Ch.

15
Chemical Equilibrium
 Sketch/draw something that demonstrates “equilibrium” to you
(does not have to be chemical).
 Physical Equilibria:
Vapor Pressure Equilibria;
If a liquid is placed in an open container, evaporation occurs.

No lid
Equilibrium
18 min.

evaporation (liquid to vapor)

 If the liquid is placed in a closed container (a closed
system), evaporation will occur initially.
Soon thereafter, condensation will also begin.

closed

condensation
evaporation
At the start, evaporation will be faster, but as the
amount of vapor above the liquid increases, the rate of
condensation will increase.
Eventually:

Rate of evaporation = Rate of condensation

H2O(l) H2O(g)

This is vapor-pressure equilibrium.

At any given temperature, vapor pressure has a definite
value.

e.g. at 20oC, water has a vapor pressure of 2.33 kPa.

At 40oC water has a vapor pressure of 7.37 kPa

 Saturated Solutions:
A saturated solution of AgCl at 20oC can hold 34.7 g of
solute (AgCl) in 100 mL of water. If more AgCl is added, we
have been taught that it will sit, undissolved, on the
bottom.
This is NOT what
actually happens. Some
AgCl will recrystallize
out of the solution and
an equal amount of AgCl
will dissolve .

AgCl(s) AgCl(aq)
**Solutions are naturally closed systems.
Solution Equilibrium:

rate of dissolving equals the rate of recrystallization

AgCl(s) AgCl(aq)

Both vapor pressure equilibrium and solution

equilibrium are physical processes in which there is
continuous change, but there is no net change.

This is referred to as dynamic equilibrium.

(Lots is happening, but it is not visible to the naked eye).
Questions: Write out the chemical equations for the
following processes

a) Iodine vapor in equilibrium with iodine solid.

I2(g) ↔ I2(s)
b) Liquid mercury in a thermometer in equilibrium with
its vapor.
Hg(l) ↔ Hg(g)

c) Solid potassium nitrate in equilibrium with aqueous

potassium nitrate.
KNO3(s) ↔ KNO3(aq)
 Irreversible Vs. Reversible Reactions and
Percent Yield

Irreversible Reactions: the products cannot be

recombined to form the original reactants.
e.g: Zn(s) + 2 HCl(aq) → H2(g) + ZnCl2(aq)

Single arrow used.

e.g: CaCO3(s) + 2HCl(aq) → CaCl2(aq) + H2O(l) + CO2(g)

If a reaction is irreversible, and conditions are favorable,
the yield is 100%.

e.g. 1 Mg(s) + 2 HCl(aq)  1H2(g) + MgCl2(aq)

at start: 1 2 0 0
at end: 0 0 1 1

All reacts and forms products.

According to the balanced equation, if 1 mole of Mg is

present, 1 mole of H2 should be produced.
Since we produced 1 mole out of a possible 1 mole (1/1), it
is 100% yield. (No reactants remain.)
 Reversible Reactions: Under suitable conditions many
products of reactions can be directly recombined to
reform the reactants.

Once C
A + B → C + D and D are C+D →A+B
(forward) produced: (reverse)

Written as: A + B C+D

Double arrow
e.g. N2(s) + 3 H2(g) ↔ 2NH3(g)
at start: 1 3 0
at end: 0.8 2.4 0.4
*In a reversible reaction, the yield is less than 100%.
 For example: In a reaction we might get:
e.g. N2(s) + 3 H2(g) ↔ 2 NH3(g)
at start: 1 3 0
at end: 0.8 2.4 0.4

Only a 20% yield because ammonia (NH3)

Reacts in the reverse direction once it is produced.
A reversible reaction:
 If a reversible reaction occurs in a closed container
(nothing allowed to enter or escape), a point is reached
where:

rate of the forward reaction = the rate of the reverse reaction

At this time, there will be no observable change in the

container and both reactants and products will be
present. (Dynamic Process)

This is called chemical equilibrium. (4 min)

Example: A+ B  C + D

If we start with
A little later: At equilibrium.
A and B
These are all CLOSED containers.

Note – the reverse won’t occur if anything is allowed

to escape.
Equilibrium occurs only in a closed system. In an
open system, steady state can be reached, but not
equilibrium.
 Equilibrium is a dynamic state

– only microscopic changes are occurring,

none are visible.
 N2O4(g)  2 NO2(g)
(colourless) (brown)

N2O4(g)  [2 NO2(g), N2O4(g)]  2 NO2(g)

00C 25oC 100oC
colourless brown dark brown

At equilibrium no colour change can be observed.

Activity:
Coin Flip and Equilibrium
 Characteristics of an Equilibrium
Equilibrium is a state of balance between rates of
opposing changes (2 opposing processes are taking
place at the same time and at the same rate).

Rate vs. forw A→B

a rd r A ↔B
time graph x n
Rate fwd = Rate rev
rate n
r x
e rse
rev A ← B
time
time to reach equilibrium
 Concentration vs. Time graph: A ↔ B
A → B, A getting used up Concentration
rea
c tan remains unchanged at
t
[A] @ equilibrium.
concentration

equil.

[B]@
equil. u c t A → B, B being produced
rod
p
time

At any equilibrium condition, the amount (moles, mass, # of

molecules) of reactants and products are NOT necessarily
equal. Only the rates of the forward and reverse reactions are
equal.
 Edvantage: A Mathematical Model of Dynamic Equilibrium That Makes Cents (page 102)

1. What does turning over a coin represent?

2. ~1/2 of reactants turn to products each s, but only ~1/6th of products convert to
reactants. Identify 2 possible reasons for the reverse reaction being more difficults to
complete than the forward?
3. Why should the percentage of tails that react actually increase as the number of tails
increase?
 However, at equilibrium, the amounts of reactants, and
amounts of products remain unchanged. (They plateau
on the graph)

Equilibrium can be affected by:

1. temperature

2. pressure

3. concentration
The Significance of the Double Arrow Notation:
Often you will see double arrows of equal length, but
sometimes you will see double arrows of unequal
length. These are used to provide more information
about the equilibrium system.
Forward Forward
reaction: C
A reaction:
A+B→C A+B→C
B
Reverse C Reverse
B A
Reaction: Reaction:
C→A+B C→A+B

Proportion
of A, B and C
stay the
same.
[reactants] < [products] [reactants] > [products]
Favours products Favours reactants
% yield is High % yield is LOW
**The double arrow notation says nothing about the speed of
the reaction – rates are equal!
 Chemists discovered that for any
chemical reaction at equilibrium
Mass there is a mass action equation
Action (MAE) (Equilibrium Law) that
Expression describes the system.

