Topic 7

Equilibrium

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 Definitions

Dynamic state: where the rate of the forward chemical reaction is equal to the rate of
the reverse chemical reaction.

A static state occurs in many physical systems when all movement ceases once equilibrium
has been reached.

Chemical Equilibrium: A state in which the rate of the forward reaction equals the rate of
the reverse reaction.

 Once equilibrium is reached, the concentrations of the reactants and the

concentrations of the products do not change.

 The reaction continues but no change in concentrations

Homogeneous reaction: All the reactants and products are in the same phase. e.g. Haber
process to manufacture ammonia.

Equilibrium Constant: For a reaction aA + bB -> cC + dD, where the small letters are
coefficients and capital letters are the reactants, the equilibrium constant is
[C]c[D]d/[A]a[B]b. Variable units.

 A small value for K means that very little of the reactants were converted into
products before equilibrium was reached. (reactants are “favoured”)

 A large value of K means that most of the reactants were converted into products
before equilibrium was reached. (products are “favoured”)

Closed system: A system in which neither matter nor energy can be lost or gained. An
equilibrium can never occur in a system that is not closed.

Contact process: The synthesis of sulphur trioxide, (V2O5 is used as a catalyst).

Haber process: The synthesis of ammonia, where Fe is used as a catalyst.

Le Chatelier’s principle: If an equilibrium is subjected to a stress, the equilibrium will

shift to minimize the effect of the stress.

Phase equilibrium: When the rate of vaporization is equal to the rate of condensation.

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Vapour pressure: The partial pressure of a vapour. Boiling occurs when a liquid‟s vapour
pressure equals the external pressure. The stronger the intermolecular forces the lower
the vapour pressure at a particular temperature.

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 Characteristics of Dynamic Equilibrium
1. Realize that reactions can go both in forward and in reverse.
2. Define equilibrium.
3. Understand the concept of dynamic equilibrium.
4. State the characteristics of a system at equilibrium

It's important to know that many chemical reactions are reversible. That is:
Reactants  Products or Reactants  Products
Reactants form Products Products form Reactants
For example, under certain conditions, one mole of the colourless gas N2O4 will decompose to
form two moles of brown NO2 gas:
N2O4  2 NO2
colourless brown
Under other conditions, you can take 2 moles of brown NO2 gas and change it into one mole of
N2O4 gas:
N2O4  2 NO2
colourless brown
In other words, this reaction, as written may go forward or in reverse, depending on the
conditions.

NOW, here's something to think about! If we were to put some N2O4 in a flask, the N2O4
molecules would collide with each other and some of them would break apart to form NO2 .

This process, of course is indicated by the forward reaction:

N2O4  2 NO2
Once this has happened for awhile, there is a buildup of NO2 molecules in the same flask. (After
all, this is what the reaction is making.)
Now these NO2 molecules don't just sit there! They are of course moving around and colliding
with things. Once in awhile, two NO2 molecules will collide with each other and guess what?
They join to form a molecule of N2O4 !

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This process, as you might have guessed is indicated by the reverse reaction:
N2O4  2 NO2
Two things you'll have to realize is that as long as there is N2O4 present, the forward
reaction will keep on happening and as long as there is NO2 present, the reverse reaction
will keep on happening!
Also, you must keep in mind that all these molecules are mixed in the same container!

At one particular time a molecule of N2O4 might be breaking up, and at the same time two
molecules of NO2 might be joining to form another molecule of N2O4! So here's an important
thing to understand:

In any reversible reaction, the forward reaction and the reverse

reaction are going on at the same time!

Now what we're going to do is look at how the rate of the forward reaction changes if we put
some pure N2O4 in a flask:
If we put some pure N2O4 in a flask (No NO2 yet!), there will be a high concentration of N2O4.
That is, there will be lots of N2O4 molecules to collide with each other. So at the beginning of
our little experiment, (which we will call " time " 0 ") the rate of the forward reaction is quite
fast.
N2O4  2 NO2
So if we were to make a graph of the rate of the forward reaction vs. time, the graph might
start out something like this:

OK, now you might ask: "Why does the rate of the forward reaction go down?
Well, if you recall Unit 1, as the forward reaction proceeds:
N2O4 2 NO2
the N2O4 is used up and so it's concentration goes down. Also, you must remember that if the
concentration of a reactant goes down, there is less chances of collisions and the rate of the
reaction decreases.
As the reaction continues, the slower rate will use up N2O4 more slowly, so the [N2O4] will not
decrease so quickly and therefore the rate will not decrease quite as quickly. (Read the last
sentence over a couple of times and make sure it makes sense to you!) For those "graph wise"

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people, you will probably guess that this means that the slope of the line on the graph gets more
gradual. The rest of the graph might look something like this:

NOW, it's time we consider the rate of the reverse reaction.

As you might recall, when we have a container full of pure N2O4 , initially there is no NO2 in the
container.
Since there is no NO2, there are no NO2 molecules to collide with each other, and the rate of
the
reverse reaction is zero.
But of course, as time goes on, NO2 is formed from theforward reaction (N2O4 à 2 NO2) so in
a short time, some NO2 molecules can start colliding and the reverse reaction will begin.
As MORE NO2 is formed by the forward reaction, the rate of the reverse reaction gradually
increases. Now, for you "graph buffs", the graph of the Rate of the reverse reaction vs. Time
might look like this:

OK. Now, lets look at the graph for the forward rate and the reverse rate together:

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NOW, focus your attention on the graph at " Time = 4 minutes " . You will notice that at this
point:
the rate of the forward reaction = the rate of the reverse reaction
At this point, NO2 is being used up at the same rate that it is being formed:
Because this is so, you should be able to convince yourself that the [NO2] is no longer changing!
Because the reverse rate is equal to the forward rate, N2O4 is being formed at the same rate
it is being used up. So, also the [N2O4] is no longer changing either!
Can you predict what will happen to the graph after 4.0 minutes?
YOU GUESSED IT! The rates of the forward reaction and the reverse reaction, no longer change
because the [N2O4] is constant and the[NO2] is also constant. The graph will look like this:

The situation happening from 4.0 minutes on in this graph has a special name and a special
significance. At this point, the system (meaning the container, the N2O4 and the NO2 ) is said to
be at equilibrium. To describe it even more precisely, we can say that we have reached a state of
dynamic equilibrium..
Here are some things that you must understand about dynamic equilibrium:

1. The reaction has not stopped!

2. The forward and the reverse reaction continue to take place, but their rates are equal so
there are no changes in concentrations of reactants or products. (The forward and reverse
reactions are said to be " balanced ") eg. for the reaction.

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For each N2O4 molecule that breaks up to form two NO2 molecules, two other NO2 molecules
combine to form another N2O4 molecule. All this is happening on the microscopic level, so we
don't see individual molecules reacting.
3. As far as we can see from the "outside", there appears to be nothing happening. All observable
properties are constant. These include the concentrations of all reactants and products, the total
pressure, colour, temperature etc.
4. If no changes were made in conditions and nothing is added or taken away, a system at
equilibrium would remain that way forever, the forward and reverse reactions "ticking away", but
balanced so that no observable changes happen.
Here are a couple of other things to consider before we summarize everything:
1. Changing the temperature can alter the rates of the reactions at equilibrium. This could "throw
off" the balance. So, for a system at equilibrium, the temperature must remain constant and
uniform throughout the system.
2. Letting material into or out of the system will affect rates so a system at equilibrium is a
closed system.

