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Chemistry Notes: Essential Knowledge for
University Chemistry of Any Level
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By Josh Walker
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Includes:
Acids and Bases
Bonding
Electro Chemistry
Equilibrium
Rate of Reaction
Redox
Titrations

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By Josh Walker

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Contents

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Acids and Bases3

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Bonding21
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Electro Chemistry50
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Equilibrium76
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Rate of Reaction76
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Redox97
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Titrations105
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By Josh Walker

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By Josh Walker

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Introduction/Revision:
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Acids and Bases

Strong Acids:
And acid is generally defined as:
A substance that produces hydrogen ions or protons in water Arrhenius Theory
A SUBSTANCE THAT DONATES PROTONS DURING A CHEMICAL REACTION
Bronsted/Lowrey theory.
A strong acid is a substance that completely ionises when dissolved in water:
If we look at HCl this is represented by:
!

HCl(aq) !Water
!!
H + (aq) + Cl (aq)

However, the actual reaction is that of the proton reacting with the water molecule as below:

HCl(aq) + H 2O(l ) H 3O+ (aq) + Cl (aq )

!
Some important strong acids are:
HCl hydrochloric acid
HNO3 Nitric Acid
HClO4 perchloric acid
HI iodic acid
HBr bromic acid
H2SO4 sulfuric acid.

Hydronium Ion

"

It is important to note that when a strong acid ionises the concentration of the molecules is zero
you can only have a concentration of the ions.
We can categorize acids by the number of protons H+ they produce when they ionise:
Monoprotic ionise to produce one proton.
o HCl.
o HNO3
Diprotic ionise to produce two protons.
o H2SO4.
o H2C2O4.
Triprotic ionise to produce three protons.
o H3PO4.

"

When we show the ionisation of a diprotic or triprotic acid it is important we show it in steps. I.e.
the ionisation of sulfuric acid can be shown:

First Ionisation: H 2 SO4(aq) H + (aq) + HSO4 (aq)

Second Ionisation: HSO4 (aq) ! H + (aq ) + SO4 (aq)
!!
IT is important to note that for every mole of H2SO4 you get around 1.6 moles of H+ ion. So the
correspondence IS NOT A ONE TO ONE RATIO AS THE H2 SUGGESTS.

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By Josh Walker

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We also need to remember that because water molecules are polar they react with the H+ ion to
form hydronium ions as shown below.

H 2O(l ) + H + (aq) H 3O+ (aq)

!
This is the bases for acids and strong acids.

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Strong Bases:
You can generally define bases or ALKALIS as:
A substance that produces hydroxide ions in solution Arrhenius Theory
A SUBSTANCE THAT ACCEPTS PROTONS DURING A CHEMICAL REACTION
Bronsted/Lowrey theory.
A strong base like a strong acid is a substance that completely ionises into ions
As you can see NaOH is a strong base:

NaOH (s) !Water

!!
Na + (aq ) + OH (aq)

!
Basically ALL METAL HYDROXIDES ARE STRONG BASES. Even though they are not very
soluble they are still strong bases because WHEN they do dissolve they completely ionise.

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Weak Acids:
Weak acids are simply the opposite from strong acids THEY ONLY PARTIALLY IONISE IN
SOLUTION.
Common weak acids that we need to remember are:
ALL organic acids (CH3COOH, HCOOH)
Carbonic Acid H2CO3
Sulfurous acid H2SO3
Hydrofluoric acid HF

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If we look at acetic acid dissolving in 1.0l of water:

CH 3COOH (l ) ! CH 3COO (aq) + H + (aq )

Molecules
!!0.99molL

Ions

Ions

0.01molL

0.01molL

As you can see the concentration of the ions in the solution is far less than the concentration of the
molecules in the solution. SO THE ACID ONLY PARTIALLY IONISE, there is only a small
number of H+ ions, which CAN be donated in a reaction and we have a weak base.
It is important to know that you cannot calculate the above concentration in the exam you can only
calculate them when given tables of their values.

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Weak Bases:
As with weak acids we bases TEND TO REMAINS AS MOLECULES THEY ONLY
PARTIALLY IONISE.
NH3 Is a weak base as it only partially ionises by accepting a proton from water:

NH 3(g) + HOH (l ) ! NH 4 + (aq) + OH (aq)

!!

METAL OXIDES also react or HYDROLYSE with water and are thus weak bases:

MgO(s) + H 2O(l ) ! Mg2 + (aq) + 2OH (aq)

!!
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It is very important to note that almost ALL metal oxides are insoluble in water. So most of them
will not ionise at all.

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Concentration Note:
It is important that you understand the difference between strong and weak and concentrated and
dilute. For example:
The hydrochloric acid in our stomachs is a very dilute STRONG acid.
The tannic acid in a strong cup of tea is a concentrated WEAK acid.
So whether an acid is strong or weak is determined by how it ionises.
Whether an acid is concentrated or dilute determines how much of that acid is in the solution you
are using.
This is a common mistake in answering simple questions so make sure it is not one of yours.

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Water Acting As Acid/Base/Neutral:

Water is a very special substance in that it can react as an acid, as a base or as a neutral substance.
Below are examples of it reacting in different ways:

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Water as an Acid:
The most common example of this is water reacting with ammonia:

NH 3(g) + H 2O(l ) ! NH 4 + (aq) + OH (aq)

!!

As you can see the WATER has DONATED a proton to the ammonia so it ACTS AS AN ACID.

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Water as a Base:
Here a common example is water reacting with hydrochloric acid:

HCl(aq) + H 2O(l ) ! H 3O+ (aq) + Cl (aq )

!!

As you can see the WATER has ACCEPTED a proton from the HCl so it ACTS AS A BASE.

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Water acting Neutral:

The standard equation for this is:

H 2O(l ) ! H + (aq ) + OH (aq)

!!

In this equilibrium equation the concentrations of H+ and OH- are equal.

It is worth having these on your calculator as the WILL come in useful.

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Non-Electrolytes:
These are substance that dissolve in water but remain as molecules. So they DO NOT
DISSOCIATE OR IONISE.
Substances like this include:
Glucose C6H12O6
Sucrose C12H22O11
Ethanol CH3CH2OH

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With non-electrolytes you need to remember they do not conduct an electric current and are neither
acidic nor basic.

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pH:

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Introduction to pH:
pH is essentially looking at the concentration of the hydrogen ion in the solution and it is given by the
formula:

pH = log "# H + $%

!
If we look at water dissociating into a small number of ions:
+
2
(aq)
!

+ OH (aq )

H O! H
!

We know that there is a large number of water molecules but a very small amount of ions in fact:
For 1 MOLE of H2O molecules there are:
1 x 10-7 moles of H+ ions and 1 x 10-7 moles of OH- ions.
So from this we can say that:

!" H + #$ !"OH #$ = 1.0 10 14

!
This is a very important point to remember because we KNOW THAT WATER IS NEUTRAL.
So Therefore it follows that THE CONCENTRATION OF H+ IONS MULTIPLIED BY OHIONS MUST ALWAYS EQUAL 1.0 X 10-14.
It is far easier however to simply say:
!

pH + pOH = 14

log "#OH $%
Where pOH is given by !
.
Before we move on to look at calculating pH it is important to remember what the pH scale means:

0
Higher concentration of
H+
Acidic

7
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Neutral

14
Lower concentration of H
+

Basic (alkaline)

NOTE: pH can be negative if the H+ concentration is GREATER than 1mlL-1.

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Worked examples of finding pH or concentration:

Below are a few examples including descriptions of what is being done on how to find the pH of
different solutions and the concentration of H+ ions from the solution:
Example 1 The easiest:
Calculate the pH of 1.00 x 10-3 molL-1 HNO3:
WRITE IONIC EQUATION
+

! HNO3 H + OH
So it is a one to one correspondence from molecules to ions so we do not need to alter given
concentration.
SUB INTO FORMULA
!

pH = log #$1.0 10 3 %& = 3.0

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Example 2 Diprotic:
Calculate the pH of 0.040 molL-1 H2SO4:
WRITE IONIC EQUATION
+

H
S
O

2H
+
OH
2
4
!

So we need to multiply concentration given by 2 to get concentration of H+ ionsthus it is 0.08molL-1

USING ADJUSTED CONCENTRATION SUB INTO FORMULA

pH = log [0.08 ] = 1.1

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Example 3 Simple Concentration:

What is the concentration of a pH 2.5 HClO4 solution:
WRITE IONIC EQUATION TO CHECK IT IS 1 1 CORRESPONDENCE:
+

! HClO4 H + ClO4
1 mole of the acid goes to 1 mole of the hydrogen ion so this is no problem.
SIMPLY WRITE AS 10-pH:
2.5
In this case this is !
But this is not correct scientific notation
PLUG INTO CALCULATOR TO GET CORRECT FORM:

10

3
pH
=
3.2

10
!

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Example 4 pH from pOH:

Calculate the pH of 0.025 molL-1 Ba(OH)2:
WRITE IONIC EQUATION TO CHECK CORRESPONDENCE:
!

Ba(OH )2 Ba2 + + 2OH

1 mole of the reactant goes to two moles of OH- so we must alter the concentration of OH- to equal =
0.05molL-1.
CALCULATE pOH AS GIVEN ABOVE USING ADJUSTED CONCENTRATION:

pOH = log [0.05 ] = 1.3

!

USE pH=14-pOH TO FIND pH:

pH = 14 1.3 = 12.7

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Example 5 Concentrations from pH:

A solution has a pH of 4.5. Find the concentration of H+ and OH- separately:
WORK OUT pOH:

pOH = 14 4.5 = 9.5

!

TREAT BOTH pH and pOH AS IN EXAMPLE THREE:

!" H + #$ = 10 4.5 = 3.2 10 5 mol L1

!"OH #$ = 10 9.5 = 3.2 10 10 mol L1
!

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Example 6 Doing some Calculating:
5.0g of NaOH is dissolved in 2.5L of water. What is the pH:
FIND HOW MANY MOLES OF OH- THIS IS:
5
n (NaOH ) =
= 0.125mol
40
NaOH Na + + OH

! n(OH ) = 0.125mol

CALCULATE CONCENTRATION:
n 0.125
c= =
= 0.05mol L1
v
2.5
!
FIND pOH:

pOH = log [0.05 ] = 1.3

!

FROM THIS FIND pH:

pH = 14 1.3 = 12.7
!

It is essential that all the above worked examples are understood before we move on to the more
complicated topic of limiting reagent problems.

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pH and Limiting Reagents:

In this course we only look at neutralisation reactions. Basically in a BADLY DONE
neutralisation reaction one of the reactants will not be all used up it will be in excess (XS) or
(INXS):
If an ACID (H+) is IN EXCESS then the pH will be lower than 7.
If a BASE (OH-) is IN EXCESS then the pH will be higher than 7.
Limiting reagent calculations are actually overly simple but below are two examples of the method
used:
Example 1 The simplest type:
100mL of 0.07mol L-1 LiOH solution is mixed with 200ml of 0.02mol L-1 HBr solution what is the
resultant pH:
FIRST IDENTIFY LIMITING REAGENT
n(LiOH ) = 0.1 0.07 = 0.007

LiOH Li + + OH

! n(OH ) = 0.007mol

n(HBr ) = 0.2 0.02 = 0.004

HBr H + + Br
+

! n(H ) = 0.004mol

EquationH + + OH H 2O
+
! So because it is 1-1 H is the Limiting Reagent
CALCULATE REAMING MOLES OF SUBSTANCE INXS

n(OH ) = 0.007 0.004

! n(OH ) = 0.003mol

Because OH- is in XS pH will be above 7.

CALCULATE CONCENTRATION OF THIS SUBSTANCE

THE VOLUME HAS CHANGED!!!!!

You must here be aware that

n
0.003
0.003
c= =
=
= 0.01mol L1
v 0.1 + 0.2
0.3

HENCE FIND pH:

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pOH = log [0.01] = 2

pH = 14 2 = 12.0
!

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Example 2 The slightly more complicated type:

Assuming all species are soluble what is the final pH when 2.0L of 0.025mol L-1 of Aluminium
hydroxide are added to 0.5L of 0.03 mol L-1 oxalic solution:
IDENTIFY LIMITING REAGENT (Remember to multiply to find concentration of ions)
n(Al (OH )3 ) = 2 0.025 = 0.05
n(H 2 C2O4 ) = 0.5 0.03 = 0.015

Al (OH )3 Na 3+ + 3OH

H 2 C2O4 2H + + C2O4 2

! n(OH ) = 3 0.05 = 0.15mol

! n(H ) = 2 0.015 = 0.03mol

EquationH + + OH H 2O
+
! So because it is 1-1 H is the Limiting Reagent
CALCULATE REMAINING MOLES OF SUBSTANCE IN EXCESS

n(OH ) = 0.15 0.0.03

! n(OH ) = 0.12mol

Because OH- is in XS pH will be above 7.

CALCULATE THE CONCENTRATION OF THIS SUBSTANCE
n
0.12
0.12
c= =
=
= 0.048mol L1
v
2
+
0.5
2.5
!
HENCE FIND pH:

pOH = log [0.048 ] = 1.3

pH = 14 1.3 = 12.7
!
This is pretty much as complicated as equations involving limiting reagents and pH will get!!

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Advanced pH problems:
Below are a few examples of interesting and challenging problems involving pH they are good to
know because they are common occurrences in exams:
Example 1 Mixing and Finding New pH:
Equal volumes of solutions pH=1.0 and pH=2.0 are mixed what is the final pH:
CALCULATE CONCENTRATION OF H+ IN EACH SOLUTION ORIGINALLY

Solution.1 = 10 1 = 1 10 1 mol L1
! Solution.2 = 10 = 1 10 mol L
ASSUME VOLUME TO BE 1 AND THUS FIND MOLES OF H+ IN EACH SOLUTION
2

n = cv so

Solution.1 = 1 10 1 mol
! Solution.2 = 1 10 mol
FIND TOTAL NUMBER OF MOLES OF H+ WHEN COMBINED
2

! n(total) = 1 10 + 1 10 = 0.11mol
DIVIDE BY NEW VOLUME (2) TO SOLVE FOR FINAL CONCENTRATION
1

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!

c(new) =

0.11
= 0.055mol L1
2

HENCE CALCULATE pH:

pH = log [0.055 ] = 1.26

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Example 2 Neutralising:
The pH of a swimming pool was too high at 9. What approximate volume of 10M HCl would you need
to lower the pH to 6:
CALCULATE CONCENTRATION OF H+ AND HENCE NUMBER OF MOLES WHEN
pH=6
+
!" H #$ = 10 6 = 1 10 6

n = cv
! n = 1 10 50000 = 0.05mol
USING THIS we know that a certain volume of 10M HCl must equal this in order to
give that number of H+ ions cause that concentration SO SOLVE ALGEBRAICALLY:
n = cv
6

0.05 = 10v
! v = 0.005 L
So you need to ad 5mL of HCl to lower the pH to 6.

