Module 5: Equilibrium and Acid Reactions

Static Equilibrium Vs Dynamic Equilibrium

The reversibility of chemical reactions

Reversible reactions
Where products can be converted back to the reactants.

Irreversible reaction
Where products cannot be converted back to the reactants.

Cobalt (II) Chloride hydrated and dehydrated

When hydrated cobalt (II) chloride (CoCl2) becomes cobalt (II) chloride hexahydrate (CoCl2 . 6H2O).
The hydrated form of Cobalt (II) Chloride is purple whereas the anhydrous (dehydrated) form is sky blue
in colour.
CoCl2 (aq) + 6H2O (l) CoCl26H2O(l)

Iron (II) Nitrate & Potassium Thiocyanate

Iron ions are yellow as a solution and the Potassium Thiocyanate is clear. When the two react together
it forms blood red Iron Thiocyanate.
Fe+3(aq) +NCS-(aq) FeNCS+2(aq)

Method:
Using a pipette add 2mL of Fe(NO3)3 to a test tube. Add 2mL of KSCN to the Fe(NO3)3. the
reaction forms FeNCS+2. record the three different coloured solutions. Divide the FeNCS+2
equally into 2 test tubes. Add 10 drops of Fe(NO3)3 to one test tube. Record changes. Add 10
drops of KSCN to the other test tube. Record changes.
• Fe(NO3)3 yellow
• FeNCS+2 red
• KSCN colourless
• FeSCN + KSCN deep red
• FeSCN + Fe(NO3)3 deep red

Burning Magnesium
Rusting and combustion are not reversible. So much energy is released that it would be
difficult/impractical to try and reverse the reaction.
2Mg(s) +O22MgO(s) + energy

Method:
Light Bunsen burner and record the colour of the colour of the magnesium ribbon. Hold one
end of the ribbon with tongs and heat other end in flame until it ignites. Do not look directly at
the light. Record colour of powder produced.
• Mg ribbon grey/silver
• MgO (product) white

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Burning Steel Wool
The reaction is a combustion reaction and occurs very similar to burning magnesium.
2Fe (s) +32O2 (g) Fe2O3 (s)

Method:
Make a small ball of steel wool and place on a metal lid. Quickly touch a 9V battery to the steel
wool. Record what you observe.

Result:
When the battery comes into contact with the steel wool the electrical current starts a fire.

Models of static and dynamic equilibrium

Dynamic equilibrium
The particles shift back and forward but at a rate that is equal.

Static equilibrium
All particles are at rest. The reaction will go to completion with no rate of reverse reaction.

Equal rate To completion

Closed system
A reaction where no products only energy can be exchanged with the surroundings.

Open system
Products and energy may be exchanged with the surroundings. The external environment will have an
effect on the equilibrium being reached.

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Non-equilibrium systems

Combustion reactions
The combustion reaction energy decreases and entropy increase meaning that combustion reactions
are spontaneous reactions.

Photosynthesis
Stores energy in chemical bonds. A second reaction must occur to break these bonds. Photosynthesis
is a non-spontaneous, non-equilibrium process, driven by spontaneous reactions.
The increase in entropy caused by the spontaneous reactions in photosynthesis is greater than the
decrease in entropy from the photosynthesis reactions.

Collision theory & reaction rate

Collision theory is a model of gas interaction that accounts for the various factors relevant to the rate of
reaction.

Activation energy
If particles don’t have enough energy they will not react even if they collide. Activation energy is the
minimum energy required for the particles to form a product. The higher the activation energy the more
likely a reaction is to occur.

Collisions
If you want more collisions to occur, you don’t only need more kinetic energy, but you must ensure the
collisions actually occur. This can be done in two ways; increase the concentration of the reactants or
increase the speed of the reactants.

Molecular orientation
Molecules are complex and may require bonds in particular areas to break, instead of just colliding.

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Factors that Affect Equilibrium

Le Chatelier’s principle
Le Chatelier's Principle states that if an equilibrium system is subjected to change, the system will
adjust itself to partially oppose the change.

Change to system in Predicted Effect Collision Theory Explanation of effect of change

Equilibrium on the Position on position of Keq
of Keq

Adding reactant Shift to the right • Increased reactant concentration = more

(forward reaction) frequent collisions = increase the rate of
forward reaction
• Reactants are consumed = more products
formed
• A new equilibrium forms when rates are
equal

Adding product Shift to the left • Increased product concentration = more

(reverse reaction) frequent collisions = increased rate of
reverse reaction
• Produces are consumed = more reactants
form
• A new equilibrium forms when rates are
equal

Decreasing pressure by Shifts in the Less frequent collisions; the reaction that is less
increasing volume (gas) direction of the dependent on collisions occurs to a greater extent.
most particles

Increasing pressure by Shifts in the More frequent collisions; the reaction that is more
decreasing volume (gas) direction of the dependent on collisions occurs to a greater extent.
fewest particles

Adding an inert/noble No change No change in concentration of the reacting gases so

gas (volume remains the no change to the rates of the forward and reverse
same) reactions