3. Again, consider the equilibrium reaction: N2O4 ↔2 NO2

In the example that we did to construct the graphs, we had started with pure N2O4 and no NO2.
The forward reaction rate was high at the start, but the reverse reaction rate eventually "caught
up", the rates became equal and equilibrium was established. Can you guess what would happen if
we had started with pure NO2 instead (no N2O4)?
To make a long story short, the reverse reaction rate would start out high, but the forward rate
would eventually " catch up ". When the rates became equal, again equilibrium would be
established.
We can summarize all this by saying that the equilibrium can be approached from the left
(starting with reactants) or from the right (starting with products)
Just a little term before we summarize: The word macroscopic means large scale or visible or
observable. (The opposite is microscopic, which means too small to see eg. molecular level). Some
macroscopic properties are total pressure, colour, concentrations, temperature, density etc.
Alright, let's summarize:
Characteristics of a System at Equilibrium
1. The rate of the forward reaction = The rate of the reverse reaction
2. Microscopic processes (the forward and reverse reaction) continue in a balance which yields no
macroscopic changes. (so nothing appears to be happening.)
3. The system is closed and the temperature is constant and uniform throughout.
4. The equilibrium can be approached from the left (starting with reactants) or from the right
(starting with products).

In our previous examples you will recall that when we started with N2O4 or with NO2,
things happened and equilibrium was eventually established. In general:

If sufficient activation energy is available, systems not at equilibrium will tend to

move toward a position of equilibrium.

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 Self Test on Tutorial 1 - Characteristics of Dynamic Equilibrium
This may be done right on this sheet.
1. Given the reaction: NO2(g) + CO(g) NO(g) + CO2(g)
a) If one mole of NO2 and one mole of CO are mixed in a 1.0 litre container, the rate of
the forward reaction will initially be (fast / slow) ______________________________
b) Immediately after mixing, the rate of the reverse reaction will be _________________
c) While the forward rate > the reverse rate, the [NO] and the [CO2] will be (increasing /
decreasing) __________________________________________________
d) After the initial mixing, the rate of the forward reaction will be ________________ing.
The rate of the reverse reaction will we __________________________________ing.
e) Once equilibrium is established, what can be said about the rates of the forward and
reverse reaction? ______________________________________________________
f) Once equilibrium is established, what is happening to the [NO]? ________________
g) Once equilibrium is established, what is happening to the [CO2]? ________________
h) Once equilibrium is established, what is happening to the [NO2]? ________________
i) Once equilibrium is established, what is happening to the [CO]? ________________
j) NO2 is a dark brown colour. All of the other gases are colourless. Describe what will happen to
the colour of the gas mixture from when the NO2 and the CO are mixed until equilibrium is
established.
___________________________________________________________________
k) One mole of NO and one mole of CO2 are mixed. If left alone at a constant temperature
______________________________________ will be established. Once this equilibrium is
reached, will be colour be different than the equilibrium in question "j" ?
2. Given the reaction: CO(g) + Cl2(g) COCl2(g)
One mole of CO and one mole of Cl2 are mixed at a certain temperature. On the axes below, draw
graphs which show how the rates of the forward reaction and the reverse reaction vary with
time.

3. Give four characteristics of a system at equilibrium.

1. ___________________________________________________________________
2. ___________________________________________________________________
3. ___________________________________________________________________
4. ___________________________________________________________________

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 Exercises
o
1. An example of phase equilibrium is ice in liquid water at 0 C as shown in the photo.

(http://www.raynewater.com/Glass%20with%20ice%20and%20lemon.GIF)

In the space below, draw a particle model diagram that shows ice and water as a dynamic
equilibrium between the solid phase and liquid phase of water.

2. A saturated solution that contains some of the solid solute at the bottom of the container is
called a solution equilibrium system. An example of solution equilibrium with table sugar
(sucrose) is shown by the equation below.

C H O (s)
12 22 11
← →C H O
12 22 11
(aq)
What do you see in this equation that indicates this is a dynamic equilibrium system?

3. In the space below, draw a particle model diagram for this solution equilibrium system.

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An example of a chemical equilibrium can be found in the production of ammonia by the Haber
process. In this reaction, nitrogen and hydrogen react to form ammonia as shown in the
equation below.
N (g) + 3H (g) 2NH (g) + 91.8 kJ
2 2 3

The data table below shows measured amounts of nitrogen, hydrogen, and ammonia over a period
of time in a system that starts out containing only nitrogen and hydrogen.

Concentration Concentration Concentration

Time of nitrogen of hydrogen of ammonia
(min.) (M) (M) (M)
0 1.00 1.00 0
1 0.97 0.91 0.06
2 0.94 0.82 0.12
3 0.92 0.76 0.16
4 0.92 0.76 0.16
5 0.92 0.76 0.16

Label and mark appropriate scales on the axes and plot the data from the table. Label the x-
axis “time” and the y-axis “concentration.” Use a different symbol for each of the components
in the reaction.
Concentrations of reactants and products
in the Haber process versus time

5. At what time does the system in question 4 reach equilibrium? Explain.

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Applications
1. Write an equilibrium equation for the phase equilibrium that occurs in a sealed bottle of
bromine at 25°C.

2. Go to the Website for the “Mission to Mars”

www.sasked.gov.sk.ca/docs/chemistry/mission2mars/
Copy the equilibrium equation found on the first page of the website. This equation shows the
production of methane and water.

3. On the “Mission to Mars” site click on the link, “single user logon”. Look in the menu on the left
and click on “Changing Equilibrium”. Look in the menu on the left again and click on “Methane for
nothing?”
Is this process endothermic or exothermic?

4. Rewrite the equation from answer #2 with the energy term written on the correct side of the
equation.
For the Mission to Mars, it says, “Methane for nothing and the oxygen is free.” Explain, in
terms of materials and energy, why neither the methane nor the oxygen is really free.

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 LeChatelier's Ship: An Equilibrium Exercise

Lean to the left! Shift to the right! Evaluate the changes to the following phase change
equilibriums. Decide if the stress will cause the reaction to shift to the left, or shift to the right.
Compare the total number of left shifts to the total number of right shifts to decide if
LeChatlier's
Ship will sink to the left, sink to the, right, or stay afloat.

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 Le Châtelier’s Principle Questions

1) Predict how the listed changes will affect the following equilibrium reaction.
2 HI (g) ↔ H2(g) + I2(g) ΔH = - 9.4 kJ
a) small amount of H2 is added.

b) pressure on system is increased.

c) temperature is increased.

d) a catalyst is added.

e) if Keq = 1.88 x 10-7, are the reactants or products favored?

2) Predict the effect of the following changes on the equilibrium concentration of CH3OH(g).
CO (g) + 2H2 (g) ↔ CH3OH (g) + energy
a) a decrease in temperature.

b) an increase in pressure.

c) addition of H2(g).

d) addition of a catalyst.

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3) Predict the direction of equilibrium shift if the following changes occur.
4 HCl (g) + O2 (g) ↔ 2H2O (g) + 2 Cl2 (g) + 114.4 kJ
a) the pressure is increased.

b) energy is added.

c) oxygen is added.

d) HCl is removed.

e) a catalyst is added.

4) In an experiment, 4.95 mol of CO2, 0.050 mol of CO and 0.050 mol of O2 are placed in a 5.0 L
reaction vessel at 1400 °K.
-5
If Kc = 1.05 x 10 , will the mixture form more CO or more CO2 ?
CO (g) + 1/2 O2(g)↔ CO2(g)

5) The following equilibrium is of interest to scientist who study acid rain. The concentrations at
the beginning of an
experiment are: [SO2] = 0.015 M; [O2] = 0.012 M; [SO3] = 1.45 M.
2 SO2(g) + O2(g) ↔2 SO3(g)
6
If Kc = 5.0 x 10 , will the mixture form more SO2 or more SO3 ?