The MAE relates the rate laws for

(MAE) the forward and reverse
reactions, knowing that, at
equilibrium, the
 If: aA + bB ↔ cC + dD

Rate Forward = Rate Reverse

kf [A]a[B]b = kr [C]c[D]d
kf = [C]c[D]d
kr [A]a[B]b
Keq = [C]c[D]d
[A]a[B]b
At a state of equilibrium, the mass action
expression will equal a constant, Keq (Kp or Kc) for
that given temperature.
General Equation: aA + bB  cC + dD

molar Elements and/or compounds

coefficients

Keq can be in terms of concentration (Kc) or pressure (Kp)

depending on the information provided.
*For Kc, do For Kp,
NOT include Kc = [C] [D]
c d
≠ Kp = only use
solids or (PC)c(PD)d gases.
liquids
[A]a[B]b
*concentrations / pressures are those found at equilibrium
(PA) (PB=)moles/litre
a
concentration
b

*Always set up Kc or Kp according to how the equation is

written.*
 Starting and Equilibrium concentrations for the reaction
between hydrogen and iodine at 490oC: H2 + I2 ↔ 2 HI
Starting Concentrations Equilibrium Concentrations
experiment [H2] [I2] [HI] [H2] [I2] [HI]
Kc = [HI]2
1 1.00 1.00 0 0.228 0.228 1.544
[H2] [I2]
2 0 0 1.00 0.114 0.114 0.772
3 0 0 1.5 0.171 0.171 1.158
Using [ ]s at
4 0.600 0.400 0 0.245 0.045 0.711
equilibrium.
5 0.800 1.200 0 0.090 0.490 1.423

1. Kc = [1.544]2 = 45.9 3. Kc = [1.158]2 = 45.9

[0.288] [0.288] [0.171] [0.171]
4. Kc = [0.711]2 = 45.9
2. Kc = [0.772]2 = 45.9 [0.245] [0.045]
[0.114] [0.114]
5. Kc = [1.423]2 = 45.9
[0.090] [0.490]
A chemical reaction between R2 (red) and B2 (blue) produces
RB (red-blue). All compounds are in a gaseous state. The
picture shown here represents the equilibrium mixture.

Calculate the equilibrium constant for this reaction.

The series of images below show the reaction:
CO + H2O → H2 + CO2

When is equilibrium established?

The series of images below show the reaction:
NO2 + NO2 → N2O4

Is equilibrium established?
Examples:

For the reactions below, write out the mass action

expression in terms of both concentration (Kc) and
pressure (Kp).

a. CO(g) + Cl2(g)  COCl2(g)

*For Kc, include only aq
and g substances. *For Kp, include only gases

Kc = [COCl2]1 ≠ Kp = (PCOCl2)
[CO]1[Cl2]1 (PCO)(PCl2)

square brackets = concentration P =pressure

b. Cu(H2O)62+(aq) + 4 Br-(aq)  6 H2O(g) + CuBr42-(aq)

Kc = [H2O]6[CuBr42-]
Kp = (PH2O)6
[Cu(H2O)62+][Br-] 4

c. Mg(OH)2(s)  Mg2+(aq) + 2 OH-(aq)

omit

Kc = [Mg2+][OH-]2 There’s no Kp because

there are no gases.

*Keq (Kc or Kp) can never be negative and has NO units.

Example: Given the reaction: PCl3(g)+ Cl2(g)  PCl5(g)
If the equilibrium concentrations are: [PCl3] = 0.71M,
[Cl2] = 0.71M and [PCl5]= 0.29M, what would be the
value of Kc ? At equil. – values can go directly into your MAE.

Kc = [PCl5] = [0.29] = 0.57

[PCl3][Cl2] [0.71][0.71]

Kc represents this reaction at equilibrium

at this temperature.
If Kc is large (>1): % yield is high, [PRODUCTS]
arrow notation: [reactants]

If Kc is small (<1): % yield is low, [products]

arrow notation: [REACTANTS]
Size of Kc?
2 O3(g) ↔ 3 O2(g) Kc = 2.0 x 1057

Kc is very large, indicating that mostly O2 is present

in an equilibrium system, with very little O3.

N2(g) + O2(g) ↔ 2 NO(g) Kc = 1.0 x 10-25

Very little NO is produced by this reaction.

(N2 and O2 do not react readily to produce NO.

 Which system below (all at equilibrium) has the
largest equilibrium constant? Why?

A2 + B2 ↔ 2 AB A2 + C2 ↔ 2 AC A2 + D2 ↔ 2 AD

Work on page 3, 6.
Practice:
Mass Action Expression Problems
NOT IN NOTES How do we obtain a rate law from a mechanism that
has an equilibrium step?

E.g. NO(g) + Cl2(g) ↔ NOCl2(g) step 1

NOCl2(g) + NO(g) → 2 NOCl(g) step 2 (RDS)
Kinetics  Write a temporary rate law based on the slowest step:
R = k’[NOCl2][NO]
Reaction mechanisms  Write an equilibrium expression for the double arrow
that include an reaction. Rearranging to solve for the intermediate in
equilibrium step.
the temporary rate law:
Kc = [NOCl2] [NOCl2] = Kc[NO][Cl2]
[NO][Cl2]
 Substitute the expression into the rate law.

R = k’Kc[NO][Cl2][NO]

R = k[NO]2[Cl2]
 What would be the rate law for the reaction
(I- + OCl- →IO- + Cl- in basic solution) that follows the
3-step mechanisms as follows?

OCl- + H2O(l) ↔ HOCl(aq) + OH- step 1

I-(aq) + HOCl(aq) →HIO(aq) + Cl-(aq) step 2 (RDS)

HIO(aq) + OH-(aq) →- H2O(l) + IO-(aq) step 3

R = k’[I ][HOCl] R = k[I-][OCl-][OH-]-1

Kc = [HOCl][OH-]
[HOCl] = [OCl-]Kc
[OCl-]
[OH-] (Edvantage page 88, 94-96)
NOT IN NOTES

Although we have the mass action

expression to describe a system at
equilibrium, a reaction can be written
Relating Kc differently (phase change, starting
substances).
and Kp

and
This results in more than one way to
write the expression for a given reaction.
Forms of K
The relationship between Kc and Kp:
In general, Kc ≠ Kp, since concentrations do not equal
partial pressures.
However, if either Kc or Kp is known, then the other can
be determined using:

Kp = Kc(RT)∆n

R = universal gas constant 0.0821 L atm / mol K

T = temperature in Kelvin (oC + 273)
∆n = moles of gas product – moles of gas reactants
Example: If Kc for the reaction: CO(g) + Cl2(g) → COCl2(g) is
216 at 74oC, what is the corresponding Kp value?

Kp = Kc(RT)∆n

= (216) [(0.08206)(74 + 273)]1 – 2

= 7.6
Form of K
The value of K depends on how the equilibrium equation
is balanced.
For example:
2 ½ N2O4(g) ↔ NO2(g) Versus: N2O4(g) ↔ 2NO2(g)
(equation 1) (equation 1)(x2)

Kc1 = [NO2] Kc2 = [NO2]2

[N2O4]1/2 [N2O4]
Since each concentration term is raised to a power
equal to its molar coefficient in the balanced equation,
• doubling an equation throughout will square the
original Kc value

Kc2 =
OR halving the concentration will square root the
original Kc value.

For example:
½ N2O4(g) ↔ NO2(g) Versus: 1/2 N2O4(g) ↔ 2NO2(g)
(equation 2) (x ½) (equation 2)

Kc1 = =
If an equation is reversed, the reciprocal of the original
Kc value is taken.

Kc’ = 1
Kc” *Therefore, when the equilibrium
constant is given, the equation should
also be written.
Examples:

a. N2(g) + 3H2(g) ↔ 2NH3(g) Ka

b. 1/2 N2(g) + 3/2 H2(g) ↔ NH3(g) Kb

c. 1/3 N2(g) + H2(g) ↔ 2/3 NH3(g) Kc

d. 2NH3(g) ↔ N2(g) + 3H2(g) Kd

Multiple Equilibria
Multi-step reactions have multiple equilibrium
constants (one for each step).

If we add the two reactions together, we get:

Net: A + B ↔ E + F Kc = [E][F]
[A][B]
 We would obtain the same result for Kc if the individual
Kc values for each step are multiplied together.

