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Equilibrium Le Chteliers Principle LE 07/15

Brick 702: NAME: __________________________________

Le Chteliers Principle
Manipulation of Systems Change Position of Equilibrium
IB Syllabus Point: 07.1 Textbook Pages:

NOTE: This is Part 2 of the summer assignment. Annotate it and answer all questions.

Demonstrations:

Laboratory Opportunities:

The effect of changing experimental conditions on the equilibrium constant

When equilibrium is established, the position of the equilibrium remains constant provided that the
temperature and pressure do not change. A change in experimental conditions can affect the equilibrium
position. However, the value of Kc remains constant unless the temperature changes.

Change in condition Equilibrium position Kc

Changes in response to a change in

Concentration of product or reactant No change
[reactants] or [products]

In a reaction with gaseous reactants or

Pressure products, pressure can affect the No change
equilibrium position

Usually changes: the direction of change

Changes, unless
Temperature depends on whether the reaction is
H = 0
exothermic or endothermic

Catalyst No change No change

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Le Chteliers principle

Le Chteliers principle is a useful tool for predicting the effect that changing conditions will have on the
equilibrium position:

If a change is made to a system that is in equilibrium, the balance between the forward and reverse
reactions will shift to offset this change and return the system to equilibrium.

At a given temperature, the table above shows that changing the concentration of reactants or products
does not result in a change in the value of equilibrium constant, Kc. The equilibrium position of the reaction
will change in response to the change in concentration so as to return Kc to its original value. For example,
consider the chromate-dichromate equilibrium:

(The Cr2O72 ion appears orange while the CrO42 ion is yellow.)

If the concentration of a reactant is increased, Le Chteliers principle tells us that the forward reaction will
be favored to counteract this change. Decreasing the concentration of a product will also favor the forward
reaction. The addition of hydroxide ions, OH, to the reaction mixture results in a reduction of H+
concentration as OH ions react with H+ to form water. The equilibrium mixture becomes a paler color as
more orange dichromate reacts to form yellow chromate.

The reverse reaction is favored if the concentration of a product is increased or the concentration of a
reactant is decreased. The addition of H+ ions in the form of concentrated hydrochloric acid, HCl, results in
the reverse reaction being favored and a deeper orange color being observed. In both cases, the value of the
equilibrium constant, Kc, remains unchanged as long as the temperature remains the same.

Le Chteliers principle allows industrial chemists to manipulate reaction conditions to maximize the
amount of the desired product formed in an equilibrium reaction. The Haber process for the manufacture
of ammonia uses the following reaction:

The yield is increased by using high concentrations of reactant gases nitrogen and hydrogen, and removing
the product ammonia from the equilibrium mixture.

Cause and effect

Cause and effect or causation refers to the situation where a second event (the effect) is a direct
consequence of the first event (the cause). Scientists understand this concept and often develop a
hypothesis that suggests a relationship or causation between factors that may be true or false. They then
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test the hypothesis by experimentation and collection of empirical data, which is used to either support,
modify, or disprove the hypothesis.

Le Chteliers principle is a useful tool in helping to predict the qualitative effects of changes in
temperature, pressure, and concentration on the position of an equilibrium reaction and the value of the
equilibrium constant. However, the principle does not provide an explanation for the effects of these
changes on the equilibrium reaction: it does not demonstrate a cause-and-effect relationship between
changing these conditions and the resultant change in the equilibrium system.

The Haber process

Over the past century, advances in the science of agriculture have resulted in over one-third of the Earths
land being cultivated with crops and the population of the planet increasing to over 7 billion people.
Agriculture is a major employment sector in developing countries, and food security remains of great
concern to many, including international bodies such as the World Trade Organization (WTO), the Food and
Agriculture Organization (FAO), and the World Health Organization (WHO).

Global demand for food increases exponentially every decade, and we will not be able to meet demands for
food and water without scientific endeavors in the fields of biotechnology and fertilizers. More than 50% of
current food production relies on the use of fertilizers.

Fritz Haber (1868-1934) was a German chemist who was awarded the Nobel Prize in Chemistry in 1918 for
his work on the synthesis of ammonia, NH3, from its elements. A shortage of natural fertilizers at the
beginning of the 20th century prompted Haber to research a process that could manufacture ammonia on a
large scale. Ammonia manufacture is now one of the most widespread industrial processes in the world.
As well as its major application in fertilizers, ammonia is also used in the manufacture of plastics, fibers,
explosives, and pharmaceuticals.

With the onset of the first world war, Haber worked with the German military to advance the production of
explosives. Ammonia reacts with nitric acid to form ammonium nitrate, which is used to this day as a
fertilizer.