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 Le Châtelier’s Principle

Explain how the following changes in reaction conditions will affect the position of the equilibrium
below, and explain your reasoning.

A(g) + B(aq)  C(s) ΔHrxn= -453 kJ/mol

1) The pressure of A in the reaction chamber is increased.

2) The temperature of the reaction is increased by 200 C.

3) A catalyst is added to the system.

4) As the reaction progresses, more of compound B is steadily added to the reaction

chamber.

5) An inhibitor is added to the reaction chamber.

6) Argon gas is added to the reaction chamber, doubling the pressure.

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 Making Use of Le Chatelier’s Principle

Le Chatelier‟s Principle is very useful in predicting how a system at equilibrium will respond to
a change. It states that when a system at equilibrium is disturbed, the equilibrium shifts so as to
undo, in part, the effect of the disturbance.
There are three common ways an equilibrium may be disturbed:
 Change in the concentration (or partial pressure) of one of the reactants or products.
 Change in the temperature.
 Change in the volume of the container.

Effect of Changes in Concentration (or Partial Pressure)

If a system at equilibrium is disturbed by the addition of a reactant (or the removal
of a product), Le Chatelier‟s principle predicts that the equilibrium will shift right.
Shifting right will use up some of the added reactant (or replace some of the removed
product), and therefore “undo, in part” the disturbance.
Similarly, if the disturbance is the removal of a reactant (or the addition of a
product), Le Chatelier‟s principle predicts that the equilibrium will shift left. Shifting
left will replace some of the removed reactant (or use up some of the added product),
and therefore “undo, in part” the disturbance.
Since concentrations of solids are constants and do not appear in expressions for Q or
K, removing or adding some solid does not cause shifts. However, shifts in the equilibrium
do change the amount of solid present!

Effect of Changes in Temperature

If a reaction is endothermic (∆H > 0), heat is absorbed in the forward reaction and
released in the backward reaction; thus in endothermic reactions, heat behaves like a
reactant. Increasing the temperature (adding heat) shifts the reaction right, since that
is the direction which absorbs heat and “undoes, in part” the disturbance. Similarly,
decreasing the temperature of an endothermic reaction shifts the reaction left.
Exothermic reactions (∆H < 0) release heat in the forward direction, and absorb heat
in the reverse direction; thus heat acts like a product in exothermic reactions.
Increasing the temperature (adding heat) shifts the reaction left since that is the
direction that absorbs heat and “undoes, in part” the disturbance. Conversely, lowering
the temperature shifts it right.
The equilibrium constant K is temperature dependent and the shifts above change its
value.

Reaction Type Role of heat Effect of T Effect of T

Endothermic (H > 0) reactants + heat  products K K
Exothermic (H < 0) reactants  products + heat K K

Effect of Changes in the Volume of the Container

When the volume of a reaction vessel is decreased, the partial pressures of all gases
in the container increase so the total pressure increases. Following Le Chatelier‟s

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principle, the reaction shifts to reduce the total pressure since that “undoes, in part” the
disturbance. This means that the shift is in the direction which contains the fewest
moles gas.
Similarly, if the volume of the reaction vessel is increased, the total pressure
decreases, and the shift is in the direction which contains the most moles gas.
In either case, if both sides of the equation have the same number of moles gas, the
change in the volume of the container has no effect on the equilibrium.
Effect of the Addition of a Catalyst
Catalysts speed up the rate at which equilibrium is obtained, but have no effect on the
magnitude of K. They increase both the forward and backward rate of reaction. Since
catalysts do not appear in the net equation for a reaction, they are not involved in the
expressions for K.
______________________________________________________________________________

Exercises
In the problems below, for each change given in the first column of the table, use Le Chatelier's
principle to predict

• the direction of shift of the equilibrium.

• the effect on the quantity in the third column.

______________________________________________________________________________

1. For the following reaction

5 CO(g) + I2O5(s)  I2(g) + 5 CO2(g) ∆Ho = -1175 kJ

for each change listed, predict the equilibrium shift and the effect on the indicated quantity.

Direction Effect on Effect

Change of Shift Quantity (increase,

decrease,
( ; ; or no change)
or no change)

(a) decrease in volume Kc

(b) raise temperature amount of CO(g)

(c) addition of I2O5(s) amount of CO(g)

(d) addition of CO2(g) amount of I2O5(s)

(e) removal of I2(g) amount of CO2(g)

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_____________________________________________________________________________
2. Consider the following equilibrium system in a closed container:

Ni(s) + 4 CO(g)  Ni(CO)4(g) ∆Ho = - 161 kJ

In which direction will the equilibrium shift in response to each change, and what will be the
effect on the indicated quantity?

Direction Effect on Effect

Change of Shift Quantity (increase, decrease,

( ; ; or no change) or no change)

(a) add Ni(s) Ni(CO)4(g)

(b) raise temperature Kc

(c) add CO(g) amount of Ni(s)

(d) remove Ni(CO)4(g) CO(g)

(e) decrease in volume Ni(CO)4(g)

(f) lower temperature CO(g)

(g) remove CO(g) Kc

Answers: # 1(a) , no change; (b) , increase; (c) no change, no change; (d) , increase; (e) , increase.
# 2(a) no change, no change; (b) , decrease; (c) , decrease; (d) , decrease; (e) , increase; (f) , decrease; (g) , no
change.

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 2NO2 ⇄ N2O4 ΔH = - 58 kJ/mol
brown colorless
Change Quantity Shift towards Direction [reactants] [products] Color Kc


increase [NO2] N2O4 Colourless

decrease [NO2]

increase [N2O4]

decrease [N2O4]

increase pressure

decrease pressure

increase volume

decrease volume

increase temperature

decrease temperature

Add catalyst

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 Lab: Online Equilibrium Experiments

Go to this website:
http://mc2.cchem.berkeley.edu/Java/equilibrium/index.html

1) For this experiment you may find this helpful:

#red/#blue = redness, or #blue/#red = blueness.
a) Is the forward reaction exothermic or endothermic? Give supporting data (detailed) [3] and
relate your answer to Le Chatelier‟s principle. [2]

b) Using the default settings, hit the equilibrate button.

i) It seems that red turns to blue more than blue turns to red at the start (before equilibrium
is reached). What is it called when the rate of the forward reaction (eventually) equals
that of the backwards reaction? [1]

ii) How do you know this has happened? [1]

iii) Is it ok that the concentrations of red and blue are not the same at equilibrium or is this an
error in the model? [1]

iv) Has the reaction stopped at equilibrium? [1] How do you know? [2]

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2) Reset the model, increase temperature to the maximum, and hit equilibrate (max temp gives us
more collisions and reduces time to get equilibrium). At equilibrium press pause, and increase the red
to the maximum. Le Chatlalier „s principle expects the solution to turn blue(er). Give quantitative
data to support this. [3]

3) Repeat the above step but add blue to the maximum, (not red). Explain the limit of this java
model. [3]

Finally
Go to http://www.chm.davidson.edu/ronutt/che115/EquKin/EquKin.htm and answer the questions.
(Yes I know he has the answers there too, yes I did cheat too, no you should try them first on your
own, no you do not need to type the answers here, yes I know you would have cut and pasted, yes you
can check the answers when you are done. Phew)

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 Equilibrium constant Practice
1. Write the equilibrium expression for the following reactions:
a. 2HI(g)  H2(g) + I2(g)

b. 3H2(g) + N2(g) 2NH3(g)

c. H2(g) + O2(g)  H2O(l)

d. 2AgNO3(aq) + CaCl2(aq)  AgCl(s) + Ca(NO3)2(aq)

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 e. H+(aq) + Cl-(aq)  HCl(aq)

f. CuSO4(aq) + Na2CO3(aq)  CuCO3(s) + Na2SO4(aq)

2. The equilibrium constant for the reactions above are as follows at 25C.
a. Keq = 1.20
b. Keq = 7.6 x 10-3
c. Keq = 340
d. Keq = 1.4x1013
e. Keq = 9.2 x 10-12
f. Keq =6.2x108

i. Predict which reactions go to completion

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ii. Which reactions have a low percent yield?

iii. In which reactions are the reactants favored?

iv. In which reactions is the reverse reaction more favored than the forward
reaction?

v. Which reaction are the fastest?

vi. Which reactions have the greatest difference in the rate of the forward and
reverse reactions?