* If a reaction can be expressed as the sum of 2 or

more reactions, Keq for the overall reaction is
given by the product of the equilibrium constants
of the individual reactions. *
However, the equations may not always be in the form
you need them to be. You may need to rearrange the
equations before you combine them.
Eg: Use the two equations below to find Keq for the
reaction: 2 A ↔ 2D How would these equations be
re-arranged in order to obtain the
A + B ↔ C + D Kc1 given equation.
B + D ↔ A + C Kc2 → flip to get A as a reactant

A + B ↔ C + D Kc1 Work on
A + C ↔ B + D 1 / Kc2 pages 4-5.
Add:
2A ↔ 2D Keq = (Kc 1
)(1/Kc 2
)
Types of Equilibrium Problems
A: Looking for Concentration
• Given Kc and concentrations already at equilibrium
(or Kp and pressures)

• Set up MAE and solve for unknown

Recall MAE:
Kc = [products]x Omit solids Kp =(Pproducts)x gases only
[reactants]y and liquids! (Preactants)y
Example 1 :
If Kc = 28 for the reaction A(g) + 2B(g)  C(g), what
concentration of C would be in equilibrium with 0.50
mol/L of B and 0.35 M of A?
Directly to MAE

Kc = [C] 28 = [C] [C] = 2.5 M

[A][B]2 [0.35][.50]2
Example 2:
If Kc = 15 for H2(g) + I2(g)  2 HI(g), find the number of moles of
HI at equilibrium in a 2.50 L container if [H2] = 4.0 M and [I2] =
6.0 M.

Kc = [HI]2 15 = [HI]2 Complete

[H2][I2] [4.0][6.0] worksheets
#1, 2, and 3
[HI] = 19 M
moles = C x V

moles = (19 M)(2.50 L) = 48 moles

B: Determine if the system is at equilibrium.
If not – identify which way the reaction will proceed.
To determine if a system is at equilibrium, set up a MAE and see if
the answer (Qc) equals the actual Kc. If they are not equal, system is
NOT at equilibrium.
Qc = trial equilibrium constant

To determine which way the reaction will proceed, compare

the size of Qc to Kc. Place them on a “number line” to see
which way you need to move from Qc to approach Kc.
Qc Kc Reaction would go forward to
get to equilibrium.
Kc Qc

Reaction would go reverse to get to equilibrium.

In summary:
If Q = Keq, reaction at equilibrium A+B↔C
If Q > Keq, reaction proceeds R to L A+B←C

If Q < Keq, reaction proceeds L to R A+B→C

 Example: For the reaction: 2SO2(g) + O2(g) ↔ 2SO3(g) Kc = 3.5. In
a mixture, we have the following concentrations: [SO2] = 0.12 M,
[O2] = 0.018 M, and [SO3] = 0.035 M.
a) Is the system at equilibrium?
Qc = [SO3]2 = [0.035]2 = 4.73
[SO2]2[O2] [0.12]2[.018]
trial
Qc ≠ Kc , system is NOT at equilibrium
4.73 ≠ 3.5
b) Which way is the reaction proceeding? (Which reaction is
occurring at a faster rate?)
Kc Reaction
Qc proceeds in the
reverse
3.5 direction (left).
4.73
*The larger the value, the more products you have.
Example 2:
At 25oC, Kc = 18.0 for the equilibrium PCl3(g) + Cl2(g)  PCl5(g)
Suppose a reaction vessel contained these three gases at the
following concentrations: [PCl3] = 0.0520 M, [Cl2] = 0.0140 M
and [PCl5] = 0.0060 M
• Is the system in a state of equilibrium?
• If not, in which direction will the reaction have to proceed
to get to equilibrium?

Qc = [PCl5] = (0.0060) Qc 8.24 < 18.0 Kc

[PCl3][Cl2] (0.0520)(0.0140) NOT at equilibrium.
Qc Kc Reaction
proceeds in the
forward
8.24 18 direction (right).
Example 3:

Kc = 0.25 for the gas equilibrium A + B  C + 2D. If the

concentrations are
[A] = 0.020M, [B] = 0.15 M, [C] = 0.30 M and [D] = 0.40 M.
a) Is the system at equilibrium?
b)
QcIf=not,
16 ≠in 0.25
which= direction
Kc Qc will> Kc,it reaction
proceed?goes left

Example 4:
For the reaction below, Kp = 333 at 700 K. Suppose that
initially 3.0 atm of H2(g), 0.10 atm of I2(g), and 1.0 atm of
HI(g)
Qp =are mixed
333 at =700
= 333 KpK. Will reaction occur? If so, in
which direction? H2(g)Qc + I=2(g)
Kc,---> 2HI(g)is at equilibrium.
system
C: Finding the equilibrium constant, Kc, given initial or
starting amounts.

•These require the use of an ICE chart.

•I.C.E. Charts are simply a way of organizing the various
[ ] of species as follows:

[I] = [initial] [C] = [change] [E] = [equilibrium]

Amount reacting or Amounts for

starting the MAE
amount produced.
amounts
Note:

If concentrations are provided for initial

reactants BEFORE they are combined in a
reaction vessel, You must find the new
concentration for [I].

You may have to solve for Q to determine the

direction of the reaction.

(Try some Edvantage fill – in boxes).

 initial divide by volume
Example 1: We begin with 4.0 moles of A and 2.0 moles of B in a
1.0 L container. At equilibrium the container has 5.0 moles of C
produced. Calculate the value of the equilibrium constant, Kc.
2 A(g) + B(s)  3 C(g)
[I] Ratio is the same
mole = 4.0 mol A solid can’t
initial vol. 1.0 L have a ∆[ ] - 0M
4.0 M omit
[C]
2A : 3C
change X 5.0 5.0 M
3.3 M
[E] [I] + [C]
[I] – [C]
mole = 5.0 mol =
4.0 – 3.3 = vol. 1.0 L
equilibrium 0.7M 5.0 M
Kc = [C]3 = [5.0]3 = 255 = 260
[A]2 [0.7]2
 Example 2:
In a 1.0 L container, 0.500 mol of SO2 and 0.500 mol of O2 are
initial
added. The following reaction reaches equilibrium:
2 SO2(g) + O2(g) ↔ 2 SO3(g) At equilibrium, the concentration of
SO3 = 0.150 mol/L. Calculate Kc and the % yield of the reaction
2 SO2(g) + O2(g) ↔ 2 SO3(g)
[I] 0.500 mol = .5 M 0.500 mol = .5 M 0
1.0 L 1.0 L
[C] 2 : 2- X -X +
X 0.150 0.150M 2 : 1 0.075 0.150 M
0.150 X
[E] [I] – [C] = [I] – [C] = =
.5 - 0.150 = 0.350 0.150 mol/L
.5 - 0.075 = 0.425
Kc = [SO3]2 = [0.150]2
= 0.432
[SO2]2[O2] [0.350]2[0.425]
 % yield?
2 SO2(g) + O2(g) ↔ 2 SO3(g)
[I] .5 M .5M
[C]
[E] 0.150 mol/L

% yield = amount produced 100 = 0.150 mol/L 100 = 30%

maximum product possible .5
If all reacts.

ratio of reactants : If ALL the SO2 reacts, how

2 SO2: O2 much product will we get?
mole ratio: 2 1 SO2 : SO3
We have: .5 .5 equation 2 : 2
SO2 is the limiting reactant question .5 X
(all gets used up) X = .5
 If you have more than one product, you may choose
which one to use in your calculations (you will get the
same result).

