EXPERIMENT

"VIOLENT FIRES SOON BURN OUT

THEMSELVES
SMALL SHOW'RS LAST LONG,
BUT SUDDEN STORMS ARE SHORT"
EQUILIBRIA
Techniques

Successive reactions
buffer preparation
use of indicators
pH estimation

Principles

equilibria
pH
buffer systems
common-ion effect
temperature effect

MSDS available for

copper sulfate, CuSO4 (aq)

ammonia, NH3 (aq)
hydrochloric acid, HCl (aq)
nitric acid, HNO3 (aq)
potassium iodide, KI (aq)
sodium sulfide, Na2S (aq)
acetic acid, CH3COOH (aq)

silver nitrate, AgNO3 (aq)

sodium carbonate, Na2CO3 (aq)
sodium acetate, NaCH3COO (aq)
sodium hydroxide, NaOH (aq)
cobalt chloride, CoCl2 (aq)
copper bromide, CuBr2 (aq)
universal indicator

Recommended Advanced Reading

Chapter 15 Silberberg, Lavieri and Venkateswaran, 1st CE, McGraw-Hill, 2013

Equilibria...57

INTRODUCTION
The beginning
This lab will give you a chance to work on some qualitative
assessments of pH, a scale used to measure acidity. In addition,
you will be able to see the effect of different reactants and
external stimuli on reaction equilibria. In today's session you will
work with your partner to:

observe shifts in equilibria

observe multiple equilibria using the silver ion

prepare a buffer system

observe the effect of strong acids and bases on a buffer

system

observe the common-ion effect on equilibria

observe how temperature affects equilibria

This is a general overview of what you will be accomplishing in

this experiment.

EXPERIMENT 5: Equilibria
Introduction

Equilibrium

The normal pH of rain is 5.6...the lowest pH of rain

recorded in the UK is 2.4, which is over one thousand

times more acidic!

Normally, when writing chemical reactions, we use a single

arrow after the reactants and before the products to indicate
that reactants are converted to products. The single arrow
implies that all the reactants are converted to products, unless
58....Experiment 5

there is the presence of a limiting reagent, in which case it

reacts to completion. In reality, however, very few reactions go
all the way to completion. Before they can do so, a stage in the
reaction is reached when the rate of reaction of reactants to
form products is equalled by the rate of reaction of products to
form reactants. This does not mean that the reaction stops!
Instead, it signifies that any additional product formed is not
guaranteed to remain in the form of the product and may well be
converted back to reactants. This state is referred to as
equilibrium, and is a dynamic state.
For some reactions, equilibrium favours the productsthat
is to say, most of the reactants will be converted into the
product. However, there are many reactions that do not favour
the formation of products. If the reaction is of no concern to
us, we don't mind whether all the reactants react or not.
However, very often, the reaction is extremely important
industrially. In such cases, it is not economically advantageous to
have a reaction that does not go to completion or as far to
completion as possible. It is thus important to know how to
influence or affect the outcome of a reaction. In order to know
this, it is important to be able to determine when a reaction will
reach equilibrium.
Equilibrium Constant
For any aqueous reaction
aA + bB cC + dD + heat

[1]

we can write an expression for the equilibrium constant, K, as

follows:

K=

[C]c [D]d
[A]a [B]b

[2]