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3. True or false: Once equilibrium is reached, the forward and the reverse chemical reactions
stop.

4. Given the following equilibrium concentrations, calculate Keq

A + 2B  C [A]= 2.0 M [B]= 3.0 M [C] = 1.5 M

5. An equilibrium mixture of PCl5, PCl3 and Cl2, at a certain temperature ian a 5.0 L conatiiner
consists of 0.80 mol PCl5, 0.55 mol PCl3, and 1.2 mol Cl2. Calculate Kc for this reaction:
PCl3(g) + Cl2 (g)  PCl5(g)

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6. Keq = 150.0 at a certain temperature for the reaction:
2NO(g) + O2(g)  2NO2(g)

What is the concentration of NO2 if the equilibrium concentration of NO and O2 are 1.00 x
10-3 and 5.00 x 10-2 respectively?

7. The following gases are added to a 1.00 L container: 2.0 mol of A; 4.0 mol B. These gases
react as follows:
A (g) + 3 B  C (g) + 2 D (g)

At equilibrium, the container contains 0.4 mol of D.

a. Calculate the moles of A, B and C in the container at equilibrium

b. Calculate the concentration of A, B, C and D at equilibrium

c. Calculate the value of the equilibrium constant for this reaction.

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 Using Equilibrium Expressions
In order to help you to write equilibrium expressions and to calculate their values, complete the
problems below. First write the expression for the equilibrium constant for the given reaction, then
use the given concentration data to calculate the value of the constant for the reaction and finally,
state whether the reactants or products are favored. Show all of your work!

1. Reaction: N2O4 ↔ 2 NO2(g) (at 520º C)

-3 -3
Equilibrium concentrations: [N2O4] = 0.014 mol dm , [NO2] = 0.072 mol dm
Keq = 0.37,reactants

2. Reaction: N2(g) + 3 H2(g) ↔ 2 NH3(g) (at 583º C)

-3 -3 -3
Equilibrium concentrations: [N2] = 0.2 mol dm , [H2] = 0.2 mol dm , [NH3] = 0.016 mol dm
Keq = 0.16,reactants

3. Reaction: SO2(g) + 1/2 O2(g) ↔ SO3(g) (at 500º C)

-3 -3 -3
Equilibrium concentrations: [SO2] = 0.02 mol dm , [O2] = 1.0 mol dm , [SO3] = 0.4 mol dm
Keq = 20,products

4. Reaction: PCl3(g) + Cl2(g) ↔ PCl5(g) (at room temperature)

-3 -3 -3
Equilibrium concentrations: [PCl3] = 1.0 mol dm , [Cl2] = 0.9 mol dm , [PCl ] = 0.12 mol dm
Keq = 0.133,reactants

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5. Reaction: 2 NH3(g) ↔ N2(g) + 3 H2(g) (at 1000 K)
-3 -3 -3
Equilibrium concentrations: [NH3] = 0.102 mol dm , [N2] = 1.03 mol dm , [H2] = 1.62 mol dm
Keq = 420.9,products

6. Reaction: 2 H2(g) + S2(g) ↔ 2 H2S(g) (at 750K)

-3 -3 -
Equilibrium concentrations: [H2] = 0.076 mol dm , [S2] = 0.0000016 mol dm , [H2S] = 0.093 mol dm
3

Keq = 940000,products

7. Reaction: 2 NO(g) + O2(g) ↔ 2 NO2(g) (at 500 K)

-3 -3 -3
Equilibrium concentrations: [NO] = 0.000349 mol dm , [O2] = 0.80 mol dm , [NO2] = 0.25 mol dm
Keq = 641415, products

8. Reaction: PCl5(g) ↔ PCl3(g) + Cl2(g) (at 500 K)

-3 -3 -3
Equilibrium concentrations: [PCl5] =0.861 mol dm , [PCl3] = 0.139 mol dm , [Cl2]=0.139 mol dm
Keq = 0.022 reactants

9. Reaction: CO2(g) + H2(g) ↔ CO(g) + H2O(g) (at 900º C)

-3 -3 -3
Equilibrium concentrations: [CO2] = 0.648 mol dm , [H2] = 0.148 mol dm , [CO] = 0.352 mol dm ,
-3
[H2O] = 0.352 mol dm
Keq = 1.29,products

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 Equilibrium Calculations – 1

1) A researcher places 0.0400 mol of sulfuryl chloride in a 4.00 L reactor. The temperature is raised
to 100 °C, and some of the sulfuryl chloride decomposes to sulfur dioxide and chlorine:
SO2Cl2(g) ↔ SO2(g) + Cl2(g)
-3 -3
At equilibrium, the concentration of chlorine is found to be 3.9 x 10 mol dm . Calculate Kc
-3
for this reaction.( Kc = 2.49 x 10 )

2) At a certain temperature, a mixture of H2 and I2 was prepared by placing 0.100 mol of

H2 and 0.100 mol of I2 into a 1.00 L flask. After a period of time the equilibrium
H2(g) + I2(g) 2 HI (g)
was established. The purple color of the I2 vapor was used to monitor the reaction, and from
the decreased intensity of the purple color it was determined that, at equilibrium, the I2
concentration dropped to 0.0200 M.
What is the value of Kc for this reaction at this temperature? (Kc = 64)

3) At very high temperatures, Kc is 0.200 for

N2(g) + O2(g) ↔ 2 NO(g)
Calculate the equilibrium concentrations of all species if the reaction starts with 5 x 10– 4
mol of NO in a 10.0 L container. ([N2] = 2.05 x 10-5 M [O2] = 2.05 x 10-5 M [NO] = 9 x 10-6 M)

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4) The reaction:
CO(g) + H2O (g) CO2 (g) + H2 (g)
has Kc = 4.06 at 500 °C. If 0.100 mol of CO and 0.100 mol of H2O(g) are placed in a
1.0 L reaction vessel at this temperature, what are the concentrations of the reactants
and products when the system reaches equilibrium? ([H2O] = 0.0332 [CO2] = 0.0668 [H2] = 0.0668)

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 Equilibrium Calculations – 2

1) Chemists have carried out studies of the high-temperature reaction of sulfur dioxide with oxygen
-3 -3
in which the reactor initially contained 0.0076 mol dm SO2, 0.0036 mol dm O2 and no SO3 .
-3
After equilibrium was achieved, SO2 concentration decreased to 0.0032 mol dm .
Complete the iCE table and use this information to calculate the Keq at this temperature for
2SO2(g) + O2(g) 2 SO3(g)
(Ka = 1.4 x 103 )

2) A 5.0-L reaction flask initially contains 0.030 mol of sulfuryl chloride at 177 ºC. Sulfur dioxide
and
chlorine form: SO2Cl2(g) ↔ SO2(g) + Cl2(g) After equilibrium is established, analysis shows that
0.0020 mol of SO2Cl2(g) remains. Complete the iCE table and use this information to calculate the
Keq forthis reaction.
(Ka = 0.17)