Remember: To determine the maximum product

possible, chose the limiting reactant (the reactant
whose [I] will be entirely used up).
Example 3:
25% reacts
At equilibrium the reaction is 25% complete. If the initial
pressure, I, of AO4 was 8.0 atm, calculate Kp.

Given: 3AO4(g) ↔ A3O6(g) + 3O2(g)

I
8.0 0 0
C
(.25)(8.0) = 2 3: 1 = 0.67 3: 3
= 2 RATIOS
25% 2 X 2 X
E (.75)(8.0) = 6
75% 0 + 0.67 = 0.67 0+2=2
or 8.0 – 2 =
Kp = (PO2)3(A3O6) Kp = (2)3(0.67)
(AO4)3 (6)3 = 0.025
Example 4: There is 2.0 M of A and B initially. At equilibrium, 60%
of A is used up. Calculate Kc.

3A(g) + 2B(g) ↔ 4C(g)

[I]
2.0 M 2.0 M 0M
[C] 60% reacts 3 : 2 2 :4
X = 0.8 X = 1.6 ratios
(2)(0.6) = 1.2 M 1.2 X 0.8 X
[E] 40% remains [I] – [C] = [I] + [C] =
(2)(0.4) =
0.8 M 2.0 – 0.8 = 1.2 0 + 1.6 = 1.6
or 2–1.2 =
Kc = [C]4 = [1.6]4
= 8.9
[A]3[B]2 ([0.8]3[1.2]2)
 Example 5: 1.00 moles of both H2 and CO2 are placed in a 1.0 L
container with 0.50 mole of H2O and 0.50 mole of CO, and are
allowed to react until equilibrium is attained. If the equilibrium
concentration of H2 is 0.66 M, what are the equilibrium
H2(g) of the
concentrations of each + other
CO2(g) ↔ H2 O
substances? What
(g)
+ Kc?
is
CO
[I] (g)
1.0 moles/1L 1.0 moles/1L 0.5 moles/L 0.5 moles/L
[C]
1 – 0.66 = 0.34 0.34 0.34 0.34
[E]
0.66 M 0.66 M 0.5+.34=.84 0.5+0.34=.84

Kc = (.84)(.84) = 1.6
(0.66)(0.66)
 D: Finding the concentration of gases at equilibrium, given initial amounts and Kc.

plug in “X” as the amount reacted in your [C] row in an I.C.E.

chart. These use the same coefficients as the balanced equation.

•There are THREE ways to solve these problems, depending on

the information given:

First: Check to see if you can take the square root of

your MAE.

If not see if: - Kc is small ( “x” can be omitted)

- Kc is large (might need the quadratic)
 Example 1 (square root of MAE):
The equilibrium constant, Kc, is 16 at a certain temperature.
If 50.0 moles of each reactant was placed in a 5.00 Litre container
and equilibrium is reached, find the amount of each substance
present. What % does this go to completion?
50.0 moles = 10 M CO(g) + H2O(g)  CO2(g) + H2(g)
5.00 L
[I] 10 M 10 M 0 0
Two
empty - -X + +
rows [C] X X X
indicate
need to [E] 10 - X 10 - X X X
use “x”

Plug into MAE.

Kc = 16 = (X)(X)
CO(g) + H2O(g)  CO2(g) + H2(g)
16 (10-X)(10-X)
= X2
(10-X)2 10 - X 10 - X X
[E] X

16 = X2
(10-X)2 [CO] = [H2O] = 10 – X = 10 – 8 = 2.0 M
moles =2M (5 L) = 10. moles

X = 8.0 M [CO2] = [H2] = X = 8.0 M

moles =8M (5 L) = 40. moles

Moles = C x V
 Example 2 (square root of MAE): 2 HCl(g)  H2(g) + Cl2(g)
Kc = 16 Two moles of HCl were placed in a 5.0 L vessel.
How much of each substance was present at equilibrium?
2 HCl(g)  H2(g) + Cl2(g) Kc =[H2][Cl2]
[HCl]2
2 mol = 0.4 M
[I] 0 0 16 =[X][X]
5.0 L
[0.4-2X]2
In ratio of
balanced [C] 2X X X 16 = [X]2
equation: [0.4-2X]2
[I] – [C] [I] + [C] [I] + [C] 16 = [X]2
[E] 0.4 - 2X X X [0.4-2X]2
4= X
[HCl] = 0.4-2X [H2] = [Cl2]= X
[0.4-2X]
= 0.4 –(2)(0.18) =0.18 M Plug in X
= 0.04 M = (0.18M) (5L) 4 (0.4 – 2X)= X
= (0.04M) (5L) = 0.90 moles 1.6 – 8X= X
= 0.20 moles 1.6 = 9 X
X = 0.18 M
Another Example : At a certain temperature the reaction:
CO(g)+ H2O(g)↔CO2(g)+ H2(g) has a Kc =0.400. Exactly 1.00 mol of each
gas was placed in a 100.0 L container and the mixture was allowed to
react. Find the equilibrium concentration of each gas.
CO + H2O ↔ CO2 + H2
1 mol = 0.01 M
[I] 0.01 M 0.01 M 0.01 M 0.01 M
100 L
[C] +X +X -X -X MAE:
[E] 0.01+X 0.01+X 0.01-X 0.01-X 0.400 = (0.01-X)(0.01-X)
(Hint –we have been given both reactants and products, so (0.01+X)(0.01+X)
we first need to determine Qc to see which way the reaction
will proceed). The mass action expression gets set up according
0.400 = (0.01-X)2
to how the equation is written above, but we determine which (0.01+X)2
substances get used up (subtracted) or produced (added)
according to the value of Qc). 0.632 = (0.01-X)
[CO] = [H2O] = 0.01+X = (0.01+X)
Qc = (0.01)(0.01) = 1
0.01+0.0023 = 0.0123 M
(0.01)(0.01) 0.632(0.01+X) = (0.01-X)
[CO2] = [H2] = 0.01-X =
Qc > Kc 0.632(0.01+X) = (0.01-X)
(1) (0.400) 0.01-0.0023 = 0.0077 M
Reaction goes backwards X = 0.0023 M
One more to try:
The reaction shown below has Kc = 4.06 at 500oC. If 10.0 moles of
each reactant is loaded into a 10.0L reaction flask, find the
concentration and moles of all components once equilibrium is
reached.
Kc =[CO2][H2]
CO(g) + H2O(g) ↔ CO2(g) + H2(g) [CO2][H2O]
10 mol = 1M
1M 0 0
[I] 10L 4.06 = [X][X]
[1-X][1-X]
[C] X X X X
4.06 = [X][X]
[E] 1-X 1-X X X
[1-X][1-X]

2.015 = X
[CO] = [H2O] = 1-X = 1-0.67 = 0.33M 1-X
Moles = 0.33M x 10.0L = 3.3 2.015(1-X)= X
[CO2] = [H2] = X = 0.67 M 2.015= 3.015 X
Moles = 0.67M x 10.0L = 6.7 X = 0.67 M
 What does a small Kc tell us about the reaction?
What does this mean?
A small Kc tells us reactants are favoured (we have
more reactants than we have products).
Low % yield! Not much is reacting.

*Whenever “x”, the change in concentration (or the

amount that reacts), is very small (small Kc is ~1x10-4)
we assume that [I] – [C] ≈ [I]. e.g. [I] 0.40 M
[C] – 0.00032
[E] = 0.39968
≈ 0.40 M
Therefore, we OMIT X in the terms that include the
initial concentrations.
We must do a validity check (called successive
approximation) to see that our assumption is correct.