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Example 3 Titration Intro:

In a titration 20ml samples of NaOH are piped into conical flasks. A volume of 17.32ml of 0.105mol L-1
of HCl was added to neutralise the solution so the pH was 7. Find the concentration of the sodium
hydroxide solution:
WORK OUT NUMBER OF MOLES OF H+ IONS ADDED
!n =

cv = 0.105 0.0173 = 0.00181mol

n = cv

USING THIS we know that the concentration of the NaOH multiplied by 20ml will give
the same number of moles SO SOLVE ALGEBRAICALLY:

0.00181 = c0.02
! c = 0.0909mol L
So the concentration of the Sodium Hydroxide is 0.091mol L-1.
1

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Further and More Detailed Revision of Acids and Bases:

Naming of Salts:
We know what salt is but there are various types of salts, basically we can say:
A Salt is a chemical produced when an acid reacts:

They are all ionic compounds.

They dissociate into ions when they dissolve.

They are all strong electrolytes.

We need to be able to name the salts produced and there are a few rules for this:
ACIDS WITHOUT OXYGEN BEGIN WITH HYDRO-:
o PRODUCE SALTS ENDING IN IDE:
Hydrochloric Acid produces chlorides.
Hydrocyanic acid produces cyanide salts.

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OXYACIDS (containing oxygen) ENGING IN IC:
o PRODUCE SALTS ENDING IN ATE
Sulfuric acid produces sulfate salts.
Phosphoric acid produces phosphate salts.

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OXYACIDS ENDING IN OUS:

o PRODUCE SALTS ENDING IN ITE
Nitrous acid produces nitric salts.

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It is vital that you understand and remember these rules.
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Reaction of Acids And Bases:

We have done this section to death over the past few years but we need to look at it just one more time:
An acid is a substance that produces hydrogen ions.
o Therefore it is only the H+ ion that reacts in acid reactions.
Like before lets for one last time look at the reactions of acids and bases in their various forms with
explanations and all that jazz:

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REACTIONS OF ACIDS AND BASES NEUTRALISATION

If the acid and base are in solution then not all ions will react so only those reacting need to be
included and you get the standard reaction.

H + (aq) + OH (aq ) H 2O(l )

!
When the acid reacts with the solid base however you need to include the entire basic compound
as a solid:

H + (aq) + NaOH (s) Na + (aq) + H 2O(l )

!
When we have a weak acid which only partially ionises you need to use the molecular form of
that acid i.e:
!

CH 3COOH (aq ) + OH (aq) CH 3COO (aq) + H 2O(l )

You need to know METAL OXIDES ARE SOLID BASES, these may hydrolyse with water to
form OH- ions, however all of them are solids so you get reactions like:

2H + (aq) + CaO(s) Ca 2 + (aq ) + H 2O(l )

!
Those are all the neutralisation reactions you need to know.

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REACTION OF ACIDS WITH METALS

All metals EXCEPT MERCURY are solid. When and IF CHECK E0 TABLE a acid reacts
with a metal then the metal ions are dissolved and H2 gas is produced:

2H + (aq) + Zn(s) Zn2 + (aq) + H 2(g)

!
IT IS WORTH NOTING THAT THIS IS ACTUALLY A REDOX REACTION. Because it
involves the transfer of an electron and not a H+ transfer.
REACTION OF ACIDS WITH CARBONATES
Once again if the substances are in solution then the non reacting ions do not need to be included
so you get the standard reaction:
!
By Josh Walker

2H + (aq) + CO32 (aq) CO2 g) + H 2O(l )

13 of 117
If however the carbonate is a solid then you need to write it as a solid:
!
This does involve

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H+

2H + (aq) + K 2CO3(s) 2K + (aq) + CO2 g) + H 2O(l )

transfer so it is an acid reaction.

REACTION OF ACIDS WITH HYDROGEN CARBONATES

These reactions are exactly the same as those for carbonates including the part about writing as
a solid. If however both substances are in solution then you get the standard reaction:

H + (aq) + HCO3 (aq) CO2 g) + H 2O(l )

!
Make sure you note the difference between number f H+ ions reaction.

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AMMONIA AS A BASE
We know ammonia is a base so it is important we know how to show the reaction where it
ACCEPTS A PROTON:

H + (aq) + NH 3(g) NH 4 + (aq)

!
Knowing this is essential to your acid and base theory but unlike previous years, this year it is
only the beginning.

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Amphoteric Substances:
Amphoteric substances are substance that react with acids and bases. These substances are:
Aluminium.
Zinc.
Chromium.
o AND THEIR HYDROXIDES AND OXIDES.
The acid reactions are just applications of those above but it is worthwhile knowing the reactions
with their BASE and putting them on the calculator so lets look at them now:
ALUMINIUM
Aluminium Metal
!

2Al (s) + 2OH (aq) + 6H 2O(l ) 2Al (OH )4

+ 3H 2(g)

(aq)

Aluminium Hydroxide

Al (OH )3(s) + OH (aq) Al (OH )4

(aq)

!
Aluminium Oxide

"

Al 2O3(s) + 2OH (aq) + 3H 2O(l ) 2Al (OH )4

(aq)

ZINC
Zinc Metal

Zn(s) + 2OH (aq ) + 2H 2O(l ) Zn(OH )4

!
Zinc Hydroxide

2
(aq)

Zn(OH )2(s) + 2OH (aq) Zn(OH )4

!
Zinc Oxide
By Josh Walker

+ H 2(g)

2
(aq)

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!

"

ZnO(s) + 2OH (aq) + H 2O(l ) Zn(OH )4

2
(aq)

CHROMIUM
Chromium Metal
!

2Cr(s) + 2OH (aq) + 6H 2O(l ) 2Cr (OH )4

(aq)

+ 3H 2(g)

Chromium Hydroxide

Cr (OH )3(s) + OH (aq) Cr (OH )4

!
Chromium Oxide

(aq)

Cr2O3(s) + 2OH (aq) + 3H 2O(l ) 2Cr (OH )4

!
These are all the amphoteric reactions you need to know.

(aq)

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Acidic, Basic and Neutral Salts:
"

Basic Theory:
The bases to understanding this topic lies in aspects we have just looked at in this set of notes:
Salts are ionic compounds that dissociate into ions when they dissolve in water they are
all strong electrolytes.
Acids and Bases may be strong electrolytes ionise completely in water.
Acids or bases may also be weak electrolytes meaning they remain mostly as the molecule
and only partially ionise.
What we also need to understand:

"

WATER IS A VERY WEAK ELECTROLYTE

H 2O ! H + + OH
!!

"

SO THAT MEANS THERE WILL BE HYDROXIDE IONS AND HYDROGEN IONS IN

SOLUTION WHENEVER THERE IS WATER.

"

That final idea is fundamental to understanding the following methods for determining the
acidity of alkalinity of salts.

"

Slightly Basic Substances:

If we consider the salt Sodium acetate or NaCH3COO we know:

"
"
"
"
"
"
"

It will dissociate into ions in water.

IN WATER there will also be the hydroxide and hydrogen ions from the water.

So if represent this as two equations one above another:

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!
Basically what we need to see is:
Because NaOH is a strong electrolyte as soon as those ions react with each other they will
dissociate so there is no change.
With the CH3COO- and H+ however they will react according to the reverse reaction of:

CH COOH

! H+

+ CH COO

(aq )
(aq)
3
(aq)
o !! 3
THE CH3COOH THEY PRODUCE HOWEVER IS A WEAK ACID.
o So it will not dissociate fully.
o THE CONCENTRATION OF THE MOLECULE IS FAR GREATER THAN
THAT OF THE H+.
So the concentration of the H+ ion will have decreased.
SOME OF THE HYDROGEN ION HAS BEEN USED UP IN REACTION.
So we get the statement [OH-]>[H+] so pH>7 and therefore the salt is basic.

"

So we can say that dissolving salts of weak acids in water will form a basic substance but it is better
to understand how to work this out.

"

Slightly Acidic Substances:

Lets consider this time ammonium chloride NH4Cl, and as before:
It will dissociate into ions in water.
You will also have the weak ion of water in the solution as well.
Once again looking at the two equations:

!
So if we are looking at this again we can say:
There is no reaction between the Cl- and H+ because they form a strong electrolyte.
However the ammonium and hydroxide react in the reverse of:

NH

+ H 0 ! NH

+ OH

3(g)
2 (l )
4 (aq)
(aq )
!
o !
ONCE AGAIN THIS PRODUCT THEY PRODUCE IS FAVOURED IN THE
REACTION:

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16 of 117
o So it does not dissociate fully backwards.
o SO SOME OF THE HYDROXIDE IONS HAS BEEN USED UP IN THE
REACTION.
o The concentration of the hydroxide solution will have decreased.
So we get the statement [OH-]<[H+] so pH<7 and therefore the salt is acidic

"

So we can say dissolving salts of weak bases in water will form a acidic solution however it is more
effective to understand the process of working this out.

"

Still Neutral Substances:

If we consider NaCl then we can represent the two equations (it dissociating and water) as usual
below:

!
BASICALLY:
THERE IS NO REACTION BETWEEN ANY OF THE IONS BECAUSE THEY ARE ALL
STRONG ELECTROLYTES AND SO AS SOON AS THE COMBINE THEY WILL BREAK
APART AGAIN.

"

"
"

So [H+]=[OH-] AND THE SALT IS NEUTRAL WITH pH=7

So we could say dissolving salts of strong acids or strong bases in water will produce a neutral
substance once again it is better just to work this out.

Classification:
We have covered the theory below but below is just a list of substances and whether they are acidic,
basic or neutral and an explanation as to why this is:
KNO3 NEUTRAL because in the reaction both the potassium and the nitrate ion will
form strong electrolytes and break up again so no reaction will occur.

"
"
"
"

KF BASIC because the hydrogen ions will react with the fluorine to form the weak
acid HF which will only partially ionise so not as many H+ will be produced. So hydrogen
ions will be used up and become basic.

KCH3COO BASIC CH3COO will reaction with H+ in water to produce weak acid
which only partially ionises, so decrease in concentration of H+ and it becomes basic.

KOH BASIC metal hydroxides are strong bases.

K2CO3 BASIC carbonates are bases.

It is worth knowing that this is because carbonate reacts:

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17 of 117
2

"
"
"
"
"
"
"

! CO3 + H HCO3
Which is a weak acid and will only partially ionise back so
therefore there will be a decrease in the concentration of the
H+ ions making it basic.

CH3(CH2)16COONa BASIC once again it will react using up H+ ion in water to form
weak acid which does no ionise so hydrogen ion concentration decreases and becomes
basic.

K2SO4 BASIC produces weak acid which partially ionises H+ ion concentration
decreases and becomes basic.

HBr ACIDIC bromic acid, must be an acid.

NH3 BASIC ammonia, acts as a weak base, should know.

NH4NO3 ACIDIC NH4+ would react with OH- in water to produce NH3 + H2O which
only partially ionises back, meaning there is a decrease in concentration of OH- and
solution becomes slightly acidic.

H2O NEUTRAL equal concentrations of OH- and H+.

NH4CH3COO NEUTRAL the NH4 would react to produce an acidic solution but the
CH3COO would react to produce a basic solution so they would cancel each other out
giving a neutral solution.
Finally to finish this section off consider the following equation of stearic acid (weak acid found in
vegetable oils):

C17 H 35COOH ! H + (aq) + C17 H 35COO (aq)

!!

Using this show whether Sodium Stearate is slightly acidic or slightly basic.

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Basically we just show:

"

So there is a reaction to produce stearic acid, which will only partially ionise back.
Therefore there is a decrease in [H+].
! H + # < !OH #$
So! " $ "
therefore it is slightly BASIC.

"
"
"
Indicators:
"

Colours of Indicators:
This is simply a table you need to remember and probably put on your calculator:

"

Litmus

Universal
Indicator

Phenolphthalein

Methyl
Orange

Bromothymol
Blue

ACID

BlueRed

Red

Clear

Red

Orange

BASE

RedBlue

Purple/Blue

Pink/Purple

Orange

Blue

"

Introduction:
Basically in an acid base titration and indicator is used so we can see when the substance has been
neutralized before we go any further we need to clear up two very important definitions:
END POINT
This is the point in a titration where a COLOUR CHANGE occurs.
i.e. the neutralisation reaction is deemed to be complete.

"

EQUIVALENCE POINT

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This is the point at which CHEMICALLY EQUIVALENT AMOUNTS (shown via equation)
HAVE BEEN ADDED.
So If we were adding HCl to NaOH then we would have the equation:
o !

"

H + + OH H 2O
So the equivalence point occurs when the same number of moles of HCl as
NaOH have been added.

So If we were adding H2SO4 to NaOH then we would have the equation:

o !

H 2 SO4 + 2OH SO4 2 + H 2O

So the equivalence point occurs when the ratio of NaOH : H2SO4 is 2 : 1.
i.e. there are twice as many moles of base as there are acid.

Now INDICATORS which are either WEAK ACIDS or WEAK BASES are used in titrations so
that:
THE END POINT IS AS CLOSE AS POSSIBLE TO THE EQUIVALENCE POINT AND A
pH of 7.
o Note that one drop near the end point can change the pH dramatically.

"

Indicators have a range of pHs they will change in:

PHENOLPHTHALEIN 8.3 TO 10.0
METHYL ORANGE 3.1 TO 4.4

"

NOW we can use the basic ideas to look at three different types of titrations and look at the type of
indicator you would use and WHY!!