Adding water (dilution of Shifts in the Less frequent collisions; the reactions less
solution) direction of the dependent on collisions occurs to a greater extent
most particles

Increasing the Shifts to the left All reactants and product molecules have more
temperature of energy and move faster; increasing temp favours
exothermic reactions rate of endothermic reaction favouring the reverse
direction

Increasing the Shifts to the right All reactants and product molecules have more
temperature of energy and move faster; increasing temp favours
endothermic reactions

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 rate of endothermic reaction favouring the forward
direction

Decreasing the Shifts to the right All reactants and product molecules have less
temperature of energy and move slower; decreasing temp favours
exothermic reactions rate of exothermic reaction favouring the forward
direction

Decreasing the Shifts to the left All reactants and product molecules have less
temperature of energy and move slower; decreasing temp favours
endothermic reactions rate of exothermic reaction favouring the reverse
direction

Adding a catalyst No change Increase rates of forward and reverse reactions to

the same extent; an equivalent change in the
frequency of successful collisions in both directions

Heating Cobalt (II) chloride hydrate

CoCl2 (aq)+6H2O(l) CoCl26H2O(l)

Increase in energy causes a shift to the left (system is exothermic). Le Chatelier’s Principle says an
increase in temp of an exothermic reaction will shift to the left.

Nitrogen dioxide and dinitrogen tetroxide

2NO2 (g)N2O4 (g) H0=-57.20 kj/mol

By increasing the concentration of nitrogen dioxide, the system will shift to the right. Increasing the
pressure of the vessel the system will shift to the products.
This equilibrium is exothermic so an increase in temp will cause the system to shift to the left.

Calculating the Equilibrium Constant Keq

The Equilibrium Expression

Steps to answer a Keq questions:
1. Write the balanced
2. Write the general Keq expression
3. Write an ICE table
4. Fill in the table, find the values and solve for the required quantity

Eg1- CINO2 (g) + NO(g) NO2 (g) + CINO(g)

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 A 1.0L glass container was filled with 0.1 moles of CINO2. at equilibrium there were 0.03 moles
of CINO2 and 0.01 moles of NO.
Calculate the equilibrium constant for this reaction.

Keq= [NO2] [CINO] / [CINO2] [NO]

CINO2 NO NO2 CINO

I 0.1 moles ? 0 0

C ? ? ? ?

E 0.03 moles 0.01moles ? ?

CINO2 - 0.1 - 0.03 = 0.07 moles

Mole ratio = 1:1:1:1

CINO2 NO NO2 CINO

I 0.1 moles ? 0 0

C -0.07 moles -0.07 moles + 0.07 moles + 0.07 moles

E 0.03 moles 0.01moles ? ?

C= n/V

Keq= [NO2] [CINO] / [CINO2] [NO] =[0.07] [0.07] / [0.03] [0.01]=16.3

Eg2- An equilibrium is established between hydrogen gas and hydrogen ions in a 5L vessel.
Some number of moles of hydrogen gas were put into this vessel, and at equilibrium 1 10-2 moles of
hydrogen ions are present. If the equilibrium constant for system is 3.3 10-4. How many moles of
hydrogen gas were in the vessel initially?

H2 (g)2H+(g)
Mole ratio= 1:2

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 H2 (g) H+

I ? 0

C -110-2moles +110-2moles

E ? 110-2moles

Keq=[ H+] / [2H2]

[H+] =n / V = 110-25=210-3mol L-1

3.310-4=(210-3)2 / [H2]
[H2] =0.01212 mol L-1
n=c / V = 0.01212 5= 0.061 moles
0.061 + 110-2= 0.071 moles

Effect of Temp on the Value of Keq

Only change in temp will change the Keq value not concentration or pressure. The direction of change
will depend on if the reaction is exothermic or endothermic.
• An increase in temp of an exothermic reaction will decrease the Keq.
• Increase in temp of an endothermic reaction will increase the Keq.

Determine Keq of a chemical equilibrium system

Iron (III) thiocyanate
Method:
1. label 4 test tubes A to D
2. Use a pipette, place 0.0020 mol/L Fe(NO3)3, 0.0020 mol/L KSCN and water into each test tube
as indicated by table. Mix each solution thoroughly with a stirring rod.

Test Tube Fe(NO3)3 (mL) KSCN (mL) H2O (mL)

A 5 2 3

B 5 3 2

C 5 4 1

D 5 5 0

3. Prepare a blank by filling the colorimeter cell to ¾ with water. Calibrate the colorimeter. Use
blue light for the experiment.
4. Rinse cell with FeSCN2+ solution and fill the cell with ¾ of FeSCN. Measure and record.
5. Repeat step 4 with each test tube.