The form of “X” cannot be larger than 5% of the [ I ].

 Example 1 (can’t square root – Kc is small):
Small – omit x?

Initially, in air, [N2] = 0.033M and [O2] = 0.0081 M for the reaction:
N2(g) + O2(g)  2NO(g). If Kc = 4.8 x 10-12, what is [NO] at equilibrium?
N2(g) + O2(g)  2NO(g) Validity check:
0.033M 0.0081 M 0 is [C] x 100
[I] [I] under 5% ?
-X -X +2X (1.8 x10-8) x 100 = 0.00022%
[C]
(0.0081) (okay to omit X)
(use smaller [I] value)
[E] 0.033-X 0.0081-X 2X
(2X)2=(2X)(2X) = 4X2

Kc = 4.8 x 10-12 = [2X] 1.28x10-15 = 4X2

2
You can’t square
[0.033-X][0.0081–X] root the MAE 3.2 x10-16 = X2
4.8 x 10-12 = [2X]2 1.8 x10-8 M = X
Omit X [NO] at equilibrium = 2X
[0.033][0.0081]
4.8 x 10-12 (0.033)(0.0081) = [2X]2 = 2 (1.8 x10-8 M ) = 3.6 x10-8 M
Example 2: 2 SO3(g) ↔ 2 SO2(g) + O2(g) Kc = 2.4 x 10-6
If 0.180 mol of SO3 is loaded into a 1.50 L flask, find the
concentration and moles of all components at equilibrium.
Kc = 2.4 x 10-6 = (2X) (X)
2

2 SO3(g) ↔ 2 SO2(g) + O2(g) (0.12-2X)2

0.180 = 0.12
[I] 1.50L
0 0 omit
2.4 x 10-6 = (2X)2(X)
[C] 2X 2X X (0.12)2
2.4 x 10-6 (0.12)2 = (2X)2(X)
[E] 0.12-2X 2X X
3.46 x10-8= 4X3
3.46 x10-8/ 4= 4X3/4
0.12-2(2.05 x10-3 ) 2.05 x10-3 M
= 0.1159 = 0.12 M
2(2.05 x10 )
-3 3 8.64 x10-9
= 3 X3

Validity check:
= 0.0041M 2.05 x10 -3
=X
is [C] x 100 under 5% ? 2X x 100 = 0.0041 x 100= 3.42%
[I] [I] .12
Example 5: At a certain temperature the reaction:
CO(g) + H2O(g) ↔ CO2(g) + H2(g) has a Kc =0.400.
Exactly 1.00 mol of each gas was placed in a 100.0 L container and
the mixture was allowed to react. Find the equilibrium
concentration of each gas.
1.00 mol = 0.01 M
CO(g) + H2O(g) ↔ CO2(g) + H2(g) 100.0L
Qc = (0.01)((0.01) = 1
[I] 0.01 M 0.01 M 0.01 M 0.01 M
(0.01)(0.01)
X X X X
[C] Qc > Kc
Reaction will go
[E] 0.01 +X 0.01 +X 0.01 -X 0.01 -X
left.

0.400 = (0.01-X)2
(0.01 + X)2
Quadratic Equations
Once in awhile, it might be necessary to solve a quadratic. This
is the case when the value of Kc is larger than our validity check
allows, and we can’t take the square root of our MAE (products
are favoured).

Quadratic General Form: Quadratic Formula:

ax2 + bx + c = 0 x = -b-+ b2- 4ac

2a

(You will obtain 2 solutions – one will NOT be possible.

Example 5: At 240oC, the value of Kc is 5.0 for the following
reaction. If a 3.00 L container holds 15 moles of PCl5, how many
moles will dissociate to form PCl3 and Cl2 ? PCl3(g) + Cl2(g) ↔ PCl5(g)
[I] 0 0 5.0 M

[C]
X X X
[E]
X X 5.0 - X

5.0 = (5.0 – X)
(X)2 X = 0.905 M or X = -1.105 M

5.0 X2 + X – 5.0 = 0 X = amount dissociating

+ = (0.905 M) (3.00L)
x = -1 -12- 4(5)(-5)
2(5) = 2.72 moles
 Example 6: consider the I.C.E. chart below. Kc = 54 for this
reaction. What are the equilibrium concentrations?
H2(g) + I2(g) ↔ 2 HI(g) Kc is large –
[I] 0.006 M 0.004 M 0.02 M can’t omit it,
also can’t
[C] square root
X X 2X the MAE
(diff. [I]
[E]
0.006 - X 0.004 - X 0.02 + 2X
Qc = ?
Qc = [0.02]2
[0.006][0.004] 54 = [HI]2
54 = [0.02+2X]2
[H2][I2]
= 17 [0.006-X][0.004-X]

54 = (0.02 - 2X)(0.02-2X)
Rxn goes forward. Simplify (0.006-X)(0.004-X)
(foil)
 0.0004 + 0.04X + 0.04X + 4X2

54 = (0.02 + 2X)(0.02+2X)
(0.006-X)(0.004-X)

0.000024- 0.006X - 0.004X +X2 (Bring across.)

54(0.000024 – 0.006X – 0.004X + X2 = 0.0004 + 0.04X + 0.04X + 4X2
Multiply through.
0.0013 – 0.54X + 54X2 = 0.0004 + 0.08X + 4X2
Group like terms.
50X2 - 0.62X + 0.0009 = 0
ax2 + bx + c = 0
50X2 - 0.62X + 0.0009 = 0 H2(g) I2(g)
ax2 + bx + c = 0 0.006 - X 0.004 - X
0.006 – 0.00168 0.004 – 0.00168
= 0.00432 M = 0.00232 M
+- 2
x = -b b - 4ac 2 HI
2a 0.02 + 2X
0.02 + 2(0.00168)
x = -(-0.62) -+ (-0.62)2- 4(50)(0.0009) = 0.0233 M
2(50)

X = 0.0107 M OR X = 0.00168 M
Not possible.
 Flow chart – solving problems
Read the problem.
Solve for Kc (amounts To see if system’s at
given are already at Initial amounts are given equilibrium
equilibrium).

Set up an ICE chart. Solve for Qc by

Plug into MAE
If [I] and one [E] given
(or % given), and you
are asked to find Kc:
plugging values
If [I] and Kc given, into MAE
asked to find [E]
Plug in “X” as the amount reacted.

Complete ICE chart, Complete ICE chart,

plug into MAE and solve. plug into MAE. Solve:

If Kc small (1x10-4) : If Kc is large:

MAE
omit the X. use quadratic
Do a validity check.
 We know that forPrinciple
Le Chatelier’s a reversible reaction at equilibrium:

the forward rate = the reverse rate

As a result, the mass (amount) of a given substance,

whether a reactant or product, remains constant , and
it appears like nothing is occurring within the reaction
chamber.
N2
N2 + 3H2 ↔ 2 NH3 H2 NH3 H2
NH3 N H2NHH2
2 3
H2
NH3 H2
 However, when something happens to disturb a system
at equilibrium, we say that it has been subjected to a
stress.

When this occurs, the equilibrium system SHIFTS to

compensate (counteract) the stress, and a NEW
equilibrium condition is reached.

This is Le Chatelier’s Principle.

 SHIFT
Think of the system trying to do the opposite in order
to re-establish equilibrium.