From this expression, we can see that when the reaction is

product favoured (ie. the concentration of the products is high),

Equilibria...59

the equilibrium constant is large. Similarly, a small equilibrium

constant indicates a reactant-favoured reaction.
LeChatelier's Principle
When a reaction is at equilibrium, we can use the
equilibrium constant to calculate the concentrations of the
reactants and/or products. What happens if, at equilibrium, we
add a reactant or product? LeChatelier's Principle states that a
reaction will always move in the direction that minimizes the
effect of any change imposed on a system at equilibrium. Thus,
in Equation [1], if more B is added, the reaction would shift to
the right to use up the excess B. Does temperature have any
effect on a reaction at equilibrium? In an exothermic reaction
(as is the case for Equation [1]), the addition of heat would cause
the reaction to shift in the direction that would consume the
added heat. Thus, the reaction would shift to the left.
Weak Acids and Bases
When the equilibrium in an equation such as [1] lies
overwhelmingly to one side (usually we write the equation so that
the equilibrium favours the right side), the species which
dissociates completely is termed as strong. In the case of a
reaction between HCl and NaOH, the HCl dissociates completely
and hence it is known as a strong acid, just as NaOH, which also
dissociates completely, is known as a strong base. On the other
hand, a weak acid or base is one that does not dissociate
completely when placed in water. Acetic acid, CH3COOH, and
ammonia, NH3, are examples of a weak acid and a weak base
respectively. In these cases, the equilibrium expression strongly
favours the left side of the equation (unless the solution is very
dilute). Thus in the case of acetic acid,
CH3COOH (aq) + H2O (l)
acid

base

H3O + (aq) + CH3COO- (aq) [2]

conj. acid

conj. base

the equilibrium lies to the left, indicating that H3O+ is a stronger

acid than CH3COOH and that CH3COO- is a stronger base than
H2O.

60....Experiment 5

Acid Dissociation Constant

How do you know, just by looking at an acid or base,
whether it is strong or weak? Since all four of the species in the
equation affect the equilibrium, we can define an equilibrium
constant for the acid, also called an acid dissociation constant,
Ka,
[CH3COO- (aq)] [H3O+ (aq)]
[3]
Ka =
= 1.8 x 10-5
[CH3COOH (aq)]
that is decided by the three aqueous terms in equation [2]. The
terms in the square brackets represent the concentrations of
the species in the brackets, where the concentration denotes
the amount of the species in a given volume of solution. For all
the aqueous species, the concentration is substituted as a
reasonable approximation for the activity of the species (which
is the correct variable to use in an equilibrium expression).
However, the activity of water is 1, as water is a pure substance,
and hence, we see that the liquid water does not appear in the
expression for Ka.
For a solution of ammonium ion, NH4+ (aq), in water, the acid
strength of the ammonium ion in the equilibrium
NH4+ (aq) + H2O (l)

H3O + (aq) + NH3 (aq)

[4]

can be expressed as
[NH3 (aq)] [H3O+ (aq)]
Ka = =
= 5.5 x 10-10

[NH4 (aq)]

[5]

Water has the capacity to act both as an acid and as a base as

shown below,
H2O (l) + H2O (l)

H3O + (aq) + OH- (aq)

[6]

and this process, where one water molecule donates a proton to

another, is called autoprotolysis. From equation [6], we can
derive an expression for the equilibrium constant of water,
Equilibria...61

KW = K [H2O (l)]2 = [H3O+ (aq)] [OH- (aq)] = 1 x 10-14

[7]

Species that are capable of behaving both as an acid and a base

are called amphoteric. Some other amphoteric ions are HCO3(aq), HSO4- (aq) and H2PO4- (aq).
If we look at the equilibrium between a weak base, such as
ammonia, NH3 (aq), and water,
NH3 (aq) + H2O (l)
base

acid

NH4 + (aq) + OH- (aq)

conj. acid

[8]

conj. base

we can define the base dissociation constant, Kb, as

Kb =

[NH4 (aq)] [OH- (aq)]

[NH3 (aq)]

[9]

Note again, that we do not include H2O (l) as it has an activity of

1. If we look at equations [5], [7], and [9], we find that there
exists a relation between the terms Ka, Kb and KW, which can be
expressed as
KW = Ka x Kb = [H+ (aq)] [OH- (aq)] = 1 x 10-14