"

Strong Acid vs Strong Base:

If we consider a strong base and strong acid:
Strong base NaOH
Strong acid HCl
Because these are both strong electrolytes they will not react with the water so the will ONLY
NEUTRALISE EACH OTHER.
THEREFORE ANY INDICATOR THAT CHANGES COLOUR IN pH RANGE 4-10 can
be used.
Which can be represented on a graph as:

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!
Now it gets more complicated.

"

Weak Acid vs Strong Base:

If we consider NaOH being titrated into a solution of the weak acid CH3COOH we get equation:

CH 3COOH (aq ) + OH (aq) CH 3COO (aq) + H 2O(l )

!
WHAT IS IMPORTANT:
From what we have looked at we KNOW the CH3COO- will react with the water to form a
slightly basic substance:
o As shown by the reaction below.

CH 3COO (aq) + H 2O(l ) CH 3COOH (aq) + OH (aq)

!
SO WHAT WE CAN SAY:
When the EQUIVALENCE POINT is reached the substances in product will continue to
react producing a basic substance.
o SO THE EQUIVALENCE WILL OCCUR IN A pH>7.
This can be shown on the following diagram:

!
SO WHAT WE DO:

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In order to account for this basic result we use AN INDICATOR THAT USES UP SOME
BASE.
An indicator which BUFFERS the base so that it will still change at equivalence point.
o An indicator that will change colour in pH of equivalence point given.
THE INDICATOR WOULD HAVE TO BE A WEAK ACID to use up base.
So we could use phenolphthalein for this situation.

"

Weak Base vs Strong Acid:

If we consider the weak base NH3aq) being titrated into a solution of the acid HCl we get equation:
!

NH 3(aq) + H + (aq ) NH 4 + (aq)

WHAT IS IMPORTANT:
From what we have looked at we KNOW the NH4+ will react with the water to form the
hydronium ion A SLIGHTLY ACIDIC SUBSTANCE:
o As shown by the reaction below.

NH 4 + (aq) + H 2O(l ) NH 3(aq ) + H 3O+ (aq)

!
SO WHAT WE CAN SAY:
When the EQUIVALENCE POINT is reached the substances in product will continue to
react producing a acidic substance.
o SO THE EQUIVALENCE WILL OCCUR IN A pH<7.
This can be shown on the following diagram:

!
SO WHAT WE DO:
In order to account for this acidic result we use AN INDICATOR THAT USES UP SOME
OF THE ACID.
An indicator which BUFFERS the acid so that it will still change at equivalence point.
o An indicator that will change colour in pH of equivalence point given.
THE INDICATOR WOULD HAVE TO BE A WEAK BASE to use up acid.
So we could use methyl orange for this situation.

"
"
"

By Josh Walker

"

22 of 117

"
"
"
Atomic Structure:
"

Bonding

The Structure of Atoms:

In this course we consider the Bohr Model of he Atom:

!
What we need to remember about this model is:
The electrons not the nuclei determine the chemical properties of the atom.
The electrons, which exist in a cloud of negatively charged particles, occupy most of the
volume of the atom.
Atoms of each element have a fixed number of electrons.
The electron cloud surrounds a very small, dense, positively charged nucleus.
The nucleus consists of positively charged protons and neutrons with no charge.
The overall charge on the atom is zero the number of protons and electrons are equal.
If there is more than one proton in a nucleus then there must be an equal or greater number of
neutrons to prevent to protons repelling one another.
The number of protons determines the type of atom and hence the element.
We also need to remember our symbols relating to this:
A = atomic mass number = number of protons and neutrons.
Z = atomic number = number of protons, and hence electrons in the atom.
The most important idea of Niels Bohr is that he defined the atom in terms of the electrons not just
lying anywhere around the nucleus but being locked into fixed orbits which have a different
energy level (n):

!
Although we will consider orbitals in more detail in a few minutes it is worth remembering and
considering:
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Each energy level can contain a maximum number of electrons.
THE HIGHEST ENERGY LEVEL (shell) IS CALLED THE VALENCE SHELL AND
CONTAINS VALENCE ELECTRONS.
During CHEMICAL REACTIONS only the VALENCE ELECTRONS are involved.
It is worthwhile also considering the periodic table of the elements here:
The ROW in the periodic table tells you the energy level that the atoms are in.
THE GROUP in the periodic table tells you how many valence electrons that element has:
o Except for helium which only has two valence electrons.
It makes sense from there that we can say:
Valence electron shells WANT TO CONTAIN 8 electrons (octet rule).
o Except for helium which wants to contain two.
This makes sense because all GROUP EIGHT ELEMENTS ARE UNREACTIVE so they
are in a stable state.
It is these ideas which lead to the more complicated situations that we will look at in this course.
You should remember how these valence electrons can be represented as electron dots but we are not
going into it here, for now this is all you need to know on an intro.

"

Isotopes:
Isotopes are simply Atoms that have the same number of protons but a different number of
neutrons.
From this we can say:
Because they have the same number of protons they will be the same element.
Because protons must equal electrons in an atom they will therefore have the same
number of electrons and they will thus be chemically identical.
Only their physical properties will change.
Isotopes like C-12 and C-14 are often useful in radioactive applications.

"

Orbitals:
Although the Bohr model is useful it doesnt quite account for the more complicated multi electron
elements.
That is why we look at a quantum mechanics theory:
States electrons are fond in regions of space called orbitals.
o An orbital is literally the statistical area in space where you MAY find an electron.
There are a few interesting points we need to know about orbitals:
Each orbital with energy level n can hold n2 orbitals:
o So energy level 1 can have 1 orbitals.
o Energy level 4 can have 16 orbitals.
Each orbital holds TWO electrons.
There exists different types of orbitals s orbitals, p orbitals, d orbitals and f orbitals:
o THE S ORBITALS:
Contain only one orbital in an energy level.
o THE P ORBITALS:
Consist of three dimensions px, py and pz and hence
Contain three orbitals in each energy level they exist in.
o THE D ORBITALS:
These contain five orbitals in each energy level they exist in.
o THE F ORBITALS:
These contain seven orbitals in each energy level they exist in.
The important thing to understand about these orbitals is that they come in at different times:
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FOR EXAMPLE:
In energy level 1 there can only be one orbital:
o Only the 1s orbital.
In energy level 2 there is 22 = 4 orbitals:
o You have the ONE 2s orbital.
o And the THREE 2p orbitals.
In energy level 3 there is therefore 9 orbitals:
o The one 3s orbital.
o The three 3p orbitals.
o And the FIVE 3d orbitals.
And finally in energy level 4 there is 16 orbitals:
o The one 4s orbital.
o The three 4p orbitals.
o The five 4d orbitals.
o And the SEVEN 4f orbitals.
It is important to notice that all of the orbitals of the same type and energy level (i.e. all 3ps) are
of equal energy:
So when they will up with electrons they each take a single electron before making a pair
as shown below:

!
Not like this:
!

This is known as the aufbau (building up) principle.

The final thing we need to look at with orbitals is there relative position to one another:
It is not as simple as filling all the ones, then all the 2s and so on.
The orbitals can be displayed as below with lowest energy at bottom.

!
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On your periodic table you can also see the orbitals.
Having looked at all of this information it would we can now see how VARYING VALENCIES in
TRANSITION METALS are formed.
Lets Consider Mn
It has two s electrons, which means it has two valence electrons.
This implies it will form an ion of 2+.
It can be shown as below.

!
HOWEVER THE 3d ORBITALS ARE SO CLOSE TO THE 4p ORBITALS THAT AN
ELECTRON CAN JUMP ACROSS TO THE 3d LEVEL

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!
As a result of this:
The substance would still be Mn because the same number of protons.
But now there is only one s level electron.
Therefore it will form a valence of +1.
That is all we need on the basics of orbitals for now.

"

Using Orbitals:
We have already briefly discussed this idea but it is important to understand:

"

THE NUMBER OF VALENCE ELECTRONS IS THE NUMBER OF S AND P ELECTRONS IN

THE HIGHEST ENERGY LEVEL OF THAT ATOM

"

So when we are looking for number of valence electrons we only need to look at the p and the s in this
highest energy level i.e. for element Rn:
1s22s22p63s23p64s23d104p65s24d105p66s24f145d106p6
o Therefore there are 2+6=8 valence electrons.
There is also a shorthand of representing this:
Consider P:
o 1s22s22p63s23p3
This has the same INNER SHELL structure as Neon:
o i.e. 1s22s22p6
So for Phosphorus we can actually represent it as:
o [Ne]3s23p3
These two ideas will often come up in tests and exams.

"

Ionisation Energy:
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Ionisation energy can quite simply be described as the energy required to remove an electron
from an atom to produce and ion.
This is the same as the activation energy in a reaction.
This ionisation energy may be in any form of energyheat, light, chemical etc.
So what happens?
FIRSTLY ions have a stable octet of 8 valence electrons.
o Therefore atoms that have two valence electrons would want to LOOSE those two
electrons in that shell to form a 2+ ion and have a stable octet valence shell.
THEREFORE an electron is removed via the IONISATION ENERGY in the reaction.
ANOTHER ELECTRON MAY BE REMOVED but this would take more energy
because the second electron is being removed from a positive ion.
o i.e. If we look at Mg the first electron is removed.
+

! Mg + IE Mg + e
o Then the second you are removing a negative electron from a positive ion so you
have to break the attraction due to opposite charges as well.
+
2+

! Mg + IE Mg + e
o So it takes more energy for the second.
From this it makes sense REMOVING ELECTRONS FROM NOBEL GASES (atoms with
stable octet) TAKES VERY LARGE AMOUNTS OF ENERGY:
Because the atoms are already an ideal energy state.
So an electron does not want to be removed.
From this simply idea we can use tables and graphs of ionisation energies to predict the valence or
number of valence electrons that an atom has:
Basically all you do is look for a jump:
o The ionisation energies will increase in a relatively linear pattern.
o When the atom reaches a stable octet however there will be a big jump in the energy
required.
o So how many electrons removed before this jump will be the number of valence
electrons in the atom.
So if we consider the following graph:

!
It is clear that the jump occurs after three electrons have been removed and thus the substance will have
a 3+ valence.
Now lets move on.

"

Electronegativity Introduction:
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Electronegativity can basically be defined as the ability of an atom to attract electrons.
Why does this occur?
o Basically atoms in the higher groups have 6 or 7 valence electrons.
o THEY THEREFORE WANT TO GAIN 1 OR 2 ELECTRONS to form a stable octet and
hence ion.
o So they are attracting electrons.
We will look at trends of electronegativity in more detail later but for now it is worth knowing.
A order of ionisation energies for this highest
can be:
! F > O > Cl > N > S> C > H
Now lets jam this together with ionisation energy to make something worthwhile.

"

Formation of Ions:
We have already looked at how metals (substance in lower groups of periodic table) LOOSE
electrons to form positive ions whilst non-metals (substances in higher groups of periodic table),
GAIN electrons to form negative ions.
We can happily say:
IONS HAVE THE SAME VALENCE ELECTRON STRUCTURE AS A NOBLE GAS 8 valence
electrons except for those near helium that have 2 valence electrons.
But atoms do not really LOOSE electrons what happens can be best described by an example
consider Sodium and chlorine:
o Sodium has the following electron dot structure.

!
o Chlorine has the following dot structure.

!
o If the two were to come near each other:
o ENERGY with energy from surrounding eventually there would be enough remove
an electron from the sodium.

!
o CHLORINE - would attract this electron and pick it up also forming a stable octet.

!
o SO the atoms form ions via EXCHANGING electrons.
We can also describe ionic bonds using this logic:
o The two atoms collide.
o AN ELECTRON IS TRANSFERRED FROM THE SODIUM TO THE CHLORINE.
o Both atoms now form ions.
o These ions are magnetically attracted to each other as shown below:
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!
o The arrow shows electron going from the sodium to the chlorine.
o You do not draw the electron dots on the sodium simply because it makes it look
complicated.
The only other thing you need to remember about ions is:
o POSITIVE IONS are often called cations.
o NEGATIVE IONS are often called anions.
That is the end of basically the revision with a few extra ideas added in. Now we can move into some
partially new information.

"

Chemical Bonding and Properties of Materials:

We know that the chemical properties of a substance are dependent on the number of valence electrons.
However the physical properties are dependent on the type of bond between the atoms.
o Bonds may be:
o Ionic.
o Metallic.
o Covalent.
Covalent molecular.
Covalent Network.
o The SHAPE and POLARITY will determine the type of bonds between individual
(DISCRETE) molecules.
o Melting points and boiling points are an indication of the strength of the chemical bond
(force).
It is also important to remember that the physical properties we are looking at are:
o Melting points.
o Boiling points.
o Hardness.
o Conductivity of electricity and heat.
o Solubility.
So lets move in and look at each of the type of bonds above separately.

"

Ionic Bonding:
When the metals form positive ions, and the non-metals negative ions these +ve and ve ions attract
electrostatically forming a 3-dimensional crystal (lattice, network) structure.
THIS ATTRACTION IS CALLED AN IONIC BOND
Ionic solids are :
o Hard.
o Because of network structure.
o Brittle.
o Because of positive and negative ions if you bend it then they will align and repel.
o Non-conductors of electricity.
o Because there are no free ions or electrons to conduct a current.
o High Melting Points.
o Because there is a strong bond in the crystal lattice.
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When they are dissolved in water or melted however they do conduct electricity:
This is because they break up into ions!!
o Consider NaCl.
o When melted or dissolved it dissociates into ions as shown below:
+

! NaCl Na + Cl
o The now mobile ions are attracted to oppositely charged electrodes and hence conduct
a current.
You can also have complex ions which remain together when dissolvedthese include:
o NO3o NH4+
o They have a covalent bond between the atoms within the ion.
So substances like NH4Cl have both ionic and covalent bonds within them.