3) If 1.0 mol each of SO2 and NO2 are sealed in a 1.0-L flask at 1500 K, they react to form SO3 and
NO SO2(g) + NO2(g) ↔ SO3(g) + NO(g) . Keq is 1.98.
Complete the iCE table and use this information to write the expression for the equilibrium constant
in polynomial form.
( Ka =
1.98)

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4) Exactly 2.0 mol of carbon monoxide and water are sealed in a 4.0-L flask at 1100 K.
CO(g) + H2O(g) ↔ CO2(g) + H2(g) Keq is 0.55 for this reaction.
Complete the iCE table and use this information to write the expression for the equilibrium
constant in polynomial form.
(Ka = 1.4 x 103 )

5) Consider 0.200 mol of phosphorus pentachloride sealed in a 2.0-L container at 620 K. Keq =
0.60 for:
PCl5(g) ↔ PCl3(g) + Cl2(g)
Complete the iCE table and use this information to calculate the concentration of all species
after equilibrium has been reached.
( [PCl5 = 0.015M, [PCl3] = [Cl2] = 0.085M)

6) Consider a system that initially contains 0.100 mol each of phosphorus trichloride and
chlorine sealed in a 10.0-L container. The temperature is raised to 291 ºC where Keq = 8.18
for :
PCl3(g) + Cl2(g) ↔ PCl5(g)

Complete the iCE table and use this information to calculate the concentration of all species
after equilibrium has been reached.
( [PCl3 = [Cl2] = 0.009M, [PCl5] = 7.335 x 10-4)

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7) Calculate the concentrations of all species formed when 1.00 mol of sulfur dioxide and
2.00 mol of chlorine are sealed in a 100.0-L reactor. The temperature is raised to 400 K
where Keq is 89.3 for:
SO2(g) + Cl2(g) SO2Cl2(g)
Complete the iCE table and use this information to calculate the concentration of all species
after equilibrium has been reached.
([SO2] = 4.34 x 10-3M, [Cl2] = 1.43 x 10-2M, [SO2Cl2] = 5.66 x 10-3M)

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 Equilibrium Constant Practice

1. At a particular temperature, a mixture of nitrogen monoxide and oxygen is allowed to reach equilibrium
according to the equation:
2 NO(g) + O2(g) ↔ 2 NO2 (g)
-3
The equilibrium concentrations of the gases are 0.03 mol dm -3 nitrogen monoxide, 0.04 mol dm oxygen, and
-3
0.02 mol dm nitrogen dioxide. What is the value of the equilibrium constant, K c ?
(by the way: 1 dm3 = 1 L)
A. 0.02/ (0.03 x 0.04) mol -1 dm3
B. 0.02/(0.03 x 0.042) mol-1 dm3
C. 0.022/(0.032 x 0.04) mol-1 dm3
D. (0.3 x 0.04)/0.02 mol-1 dm3

2. When 0.01 moles of iodine is added to 1 dm3 of 0.2 mol dm-3 aqueous potassium iodide, 99% of it is converted
to
the triiodide according to the equilibrium
- 3-
I2 (aq) + I (aq) ↔ I (aq)
What is the approximate value of the equilibrium constant?
A. 500 mol-1 dm3
B. 100 mol-1 dm3
C. 2 mol-1 dm3
D. 0.002 mol-1 dm3

3. The equilibrium constant for the dissociation of hydrogen iodide into its elements, according to the equation
-3
below, at 900 K, is 0.04. If the equilibrium concentration of hydrogen iodide is 0.2 mol dm , what is the
approximate equilibrium concentration of iodine?
2 HI (g) ↔ H2 (g) + I2 (g)
A. 0.3
B. 0.04
C. 0.008
D. 0.0016

4. When ammonia hydrogen sulphide is heated it dissociates according to the equilibrium below. The value of K c
for
-6
this equilibrium is 0.00001 mol2 dm .
NH4HS(s) ↔ NH3(g) + H2S(g)
a. Explain the units of the equilibrium constant.

b. Calculate the concentration of ammonia at equilibrium.

c. If some ammonia gas was injected at constant pressure, how would this affect
i. the mass of solid present?

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 ii. the concentration of hydrogen sulfide?

iii. the value of Kc?

5. Consider the synthesis equilibrium reaction for ammonia:

N2(g) + 3 H2(g) ↔ 2 NH3 (g)

3
In a certain experiment, 1.000 mole of N2(g) and 1.000 mole of H2(g) were placed in a 1.000 dm flask at 500°C
and allowed to react. After the system reached equilibrium, the flask was found to contain 0.921 mole of N2.
Calculate the equilibrium concentrations of H2 and NH3 and calculate the Kc for this reaction at 500°C.

6. In a different experiment with the same equilibrium system as in problem 5, the following experimental
details were recorded: 2.00 moles of N2(g), 1.00 mole of H2(g) and 3.00 moles of NH3(g) were mixed in a 1.00
dm3 flask. At equilibrium, 2.77 moles of H2 were found to be present in the flask. Calculate the concentrations
of N2 and NH3 at equilibrium and then calculate the Kc for this reaction. Compare the result with that of
problem 5. At what temperature was this experiment conducted ? – justify your answer.

For questions 7-8 consider the reaction

PCl3(g) + Cl2(g) ↔ PCl5(g) (equation 7a)
7. Write the equilibrium expression.

At a certain temperature, the following equilibrium concentrations were observed:

[Cl2] = 2.0 x 10-3 mol dm-3
[PCl3] = 3.0 x 10-1 mol dm-3
[PCl5] = 6.7 x 10-3 mol dm-3

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 a. Calculate the value of K at this temperature.

b. Calculate the value of K for the reaction

PCl5(g) ↔ PCl3(g) + Cl2(g) (equation 7b)

at the same temperature.

8. Cl2(g), PCl3(g), and PCl5(g) are mixed at the following concentrations at the same temperature as in question 7:
[Cl2]o = 5.0 x 10-4 mol dm-3
[PCl3]o = 6.3 x 10-2 mol dm-3
[PCl5]o = 3.8 x 10-3 mol dm-3
Consider the reaction as written by equation 7a; in which direction will the system shift to reach equilibrium?

9. For the reaction

2 SO2(g) + O2(g) ↔ 2 SO3(g)
Kc = 4.00 x 102 mol dm-3 at 750°C. What concentration of SO2 must be in equilibrium with the concentrations
[O2] = 2.0 x 10-1 mol dm-3 and [SO3] = 3.0 mol dm-3?

10. Consider the reaction

H2(g) + I2(g) ↔ 2 HI(g)
At a certain temperature, 1.00 mole of H2, 5.00 mole of I2, and 2.50 moles of HI were mixed in a 3.00 dm3
vessel.
When equilibrium was reached, the concentration of H2 was found to be 3.00 x 10-2 mol dm-3. Calculate the
equilibrium concentrations of I2 and HI and calculate the equilibrium constant at this temperature.

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 Le Chateliers's Principle
States that if an 'instantaneous' change is imposed on an equilibrium, the position of the equilibrium will
further change to minimise the 'enforced' change.

Rule 1 - Temperature and energy changes

1a. Raising the temperature favours the endothermic direction (ΔH +ve). The system absorbs the heat energy
from the surroundings to try to minimise the temperature increase.
1b. Decreasing the temperature favours the exothermic direction (ΔH -ve). The system releases heat energy
to the surroundings to try to minimise the temperature decrease.