[10]

where H+ (aq) is a simplified form for H3O+ (aq). This relation

holds true for any acid and its conjugate base.
pH
From equation [7], we can determine that in pure water,
the concentrations of the hydrogen (or hydronium) and hydroxyl
ions must be equal and have a value of 1 x 10-7 mol L-1. If the
solution has a greater concentration of hydronium ions, it will be
acidic, and [H+ (aq)] > 1 x 10-7 mol/L. If the solution has a
greater concentration of hydroxyl ions, it will be basic, and we
would find [H+ (aq)] < 1 x 10-7 mol/L. However, the product of the
two concentrations must always equal 1 x 10-14. From these
62....Experiment 5

facts, it can be seen that the concentrations of [H+(aq)] and [OH(aq)] vary over a large range, spanning orders of magnitude. It
thus becomes useful to express their concentrations on a
logarithmic scale, called the pH scale, which is defined as
pH = - log [H+ (aq)]

[11]

where the log scale mentioned is base ten. A similar scale can be
applied to the species OH-, and to Ka or Kb. In general, for any
term X,
pX = - log X
[12]
Indicators
How then do we determine the pH of a solution? We can
use pH meters, but an even simpler method is to use an
indicator. Indicators are complex organic compounds. An
indicator is usually a weak acid that dissociates to different
extents in a solution depending on the acidity of the solution. If
we designate the indicator as HIn, we can write
HIn (aq)

H+ (aq) + In- (aq)

[13]

and the equilibrium constant for dissociation of the indicator is

KIn =

[H+ (aq)] [In- (aq)]

[HIn]

[14]

The important quality of an indicator is that it is coloured.

Generally the undissociated and the dissociated species of the
indicator have different colours. More than one colour is possible
if the indicator is capable of establishing different equilibria in
solution.
Concept of the Experiment
In this experiment, there are five main parts. First, you
will observe the effect of adding and consuming reactants on a
system at equilibrium.
Second, you will establish multiple
equilibria using the silver ion. Third, you will prepare a buffer
Equilibria...63

solution and test the effect of adding a strong acid and a strong
base to the buffer. Fourth, you will observe the effect of the
addition of a common ion. Finally, you will determine the effect
of temperature on a system at equilibrium.
The reactions that you will be studying are provided in a table at
the end of the experiment.

(TTD) Things to Do

Complete the prelab exercises before coming to the laboratory.

Observe the effect of adding and removing a reagent on equilibrium.

Observe multiple equilibria with the silver ion.

Prepare a buffer system.

Compare the effects of adding strong acid/base to water and to a buffer.

Observe the common-ion effect.

Observe the effect of temperature.

Use safe laboratory procedures at all times.

Safety Precautions

64....Experiment 5

1.

Wear approved eye protection at all times.

2.

Acids and bases, even in dilute solutions, are corrosive.

Ensure that if you spill any acid or base, you clean up
immediately (it is easy to mistake these solutions for
water). If any is spilt on skin or clothing, rinse thoroughly
with water for at least 15 minutes.

3.

Silver nitrate stains. Sodium sulfide and ammonia STINK!

PROCEDURE
Equipment and
chemicals needed

Chemicals

0.1 M and 1 M HCl

0.1 M CuSO4
0.1 M CH3COOH
0.01M AgNO3
0.1 M Na2CO3
0.1 M NaCH3COO
1 M CoCl22
0.1 M KI
solid CuBr2, KBr
6M HNO3, conc NH3
0.1 M Na2S
0.1 M NaOH

Equipment

test tubes
transfer pipets
spatula
well plate
toothpicks
hotplate
test tube racks
250 mL beaker

Equilibria

NOTE: This is a qualitative experiment.

observations as possible!

Starting the
experiment

Equilibrium Shift

Make as many

1.

Add approximately 1 mL (~20 drops) of 0.1 mol/L CuSO4

to a clean test tube(a).

2.

Dropwise, add concentrated NH3 solution (NOTE:

Ammonia has a VERY strong smelldo not breathe
directly!!!) until you observe a change(b).

3.

Dropwise, add 1 mol/L HCl until you observe a change(c).

4.

What happens if you try to repeat Steps 2-3?

Moving on
Multiple Equilibria
5.