To counteract the stress (the change in conditions),

the reaction will proceed faster in ONE direction
(either forward OR backward) until it reaches a new
equilibrium.
A stress could be a change in:

•concentration of one of the substances

•temperature

•pressure

**A change in temperature is the only stress that

alters the value of Keq.
CONCENTRATION (M)
To change the concentration of a substance we can do
a variety of things. Such as:
add more of the substance or solute

For example: 3H2(g) + N2(g) ↔ 2NH3(g)

Action: add H2(g) Stress: increase in [H2(g)]

Note – we could add a compound that contains an ion
from the equilibrium.
For example: NaCl(s) ↔ 2Na+ (aq) + Cl-(aq)
Action: add NaOH
Na+ and OH- Stress: increase in [Na+]
• remove a substance

For example: 3H2(g) + N2(g) ↔ 2NH3(g)

Action: remove NH3(g)

Stress: decreases in [NH3(g)]

add water to the system (affects aqueous substances)

For example: Sr(OH)2(s) ↔ Sr2+(aq) + 2 OH-(aq)

action: add water(l)

If water is not found in the equilibrium, adding
water causes there to be more solvent, so it will
decrease the [ ] of aqueous substances.

Stress: decreases [Sr2+] and [OH-]

add something that would react with one of the
substances
+
+ H
For example: Sr(OH)2(s) ↔ Sr2+(aq) + 2 OH-(aq)

Action: Add HCl (an acid). (Ionizes to H+ and Cl-)

The H+ reacts with the OH-, which causes
(stress) a decrease in [OH-] as it reacts.

H+ + OH- → H2O
acid + base
OR – we could add something that would react
with the strontium ion (Sr2+)
 So now, let’s see what happens to the equilibrium
system when we alter the concentration.

Take this system at equilibrium:

A(aq) + B(aq) ↔ C(aq) + D(aq)

Apply the stress: add A (Stress: increase in [A])

The goal is to do the opposite – so the reaction will

proceed one way in order to decrease the [A].

Reaction shifts?
 Stress: increase in [A]) Goal: decrease [A]

shift
A(aq) + B(aq) ↔ C(aq) + D(aq)

Note:
In doing so, the [B] decreases (is used up), [C] and [D]
both increase (are produced).

**The value for the equilibrium constant, Kc,

remains the same.
To remember:
If you ADD, the reaction shifts AWAY from that
substance!

Or if you TAKE-AWAY a substance, the reaction shifts

TOWARD it.

Always ask yourself, do we need to make more of the

substance (have it be a product), to increase the
concentration, or do we need to have it react (use it
up) to decrease the concentration?
Other examples:
Take the system at equilibrium:
3H2(g) + N2(g) ↔ 2 NH3(g)

Complete the information:

A) Stress: decrease [N2] b) Stress: Add NH3

Goal? [N2] Make more. Goal? [NH3] Use extra.

Shift? Left or reverse. Shift? Left or reverse.

3H2(g) + N2(g) ↔ 2 NH3(g)

 TEMPERATURE

In order to determine how changes in temperature

will alter a system at equilibrium, we first need to
review the idea of endothermic and exothermic

reactions and notation.

Recall:
Endothermic – the reaction requires heatSurrounding
area cools.
(heat/energy is a reactant)(temp. dec.)
A + heat → B A → B ∆H is positive
A + 23 kJ→ B A → B ∆H = +23 kJ

Surrounding
Exothermic – the reaction releases heat/energy
area warms.
(it is a product) (temp. inc)
B → A + heat B → A ∆H is negative
B → A + 23 kJ B → A ∆H = -23 kJ
Notice how these two reactions are opposites, so
we could write it using a double arrow: endothermic (forward)
A + heat ↔ B
exothermic (reverse)
Stress: an ↑ in temperature (we are warming the whole reaction)
Goal: the system will want to decrease the temperature (cool the
system).
Reaction shift: in the endothermic direction in order to use or
absorb the extra heat.

endothermic endothermic
A + heat ↔ B B ↔ A + heat

add add
• An increase in temperature favours an endothermic
shift. (note – this will NOT always be in the
forward direction)

• A decrease in temperature favours an exothermic

reaction.

Example: 3H2 + N2 ↔ 2NH3 + 92 kJ

Stress: decrease in temperature Cools the system.

To ↑T…….we want
Goal: to heat the Shift: Forward or right.
(Makes more energy).
surroundings.
 Example: A(g) + B(aq) ↔ C(aq) ∆ H = 250kJ

250kJ + A(g) + B(aq) ↔ C(aq)

Stress: a decrease in temperature

Goal: To increase temperature.
Shift: Reverse or left.
**Unlike other stresses, a change in temperature WILL
change the value of the equilibrium constant**
Reactants ↔ Products K = products
reactants
If the reaction goes forwards, K increases.
If the reaction goes backwards, K decreases.
Pressure:
Changes in pressure have little effect on solids,
liquids, and aqueous mixtures. Therefore, if pressure
is the applied stress, ONLY look at the gaseous
substances in the reaction.

Remember:
an increase in pressure is the same as a decrease in volume

*If given “volume change” as a stress, convert this to a

change in pressure.
To determine what effect changes in pressure will
have on the system, count the number of gas
molecules on either side of the equation.
More particles exert more pressure.

If the two sides contain an equal number of

particles, a change in pressure will have no effect on
the system.
3H2(g) + 1N2(g) ↔ 2NH3(g) ∆H = - 92 kJ
4 particles 2 particles
more less
pressure pressure
With this in mind:
 A decrease in pressure will cause the reaction to
proceed to the side that increases pressure.

Therefore – it will shift to the side with more particles.

Or – an increase in pressure will cause the reaction to

proceed to the side with fewer particles.
In which direction would the following reaction shift if
the pressure were increased?
2A(g) + B(s) ↔ 3C(g)

2 particles 3 particles

Stress: ↑P (increase in pressure)

Goal: ↓P (decrease in pressure)
Need fewer particles.
Shift: backward or to the left
Another example:
PCl3(g) + Cl2(g) ↔ PCl5(g)
2 1
Which way would the reaction shift if we increased the
volume of the container?

Stress: an increase in volume = a decrease in pressure

Goal: to increase the pressure
To do so, you need more gas particles.

Shift: reverse or left

When a friend shakes up your soft drink before handing it to
you, how would tapping the lid of the container help?
 CATALYSTS

Catalysts are NOT

considered a stress because
they favour neither reaction.

They will increase the rate

of both the forward and the
reverse reactions equally.
Therefore, the system will reach
equilibrium more rapidly, but
without a shift.
To Note:

 Solids
and liquids are not part of the mass action
expression, so the addition of a solid to an equilibrium
mixture will not cause a shift.

The addition of a gas to an equilibrium system might

stress a system, depending on changes to volume and
pressure.
Two cases: the addition of an inert gas on equilibrium:

1) at constant volume (non-constant pressure)

 the total pressure will increase BUT

the concentrations of the products and
reactants
i.e. ratio of their moles to the volume of
the container will not change.

Therefore, when an inert gas is added to the system in

equilibrium at constant volume there will be no effect on
the equilibrium.
2) at constant pressure (volume changes):

 the total volume will increase.

Therefore, the number of moles

per unit volume of various reactants and products will
decrease.