Rule 2 - Gas pressure changes at constant temperature

2a. Increasing the pressure favours the side of the equilibrium with the least number of gaseous molecules as
indicated by the balanced symbol equation. The system attempts to reduce the number of gas molecules
present to reduce the pressure increase.
2b. Decreasing the pressure favours the side of the equilibrium with the most number of gaseous molecules as
indicated by the balanced symbol equation. The system attempts to increase the number of gas molecules to
minimise the pressure decrease.

NOTE:
a) States symbols (g/l/s/aq) are particularly important when considering equilibrium equations, if no (g) the pressure
rule doesn't apply since solids and liquids are virtually incompressible.
b) Rule 2 ONLY applies to a reaction with one or more gaseous reactants or products because pressure has no real
effect on the 'concentration' on the virtually incompressible liquids or solids.
c) If there is NO net change in the number of gas molecules, gas pressure has NO effect on the position of the
equilibrium, though pressure increase effectively increases gas concentration so both the forward and backward
reactions will be speeded up.

Rule 3 - Concentration changes at constant temperature

3a. If the concentration of a reactant (on the left) is increased, then some of it must change to the products
(on the right) to maintain a balanced equilibrium position.
3b. If the concentration of a reactant (on the left) is decreased, then some of the products (on the right)
must change back to reactants to maintain a balanced equilibrium position. This means if you change ANY
concentration, all the other concentrations must change too. Also, any net concentration changes must comply
with the Kc equilibrium expression.

Rule 4 - Using a catalyst

A catalyst does NOT affect the position of an equilibrium.
BUT it does is enable you get to the point of equilibrium faster!
A catalyst speeds up both the forward and reverse reactions by providing a mechanistic pathway with a lower
activation energy, but there is no way it can influence the final 'balanced' concentration ratios.
The importance of a catalyst lies with economics of chemical production e.g. bringing about reactions with high
activation energies at lower temperatures and so reducing energy requirements and time, and both reductions
save money!

Example 1
The thermal decomposition of calcium carbonate (limestone) to make calcium oxide (quicklime):

CaCO3(s) <---- > CaO(s) + CO2(g) (ΔH = +178 kJ mol-1)

Rule 1 - temperature and energy change
Increasing temperature favours the __________thermic direction (to the __________) so more quicklime is
formed.
Rule 2 - gas pressure
Decreasing the pressure of carbon dioxide .______creases the yield of quicklime.
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Rule 3 - concentration
Not applicable to the ______________ because you can't decrease or increase the concentration of a
solid but you can reduce the concentration of __________ by removing the gases to increase the
yield of quicklime.
Rule 4 - catalyst: Not applicable.

Example 2
The synthesis of ammonia: nitrogen + hydrogen → ammonia (Haber process)

N2(g) + 3H2(g) <--> 2NH3(g) (ΔH = -92 kJ mol-1)

Rule 1 - temperature and energy change

The forward and desirable reaction, to form ammonia, is ________.thermic, so _____creasing the
temperature favours its formation.
Rule 2 - gas pressure
____________crease in pressure favours ammonia formation since 4 mol of gaseous reactants ==> 2 mol
gaseous products.
Rule 3 - concentration:
In terms of enforced change => system response
Increasing nitrogen ==> ___creases hydrogen and ____creases ammonia.
Increasing hydrogen ==> ____creases nitrogen and ____creases ammonia.
Decreasing ammonia ==> ______creases nitrogen and ____creases hydrogen.
Decreasing nitrogen ==>______creases hydrogen and ____creases ammonia.
Decreasing hydrogen ==> _______creases nitrogen and _______creases ammonia.
Rule 4 - catalyst: An iron oxide catalyst is used, time = money for industrial chemical production!

Example 3
The formation of hydrogen iodide from hydrogen and iodine:
H2(g) + I2(g) <--> 2HI(g) (ΔH = -10 kJ mol-1, iodine gaseous above 200oC)

Rule 1 - temperature and energy change

Increasing temperature favours the _____ reaction, i.e. ______creases the endothermic decomposition of
hydrogen iodide.
Rule 2 - gas pressure
No effect on position of equilibrium, because
_________________________________________________________
Rule 3 - concentration
If more iodine was added to a constant volume container, the hydrogen concentration would ______crease as
some reacts with added iodine to give more hydrogen iodide as the system tries to minimise the iodine
increase.
Rule 4 - catalyst: Not applicable.

Example 4
Esterification: e.g. ethanoic acid + ethanol → ethyl ethanoate + water
CH3COOH(l) + CH3CH2OH(l) <--> CH3COOCH2CH3(l) + H2O(l) (ΔH = -2 kJ mol-1)
Rule 1 - temperature and energy change
_______crease in temperature favours the ester formation (ethyl ethanoate, forward reaction)
Rule 2 - gas pressure: (?)________________________________________________________
Rule 3 - concentration

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Sometimes it is desirable to add a large excess of the ____________ to ensure most of the acid is converted
into ester.
Rule 4 - catalyst
The forward esterification reaction is catalysed by acids e.g. a few drops of conc. Sulphuric acid.
The reverse reaction i.e. hydrolysis of the ester back to the acid and alcohol is catalysed by dilute acids.

Example 5
The formation of nitrogen(II) oxide.

N2(g) + O2(g) <--> 2NO(g) (ΔH = +181 kJ mol-1)

Rule 1 - temperature and energy change

Increase in temperature favours the __________ reaction.
This reaction does not happen at room temperature but is formed at the high temperatures
in car engines. Unfortunately when released through the car exhaust, it cools to normal temperatures when
NO irreversibly reacts with oxygen in air to form nitrogen(IV) oxide, NO 2, which is acidic, a lung irritant and a
reactive free radical molecule involved in the chemistry of photochemical smog not good!
Rule 2 - gas pressure
Pressure does not affect the position of the equilibrium since _____________________
Rule 3 - concentration
The concentration of nitrogen is high from air, but although the concentration of oxygen is low in the exhaust
gases, there is sufficient present in the combustion process to ensure a small % of NO is formed.
Rule 4 - catalyst: Not applicable.

Example 6
The oxidation of sulphur dioxide to sulphur trioxide
(e.g. in the Contact Process for manufacturing sulphuric acid)
2SO2(g) + O2(g) <--> 2SO3(g) (ΔH = -196 kJ mol-1)
Rule 1 - temperature and energy change
The exothermic formation of sulphur trioxide is favoured by ___________ temperature.
Rule 2 - gas pressure
____________pressure favours a higher yield of sulphur trioxide as 3 gas moles ==> 2 gas moles, though 1-2 only
atm is used in practice because the equilibrium is already so far to the right (about 99%).
Rule 3 - concentration
Air is used as the source of oxygen and, despite its dilution with nitrogen, the concentration
of oxygen is high enough to move the equilirium very much to the ___________
Rule 4 - catalyst
A vanadium(V) oxide, V2O5, catalyst ensures the high yield of 99% SO3 is attained fast, but no more!

Example 7
One way to produce hydrogen for the Haber synthesis of ammonia is to react methane gas
with steam.
CH4(g) + H2O(g) <--> 3H2(g) + CO(g) (ΔH = +206 kJ mol-1)
Rule 1 - temperature and energy change
______crease in temperature favours the endothermic formation of hydrogen (and carbon monoxide).
Rule 2 - gas pressure
For the desired forward reaction, 2 mol of reactant gases ==> 4 mol of product gases, so the increase in product
volume is favoured by _______________ pressure.
Rule 3 - concentration

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Theoretically increase in methane and steam concentrations will increase the hydrogen concentration, but this
essentially means increasing pressure favouring the reverse reaction, so you might not gain as much hydrogen as
you like to!
Rule 4 - catalyst
A nickel catalyst is used, but cannot affect the yield.