Place 0.5 mL of 0.1 mol/L Na2CO3 solution in a test

tube(d).
Equilibria...65

6.

Add 0.5 mL of 0.01 mol/L AgNO3 solution to the test

tube(e).

7.

Dropwise, add 6 mol/L HNO3 (NOTE: This acid is VERY

concentrated and thus CORROSIVE!!) until you see a
change(f).

8.

When the solution is clear, add 0.1 mol/L HCl dropwise

until you see a change(g).

9.

Dropwise, add concentrated NH3 until you see a change(h).

10.

What happens if you repeat Step 7 and then Step 9?

11.

Add 0.1 mol/L KI dropwise until you see a change(i).

12.

Dropwise, add 0.1 mol/L Na2S until you see a change(j).

Preparation and Testing of a Buffer Solution

66....Experiment 5

13.

Obtain a well plate.

14.

Using a plastic transfer pipet, add 10 drops of 0.1 mol/L

CH3COOH to two wells.

15.

Add 3 drops of universal indicator to each well(k).

16.

Use a strip of pH paper to note the pH of the acid in the

wells(l).

17.

Using another clean transfer pipet, add 10 drops of 0.1

mol/L NaCH3COO to each of the wells containing the
acid(m). Measure the pH using a strip of the pH paper(n).
These two wells now contain a buffer system.

18.

In each of two different wells, use a clean transfer pipet

to add 20 drops of distilled water. Add 3 drops of
universal indicator. Check the pH with pH paper(o).

19.

Use a clean transfer pipet to add 5 drops of 0.1 mol/L

HCl to ONE well containing the buffer and 5 drops of 0.1
mol/L HCl to ONE well containing water(p). Measure the
pH of both wells using two strips of pH paper(q).

20.

Use a clean transfer pipet to add 5 drops of 0.1 mol/L

NaOH to THE OTHER well containing the buffer and 5
drops of 0.1 mol/L NaOH to THE OTHER well containing
water(r). Measure the pH of both wells using two strips
of pH paper(s).

Almost there!
Common-Ion Effect
21.

Use a clean transfer pipet to place 5 drops of 1 mol/L

CoCl2 in an empty well of the wellplate(t).

22.

Dropwise, add concentrated (12 M) HCl (NOTE: VERY

CORROSIVE!!!) to the CoCl2 until you see a change(u).

23.

Dropwise, add distilled water to the above mixture until

and swirl until you see a change(v).

24.

Use a spatula to place a pinch of solid CuBr2 in an empty

well(w).

25.

Using a clean transfer pipet, add 5 drops of distilled

water(x) to the CuBr2 and then add another 10 drops(y).
Continue adding water until the total volume is close to 2
mL(z).

26.

Put a few crystals of KBr in another empty well. Add

enough distilled water to dissolve the crystals(aa).

Equilibria...67

27.

Use a clean transfer pipet to place approximately 0.5 mL

of the solution in Step 25 to a test tube. Add a pinch
of KBr and shake gently(bb). Save this solution for the
next step.

Finishing the Experiment

Temperature Effect
28.

Place the test tube from Step 27 in a boiling water

bath(cc). If no colour change is seen, add 1 mL more of
H2O.

29.

Place approximately 1 mL of 1 mol/L CoCl2 solution in a

clean test tube. Put the test tube in the boiling water
bath(dd).

30.

Rinse the well plate and other glassware thoroughly with

distilled water and return them to the demonstrator.

31.

Empty all the transfer pipets and rinse well with warm
water (draw in water, shake well, and squeeze the water
out several times).

32.

All solutions may be poured down the drain with plenty of

water, EXCEPT for the silver solutions, which should be
disposed in the container marked "SILVER WASTES".

33.

Clean your bench thoroughly and throw away all paper

towels.

Cleaning Up!

Observations
Part 1. Equilibrium Shift

68....Experiment 5

(a)

What colour do you observe?

(b)

What changes do you observe? Why do they occur?