Hence, the equilibrium will shift towards the direction in

which there is increase in number of moles of gases.
Consider the following reaction in equilibrium:

2 NH3 (g) ⇌ N2 (g) + 3 H2 (g)

The addition of an inert gas at constant pressure to the

above reaction will shift the equilibrium in the forward
direction because the number of moles of products is
more than the number of moles of the reactants.
 Le Chatelier’s Principle: more problems
When completing the following charts you may use words
(increase/decrease) or up and down arrows, etc.
1. Complete the following tables.
2 CO2(g) + H2(g) + heat ↔ CO(g) + H2O(g) 2
Stress Goal Shift [CO2] [H2] heat [CO] [H2O] Kc
(be specific)
Pressure
increase ↓P None – no effect (same # of particles) -----
Temperature
decrease ↑T ← ↑(produced)↑ − ↓(used up)↓ ↓
[CO2]
decrease ↑[CO2] ← ↑(produced)↑↓(used up)↓
− ----
[H2]
increase ↓[H2] → ↓ − ↓ ↑(produced)↑ ----
[CO]
decrease ↑[CO] → ↓(used up) ↓ ↓ − ↑ ----
[H2O]
increase ↓[H2O] ← ↑(produced)↑ ↑ ↓ − ----
Volume
increase ↓P ↑P None – no effect (same # of particles) -----
2. N2(g) + 3H2(g) ↔ 2NH3(g) + 22.0 kcal

Stress Goal Equilibrium [N2] [H2] [NH3] heat Kc

shift
Add N2 ↓N2 → ----- ↓ ↑ ↑ same
Add H2 ↓H2 → ↓ -------- ↑ ↑ same
Add NH3 ↓NH3 →
↑ ↑ ------- ↓ same
Remove N2 ↑N2 →
------ ↑ ↓ ↓ same
→
Remove H2 ↑H2 ↑ ------ ↓ ↓ same
↑NH3 → ↓ ↓ ------- ↑ same
Remove NH3
Increase ↓T → ↑ ↑ ↓ ------- ↓
temperature
Increase ↓P → ↓ ↓ ↑ ↑ same
pressure
Decrease ↑T → ↓ ↓ ↑ -------- ↑
temperature → ↑ ↑ ↓ ↓ same
Decrease ↑P
pressure
3. CoCl42-(aq) + 6 H2O(l) ↔ Co(H2O)62+(aq) + 4Cl-(aq) + heat

Stress Goal Shift [CoCl42-] H2O [Co(H2O)62+] [Cl-] heat Kc

Cool the system
↓T ↑T → ↓ ↓ ↑ ↑ ------ ↑
Add KCl
↑[Cl-] ↓[Cl-] ← ↑ ↑ ↓ ----- ↓ ------
Add AgNO3
(reacts with Cl-)
↑[Cl-] → ↓ ↓ ↑ ----- ↑ ------
↓[Cl-]
Add water
↓[ions] ↑ [ions] → ↓ ----- ↑ ↑ ↑ ------
More on products 2-
Add CoCl 4
↓CoCl42-] → ------ ↓ ↑ ↑ ↑ ------
 4. NaOH(s) ↔ Na+(aq) + OH-(aq) + 10.6 kcal

Stress Goal Shift Amount [Na+] [OH-] Kc

NaOH(s)

Add H2O ↓[ions] ↓ ↑ ↑ same

↑[ions] →
Add NaCl
↑[Na+] ↓[Na+] ← ↑ ____ ↓ same
Add KOH ↑[OH-] ↓[OH-] ← ↑ ↓ ↓ same
Add H+ → ↓ ↑ ↑ same
↓ [OH-] ↑[OH-]
Increase
temperature
↑T ↓T ← ↑ ↓ ↓ ↓
Decrease
pressure
↓P ↑P No effect – no gases in the equilibrium equation.
 Equilibrium: Le Chatelier’s Principle Experiment

Purpose: To examine several equilibrium systems, predict the effect that certain
stresses will have on these systems and then test these predictions.

Apparatus: utility clamp, ring stand, thin wire, 4 small Petri dishes, various test
tubes, two masses, various beakers, dropper bottles, eye droppers, Bunsen
burner, hot plate, safety goggles, matches, scoopulas and test tub racks.

Materials: ice cubes, iodine crystals, solid crystalline samples of KSCN, K 2HPO4,
Fe(NO3)3∙9H2O, CoCl2, aqueous solutions of KSCN, Fe(NO3)3, NaOH, NaC2H3O2,
NH4Cl, and HCl
Safety:
• Wear safety goggles at all times.
• Sodium hydroxide and hydrochloric acid are corrosive, iodine vapour is toxic if
inhaled.
• Some of the solids used in Equilibrium #5 are incompatible with each other, so DO
NOT MIX them with each other in the solid state. Be careful to use the scoopula
intended for each solid!
Prelab. Exercise:

Examine each of the equilibrium systems described in

the lab. Look at both the relevant equations and the
ways that you will change (or “stress”) the systems.

In the data table provided:

• identify the various stresses being applied (be
specific)

• show the predicted direction of the equilibrium shift,

• and mention what you will observe when the system

“shifts”.
Equilibrium System #1 H2O(s) + energy ↔ H2O(l)

Equilibrium System #2 I2(s) + energy ↔ I2(l)

Equilibrium System #3 C2H3O21-(aq) + H+(aq) ↔ HC2H3O2(aq)

Equilibrium System #4 NH41+(aq) ↔ NH3(g) + H+(aq)

Equilibrium System #5 Fe3+(aq) + SCN-(aq) ↔ FeSCN2+(aq) + heat

Equilibrium System #6 Co(H2O)61-(aq) + Cl1-(aq) + heat ↔ CoCl42-(aq) + 6H2O(l)

 Predicted Actual Direction
Equilibrium # Stress Caused Goal Direction of Shift Observations of Shift
1 H2O(s) + energy  H2O(l) ↑P ↓P None – no gases

2 I2(s) + energy  I2(g) ↑T ↓T → turn purple

purple
3(i) C2H3O2 (aq) + H (aq)  HC2H3O2
- + Add HCl ↓ [H+] → Produce acetic acid
↑ [H+] (smell vinegar)
3(ii) C2H3O2-(aq) + H+(aq)  HC2H3O2 Add NaOH ↑ [H+] ← Vinegar smell
↓ [H+] disappears
4(i) NH4+(aq)  NH3(g) + H+(aq) Add NaOH ↑ [H+] → Produce ammonia
↓ [H+] “diaper pail
odour”
4(ii) NH4+(aq)  NH3(g) + H+(aq) Add HCl ↓ [H+] ← Ammonia smell
↑ [H+] disappears
5(i) Fe3+ +SCN-  FeSCN2+ + heat Add Fe(NO3)3 ↓[Fe3+] → Turn red
yel clear red ↑[Fe3+]
5(ii) Fe3+ +SCN-  FeSCN2+ + heat Add KSCN ↓[SCN-] → Turn red
yel clear red ↑[SCN-]
5(iii) Fe3+ +SCN-  FeSCN2+ + heat Add K2HPO4 ↑[Fe3+] ← Turn yellow
yel clear red ↓[Fe3+]
5(iv) Fe3+ +SCN-  FeSCN2+ + heat Add Fe(NO3)3 or ↓[react] → Turn red
KSCN ↑[reactant]
yel clear red
↑T ↓T ← Turn yellow
5(v) Fe3+ +SCN-  FeSCN2+ + heat
yel clear red
↑T ↓T → Turn blue
6(i) Co(H2O)6- + Cl- + heat  CoCl42- + 6H2O
pink blue
6(ii) Co(H2O)6- + Cl- + heat  CoCl42- + 6H2O ↓[ions] ↑[ions] ← turn pink
pink blue
6(iii) Co(H2O)6 + Cl + heat  CoCl42- + 6H2O
- - ↑[Cl -] ↓[Cl -] → Turn blue
pink blue
 Application: Haber Process

In 1910, the German chemist Fritz Haber, developed an

efficient process that combines nitrogen and hydrogen to
make ammonia.
N2(g) + 3H2(g) ↔ 2NH3(g) + 92 kJ

According to Le Chatelier’s Principle, high pressure and low

temperatures would be optimal conditions for producing
ammonia.