Review: Unit 13 – Equilibrium

1. Chemical equilibrium is referred to as dynamic because, at equilibrium, the
A. equilibrium constant changes.
B. reactants and products keep reacting.
C. rates of the forward and backward reactions change.
D. concentrations of the reactants and products continue to change.

2. Which change will shift the position of equilibrium to the right in this reaction?
N2(g) + 3H2 (g) ↔ 2NH3 (g) ΔH =−92 kJ/mol

A. Increasing the temperature B. Decreasing the pressure

C. Adding a catalyst D. Removing ammonia from the equilibrium mixture

3. Which of the following changes will shift the position of equilibrium of this reaction in the
forward direction?
N2(g) + O2 (g) ↔ 2 NO(g) ΔH = +181 kJ/mol
I. Increasing the pressure
II. Adding a catalyst
III. Increasing the temperature

A. I only B. II only C. III only D. I and III

4. For a gaseous reaction, the equilibrium constant expression is:

Kc = [O2]5[NH3]4
[NO]4[H2O]6
Which equation corresponds to this equilibrium expression?
A. 4NH3 + 5O2 ↔ 4NO + 6H2O
B. 4NO + 6H2O ↔ 4NH3 + 5O2
C. 8NH3 +10 O2 ↔ 8NO +12H2O
D. 2NO + 3H2O ↔ 2NH3 + 5/2 O2

5. I2 (g) + 3Cl2 (g) ↔ 2ICl3 (g)

What is the equilibrium constant expression for the reaction above?

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6. Which statement(s) is/are true for a mixture of ice and water at equilibrium?
I. The rates of melting and freezing are equal.
II. The amounts of ice and water are equal.
III. The same position of equilibrium can be reached by cooling water and heating ice.
A. I only.
B. I and III only
C. II only
D. III only

7. Which statement concerning a chemical reaction at equilibrium is not correct?

A. The concentrations of reactants and products remain constant.

B. Equilibrium can be approached from both directions.
C. The rate of the forward reaction equals the rate of the reverse reaction.
D. All reaction stops.

Short answer
1. (a) Define the term rate of reaction. For a reaction of your choice, state the reactants and
outline an experimental procedure by which you could obtain a value for the rate of reaction. [5]

(b) (i) State Le Chatelier„s Principle. [1]

(ii) State the factors which affect the position of equilibrium in a reaction. Explain the influence
of one of these factors using Le Chatelier„s Principle. [3]

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(iii) Outline the main features of the Collision Theory. [4]

(iv) State the factors which affect the time taken to reach equilibrium and explain briefly the
influence of one of these factors. [3]

(c) Write an equation, including state symbols, for the synthesis of ammonia by the Haber process.
Explain the use of high pressure and moderately-high temperatures in the production of ammonia.
[4]

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2. Ammonia, NH3, is manufactured by the Haber process according to the following equilibrium
reaction:
N2 (g) + 3H2(g) ↔ 2NH3(g)
The following data gives approximate values for the yield of ammonia at various temperatures and
pressures.
Temperature (°C) Pressure (atm) Molar % of NH3 at equilibrium
400 200 40
400 300 50
400 400 57
450 200 25
500 200 18
Use the data to deduce:
(a) (i) the effect of pressure on the yield of ammonia. Explain your answer. [2]

(ii) whether the synthesis of ammonia is endothermic or exothermic. Explain your answer. [2]

(b) State what combination of pressure (i.e. high or low) and temperature (i.e. high or low) would
give the highest % of ammonia. [1]

(b) Write the equilibrium constant expression, Kc, for the formation of ammonia. [2]

(c) State and explain what happens to the value of Kc, if the temperature is increased. [2]

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 (d) How does the catalyst affect:

(i) the rate of formation of ammonia; [l]

(ii) the position of equilibrium? [1]

3. For the reversible reaction:

H2(g) + I2(g) ↔ 2HI(g) ΔH>0
the equilibrium constant Kc at a particular temperature = 60

(a) Give the equilibrium expression and explain why the equilibrium constant has no units. [2]

(b) For this reaction, what information does the value of Kc provide about the relative
concentrations of the product and reactants at equilibrium? [1]

(c) What effect, if any, will an increase in pressure have on the equilibrium position? [1]

(d) Explain why an increase in temperature increases the value of the equilibrium constant for
the above reaction. [1]

4. Ammonia is made on a large scale by the Haber process. The main reaction occurring is
N2(g) + 3H2(g) ↔ 2NH3(g) ΔH = −92 kJ/mol
(a) State two characteristics of a reversible reaction at equilibrium. [2]

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 (b) This reaction is described as homogeneous. State what is meant by the term homogeneous. [1]

(c) Write the equilibrium constant expression for the reaction. [2]

(d) When nitrogen and hydrogen are mixed together at room temperature and atmospheric pressure
the reaction is very slow. In industry, typical values of pressure and temperature used are 250
atmospheres and 450 ºC.
(i) State the effects on both the rate of reaction and the value of the equilibrium constant of
increasing the temperature. [2]

(ii) State the effects on both the rate of reaction and the value of the equilibrium constant of
increasing the pressure. [2]

(iii) Suggest why a pressure of 1000 atmospheres is not used. [1]

(e) Name the catalyst used in the Haber process. State and explain its effect on the value of the
equilibrium constant. [3]

(e) Use the collision theory to explain the effect of increasing the temperature on the rate of
reaction between nitrogen and hydrogen. [3]

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(g) A mixture of nitrogen and hydrogen is left at 450 ºC and 250 atmospheres until equilibrium is
reached. Use Le Chatelier.s principle to state and explain what will happen to the position of
equilibrium when
(i) some of the ammonia is removed; [2]

(ii) the pressure is increased. [2]

5. Hydrogen and iodine are placed in a closed container and allowed to react at 750 oC and one
atmosphere pressure. The following equilibrium is reached:
H2 (g) + I2 (g) ↔ 2HI(g) ΔH = –10 kJmol-1
(a) State the qualitative effect of an increase in pressure on the rate of the forward reaction and
on the equilibrium position. Explain your answer in each case. [4]

(b) After equilibrium has been established, some H2 is added to the system. Describe the
changes in the concentrations of I2 and HI until a new equilibrium is established. [2

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 Equilibrium Exam Questions
1. Consider the following equilibrium reaction.

2SO2(g) + O2(g) 2SO3(g) ∆Ho = –197 kJ

Which change in conditions will increase the amount of SO3 present when equilibrium is re-
established?

A. Decreasing the concentration of SO2

B. Increasing the volume

C. Decreasing the temperature

D. Adding a catalyst
(Total 1 mark)

2. Consider the following reversible reaction.

Cr2O72–(aq) + H2O(l) 2CrO42–(aq) + 2H+(aq)

What will happen to the position of equilibrium and the value of Kc when more H+ ions are
added at constant temperature?

Position of equilibrium Value of Kc

A. shifts to the left decreases
B. shifts to the right increases
C. shifts to the right does not change
D. shifts to the left does not change
(Total 1 mark)

3. What effect will an increase in temperature have on the Kc value and the position of equilibrium
in the following reaction?

N2(g) + 3H2(g) 2NH3(g) ΔH = –92 kJ

Kc Equilibrium position
A. increases shifts to the right
B. decreases shifts to the left
C. increases shifts to the left
D. decreases shifts to the right
(Total 1 mark)

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4. Which statement is always correct for a chemical reaction at equilibrium?