"

Metallic Bonds:
Metallic bonds are different to any other sort of bonds.
They form a crystal structure (lattice, network) with an array of positive metal ions surrounded
by a sea of mobile delocalised electrons not belonging to any particular atom.
This can be seen below:

!
As a result of this metals have:
o Varying melting points.
o Due to varying number of protons etc in bonds.
o Vary in hardness.
o Due to varying number of protons etc in bonds.
o Malleable and Ductile.
o Because delocalised electrons ensure there is always attraction and bending does not
align them and repel.
o Shiny when polished have lustre.
o Conduct heat and electricity well.
o Because mobile means moving so the electrons can move freely and conduct a current
and/or heat.
Metals are really quite simple to understand in terms of bonding.

"

Transition Metals:
These group of metals are Metals in which the d orbitals are filled with electrons.
o They usually have 2 valence electrons the two s electrons.
o They have all the typical metal characteristics.
o They also have some special characteristics which include:
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"

o Variable valencies.
Eg. Fe2+ and Fe3+ all exist.
o They Form Coloured Compounds.
Cr2+ - blue.
Cr3+ - green.
CrO42- - yellow.
Cr2O72- - orange
MnO4- - purple
Cu2+ - blue
o For Complex Ions.

Complex ions form when a positive transition metal ion is SURROUNDED by anions (Cl-, CN-)
or polar molecules (H2O, NH3).
You can say these ligands are bonded to the central ion by coordinate covalent bonds:

!
We need to know a few reactions for the course so lets just summarise them here:
Ammonia solution is added to copper II sulfate solution:
Ammonia solution can be seen as a mixture of NH3, H2O, NH4+ and OH- because:
+

! NH 3 + H 2O ! NH 4 + OH
!
Therefore it make sense the reaction would be:
Cu 2 + (aq) + 2OH (aq) Cu (OH )(s)
Pale Blue ppt

Excess ammonia solution is now added to this copper precipitate:

!

Cu (OH )2(s) + 4NH 3(aq) "# Zn(NH 3 )4 $%

2+
(aq)

+ 2OH (aq)

Excess ammonia is added to the initial copper II sulfate solution:

Cu 2 + (aq) + 4NH 3(aq ) "#Cu (NH 3 )4 $%

2+

(aq )
!
Zinc reacting in the same fashion as above:

Zn2 + (aq) + 4NH 3(aq) "# Zn(NH 3 )4 $%

2+

!
Silver also reacting as above:
!

Ag+ (aq ) + 2NH 3(aq) "# Ag (NH 3 )2 $%

(aq)

+
(aq)

Now we know these reactions we can deduce other onesi.e. A solution of Cobalt Nitrate reacts with
water to form the complex ion hexaaquocobalt II [Co(H2O)6]2+.
o Since it only reacts with water it follows that with a bit of logical balancing we can get:

Co 2 + (aq) + 6H 2O(l ) "#Co (H 2O)6 $%

2+

(aq)
!
Thats the extent of transition metals and complex ions in this course.

"

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Covalent Molecular Bonding:
Covalent bonds form when non-metal atoms share electrons and produce a discrete (individual) unit
called a molecule.
COVALENT BONDS are bonds formed by SHARING ELECTRONS and they are the
STRONGEST TYPE OF CHEMICAL BOND between ATOMS
However the bonds BETWEEN these individual units called MOLECULES are WEAK.
o The type of the bond between the molecules is determined by how the molecules are
arranged and determines the strength and type of substance you can expect.

"

Some properties of covalent molecular bonded substances are:

o Brittle OR soft when solid.
o Solids have low melting points.
o Liquids have low boiling points.
These last two points bring out a very important idea for the properties of these materials:
o It suggests that there is a weak force between the molecules of the substance.
o However there is still a strong force between the atoms in the molecules.
So:
MELTED BOILED OR DISSOLVED they remain as molecules
For example:
When sugar dissolves it breaks away from the crystal but remains as individual molecules in
the water.
H2O
C H O !!!
C12 H 22O11(s)
! 12 22 11(s)
The same happens for water as it boils they overcome the molecular bonds between the
molecules but the atoms within the molecules stay bonded.
H O H 2O(l ) H 2O(g)
! 2 (s)
All this brings up the final property of covalent molecular substances:
o THEY DO NOT CONDUCT ELECTRICITY OR HEAT.
o This is because all the electrons are tied up in the covalent bonds and there are no
ions so therefore there is nothing to carry the current or heat.
That is the basics of covalent network solids for now.

"

Covalent Network Solids:

There are a few substances that form three dimensional crystalline networks of covalently bonded
atoms rather than indicvisual molecules.
o Carbon (diamond) C

!
o Silicon Si.
o Silicon Carbide SiC.
o Silicon Dioxide (quartz) SiO2
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o Boron B
Carbon also forms a two dimensional network:
o Graphite C.

!
Because of its two dimensional nature graphite has some characteristics different to that of the other
covalent network solids:
o Soft.
o Because there are weak bonds between the carbon layers.
o High Melting Point.
o Because there are strong covalent bonds between the carbon atoms within the layer.
o Conducts Electricity.
o Because each carbon is only surrounded by THREE other carbons there is therefore a
free delocalised electron for each carbon.
o This electron can move through the layers and conduct electricity.
The properties for the other three dimensional covalent networks solids are all similar:
o High Melting Point.
o Hard.
o Non Conductor.
o This is all because of the strong covalent bonds that holds all electrons together,
making it hard to break apart, hard to touch and a non conductor.
Now we have completed the look at bonding properties we can move into the section of total new
work.

"

Shapes and Polarities of Molecules:

We have for a while now looked at molecules and covalent bonding and discussed the idea of polarity
but now it is time to officially understand these terms and use them.
Before we go any further we need to understand A molecule is said to be POLAR when it has a
dipole that is a positive and a negative end.
We will look at how that occurs and the different ways it can occur in this section.

"

Linear Non-Polar:
If we consider the chlorine molecule Cl2.
o Each chlorine atom has 7 valence electrons so it wants to share one with the other chlorine
molecule.

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!
o As you can see there are both bonding and non bonding electron pairs.

o
o
o

"

!
This is a LINEAR NON POLAR molecule:
The Molecule is shaped in a straight line LINEAR.
The electrons are equally attracted to both nuclei.
Therefore they are evenly symmetrically distributed so there is NO DIPOLE.
This is the same with other halogens F2 Br2 I2 and also H2

Linear Polar:
If we consider the hydrogen chloride molecule HCl.
o The hydrogen atom has one valence electron whilst the chlorine has seven so they both
want to gain one therefore they share one.

!
o As you can see there are both bonding and non bonding electron pairs.

!
This is a LINEAR POLAR molecule:

!
The Molecule is shaped in a straight line LINEAR.
Chlorine is more ELECTRONEGATIVE so inside the nuclei the electrons are attracted to
it more than they are to the hydrogen.
o There are also a far greater number of non bonding electron pairs on the chlorine atom.
o
Therefore the molecule has a slightly negatively charged end and hence a slightly
positively charged end.
We represent this with - (for negative end) and + (for positive end) with a line pointing in the
direction of the negative end with a cross over the positive end
This is the simplest type of polar molecule.
o
o

"

Bent, Polar:
If we consider water H2O
o There are two hydrogen atoms attached to the one oxygen atom.
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!
!
o Oxygen is more electronegative than Hydrogen.
o There are also free non-bonding electrons on the oxygen.
o So we have two dipoles as shown below.

!
o This adds up to give one dipole.

!
o
o
o

"

This is a BENT POLAR molecule:

The Molecule is BENT because the bonding and non bonding electron pairs REPEL so
there is an angle between them.
DIPOLE EXISTS because of oxygen being more electronegative than hydrogen and of
excess non bonding electron pairs.
The two dipoles add up to produce a NET DIPOLE.
Other molecules like this include H2S, F2O, Cl2O

Tetrahedral Non Polar.

Considering methane, CH4:
o To The one carbon atom there are four hydrogen atoms.

!
o Carbon is more electronegative than hydrogen.
o However the hydrogens are all in opposite directions so you will have four dipoles.
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!
o These dipoles all cancel so the electrons are evenly distributed and we have a non polar
molecule.

!
This is a TETRAHEDRAL NON POLAR molecule:
TETRAHEDRAL because bonding electron pairs and H nuclei repel so there is a
maximum distance between the C-H bonds (angle 109.5)spread out.
o NON POLAR because the four dipoles all cancel each other out an end to give a overall
non polar effect..
Other molecules like this include CCl4, ALL straight chain HYDROCARBONS, SiH4 (silane)
o

"

Tetrahedral Polar:
Considering CH3Cl:
o To The one carbon atom there are three hydrogen atoms and one chlorine atom.

!
o Carbon is more electronegative than hydrogen and chlorine is more electronegative than
carbon.
o So we have three dipoles (caused by the hydrogen), which are the same, and one dipole
(FROM THE CHLORINE) WHICH IS DIFFERENT.

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!
o SO THE DIPOLES DO NOT CANCEL.

!
o
o

This is a TETRAHEDRAL POLAR molecule:

TETRAHEDRAL because again there is repulsion between the bonding electron pairs
and nuclei so they spread out.
POLAR because the four dipoles do not cancel, because they are not all of the same
strength
Most molecules in form XY3Z will be polar tetrahedral molecules

"

It is worth considering the case CH2Cl2:

o THE IMPORTANT POINT IN THIS SET UP IS REMEMBERING THAT UNBOUND
ELECTRON PAIRS ARE ALWAYS LEFT TOGETHER:
o So when the hydrogen fills up two of the carbon electrons.
o The remaining two places are NEXT TO EACH OTHER.
o As a result the structure is like this:

!
NEVER LIKE THIS:

!
o So from the correct structure it is easy to see how there is a dipole.

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o
o

"

!
This is a TETRAHEDRAL POLAR molecule:
TETRAHEDRAL because again there is repulsion between the bonding electron pairs
and nuclei so they spread out.
POLAR because the four dipoles do not cancel, because they are not all of the same
strength
It is incredibly important you remember this structure note

Triangular Pyramid, Polar:

Considering ammonia, NH3:
o To The one nitrogen atom there are three hydrogen atoms.

!
o Nitrogen is far more electromagnetic than hydrogen.
o The Nitrogens are in three directions so you have three separate dipoles.

!
o Because of the repulsion between the electrons the Hydrogens spread out to form a
triangular pyramid shape and this REINFORCES THE DIPOLE.

!
This is a TRIANGULAR PYRAMID EXTREMELY POLAR molecule:
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o TRIANGULAR PYRAMID because bonding electron pairs and H nuclei repel so there
is a maximum distance between the C-H bonds and this forms a triangular pyramid.
o
POLAR because the three separate dipoles all reinforce one another to make it a very
polar molecule.
Other molecules like this include most in the form of XY3

"

Special Substances:
There are a few cases we need to consider some questions some just molecules:
Carbon Dioxide:
In carbon dioxide:
o A double bond exists between the carbon and oxygen:

!
!
o The Oxygen is more electronegative than the carbon so there are two dipoles which exist.

!
o These dipoles cancel however resulting in a LINEAR NON POLAR MOLECULE.

!
So although from looking at this CO2 formula we may think it is the same as H2O if we actually THINK
about what is happening with the bonds we will see that it is definitely not the case.

"

A Polar molecule that has a non polar bond within the molecule:
This is a common question in tests and exams and requires a simple answer hydrocarbon with more
than one carbon atom:

!
A Non Polar molecule that has a polar bond:
This is identical to the question above there are polar bonds in all the hydrogens attached to a carbon
atom so you just need a hydrocarbon:

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40 of 117

!
If you are able to understand and do this then you have a good chance of success:

"

Electronegativity and Polarity Strength:

We have already briefly looked at this but it is worth clarifying.
The greater the difference in electronegativity in a molecule the more polar the molecule will be:
So therefore:
o Cl-Cl no polar, because of zero difference in electronegativity.
o C-Cl very polar because of large difference in electronegativity.
o IONIC BONDS extremely polar because electrons are actually transferred so you have
large difference in electronegativity.
This is not the most important concept but it is useful if you need to identify the most polar molecule
in a series of molecules.

"

Co-ordinate (dative) Covalent Bonding and Ions:

A co-ordinate (dative) bond is simply a covalent bond where one atom donates bothe electrons to
the bond.
For example in the ammonium NH4+ ion:
Ammonia reacts with a proton to form the ion:

!
AS YOU CAN SEE the proton latches on to the two free electrons of the ammonia and thus the
ammonia has provided both electrons for the bond and it is a dative bond.
Dative bonding is the basis for many of the complex ions such as:
o H3O+
o SO42o NO3o And so on.
It is very important to remember:
ALL IONS ARE NON POLAR!!!!
This is because in order to be polar a molecule must have a dipole and ions only have EITHER a
positive OR a negative end.
It is essential to understand all of this before we move on to the next section.

"

Forces Between Molecules Intermolecular Forces:

It is important that we understand there are bonds within and bonds between molecules:
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o Covalent bonds exist WITHIN molecules (between the atoms)
o This is the strongest chemical bond that exists.

!
o Van der Walls forces exists BETWEEN molecules:
o These molecular forces are very weak.

!
This weakness can be easily seen if we compare the melting points of various solids (REMEMBER
MELTING POINT IS AN INDICATION OF BOND STRENGTH):

"

METALLIC

IONIC

COVALENT
NETWORK

MOLECULAR
(POLAR)

MOLECULAR
(NON POLAR)

1100C

800C

1700C

0C

-80C

As you can see the bond strength varies even in molecules. This depends on the polarity and shape of
the molecules. ALSO NOTE: There are virtually NO intermolecular forces between particles in a
GASEOUS state.

"

We can display van der walls forces in a chart below:

!
Now lets investigate each of them.

"

Dispersion Forces:
Dispersion forces ARE PRESENT BETWEEN ALL MOLECULES!!!!!!!!
The important point however is that:
o THEY ARE THE ONLY INTERMOLECULAR FORCES BETWEEN NON POLAR
MOLECULES in a liquid or solid state.
The logic behind the dispersion forces are very simple:
o Electrons can always move around inside atoms.
o OCCASIONALLY THESE ELECTRONS WILL ALIGN TOGETHER IN ONE
DIRECTION.
o THIS CAUSES ONE MOLECULE TO HAVE A TEMPORARY DIPOLE.
o Because it is next to another molecule this will induce a TEMPORARY DIPOLE in that
molecule as well.
o And as a result there is a force of attraction between the molecules.