4 min youtube
But, it is expensive to build high pressure equipment and a
high temperature is necessary for a satisfactory reaction rate
(time is money). The compromise between temperature and
pressure is used (~500oC and 3.5 x 104 kPa). A catalyst is used
to speed up the rate, and NH3 is removed from the reaction
container by liquefying it. The unreacted nitrogen and
hydrogen gases are recycled until the conversion yield is
higher.

Almost all of the nitrogen compounds used today are derived

from ammonia made by the Haber process.

Of interest: Le Chatelier tried an experiment in 1901 that was

similar to Haber’s, but a violent explosion took place and he
stopped work on the process.
 Graphing A System at Equilibrium

The progress of a reversible reaction, as shown on a Concentration

versus Time graph, provides us with a lot of information.

Simply by looking at the shape of the graph, we can identify when the
system:

 is at equilibrium (graph plateaus) or

 where a stress has been applied (noticeable change in graph shape)

since a stress causes a shift which alters concentrations of each
substance.
 What can we tell looking at these graphs?

Any addition/removal of a
substance will be drawn as
a sharp vertical line.

Concentration vs. Time:

• Concentration is on the vertical axis, time on the horizontal axis.
• A different line is drawn for each substance in the reaction.
 AT equilibrium RATES are Equal.

Rate versus Time:

• Reaction rate is on the vertical axis and time on the horizontal.
• One line is drawn for the forward reaction and one for the
reverse.
When solving these problems, ask yourself:

Concentration vs. time:

- Which way does the reaction shift?

- Will I produce more or less of the substance?

Rate vs. time:

- What will happen to the overall rate if I make this

change? (Will final equilibrium line be higher or lower
than where it started?)

- Which way does the reaction shift? (This means this

reaction is going to have a faster rate!)
For example: 2 NO2(g) ↔ N2O4(g) + heat ([NO2] < [N2O4])
Take note – shows relative
concentrations of species.
If the system shown above starts at equilibrium and then the given
stress is applied. Draw a concentration vs. time graph for each.
Stress: Addition of NO2 (↑[NO2]
N2O4 Causes a sharp ↑[NO2].
concentration Goal: ↓ [NO2]
moles/L
NO2 Shift: forward
Causes a gradual increase in
Original
equil.
product (N2O4) and a gradual
One line for decrease in reactant (NO2)
each species
Time or System reaches a new
in reaction.
Progress of the Reaction equilibrium -
concentrations plateau
For example: 2 NO2(g) ↔ N2O4(g) + heat ([NO2] < [N2O4])
↓
Stress: Removal of NO2 ↓ [NO2], shows as a sharp drop.
Goal: ↑ [NO2]
Shift: reverse
Causes a gradual decrease in
concentration N2O4 product (N2O4) as it is used up
moles/L and a gradual increase in
NO2 reactant (NO2)
System reaches a new
equilibrium -
concentrations plateau.
Time or
Concentration never
Progress of the Reaction
returns to what is was
originally.
 2 NO2(g) ↔ N2O4(g) + heat ([NO2] < [N2O4])

Stress: Increase N2O4 Stress: Decrease N2O4

Goal: ↓ [N2O4]
Shift: ←

N2O4
concentration concentration N2O4
moles/L moles/L
NO2
NO2

Time Time
Graphing Temperature changes:
When a system adjusts due to a temperature change, there
are no sudden changes in concentration or any species, so
there are no vertical lines on the graph.
shift
2 NO2(g) ↔ N2O4(g) + heat ([NO2] < [N2O4])

Stress: Increase in temperature

N2O4 Note: for every mole of

concentration
N2O4 that is consumed
moles/L
NO2 there are 2 moles of NO2
formed.

Time
 shift
2 NO2(g) ↔ N2O4(g) + heat ([NO2] < [N2O4])

Stress: Decrease in temperature

concentration
N2O4
moles/L
NO2

Time
Note: changing the pressure of the system (by altering the volume of
the container) will also change the concentration of all the species.
Therefore, a concentration vs. time graph for pressure stresses is
more difficult to draw.
2 1
2 NO2(g) ↔ N2O4(g) + heat ([NO2] < [N2O4])
Stress: decrease the volume of the container.
This increases the concentration of all gas species in
the reaction AND increases the pressure

Increasing concentration of
N2O4 both due to a decrease in
concentration
volume.
moles/L
NO2

Time
Graphing Pressure Changes:

When the stress is a change in pressure, the concentration

of each substance will initially change before the shift
occurs. This means that all substances will show either an
increase or decrease in concentration.
The above graph shows
concentration versus time for
a system containing carbon
monoxide, CO, chlorine gas,
Cl2, and phosgene, COCl2.

1. Write a balanced
equation to represent the
reaction studied.
CO + Cl2 ↔ COCl2

2. How much time was required for the system to reach equilibrium? 30 s

3. Calculate an approximate value for the equilibrium constant Kc using the

concentrations at time t = 60s. Kc = [COCl2] = 0.0065 = 41
[CO][Cl2] (0.0185)(0.0085)
4. Explain the changes 70 s after the initiation of the reaction.
Increase in [Cl2]
5. Calculate an approx. value for Kc at t = 110 s.
~40
6. What changes in conditions
Kc = [COCl2]
might have been imposed on the
system 120 s after the initiation of [CO][Cl2]
the reaction? ∆T
~100
7. Calc Kc at 280 s ~106
~43
~100
8. Are any events taking place ~43
between the interval 50s and 70s?
between 280s and 300s? Explain
your answers.
Both reactions at same rate.
9. What changes may have taken place at t=320s? ↑ COCl2
10. Calculate a value of Kc at 470. ~108
11. What differences would you have noticed if a catalyst had been present
during the entire course of this reaction? System would look the same, but
would take less time.
12. List the changes you might impose on this system if you wanted to produce a
maximum amount of phosgene, COCl2? CO + Cl2 → COCl2 ↑P ∆T
increase remove
13. How could you account for the differences in the value calculated for the
equilibrium constant Kc from the concentrations at different time points on the
graph. ∆T
 Chemical Equilibrium: Test Review

1. General concept of equilibrium:

How is it achieved? What does it look like?

2. Mass Action Expressions

How is it written? How is physical state involved?
Significance?

3. Kc or Kp: What does it mean? How do you find it?

What will change it?

Relationship to M.A.E./ balanced equations

4. Solving problems using the M.A.E.

5. Solving for Kc or Kp using ICE charts:

•given [I] and one [E] and asked for Kc

•given [I] and % completion of reaction, asked for Kc

•given [I] and Kc and asked for equilibrium amounts:

Plug in x’s and:
a) square root M.A.E. and Kc if possible
b) omit x’s (from certain terms) if Kc is small
c) use the quadratic formula if Kc is large

6. Solve for % completion in a reaction (or % yield).

7. Is a system at equilibrium?
Solving for trial Kc and deciding which way rxn. proceeds.
If trial Qc> actual Kc, (have too many products), rxn.goes in
the reverse.

8. Le Chatelier’s Principle: predict effect stress has on a system

(shift and change in amounts of substances)
• Haber process

9. Draw/ Interpret concentration vs. time graphs for systems at

equilibrium subjected to stress.