A. The rate of the forward reaction equals the rate of the reverse reaction.

B. The amounts of reactants and products are equal.

C. The concentration of the reactants and products are constantly changing.

D. The forward reaction occurs to a greater extent than the reverse reaction.
(Total 1 mark)

5. An increase in temperature increases the amount of chlorine present in the following

equilibrium.

PCl5(s) PCl3(l) + Cl2(g)

What is the best explanation for this?

A. The higher temperature increases the rate of the forward reaction only.

B. The higher temperature increases the rate of the reverse reaction only.

C. The higher temperature increases the rate of both reactions but the forward reaction is
affected more than the reverse.

D. The higher temperature increases the rate of both reactions but the reverse reaction is
affected more than the forward.
(Total 1 mark)

6. What will happen when at a constant temperature, more iodide ions, I–, are added to the
equilibrium below?

I2(s) + I–(aq) I3–(aq)

A. The amount of solid iodine decreases and the equilibrium constant increases.

B. The amount of solid iodine decreases and the equilibrium constant remains unchanged.

C. The amount of solid iodine increases and the equilibrium constant decreases.

D. The amount of solid iodine increases and the equilibrium constant remains unchanged.
(Total 1 mark)

7. Consider the following reaction taking place at 375 °C in a 1.00 dm3 closed container.

Cl2(g) + SO2(g) SO2Cl2(g) ∆HO = –84.5 kJ

(i) Deduce the equilibrium constant expression, Kc, for the reaction.
(1)

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 (ii) If the temperature of the reaction is changed to 300 °C, predict, stating a reason in each
case, whether the equilibrium concentration of SO2Cl2 and the value of Kc will increase
or decrease.
(3)

(iii) If the volume of the container is changed to 1.50 dm3, predict, stating a reason in each
case, how this will affect the equilibrium concentration of SO2Cl2 and the value of Kc.
(3)

(iv) Suggest, stating a reason, how the addition of a catalyst at constant pressure and
temperature will affect the equilibrium concentration of SO2Cl2.

(2)
(Total 9 marks)

8. Consider the following equilibrium.

2SO2(g) + O2(g) 2SO3(g) ΔHo = –198 kJ mol–1

(i) Deduce the equilibrium constant expression, Kc, for the reaction.
(1)

(ii) State and explain the effect of increasing the temperature on the yield of sulfur trioxide.
(2)

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 (iii) State the effect of a catalyst on the value of Kc.

(1)

(iv) State and explain the effect of a catalyst on the position of equilibrium.
(2)

(Total 6 marks)

9. Biodiesel makes use of plants’ ability to fix atmospheric carbon by photosynthesis.

Many companies and individuals are now using biodiesel as a fuel in order to reduce their
carbon footprint. Biodiesel can be synthesized from vegetable oil according to the following
reaction.

(a) Identify the organic functional group present in both vegetable oil and biodiesel.

......................................................................................................................................
(1)

(b) For part of her extended essay investigation into the efficiency of the process, a student
reacted a pure sample of a vegetable oil (where R = C17H33) with methanol.
The raw data recorded for the reaction is below.

Mass of oil =1013.0 g

Mass of methanol = 200.0 g
Mass of sodium hydroxide = 3.5 g
Mass of biodiesel produced = 811.0 g

The relative molecular mass of the oil used by the student is 885.6. Calculate the amount
(in moles) of the oil and the methanol used, and hence the amount (in moles) of excess
methanol.

......................................................................................................................................

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 ......................................................................................................................................

......................................................................................................................................
(3)

(c) The reversible arrows in the equation indicate that the production of biodiesel is an
equilibrium process.

(i) State what is meant by the term dynamic equilibrium.

...........................................................................................................................

...........................................................................................................................
(1)

(ii) Using the abbreviations [vegetable oil], [methanol], [glycerol] and [biodiesel]
deduce the equilibrium constant expression (Kc) for this reaction.

(1)

(iii) Suggest a reason why excess methanol is used in this process.

...........................................................................................................................

...........................................................................................................................
(1)

(iv) State and explain the effect that the addition of the sodium hydroxide catalyst will
have on the position of equilibrium.

...........................................................................................................................

...........................................................................................................................

...........................................................................................................................
(2)

(d) The reactants had to be stirred vigorously because they formed two distinct layers in the
reaction vessel. Explain why they form two distinct layers and why stirring increases the
rate of reaction.

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 ......................................................................................................................................

......................................................................................................................................

......................................................................................................................................

......................................................................................................................................
(2)

(e) Calculate the percentage yield of biodiesel obtained in this process.

......................................................................................................................................

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......................................................................................................................................

......................................................................................................................................
(2)

(f) When biodiesel is combusted it produces carbon dioxide. Explain why the use of
biodiesel as a fuel does not significantly contribute to global warming.

......................................................................................................................................

......................................................................................................................................
(1)
(Total 14 marks)

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 Equilibrium Exam Question Markscheme

1. C
[1]

2. D
[1]

3. B
[1]

4. A
[1]

5. C
[1]

6. B
[1]

[SO 2 Cl 2 ]
7. (i) (Kc) = ;
[Cl 2 ][SO 2 ]
Ignore state symbols.
Square brackets [ ] required for the equilibrium expression. 1

(ii) value of Kc increases;

[SO2Cl2] increases;
decrease in temperature favours (forward) reaction which is exothermic;
Do not allow ECF. 3

(iii) no effect on the value of Kc / depends only on temperature;

[SO2Cl2] decreases;
increase in volume favours the reverse reaction which has more
gaseous moles;
Do not allow ECF. 3

(iv) no effect;
catalyst increases the rate of forward and reverse reactions (equally) /
catalyst decreases activation energies (equally); 2
[9]

8. (i) (Kc =) [SO3]2 /[O2] [SO2]2; 1

(ii) yield (of SO3) decreases;

forward reaction is exothermic / reverse/backwards reaction is endothermic /
equilibrium shifts to absorb (some of) the heat;
Do not accept exothermic reaction or Le Chatelier’s Principle.
Do not allow ECF. 2

(iii) no effect; 1

(iv) no effect;
the rates of both the forward and reverse reactions increase equally; 2
[6]

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9. (a) ester; 1

1013.0
(b) amount of oil = = 1.144 mol;
885.6
200.0
amount of methanol = = 6.240 mol;
32.05
since three mol of methanol react with one mol of vegetable oil the
amount of excess methanol = 6.204 – (3 × 1.144) = 2.808 mol; 3

(c) (i) rate of the forward reaction is equal to the rate of the reverse reaction /
forward and reverse reactions occur and the concentrations of the
reactants and products do not change / OWTTE; 1

[glycerol] [biodiesel] 3
(ii) Kc = ; 1
[ vegetable oil] [methanol]3

(iii) to move the position of equilibrium to the right/product side /

increase the yield of biodiesel; 1

(iv) no effect (on position of equilibrium);

increases the rate of the forward and the reverse reactions equally
(so equilibrium reached quicker) / it lowers Ea for both the
forward and reverse reactions by the same amount / OWTTE;
No ECF for explanation. 2

(d) vegetable oil is mainly non-polar and methanol is polar / OWTTE;

stirring brings them into more contact with each other / increase the
frequency of collisions / OWTTE;
Do not allow simply mixing. 2

(e) (relative molecular mass of biodiesel, C9H36O2 = 296.55)

maximum yield of biodiesel = 3.432 mol / 1018 g;
811.0
percentage yield = × 100 = 79.67 %;
1018
Allow 80 % for percentage yield. 2

(f) the carbon dioxide was absorbed by plants initially so there is no net
increase / vegetable oil is not a fossil fuel / vegetable oil is formed
from (atmospheric) carbon dioxide / OWTTE; 1
[14]

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