"

It does not take a genius to work out that a force of attraction dependent on the random motion of
electrons is A VERY WEAK FORCE the weakest of all intermolecular forces.
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"

It is also important to note AS MOLECULAR WEIGHT INCREASES SO DOES MOLAR MASS:

!
This occurs because:
o An increase in molecular weight means there are more protons and electrons in the atom.
o Therefore there is a greater force of attraction in the molecules.
o Thus you need more energy to break the molecules apart.
Substances that are bonded by dispersion forces are:

"

o Noble gasses.
o Halogens.
o Hydrocarbons (alkanes, alkenes,
alkynes).
o Waxes.
o CO2.
o CS2.
o SiH4.
Thats as simple as dispersion forces are.

"

o
o
o
o
o
o

CCl4.
S 8.
P4.
O2.
N 2.
H2.

"

Dipole-Dipole Forces:
Dipole-Dipole forces EXIST BETWEEN POLAR MOLECULES in a liquid or solid state!!!
The logic here is the simplest:
o Basically every molecule has positive and negative end.
o So there is an attraction between the +ve end of one molecule and the ve end of another.
This can be shown below using HCl in liquid form as an example:

!
Because there is a set electromagnetic attraction dipole-dipole forces are STRONGER than
dispersion forces.
Substance which are dipole-dipole bonded include:

"

o SO2.
o NO2.
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o HBr.
o HI.

43 of 117
o H2S.
o Alkyl Halides (CH3Cl, CH3CH2Br
etc).
These are the easiest intermolecular forces to understand.

"

"

Hydrogen Bonding:
A PARTICULARLY STRONG dipole-dipole force that exists in some liquids and solids is A
HYDROGEN BOND!!
o Its strength is due to the fact that Hydrogen does not have many electron clouds, the electrons
are close to the nucleus and hence there is a stronger force of attraction there.
We can say:
Hydrogen Bonds Occurs in molecular substances that contain POLAR MOLECULES with
HYDROGEN BONDED TO:
o
OXYGEN.
o
NITROGEN.
o
FLUORINE.
H-FON
Common substances include:

"

o H2O.
o CH3CH2OH.
o NH3.
o CH3COOH.
o HF.
o CH3OH.
You can basically say that THE PRESENCE OF THE OH GROUP INDICATES HYDROGEN
BONDING.

"

"

If we were to draw out a hydrogen bond it would look pretty much exactly the same as a dipole-dipole
bond:

!
Hydrogen bonding can be used to explain the following two graphs:

!
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Simply, the molecules of H2O and HF are held together by hydrogen bonds. The molecules of
the other substances are only held together by dipole-dipole bonds. The hydrogen bonds are
much stronger and so therefore although the molecular mass is lower (boiling point increases
with molecular mass) the boiling point is higher.
And thats all we have to say about hydrogen bonding.

"

Explanations:
The most common question in an exam is explain why so here we will look at a few examples
of this explain scenario:
EXAMPLE ONE
Water (M=18g) boils at 100C and Methane (M=16g) boils at -161C. Although the molar masses are
similar there is a large difference in boiling points explain:
Water is a polar molecule:

!
The intermolecular forces in water are a particularly strong dipole-dipole bond called a
hydrogen bond. This is the bond between the oxygen and the hydrogen.

!
Methane CH4 on the other hand is a non-polar molecule. Therefore the molecules of
methane are only held together by weak dispersion forces that is forces of attraction
caused by the alignment of electrons in molecules. As a result of this the energy required
to separate the methane molecules is far less than that required to separate the water
molecules.
EXAMPLE TWO
The boiling points of the first 4 alcohols are:
o Methanol, CH3OH - 64C
o Ethanol, CH3CH2OH - 78C
o Propanol, CH3CH2CH2OH - 98C
o Butanol, CH3CH2CH2CH2OH - 118C
Explain why this occurs:
Simply, the boiling point is increasing because the molar mass is increasing. This means
there are more protons and more electrons in each atom. Therefore the force of attraction
between the atoms in the bonds is stronger and it takes MORE ENERGY and hence a
greater temperature to break them apart.
Thats everything for the intermolecular forces in this course.

"

Solubility:
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Solubility depends on the interactions between the bonds in the solute and the solvent:
o If the force between the solvent-solute is stronger than the force between the solute-solute or
solvent-solvent then a substance will dissolve.
So lets look at a few ways things dissolve and understand it all.

"

Dissolving Ionic Solids:

The process behind the dissolving of ionic solids is possibly the simplest and most logical to explain
which is why we begin here.
Simply we can say:
o When an ionic solid is placed in water it has a negative end and a positive end.
o The water molecules are also polar.
o Therefore:
o The positive end of the water molecule will attach to the negative ion.
o The negative end of the water molecule will attach to the positive ion.
o The subsequent KINETIC ENERGY (MOTION) of the water molecules gradually
BREAKS UP the crystal.
o Thus the ionic solid is now separated into IONS and each ion is surrounded by a water
molecule making it soluble.

"

It is important to consider:
AN IONIC SOLID IS INSOLUBLE WHEN THE ATTRACTION BETWEEN THE IONIC
BONDS IS GREATER THAN THAT BETWEEN THE IONS AND THE WATER.

"

It is also worth noting:

o SOLUBILITY OF SOLIDS IN LIQUIDS increases as temperature increases.
o Solubility of gasses decreases in liquids as temperature increases.
Now lets look at molecular substances and see how they dissolve.

"

Dissolving Polar Molecular Substances:

There are two points we need to consider about polar molecular substances:
o THEY DISSOLVE IN OTHER POLAR SUBSTANCES USUALLY:
o Because there is an attraction between the negative end of one molecule and the
positive end of another molecule.
This is particularly strong when the solute forms hydrogen bonds with the
solvent.
i.e. the following dissolve by forming hydrogen bonds with water.
Methanol (and other alcohols).
Ammonia.
Glucose.
Remember that although they have dissolved molecules are still molecules they
do NOT dissociate like ionic solids.

"

"

o HOWEVER, if the bonds between the solute are stronger polar bonds than that
which would form between the solute and the solvent (i.e. hydrogen bonds) then
they would not dissolve.

o THEY DO NOT DISSOLVE IN NON POLAR SUBSTANCES:

o This is simply and logically because the dipole-dipole OR hydrogen bonds between
the solute are far stronger than the dispersion forces in the solvent.
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So there is NO BOND which could possibly be strong enough to break the
polar substance up.
We will look at this more later but long chain hydrocarbons attached to an OH at the end i.e.
CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OH usually are only slightly soluble because the non
polar hydrocarbon end MASKS the polar OH end.
And thats all there Is to the dissolving of polar molecular substances.

"

Dissolving Non Polar Molecular Substances:

Once again with non-Polar molecular substances we need to again consider two scenarios:
o THEY DISSOLVE IN NON POLAR MOLECULAR SUBSTANCES:
o This is simply because there is dispersion forces in the non polar solvent.
o When the molecules of the solute enter into it they will be affected by the dispersion
forces.
o Therefore temporary dipoles will be induced in them as well and they will dissolve.
Common examples of this include:
Oil C16H34 dissolving in petrol C8H18.
Iodine I2 dissolving in tetrachloromethane CCl4.

"

o THEY DO NOT DISSOLVE IN POLAR MOLECULAR SUBSTANCES:

o This is simply because they cannot form any electromagnetic bonds with the water.
o SO THE WATER-WATER or (POLAR-POLAR) hydrogen or dipole-dipole bonds
are far stronger than POLAR-NON POLAR bond.
o The polar bonds overpower the dispersion forces of attraction between them.
Thats all there is to non polar substances.

"

The Rule:
So these two investigations above will lead us to a useful rule (which although not good for explaining
can help for identifying):
LIKE DISSOLVES LIKE
Polar dissolves polar
Non polar dissolves non polar
Solubility is really that simple.

"

Ionisation and Hydrolysis:

Sometimes polar molecules form such strong bonds with the water that the covalent bonds is
broken and the molecule IONISES:
e.g. the formation of the hydronium ion.
+

! HCl + H 2O H 3O + Cl
Another important idea is when polar molecules dissolve by REACTING (HYDROLYSIS) with
water forming acids and bases:
e.g. reaction of ammonia.
+

! NH 3 + H 2O NH 4 + OH
Thats all there is on solubility in this course for now.

"

Periodic Table Summary:

The periodic table gives many trends so it is worth summarising them here and understanding them
so they can be used in an examination.

"

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Ionisation Energy:
In two parts:
INCREASES ACROSS A ROW IN THE PERIODIC TABLE
Because:
o The number of valence electrons increases.
o Therefore there is a greater attraction between the nucleus and the electrons.
o So it takes more force and more energy to remove an electron.

"

DECREASES DOWN A GROUP IN THE PERIODIC TABLE

Because:
o There is an extra energy level of electrons each time.
o Therefore the space between the protons and the valence electrons is greater.
o Thus the force between them decreases.
o This makes it easier to remove an electron from the valence shell.

"

Electronegativity:
In two parts:
INCREASES ACROSS A ROW IN THE PERIODIC TABLE
Because:
o The number of electrons is getting closer and closer to a stable octet,
o Therefore it just wants to gain electron/s to reach that stable octet.
o So it attracts electrons with much more strength.
o NOTE: THE NOBEL GASSES HAVE A IONISATION ENERGY OF ZERO BECAUSE
THEY HAVE A STABLE OCTET AND THUS WILL NOT ATTRACT ELECTRONS AT
ALL.

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48 of 117

"

DECREASES DOWN A GROUP IN THE PERIODIC TABLE

Because:
o There is more space between the protons and the valence electrons.
o Thus there is less force of attraction between the valence electrons and the nucleus.
o Thus the atoms are less likely to attract an electron.

"

Atomic Size:
In two parts:
DECREASES ACROSS A ROW IN THE PERIODIC TABLE
Because:
o Because the number of valence electrons increases.
o Thus the force of attraction between the nucleus and valence electrons also increases.
o This brings the valence electrons closer to the nucleus thus decreasing the size of the atom.

"

INCREASES DOWN A GROUP IN THE PERIODIC TABLE

Because:
o There is always an extra energy level (series of orbitals) between the valence electrons and the
nucleus.
o Thus the atoms must obviously increase in size simply because there is another layer of stuff.

"

Oxidising/Reducing Agents:
Before we look at this we need to revise oxidation and reduction:
o OXIDATION is where the substance LOOSES ELECTRONS.
o REDUCTION is where the substance GAINS ELECTRONS.
o A REDOX reduction-oxidation REACTION is where the loss and gain of electrons
attract.
o ALL REACTIONS OF ELEMENTS ARE REDOX.
Knowing this it makes sense to say
The ease of reduction or strength as an oxidising agent:
INCREASES ACROSS A ROW IN THE PERIODIC TABLE
Because:
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49 of 117
o Because electronegativity also increases.
o So it becomes easier for the substance to gain electrons.
o And thus it becomes easier for it to be reduced and substances that are reduced are good
oxidising agents.

"

The ease of oxidation or strength as a reducing agent:

INCREASES DOWN A GROUP IN THE PERIODIC TABLE
Because:
o Because the ionisation energy is also decreasing.
o So it becomes easier for the substance to loose electrons.
o Thus it becomes easier for it to be oxidised and oxidised substances are reducing agents.

!
That is as far as we need to go in bonding for now.

"
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"

Electro Chemistry

"
"

Electrochemical Cells:
We can safely say that:

"

Electrochemical cells convert chemical energy into electrical energy

They do this via a chemical REDOX reaction

"

But as with most things,simple definition will not get you far we need to have a much deeper
understanding of what is happening, so what do we know:
o Redox reactions involve the transfer of electrons.
o An electrical current is the flow of electrons.
o So there seems to be a connection there.
Also we need to remember that redox reactions occur due to the varying ability of substances to
gain or loose electrons:
o The abilities are shown on the E0 table:
o Given a reaction on the left side anything below it will react.
o Given a reaction on the right side anything above it will react.

"

To understand the logic behind electrochemical cells we need to consider a piece of zinc metal being
placed in a solution of copper sulfate:
o The zinc metal will be oxidised to produce Zn2+ ions.
o The Cu2+ will be reduced to form copper metal.

"

o This can be shown on the diagram below:

"

!
o The reaction of this will be:
Reduction: Cu 2 + (aq) + 2e Cu(s)
!

Oxidation: Zn(s) Zn2+ (aq) + 2e

"

Zn(s) + Cu

2+

2+

(aq)

Zn

(aq )

+ Cu(s)

The idea for an electrochemical cell is now very simple to understand:

o If you could spit this reaction up so the electrons transferred had to travel along a wire
to complete the reaction then you would be generating a current.
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Because a current is a flow of electrons:
o And voila, below is the first electrochemical cell:

!
The reactions have been separated so electrons travel along a wire (hence we
have a current)
The circuit is completed with a salt bridge containing some ionic substance.
It is important however that we look at how exactly this works and understand the logic behind it
further.

"

Introductory Logic:
To understand lets consider a more proficient diagram of the electrochemical cell above:

!
Above we have:
o Two half cells:
o One where reduction occurs.
o One where oxidation occurs.
The Cu metal electrode in Cu2+ electrolyte is the Cu/Cu2+ half-cell.
The Zn metal electrode in the Zn2+ electrolyte is the Zn/Zn2+ half-cell.
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We know from previous studies involving electricity and electrolytes:
o Anode = negatively charged electrode.
o Cathode = positively charged electrode.
This becomes essential when we look at the definitions of anode and cathode in an
electrochemical cell:

"

ANODE: The electrode where OXIDATION occurs

Anode
Negative
Oxidation
CATHODE: The electrode where REDUCTION occurs
Cathode
Positive
Reduction

"

It is worth understanding why this occurs:

o OXIDATION
o Electrons are produced.
o Therefore there would be an excess of electrons which would make that electrode
negative.
o REDUCTION
o Electrons are used up.
o Therefore there would be a reduction in the number of electrons which would make that
electrode positive.

"

Continuing to look at the same example we know that within the two cells we have:
o Zn metal.
o Zn2+ ions.
o Cu metal.
o Cu2+ ions.
Now BY USING THE E0 TABLE TO DETERMINE WHAT WILL REACT FIRST we can say:

Cu 2+ ions are reduced: Cu 2+ (aq) + 2e Cu(s)

!