Ammonium nitrate will also undergo explosive decomposition when detonated:

Haber is sometimes referred to as the father of chemical warfare, advancing the research into and
utilization of many poisonous gases during the first world war. He was not alone in making significant
advances in science with military applications during this time. Gustav Hertz and James Franck were
physicists who devised investigations to support Niels Bohrs model of the atom and lay the groundwork for
quantum mechanics. They were awarded the Nobel Prize in Physics in 1925, while Otto Hahn received the
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Nobel Prize in Physics in 1944 for his discovery of the fission of heavy atomic nuclei. Later in life, he
continued to receive an impressive range of awards for his scientific achievements and was nominated on
several occasions for the Nobel Peace Prize. He is regarded as the founder of the atomic age.

Hertz, Franck, and Hahn were all members of Habers research team who worked on developing chemical
weapons. Their stories serve to illustrate the Nature of Science (NOS). Their research significantly
advanced scientific understanding while raising questions about the ethical considerations of the results of
some of their work, the concept of intellectual property, and how society goes on to utilize scientific
discoveries.

The effect of pressure on reactions in the gas phase

We have seen how Le Chteliers principle can be used to predict the effect of a change in concentration of a
product or reactant on the position of equilibrium. A system that involves substances in the gaseous rather
than the aqueous phase will be affected by changes in applied pressure:

In this reaction, there are 5 moles of gas on the reactant side and 4 moles on the product side. A change in
pressure applied to the system will result in a shift in the equilibrium position. If the pressure is increased,
Le Chteliers principle says that the equilibrium will shift to reverse this change. The forward reaction
becomes favored to reduce the pressure of the system. In the same way, a decrease in pressure will result in
the reverse reaction being favored.

In the Haber process:

There are four moles of gas on the reactant side and only 2 moles of gas on the product side. A high
pressure will favor the forward reaction, to decrease the pressure of the system.

Such a change in the equilibrium position will not affect the value of the equilbrium constant, Kc, if the
temperature remains constant.

Temperature and the equilibrium constant

An understanding of the thermodynamics of a reaction is required when considering the effect of changing
the temperature on the equilibrium constant. For example:
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In this reaction, energy can be considered a product and is released to the surroundings. The forward
reaction is exothermic. Therefore, the reverse reaction is endothermic it requires energy from the
surroundings.

At equilibrium, the forward and reverse reactions occur at equal rates, and there is no net change in energy.

For the exothermic reaction, an increase in temperature will shift the equilibrium in the direction that will
consume the extra energy. In accordance with Le Chteliers principle, the equilibrium position will move
to the left, favoring the reactants, to minimize the effect of the change. The concentrations of nitrogen and
hydrogen will increase. This results in a decrease in the equilibrium constant, Kc. Conversely, a decrease in
temperature for the exothermic reaction will shift the equilibrium to the right, favoring the forward
reaction and increasing the concentration of ammonia, NH3. This results in an increase in Kc. The following
table summarizes the effects on the equilibrium system of changing temperature:

Type of reaction Change in temperature Equilibrium position Equilibrium constant, Kc

Moves to the left,

Increase Decreases
favoring reactants
Exothermic
Moves to the right,
Decrease Increases
favoring products

Moves to the right,

Increase Increases
favoring products
Endothermic
Moves to the left,
Decrease Decreases
favoring reactants

The effect of a catalyst on equilibrium reactions

The addition of a catalyst provides an alternative pathway for a reaction, lowering the activation energy. In
a reaction that goes to completion, a catalyst means that a greater proportion of reactants have sufficient
energy to overcome the activation energy barrier and become products. In a reversible reaction, the
lowered activation energy has an equal effect on both the forward and reverse reactions. The rates of the
forward and reverse reactions increase by an equal amount. The position of the equilibrium will not
change and there is no effect on the equilibrium constant, Kc
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Reaction quotient

If a system has not reached equilibrium, the ratio of concentration of product to reactants will not equal Kc.
This ratio is called the reaction quotient, Q, and this helps you to determine the progress of the reaction as
it moves toward equilibrium and the direction of the reaction that is favored to establish equilibrium.

The concentration of products is greater than at equilibrium and the reverse reaction is
Q > Kc
favored until equilibrium is reached.

The concentration of reactants is greater than at equilibrium and the forward reaction is
Q < Kc
favored until equilibrium is reached.

Q = Kc The system is at equilibrium and the forward and reverse reactions occur at equal rates.

EFQ 01 Circle the letter corresponding to the best answer. In the box, support your answer with a brief explanation.
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EFQ 02 Circle the letter corresponding to the best answer. In the box, support your answer with a brief explanation.

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