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Results-
Solution Absorbance

FeSCN2+ 0.3

A 0.48

B 0.48

C 0.49

D 0.5

Results of calculations-

A B C D

Fe3+initial 0.001 0.001 0.001 0.001

SCN initial 0.0004 0.0006 0.0008 0.001

[FeSCN] equ 0.000125 0.000125 0.000122 0.00012

[Fe] equ 0.000875 0.000875 0.000878 0.00088

[SCN]equ 0.000275 0.000475 0.000678 0.00088

Keq 519.48 300.75 204.94 154.96

The use of Keq for different reactions

Dissociation of Ionic solutions
eg.) NaCl(aq)Na+(aq)+ Cl-(aq)

We can use Keq to define the extent of the ionisation that occurs.

Keq=[Na]+[Cl-] / [NaCl]

Dissociation of Acids and Bases

Strong acids completely ionise in water.
The equilibrium constant for the ionisation of an acid is called the acid dissociation constant, Ka.
The general equation for the dissociation of a weak acid is: HA (aq) + H2O (l) H3O+(aq) + A- (aq)
AND Ka = [H3O]+[A-] / [HA] [H2O]

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Solution Equilibria
Dissolving is a physical change made by the molecules pulling apart. The molecules have to overcome
an intermolecular force in order to disperse.
Polarity
A polar substance is one with a positive end and a negative end. A nonpolar substance is one that is
neutral everywhere.
Water molecules are polar. When an ionic substance is added to water, the hydrogen atoms of water
molecules are attracted to polar charged ions. The attraction between the water molecules and the ions
is known as ion-dipole attraction. The process of separating positive and negative ions from a solid
ionic compound to form hydrated ions when an ionic compound dissolves in water is called
dissociation.
Intermolecular forces
• Dispersion intermolecular forces as the weakest intermolecular force as the electrons are
moving around and the dispersion may not be even throughout the molecule/compound.
• Dipole-dipole intermolecular forces are stronger than dispersion forces and occur when polar
substances line-up.
• Hydrogen bonds are the exact same as dipole-dipole intermolecular forces but much stronger.

Removing toxicity from foods

Cycad fruit/seeds
The seeds are crushed to expose the inner kernel and then soaked in water in water to leach out the
toxins. Leaching fruit for longer meant it lasted longer.

Solubility rules and predict the composition of a solution

Solubility Rules
N- Nitrates
A- Acetates
G- Group 1
S- Sulfate
A- Ammonium
G - Group 7

L- Lead
M- Mercury
S - Silver

C- Calcium
A
S- Strontium
T
R
O
B- Barium
A
R

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Exceptions

Soluble in water Exceptions (insoluble) Exceptions (slightly soluble)

Most chlorides, bromides and iodides AgCl, AgBr, AgI, PbI2 PbCl2 , PbBr2

Most Sulfates (SO42-) SrSO4 , BaSO4 ,PbSO4 CaSO4 , Ag2SO4

• There are no exceptions for all nitrates, ammonium salts, sodium salts, potassium salts and
acetates.

Insoluble in water Exceptions (soluble) Exceptions (slightly soluble)

Most hydroxides NaOH , KOH , Ba(OH)2 Ca(OH)2 , Sr(OH)2

NH4OH , AgOH

Most carbonates Na2CO3 , K2CO3 , No exceptions

(NH4)2CO3

Most Phosphates Na3PO4 , K3PO4 No exceptions

(NH4)3PO4

Most Sulfides Na2S , K2S , (NH4)2S No exceptions

Potassium chloride and Silver nitrate

Chloride is in group 7 and therefore soluble however it is not soluble with silver. So, potassium chloride
is not soluble but silver nitrate is soluble. According to the table of standard potentials potassium is
more reactive than silver. The rule is therefore that more reactive metals will replace fewer active
metals in solution.
Our equilibrium becomes: KCl(s)+AgNO3 (aq)AgCl(s)+KNO3 (aq)

Sodium sulphate and Barium nitrate

All nitrates are soluble, so barium nitrate is soluble. Sulphates are soluble however due to exceptions
sodium sulphate is not soluble. Barium is higher in reactivity than sodium so no displacement will occur.

Equilibrium expressions for solutions in terms of Ksp

Lead chloride has a Ksp value of 1.70 x 10-5 at 25 degrees. Calculate the molar solubility of lead (II)
chloride at this temp.

PbCl2 <~> Pb2+ + 2Cl-

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 Pb Cl

I 0 0

C +x +2x

E x 2x

Ksp=[Pb] [Cl]^2
1.7 x 10-5 = (x) (2X)
1.70 x 10-5 = 4x^3
4.25 x 10^-6 =x^3
x= 1.62 x 10^-2 mol/L

Formation of precipitate given the standard reference values of Ksp

Barium sulfate has a Ksp value of 1.08 x 10^-10 at 25 degrees. If 1.0 x 10^-3 of barium sulfate is added
to 1L of water at 25 degrees predict whether a precipitate will form.

N (BaSO4) = m/MM
= 1.0 x 10^-3 / 233.43
= 4.3 x 10^-6 mol

c= n / V
= 4.3 x 10^-6 / 1
= 4.3 x 10^-6 mol

Ksp= [Ba] [SO4]

= (4.3 x 10^-6) (4.3 x 10^-6)
= 1.8 x 10^-11

This is smaller than the Ksp value so No precipitate will form.

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