!
!

Zn metal is oxidised: Zn(s) Zn2+ (aq) + 2e

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53 of 117

!
Using our definitions above this means that:
o The Cu electrode will be the CATHODE.
o Hence positive.
o The Zn electrode will be the ANODE.
o Hence negative.
Since current is the flow of electrons and electrons flow from negative to positive:
o The electron flow or current will be from the anode to the cathode.
o The Zn electrode to the Cu electrode.

"

So basically:
o The electrons are produced in the oxidation reaction at the Zn elecrode.
o These electrons (two for every Zn atom oxidised) pass through the external circuit.
o They then reach the Cu electrode where they PROVIDE the electrons for Cu2+ ions to be
reduced.
o And hence the reaction is complete.

"

With all these charges moving it makes sense that the solution would no longer be electrically
neutral. HOWEVER ELECTRICAL NEUTRALITY IS MAINTAINED:
o The Zn2+ ions will move into the salt bridge and across into the Copper half cell:
o Because positive Cu2+ ions are being consumed.
o So the positive zinc ions move across to replace those positive charges being
consumed.
Much like Le Chateliers principle in Equilibrium.
2o The SO4 ions will move into the salt bridge and across to the Zinc half cell:
o Because there is a build up of positive charges so the ions move across to balance out.

"

This idea can be summarised in the very important rule:

"

TO MAINTAIN ELECTRICAL BALANCE the ANIONS (negative ions) move

through the salt bridge (Porus Barrier) to the cell containing the ANODE and the
CATIONS (positive ions) move to the cell containing the CATHODE
You can remember this but it is good to always have an understanding.

"

We also need to consider SALT BRIDGE:

o THE CELL WOULD NOT WORK UNLESS THERE WAS A COMPLETE CIRCUIT:
o The salt bridge is soaked in a electrolyte solution (in this case KNO3).
When the positive and negative charges appear on the cathode and anode the
ions in this solution are attracted respectively.
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They therefore move through the solutions ensuring the current is carried on
in the form of the ions.

"

The last point of importance is THE EXPECTED VOLTAGE:

o We know from our previous topic of REDOX that a redox reaction has a voltage potential.
o Therefore the EXPECTED VOLTAGE of any cell will be the two E0 values for each
half cell added together.
Looking at essential basics this is about all we need to cover for now.

"

Step-by-Step Worked Example:

Now we have got the basics it is worthwhile considering an example and working through it step by
step so lets consider the following question:
A half cell with a strip of manganese metal is placed in manganese chloride solution and is
joined to a cobalt metal strip placed in cobalt nitrate solution via a salt bridge:
Determine:
*Anode and cathode.
*Positive and negative electrode.
*Sites of Oxidation and Reduction.
*Direction of electrons moving through external circuit.
*Direction of ions moving through salt bridge.
*Half equations at each electrode, and overall redox equation with expected voltage.
STEP ONE: Get the Diagram
The first thing we need to do is make sure we have a clear diagram of what we are looking at in
front of us:

!
STEP TWO: Identify What You Have
The second step is to consider what we have which is in this case:

"

*Mn.
*Mn2+.
*Cl-.
*Co.
Now you locate these on the diagram:

By Josh Walker

"

*Co2+.
*NO3-.

55 of 117

!
STEP THREE: Use E0 table to work out what is oxidised and what is reduced and hence which
electrode is your anode and which is your cathode:
Now you basically look for whether the Co or Mn will be more easily oxidised and which ions
will be more easily reduced and you work out what reaction will occur at each elecrode.
From there you can use standard definitions to solve:

!
STEP FOUR: Now Find Movement of Ions, Direction of Electron Flow, +ve and ve etc:
Use the rule that cations go to the cell with the cathode and anions go to the cell with the anode
to determine the movement of the ions.
Electrons flow from negative to positive.
By definition we know the anode is negative and the cathode positive.
Draw this all on the diagram:

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!
STEP FIVE: Combine to one Redox equation and find predicted voltage E0:
We can say:
Reduction: Co 2 + (aq) + 2e Co(s)
E0 = 0.28V
!

Oxidation: Mn(s) Mn2+ (aq) + 2e

E0 = +1.18V

Redox: Mn + Co 2 +

E0 = 0.9V

Co + Mn2 +

(s)
(aq )
(s)
(aq)
!
Following these steps should enable you to answer any electrochemical cell question.

"
"

Inert Electrodes:
You do not always need reactive metal electrodes to produce an electrochemical cell:
Platinum Electrodes are Chemically Inert However:
The Hydrogen Will be oxidised.
The Chlorine will be reduced.
They will produce a cell with expected voltage 1.36V.

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!
NOTE: Because there are no solutions, which would mix, these share a common electrolyte of
HCl.
And that is pretty much all there is to electrochemical cells in the straightforward manner.

"

Commercial Cells:
Although we may know how cells operate it is important to understand how they are produced and
used in the commercial environment. Below therefore are examples of the three most common types of
electrochemical cells and an explanation about how they work.

"

Dry Cells:
This is the most common cell and is used inn torches, as well as other electrical appliances. The basic
structure can be seen on the diagram below:

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!
As you can see there are a few essential elements to the structure:
o OUTER ZINC COATING:
o By looking at E0 table we can see this is the anode (-).
o Therefore the zinc will oxidised according to:

Zn Zn2+

+ 2e

(aq)
! (s)
o GRAPHITE ROD SURROUNDED BY MANGANESE DIOXIDE PASTE:
o This rod is the Cathode (+)
o The manganese around it in the paste is reduced making the cathode reaction as
follows:

2MnO

+ 2H +

+ 2e Mn O H O

2(s)
(aq)
2 3(s) 2 (l )
!
o ALUMINIUM AND ZINC CHLORIDE IN PASTE:
o These are both ionic substances, which will break into ions in solution.
Hence they are the Electrolyte for the reaction.
Also the ammonium ions provide the hydrogen ions needed for the
cathode reaction via:

"

NH 4 + (aq) NH 3(aq ) + H + (aq)

From the reactions above we can now identify that:

o The cell has potential maximum e.m.f of 1.48V.
Also another VERY IMPORTANT POINT THAT:
o The cell is a primary cell that is once it has been discharged (reaction complete) it cannot
be recharged and therefore must be discarded.

"

Another interesting idea surrounding the dry cell is the ALKALINE VERSION of the dry cell that
has a superior performance to the acid form:
o A powdered Zinc anode is used instead.
o The electrolyte is KOH.
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"

o Basically this type of cell will work for longer and supply current more rapidly
however it is also more expensive.

So if we were to look at the reactions taking place:

o ANODE:
Zn + 2OH (aq ) Zn (OH )2(s) + 2e
o ! (s)
o CATHODE:

Ag2O(s) + H 2O(l ) + 2e 2Ag(s) + 2OH (aq)

or (depending on what substances are used in the cell)

o !

HgO + H O + 2e Hg(l ) + 2OH (aq)

(s)
2 (l )
o !
Thats all there is for the simple dry cell.

"

Wet Cells:
Also known as the LEAD ACID BATTERY this cell is commonly used in motor vehicles. The
standard characteristics include:
o A number of cells each cell has a voltage of approx 2.0V.
o Inside each cell there is:
o Heavy-duty external casing (on outside).
o Bank of lead grids supporting a large surface area of the electrode material:
Negative electrode grid is filled with spongy metallic lead.
Positive electrode grid is filled with brown lead dioxide.
o Electrolyte used is sulfuric acid.
This can be seen below:

!
The main difference in this cell is that:
o THE CELLS IN THIS BATTERY CAN BE RECHARGED therefore it is described as a
secondary cell.

"

If we consider the reactions occurring we can say:

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Reduction (Cathode): PbO2(s) + 4H + (aq) + SO4 2 (aq) + 2e PbSO4(s) + 2H 2O(l )

"

Oxidation (Anode): Pb( s) + SO4 2 (aq) PbSO4(s) + 2e

!

Redox (Overall): Pb(s) + PbO2(s) + 4H + (aq) + 2SO4 2 (aq) 2PbSO4(s) + 2H 2O(l )

Now what we need to consider:

o As the batter is discharged, electrodes become coated with insoluble lead sulfate and the
sulfuric acid is used up:
o Thus the density of the electrolyte decreases.
Hence the degree of charge of battery can be checked by testing electrolyte
density.

"

Basically this battery can be recharged simply by connecting the terminals to another electrical
source of higher voltage and reversing the current through the circuit.
o Hence the reaction is reversed and we have:

2PbSO

+ 2H O Pb + PbO

+ 4H +

+ 2SO

4(s)
2 (l )
(s)
2(s)
(aq)
4 (aq )
!
Once again, in this battery electrical energy is STORED as chemical energy in the RECHARGING
PROCESS before it is AGAIN RELEASED AS ELECTRICAL ENERGY.
And that, is all there is to wet cells.

"

Ni-Cad Cell:
One of the more common and modern batteries is the nickel-cadmium or ni-cad cell. This is the cell
commonly used in:
o Video Cameras.
o Portable CD players.
o And any other cordless electrical device where you can recharge the battery from.
The reactions also are reasonably simple:
Anode: Cd(s) + 2OH (aq) Cd (OH )2(s) + 2e

Cathode: NiO (OH )(s) + H 2O(l ) + e Ni (OH )2(s) + OH (aq)

!
Once again note to recharge these batteries the reactions are reversed.

"

Fuel Cells:
Fuel cells differ from primary cells in two major ways:

"

o STORE NEITHER REACTANTS OR PRODUCTS:

o The reactants are fed in at a constant rate.
o They convert this to supply electricity at a constant rate.

"

"

o REACTANTS ARE USUALLY GASEOUS:

o This is unlike the solid substances that you will usually find in primary or
secondary cells.

The most successful fuel cell so far is that based on the combination of oxygen and hydrogen:
o Hydrogen gas is supplied to the anode chamber.
o Oxygen gas is supplied to the cathode chamber
o The gasses then diffuse through the electrodes:
o These are usually porus metals such as platinum or nickel.
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o They act as catalysts.
o The gasses then react with the electrolyte, which may be acidic or alkaline.
This set up can be shown below:

!
Now if the electrolyte was acidic.
Anode: H 2( g) 2H + (aq) + 2e

Cathode: O2(g) + 4H + (aq ) + 4e 2H 2O(l )

!
If the electrolyte was alkaline:
Anode: H 2( g) + 2OH 2H 2O(l ) + 2e
Cathode: O2(g) + 2H 2O(l ) + 4e 4OH (aq)
!
It is important to note, whether the electrolyte is acidic or alkaline we get the same combined
reaction:
2H 2(g) + O2(g) 2H 2O(l )
!
This cell has a theoretical e.m.f of 1.23 Volts however this is difficult to attain:
o The H+ and OH- ions (whether it is acidic or alkaline) do not migrate quickly between
electrodes, thus being a limiting factor on the speed of reaction.
o The electrodes do not have a great amount of contact with the gaseous molecules some
inventions including pores to help interaction has partially solved these problems.

"

Fuel cells are still part of a developing technology:

o They are relatively small.
o High fuel efficiency.
o This is why they are used in spacecraft.
And for this course that is as far as we need to go in the realm of fuel cells.

"

Electrolytic Cells & Electrolysis:

What we know so far is that ElectroCHEMICAL cells convert chemical energy into electrical
energy through redox reactions:
o Dry cells.
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62 of 117
o Batteries et.
Basically there is an electron transfer (current) and to varying abilities the chemical energy produces
electricity.
AN ELECTROLYTIC CELL HOWEVER PASSES AN ELECTRIC CURRENT THROUGH A
SOLUTION AND TURNS ELECTRICAL ENERGY INTO CHEMICAL ENERGY!!!

"

Electrolysis Introduction:
Basically we can say:
The Process of using an electric current to produce a chemical change is called ELECTROLYSIS
The important point to note here:
BECAUSE THE DIRECTION OF THE CURRENT IS REVERSED THE ELECTRICAL
CHARGE WILL BE REVERSED
So because of that we say:
o CATHODE:
o Electrode where reduction occurs.
WILL BE NEGATIVE.
o ANODE:
o Electrode where oxidation occurs.
WILL BE POSITIVE.
There are still certain points that remain similar:
o Current Outside Cell caused by flow of electrons.
o Current inside Cell caused by movement of ions.
It is also worth noting:
o The E0 for an ELECTROLYTIC CELL is NEGATIVE.
The only other point that is likely to come up is rather important:

ELECTROCHEMICAL CELLS EXOTHERMIC

"

ELECTROLYTIC CELLS - ENDOTHERMIC

Thats all there really is to it some important features about ELECTROLYTIC CELLS (where
electrolysis occurs) are:
o Do not need to separate half cells because the reaction will not occur spontaneously:
o However often the products of the electrolysis CAN recombine, in which case you DO
need to separate them.
o Power Supplied the electrodes are connected to an external power source (battery) so
they are charged.
Now we can safely move on to look at some examples of Electrolysis.

"

Electrolysis: Molten Salts:

WHENEVER you melt and ionic salt IT SPLITS UP INTO IONS:

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63 of 117

!
Now logically:
o The positive ion will be attracted to the negative electrode.
o The negative ion will be attracted to the positive electrode.
It follows on from that:
o Positive ion will gain electrons reduction cathode.
o Negative ion will loose electrons oxidation anode.
So using that simple logic you can identify the ANODE, and CATHODE and from there you just
look down the E0 table to find the equations:

!
If we chose to find the combined reaction you add them together and get:
Reduction (Cathode): Na + (aq ) + e Na(s)
!

Oxidation (Anode): 2Cl -(aq) Cl2(g) + 2e

Redox (Overall): 2Na +

+ 2Cl

2Na + Cl2(g)

(aq )
(aq)
(s)
!
Thats all there is to the electrolysis of molten salts.

"

E 0 = 4.07

Electrolysis: Water:
Although it is easy to find on the E0 table it is worthwhile knowing the oxidation and reduction
equations for water:
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Reduction (Cathode): 2H 2O(l ) + 2e H 2( g) + 2OH (aq )

Oxidation (Anode): 2H 2O(l ) O2(g) + 2H + (aq) + 4e

!
This can be represented on a diagram as below:

!
The very important fact here to remember is:
VOLUME OF H2 GAS PRODUCED IS TWICE THAT OF O2 GAS PRODUCED
That is where the ratio H2O comes from.
There is nothing else to the electrolysis of water.

