It begins with a horizontal region at about 2. The curve then rises sharply near the middle to reach a maximum of about 43 and similarly falls to another horizontal segment at 15. In b, the curve begins and ends similarly, but the maximum reached near the center of the graph is only about 32.

(c)

In this figure, two graphs are shown. The x-axes are labeled, “Extent of reaction” and the y-axes are labeled, “Energy (k J).” The y-axes are marked off from 0 to 50 at intervals of 5. In a, a blue curve is shown. It begins with a horizontal segment at about 2J. The curve then rises sharply near the middle to reach a maximum of about 46, then sharply falls to about 35, again rises to about 38 and falls to another horizontal segment at about 15. In b, the curve begins and ends similarly, but the first peak reaches about 46, drops to about 35, then rises to about 43 before falling to the horizontal region at about 15.

(d)

In this figure, two graphs are shown. The x-axes are labeled, “Extent of reaction,” and the y-axes are labeled, “Energy (k J).” The y-axes are marked off from 0 to 50 at intervals of 5. In a, a blue curve is shown. It begins with a horizontal segment at about 34. The curve then rises sharply near the middle to reach a maximum of about 45, then sharply falls to about 25, again rises sharply to about 35 and falls to another horizontal segment at about 15. In b, the curve begins and ends similarly, but the first peak reaches about 40, drops to 25, then rises to 35 before falling to the horizontal region at about 15.

Footnotes

  • 1 Herrlich, P. “The Responsibility of the Scientist: What Can History Teach Us About How Scientists Should Handle Research That Has the Potential to Create Harm?” EMBO Reports 14 (2013): 759–764.
  • 2 “The Nobel Prize in Chemistry 1995,” Nobel Prize.org, accessed February 18, 2015, http://www.nobelprize.org/nobel_prizes/chemistry/laureates/1995/.

Glossary

catalyst
something that speeds up the rate of a reaction by lowering the activation energy
activation energy
the energy required to change reactants into products

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