(c)

What changes do you observe? Why do they occur?

1.

In Step 4, are you able to see the same changes or are

they different?

Part 2. Multiple Equilibria

(d)

What do you observe?

(e)

What changes do you observe? Why do they occur?

(f)

What changes do you observe? Why do they occur?

(g)

What changes do you observe? Why do they occur?

(h)

What changes do you observe? Why do they occur?

2.

Can you observe the same changes if you repeat Steps 7

and 9?

(i)

What changes do you observe? Why do they occur?

(j)

What changes do you observe? Why do they occur?

Part 3. Buffers
(k)

What colour do you observe with the universal indicator?

With what pH does this correspond?

(l)

What pH does the pH paper indicate? Do the two pHs

correspond?

(m)

What happens to the pH when you add the salt? What is

the solution that results after you add the salt solution
to the acid solution?

(n)

Do the pHs determined by the indicator and the pH

paper correspond?

Equilibria...69

(o)

What colour is the universal indicator in distilled water?

To what pH does this colour correspond?

(p)

How does the addition of acid affect the pH of the

water? How does it affect the pH of the buffer
solution? What is the colour of the indicator in each
solution?

(q)

How does the pH compare using the indicator and the pH

paper?

(r)

How does the addition of base affect the pH of the

water? How does it affect the pH of the buffer
solution? What is the colour of the indicator in each
solution?

(s)

How does the pH compare using the indicator and the pH

paper?

3.

If we assume 5 drops to equal 0.25 mL, calculate the

change in the pH of the buffer and the change in the pH
of the water upon addition of 5 drops of 0.1 M HCl and 5
drops of 0.1 M NaOH.

Part 4. Common-Ion Effect

70....Experiment 5

(t)

What is the appearance of the solution at room

temperature?

(u)

What changes do you see? Why do they occur?

(v)

How and why does the addition of water change the

equilibrium?

(w)

What is the appearance of the solid?

(x)

What is the appearance of the solution?

(y)

How does the further addition of water change the

appearance of the solution? Why?

(z)

What happens if more water is added? What equilibria

are involved?

(aa)

What is the appearance of the dissolved crystals? What

does this tell you about the colour of each of the ions in
the salt?

(bb)

How does the addition of the solid change the

appearance of the solution?

Part 5. Temperature Effect

(cc)

What happens when heat is added to the solution?

(dd)

What is the appearance of this solution? How does it

compare to the appearance of the same solution at room
temperature (Observation t)?

Wherever possible, use BALANCED chemical equations to describe what is

occurring.
Points to Ponder

Are there other ways to affect the equilibrium?

Refer to page iii in the FYI section and the lab report
section in experiment 1.

You may choose to write your observations and discussion

separately or to combine the two sections in your report.
Remember to use CHEMISTRY to explain all your
observations!

Lab Report

Equilibria...71

Table 1. Reactions Being Studied

[Cu(H2O)4]2+ (aq) + 4 NH3 (aq) [Cu(NH3)4]2+ (aq) + 4 H2O (l)

2AgNO3 (aq) + Na2CO3 (aq) Ag2CO3 (s) + 2 NaNO3 (aq)

2 H+ (aq) + CO32- (aq) H2CO3 (aq) H2O (l) + CO2 (g)

Ag+ (aq) + Cl- (aq) AgCl (s)

Ag+ (aq) + 2NH3 (aq) [Ag(NH3)2]+ (aq)

H+ (aq) + NH3 (aq) NH4+ (aq)

Ag+ (aq) + I- (aq) AgI (s)

2Ag+ (aq) + S2- (aq) Ag2S (s)

CH3COOH (aq) + H2O (l) H3O+ (aq) + CH3COO- (aq)

4Cl- (aq) + [Co(H2O)6]2+ (aq) [CoCl4]2- (aq) + 6 H2O (l)

4 Br - (aq) + [Cu(H2O)4]2+ (aq) [CuBr4]2- (aq) + 4 H2O (l)

72....Experiment 5