"

Electrolysis: Aqueous Solutions:

When you consider the electrolysis of aqueous solutions you need to consider two options:
o DISSOCIATED IONIC SALTS ELECTROLYSE.
o WATER IS ELECTROLYSED.
Basically you need to use the E0 table to see what will react first:

"

Consider electrolysis of a solution of sodium iodide:

In the solution you will have:
o Na+ ions.
o I- ions.
o H2O.

By looking at the
By Josh Walker

E0

!
table we can determine:

65 of 117
o OXIDATION = ANODE:
o The I- ion will oxidise before the water and before the Na+ ion.
o REDUCTION = CATHODE:
o Here the WATER will be reduced before any of the ions.
So we would illustrate this on a diagram as:

!
You could then combine reactions and calculate E0.
Sometimes however the water will have no effect on the electrolysis process i.e. electrolysis of a
solution of copper iodide:
o Using the E0 table we will see that the water is not involved i.e:

!
Thats all there is to electrolysis of aqueous solutions.

"

Electrolysis: Dilute Acids:

There is nothing different about he process of working out this electrolysis reaction however we can
say:
THE PRODUCTS ARE ALWAYS:
o
H2 at the cathode.
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66 of 117
o
O2 at the anode.
So for example electrolysis of a dilute sulfuric acid solution:

!
Thats all there is to it.

"

Electrolysis: Electrode Participation in Reaction:

Normally inert electrodes are used in electrolysis common inert electrodes are:
o Carbon.
o Platinum.
SOMETIMES MORE REACTIVE METALS MAY BE USED then you need to consider:
o Whether the ions in the solution will be electrolysed.
o Whether the water will be electrolysed.
o WHETHER THE METAL ELECTRODE WILL BE OXIDISED.
o So you also need to check the reactivity of the metal on the E0 table.

"

So if we consider electrolysis of copper (II) sulfate solution using copper electrodes:

o E0 Table OXIDATION:
o Before the water and SO42- ions THE Cu ELECTRODE WILL BE OXIDISED.
0
o E Table REDUCTION:
o The Cu2+ ions will be REDUCED before the water.
This can be illustrated as:

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67 of 117

!
So if we consider electrolysis of potassium chloride solution using magnesium electrodes:
o E0 Table OXIDATION:
o Before the water and Cl- ions THE Mg ELECTRODE will oxidise DISSOLVING.
o E0 Table REDUCTION:
o The water will be reduced before the K+ ions.
This can be illustrated as:

!
Thats basically as hard as it is going to get.

"

Electrolysis: Prediction of Reactions:

Often you will be asked to predict the possible products of an electrolysis reaction.
The process to do this is really exceptionally simple:
o Identify all the substances in solution.
o Write down all possible reduction/oxidation equations for those reactants.
o Hence identify the products.
o If asked to identify the MOST LIKELY product you then used the E0 table to work
out reactivity.
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68 of 117
So what are the possible (and most likely) products of the electrolysis of a dilute solution of sodium
chloride:
ANODE (OXIDATION)
2H 2O 4e + O2 + 4H +

2Cl Cl2 + 2e
Possible Products are Cl2 Gas and O 2 Gas
Most Likely = O 2 Gas

!
CATHODE (REDUCTION)
2H 2O + 2e H 2 + 2OH

Na + + e Na
Possible Products are Na Solid and H 2 Gas
Most Likely = H 2 Gas
!
It is important to understand that the E0 TABLE IS NOT A FOOLPROOF WAY OF
PREDICTING PRODUCTS. Often the products actually produced can be effected by:
o Electrolyte concentrations.
o Current.
o Applied voltage.
o Nature of electrodes.
The ONLY SAFE WAY to determine the products of electrolysis is THROUGH
EXPERIMENTATION.
So always be careful when using the E0 table to make predictions.

"

Electrolysis: Concentration:
Concentration has an interesting effect on the electrolysis process. If we consider the anode reaction
from above:
ANODE (OXIDATION)
2H 2O 4e + O2 + 4H +
E0 = 0.82V

E0 = 1.36V
! 2Cl Cl2 + 2e
From this we can say:
o The oxidation of water will be more favourable because of its higher E0 value.
o HOWEVER AT A HIGHER CONCENTRATION OF Cl- IONS:
o The discharge of chlorine becomes more favourable.
o Therefore chlorine gas is produced at the anode.
This proves that the E0 table can ONLY be used as a means to predict the most likely products.

"

Applications of Electrolysis:
There are numerous times in industry, or in the natural environment where electrolysis can be seen in
action. As this chemistry course is relevant to the real world below are a few examples of when we
see applications of electrolysis out in the real world, both in the industrial scene and also in the natural
environment.

"

The Electrorefining of Copper:

Copper is usually extracted from sulfide ores such as chalcopyrite CuFeS2:
o Smelting process is used to obtain crude copper of about 98% purity:
o Strong heating of the ore oxidises the sulfide to gaseous sulfur dioxide and reduces the
copper to the metal.
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! 2CuFeS2(s) + 5O2(g) + 2SiO2(s) 2Cu(l ) + 4SO2(g) + 2FeSiO3(l )
o The silica removes iron as a slag.
o This copper is called blister copper:
o Because of bubbly appearance produced by escaping sulfur dioxide.
o TO OBTAIN 99.9% purity required BLISTER COPPER is refined electrolytically.
The logic behind this process is very simple:
o IMPURE COPPER cast into slabs and made anode.
o THE CATHODE is pure copper in thin sheets.
o THE ELECTROLYTE is copper sulfate solution acidified with sulfuric acid.
o Bascially COPPER and other impurities (zinc, iron, nickel) in the anode are
oxidised and enter solution as ions.
o The more inert metal impurities such as gold silver and platinum fall to the bottom
of the cell.
o A SMALL VOLTAGE is used so that the pure copper deposits at t he cathode.
o Ions of more reactive metals remain in solution periodically removed so they do not
build up sufficiently to cause them to be reduced.
This process can be demonstrated simply below:

!
This is a highly effective way of obtaining VERY PURE copper.

"

Extraction of Metals from their Ores:

The extraction of metals from their Ores is an essential component:
o ORES consist of minerals (oxides, sulfides of metals) and rock.
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70 of 117
o USUALLY:
o Mineral separated from its ore by physical means.
o Metal is extracted chemically.
The separation techniques used depend on the reactivity of the metal and
economics.
Some of the more common techniques include:
o HEATING IN AIR reduction of the ore removing the oxygen or sulfur:
PbS + O2 !heat
!!
Pb + SO2
heat
2Sn + O2
o For example:! 2SnO !!!
o CARBON REDUCTION the ore is heated with carbon to remove the oxygen:
CuO + C Cu + CO

o For Example:! Fe2O3 + 3CO 2Fe+ 3CO2

o ELECTROLYSIS
o This is used to refine PURIFY metals:
E.g. Impure copper blocks are made the anode in a sulfuric acid electrolyte:
o The Cu is oxidised:
Cu Cu 2 + + 2e
! Impure
o Then the Cu2+ is reduced to pure copper metal at the cathode:
Cu 2 + + 2e Cu
Pure
!
Now we have looked at the base ideas it is worthwhile considering the extraction of certain metals
individually.

ALUMINA and ALUMINIUM from BAUXITE (gibbsite)

Aluminium is the most abundant metal in the earths crust however it is very expensive to extract and
refine. Aluminium is very useful however:
o Low density.
o Resists corrosion.
o Excellent conductor.
o Highly reflective.
o Used in electrical transmission lines, telescope reflectors, saucepans.
The source of aluminium is bauxite:
o High levels of the mineral gibbsite Al(OH)3 or Al2O3.3H2O
o Kaolinite clay Al2O3.2SiO2.2H2O
o Quartz SiO2.
o Hematite Fe2O3.
o Al2O3.
There are few stages you must go through in the extraction of aluminium:

"

BAYER PROCESS purification of bauxite:

Basically the hydrated crystals of Aluminium oxide Al2O3.3H2O (can be written as) Al(OH)3:
o Mined and milled.

"

o Heated in hot caustic soda (NaOH) under pressure.

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71 of 117
o Because Al(OH)3 is AMPHOTERIC it dissolves leaving the other insoluble
impurities and forms aluminate solution:

Al (OH )3(s) + OH (aq ) #$ Al (OH )4 %&

(aq)
!
o This solution is now:
o Filtered.
o Cooled.
o Seeded with crystals of pure aluminium hydroxide.
This causes a precipitation reaction the reverse of what occurred before:

! Al (OH )4 #$
!"

(aq)

Al (OH )3(s) + OH (aq)

o From there it is a simple matter of:

o Filtering of aluminium hydroxide.
o Heating aluminium hydroxide to produce alumina
Al(OH )3(s) !heat
!!
Al 2O3(s) + 3H 2O(g)
Pure alumina
!
Once we have this alumina we can move on to extracting the aluminium.

"

HALL-HEROULT electrolytic reduction of alumina:

This process involves the electrolytic reduction of molten alumina Al2O3 to pure aluminium:
o However high melting point of alumina (2045C) makes it too expensive to maintain
electrolyte at that temperature:
o FLUXING AGENT CRYOLITE (Na3AlF6) is used to lower melting point.
Molten state is maintained at about 950C for electrolysis.
The actual electrolysis process is standard:
o CARBON ANODES:
o ARE OXIDISED TO FORM GASEOUS PRODUCTS.
Mainly carbon dioxide by combining with the O2-.
o ALUMINIUM IONS:
o ARE REDUCED TO FORM ALUMINIUM METAL.
At the carbon cathode that lines base and wall of the cell.
o This molten aluminium is periodically removed from the cell an cast into ingots.
o The overall equation for electrolysis is:
2Al 2O3(l ) + 3C(s) 4Al (l ) + 3CO2(g)
!

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72 of 117

!
NOTE: although only small current is needed for the electrolysis HUGE CURRENT is needed to
maintain temperature of electrolyte, hence it is very expensive.

"

IRON from IRON ORE:

Iron is the major component of steel and it is the most significant metal extracted from the earths
crust:
o Iron is found from mining hematite:
o This is red-brown in colour and nearly pure Fe2O3.
o 70% of its mass is iron.
o You can also find it in limonite:
o Yellow brown, 2Fe2O3.3H2O
o 56% of iron by mass.
Iron is extracted by smelting iron ore in a blat furnace:
o Furnace is charged with a mixture of:
o Iron Ore.
o Coke.
o Hard form of carbon.
o Limestone.

"

The process that goes on to extract the iron is rather interesting:

o Coke is burned in oxygen:
o Burnt by the periodic blasts of preheated air, which is blown in part way up the
furnace.
o This forms carbon dioxide:

C +O

CO

2(g)
2(g)
! (s)
o Carbon Dioxide form is reduced by more coke:
o This is reduced to carbon monoxide:

CO

+ C 2CO

2(g)
(s)
(g)
!
o Carbon monoxide acts as a reducing agent:
o This reduces the iron ore to metallic iron.
o This is a series of reactions, but it can be written as one below:

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73 of 117

Fe O

+ 3CO

! 2Fe + 3CO

(g)
(l )
2(g)
!! 2 3(s)
This is a reversible reaction but it can be made to favour the formation
of the iron by using large excess of carbon monoxide from the blast.
This blast also sweeps away the carbon dioxide moving equilibrium
right.
The molten iron then trickles to the bottom of the furnace.
o The limestone decomposes at the temperatures in the blast furnace:
o This forms lime (CaO) and carbon dioxide:

CaCO3(s) CaO(s) + CO2(g)

The carbon dioxide combines with the coke to generate more carbon
dioxide as above.
o The lime forms a slag with the siliceous rock and sand of the ore:
o This follows the simple equation:
!

CaO(s) + SiO2(s) CaSiO3(l )

This floats on the denser iron layer at the bottom of the blast furnace.
Protects the iron from oxidation by the hot air blast.
Periodically tapped off from the iron and solidified so it can be used for:
o Road surfacing.
o Cement manufacture.
o Insulating material.
Possibly the best way to accurately understand this process is via looking at a diagram of the entire set
up:

!
Once the iron is run off it can one of two things:
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74 of 117
Be taken separately to make steel.
Run into sand-formed mounds to form pig iron.
o This is more commonly known as cast iron, and is brittle and difficult to weld.
However it is also hard and does not readily rust. Expands when solidifying
thus making sharp casts.
As you can see the extraction of iron from iron ore is really rather simple.

"

GOLD (Cyanide and carbon in pulp process CIP):

Gold is often considered as a free element because it is chemically uncreative:
Can be found in nuggets pure.
Often found in small specks within quartz rocks and alluvial sand formed by weathering
of such rocks.
MOST COMMONLY in microscopic form with a variety of minerals:
o Physically bound or chemically combined.
Today the extraction of gold involves cyanidation in the carbon-in-pulp process. This is a very
effective process for low-grade gold ores:
First the gold bearing ore is crushed and ground into a fine powder:
o This ore is then fed into leach takes.
o Tanks contain alkaline sodium cyanide solution.
This resulting slurry, or pulp is agitated continuously with air:
o Thus the gold is leached into solution as the aurocyanide ion [Au(CN)2]-.
o Because of the ion, the gold can be oxidised by oxygen.
The overall reaction for above can be represented as:
o !

4Au(s) + 8CN (aq) + 2H 2O(l ) + O2(g) 4 #$ Au (CN )2 %&

(aq)

+ 4OH (aq)

Reduction: O2(g) + 2H 2O(l ) + 4e 4OH (aq )

Oxidation: Au(s) + 2CN (aq) #$ Au (CN )2 %&

+ e
(aq)
!
The dissolved [Au(CN)2]- is separated from the pulp by absorption on activated carbon:
o The activated carbon is in adsorption tanks.
Activated carbon mad from vegetable matter like fruit pits, coconut husks
or peat by heating to about 900C in presence of steam and absence of air.
o The activated carbon contains many tiny holes which absorb the aurocyanide ion.
This activated carbon is then separated from the pulp:
o The activated carbon holding the absorbed aurocyanide ion is separated from the
rest f the pulp and transferred to a tall column.
o The aurocyanide ion is then stripped from the carbon:
Column is washed with hot NaCN/NaOH solution.
Produces concentration of [Au(CN)2]- high enough to allow direct recovery
of gold via electrolysis.
ELECTROLYSIS IS THEN UNDERGONE ON THE AUROCYANIDE ION SOLUTION:
o Electric current is passed through alkaline solution containing the [Au(CN)2]- ions.
o ANODE:
Stainless steel.
Oxygen gas is produced here.
o CATHODE:
Steel wool.
[Au(CN)2]- ion completely reduced.
Gold deposits on the steel wool.
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75 of 117
o You can see a pictorial representation of this here:

"
"
"
"
"
"
"
"
"
"
"
"
"
"
"
"
"
"
"
"
"
"
"

o The gold coated steel wool is then treated with Hydrochloric acid:
The steel wool dissolves.
A gold sludge or MUD remains.
The gold mud is then smelted:
o Heating to about 1200C with a flux:
Flux usually contains silica, sodium cabonate and borax.
o At this temperature the gold is molten most of the impurities are oxidised to form
a slag layer which floats on top of the gold.
Gold then poured into moulds and solidifies as gold bullion about 98% pure.

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76 of 117

Equilibrium

"
"
CHEMICAL REACTIONS Revision:
"

Chemical reactions occur due to successful collisions between atoms, ions and molecules

"

We also learnt that:

All chemical reactions follow a reaction path.
All chemical reactions need an energy input for initiation.
Once begun some reactions are self sustaining (until one of the reactants is used up)
Other reactions need constant energy input.
For a reaction to begin the energy of the colliding particles must be greater than the EA
Activation Energy.

"
"

Energy In Chemical Reactions:

In many chemical reactions energy is required to be put in to create the reaction whilst in others energy
is released during the reaction.
When you burn an object energy is released in the form of heat and light.
But energy can be released in different forms.
Energy is measured in KJ kilojoules, or KJ mol-1.

"

If we consider this idea of energy in a reaction when we burn methane in a Bunsen burner:
The bonds are broken in the CH4 and O2 and reformed as CO2 and H2O with the release of
energy.
! CH 4(g) + 2O2(g) CO2(g) + H 2O(g) + energy
WE CAN ALSO SAY THE ENTHALPY OF THIS REACTION DECREASES.

"

That is because ENTHALPY is the stored chemical potential energy (H) of the substances. So as
this reaction releases energy some of the stored potential energy is used up and thus the new
molecules have less potential energy.
Now lets look at the difference between reactions which release energy and reactions which absorb
energy:

"

Exothermic Reactions:
EXOTHERMIC REACTIONS RELEASE ENERGY
That is, bonds are broken within the reactants, energy is released and products form with lower
potential energy

"

If we consider enthalpy (Heat) of reaction then the

CHANGE IN ENTHALPY WILL BE NEGATIVE
Because H=Hp-Hr and Hp<Hr
An example of an exothermic reaction written in two ways can be taken from our previous example:
CH 4(g) + 2O2(g) CO2(g) + H 2O(g) + 75KJ
!
By Josh Walker

or CH 4(g) + 2O2(g) CO2(g) + H 2O(g)

H = 75KJ

77 of 117
Below a reaction pathway for a typical exothermic reaction is shown WITH ALL THE IMPORTANT
FEATURES MARKED.

!
It is imperative you understand exothermic reactions.

"

Endothermic Reactions:
ENDOTHERMIC REACTIONS ABSORB ENERGY
That is, bonds are broken within the reactants and they reform as products with higher energy after
absorbing energy.

"

If we consider enthalpy (Heat) of reaction then the

CHANGE IN ENTHALPY WILL BE POSITIVE
Because H=Hp-Hr and Hp>Hr
An example of an endothermic reaction written in two ways is water breaking up into hydrogen gas
and oxygen gas:
2H 2O(l ) + 90KJ 2H 2(g) + O2(g)

or 2H 2O(l ) + 90KJ 2H 2(g) + O2(g)

H = +90KJ
!
Below a reaction pathway for a typical endothermic reaction is shown WITH ALL THE
IMPORTANT FEATURES MARKED.

!
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78 of 117
It is imperative you understand endothermic reactions.

"

Rate of Chemical Reaction:

The rate of a chemical reaction can be very important in the real world and it can be measured by:
Volume of Gas Produced.
Colour Change (indicators)
Change of mass of a solid (dissolving).
Change in concentration.
Change in temperature.
The rate of a chemical reaction usually changes as a reaction proceeds because the
REACTANTS ARE ALL USED UP i.e. they run out.

"

Before we look at the factors affecting the rate of reaction it is important to remember that NOT ALL
COLLISIONS ARE SUCCESSFUL they only occur when particles collide in a particular way.

"

Factors Affecting the Rates of Reaction:

The following factors are not explained in the depth that is necessary for the course this is of course
only a revision:
1. STATE OF SUBDIVISION (SURFACE AREA)
The greater the state of subdivision the larger the surface so the more chance of a collision,
thus the faster the rate of reaction.
For example, steel wool burns more rapidly than a solid piece of Fe.

"

2. TEMPERATURE
The kinetic energy of the particles increases, so there are more collisions which speeds up the
reaction rate.
Also there are now more particles with enough energy to overcome the activation energy so more
particles will react, increasing the reaction rate.

"

3. CONCENTRATION
The higher the concentration, the greater the number of particles, hence the greater number of
successful collision, hence a faster reaction.
Examples are concentrated acids reacting more rapidly than dilute acids.

"

4. GAS PRESSURE
Basically, the higher the gas pressure, the greater number of molexules in one space hence the
greater number of successful collisions and an increase in the reaction rate.
One good example of this is blowing on coals in a fire place to start a fire.

"

5. NATURE OF REACTANTS
Basically the more reactive (unstable, type of bond) the faster the reaction rate.
For example:
Zn is more easily oxidised than Cu.
Weak acids are less reactive than strong acids.
It is important to note that molecular reactions are much slower than ionic reactions. This is
because in an ionic reaction the ions are just attracted to each other whereas in a molecular
reaction the bonds must be broken and THEN they reform.

"

6. CATALYSTS

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Catalysts are substances which speed up a reaction without themselves being changed. THEY
LOWER THE ACTIVATION ENERGY OF THE REACTION so more particles have enough
energy to react.

"

Some examples of catalysts:

MnO2 for decomposition of H2O2
H2SO4 for many organic reactions
Pt fuel cells, car exhausts
Enzymes biological reactions such as digestion
V2O5 In SO2SO3 sulfuric acid manufacturing
Fe production of ammonia

"

Now that we have a basic understanding and remembrance of those topics already covered we can
move on to Equilibrium and this years course.

"

EQUILIBRIUM:
When we look at equilibrium we need firstly need to consider the type of reaction systems you can
have:
Open System
This is the kind of system you would usually see and usually expect to see. It is a system which is
open so the reaction is open to the external environment, this is shown in the diagram below:

!
The above system is looking at the evaporation of water, and if we look at a graph of the
concentration of H2O GAS against time we will get something like this:

!
As you can see in an open system the concentration continues to increase until the reaction is
complete (i.e. all water has evaporated).
Closed System
This is the kind of system you do not usually see, but which we often talk about in relation to super a
accurate experiments and factories. It is a system which is closed so the reaction is closed to the
external environment and contained within itself this is shown in the diagram below:

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!
Once again the above system is looking at the evaporation of water except t his time in a closed system.
If we look at a graph of the concentration of H2O GAS against time we will get something like
this:

!
As you can see in a closed system the concentration reaches a point where it no longer increases
and it stays the same this point is called the equilibrium point.

"

Now we need to consider a few important ideas about this point.

The energy is still going into the water so therefore that there MUST BE a reaction still going.
But there is no change in the concentration of the water vapour in the system, so we can assume
that:
The rate of condensation of the water vapour must equal the rate of evaporation of the
water.
H 2O(l ) ! H 2O(g)
Or as an equation we can say: !!
.
The concentrations of the two may be different though we just know that they are staying the
same.
We can bring these observations all together to write a statement about what equilibrium is:
EQUILIBRIUM IS ESTABLISHED WHEN THE RATE OF THE FORWARD REACTION
EQUALS THE RATE OF THE REVERSE REACTION
NOTE: the concentrations of the reactants and products may not be the same they just dont
So if we were to once again look at the closed system above, and this time draw a graph of the rate of
each reaction against time we would get something like this:

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!
From this graph you can see:
Equilibrium is reached at the point where the two rate of reactions meet.
Before we move on it is important to clarify some of the terminology:

H O ! H 2O(g)
!!2 (l )

This shows the reaction is reversible:

The forward reaction is defined as being the reaction from left to right.
The reverse reaction is defined as the reaction from right to left.
As long as you remember this and remember CONCENTRATIONS OF THE REACTIONS AND
PRODUCTS ARE NOT NECESSARILY THE SAME then you are on your way to understanding
equilibrium.

"

Looking at Reaction Situations:

What we have determined from looking at open and closed systems is hat there are two main types of
reactions:
1. COMPLETE REACTIONS:
Reactions that only go one way.
Usually occur in open systems.
o i.e. Burning Hydrogen in the pop test:
H + 1 2 O2(g) H 2O(g)
! 2(g)
2. REVERSIBLE REACTIONS:
These are reactions that go both ways.
Usually occur in closed systems.
Some Common examples of reversible reactions are:

"

Ammonia in solution:

NH + H 2O(l ) ! NH 4 + (aq) + OH (aq)

!! 3(g)
The ammonia molecules are reacting with the water molecules to produce ammonium ions and
hydroxide ions as fast as the ions are reacting to produce ammonia and water.

"

Soda water in a sealed bottle of cool drink also the reaction that goes on in your body:

CO2(g) + H 2O(l ) ! H + (aq) + HCO3 (aq )

!!

The carbon dioxide gas reacts with water to produce ions as fast as the ions react with each other to
produce carbon dioxide and water.

"

Ozone Layer (NOTE: EARTH ATMOSPHERE IN ITSELF IS A CLOSED SYSTEM):

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3O ! 2O3(g)
!! 2(g)

Diatomic oxygen molecules react to produce triatomic oxygen (ozone) molecules as fast as ozone reacts
to produce oxygenthe reason the ozone layer is decreasing is because of this equilibrium reaction
and how we (humans) have altered it more later

"

There are three other types of reversible reactions we need to look at:
Dissolving Molecular Solids in Water or Solutions
If we were to add something like solid I2 into a solution:
Initially the rate of dissolution would be greater than the rate of precipitation.
After some time however the rate of dissolution would equal the rate of precipitation/
crystallisation.
So we would have the equation:

I 2(solid) ! I 2(liquid)
!!

If we look at a diagram of this the arrows show how the molecules in solution are going to molecules
in solid crystal just as fast as the molecules in the crystal are going to those in solution.

!
We can also draw a graph of rates to represent this:

!
It is important to note when this occurs in a solution THE SOLUTION IS SATURATED AND
WILL NOT DISSOLVE ANY MORE SOLID.
Ionic Solids in Solution
It is very important that we remembered:
EVERYTHING IS SLIGHTLY SOLUBLE IN WATER TO SOME EXTENT EVEN GOLD
NUGGETS
So it makes sense from that statement to say that:
When you put excess amounts of ionic compounds in water they will dissolve (however
slightly) by disassociating into ions.
This will occur when ALL IONIC SOLIDS are dissolved.
So if we get PbI2 and dissolve that then you will have the equation:

PbI 2(s) ! Pb2 + (aq) + 2I (aq)

!!
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And on a diagram we can see how they only slightly dissolve:

!
Once again it is important to remember that at equilibrium in this reaction:
Rate of dissolving is equal to the rate of precipitation.
The concentration of all the species will remain constant.

"

Reactions of Water
We have generally learnt that water is neutral H2O and it does not react at all. But in fact water is just a
substance at equilibrium:
The H2O molecules are constantly IONISING to produce H+ and OH- ions and these ions are
constantly reacting forming H2O molecules.
Because the concentration of the ions is equal the pH remains at 7.0.

H 2O ! H + (aq) + OH (aq )
1mol
!!

10

10

We can again represent this by a diagram:

!
It is important to remember:
Ionisation: Occurs in molecules and is a REACTION with other molecules to break up.
Dissociation: Occurs in ionic substances and is to do with electrical attractionnot
reaction.
We will look at the idea above in more detail later in this course.

"

Recognising Equilibrium
It is very important that you note:
IF THE MACROSCOPIC (OBSERVABLE) PROPERTIES REMAIN CONSTANT THEN THE
SYSTEM IS AT EQUILIBRIUM
These properties include:
Constant Colour.
Constant Pressure.
Constants Concentration.
Constant Temperature.
Constant pH.
Remember: Although the macroscopic properties remain constant the reaction is still continuing at the
molecular level.

"

Changing the Position of Equilibrium:

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We know what affects the rate of reaction:
Temperature.
Concentration.
Pressure.
Surface area.
Nature of Reactants.
Catalyst.
Those highlighted in red and bold above are the factors that effect the position of equilibrium.
The reason this works is quite simply because of the definition of equilibrium:
Since the rate of the forward reaction equals the rate of the reverse reaction you can change rates
and thus change relative concentrations of the reactants and products.
The three that do not have an effect:
Nature of reactants, Surface area and Catalysts.
Do not have an effect because they change the rate of reaction of both the forward and reverse
reactions.
For example consider the reaction !
! A + B ! C + D we can see the difference in the reaction pathway
on the diagram below:

!
The forward reaction will certainly be quicker BUT the activation energy has also been lowered
for the reverse reaction so it too will be quicker.
So in the end you can say there is no change in relative rates, hence no change in concentration
hence no change in the position of equilibrium.

"

BEFORE YOU GO ON REMEMBER:

WHEN A REACTION IS AT EQUILIBRIUM ONE OF THE REACTIONS (FORWARD OR
REVERSE) IS ALWAYS FAVOURED OVER ANOTHER
Changing equilibrium involves changing how much it is favoured or even which reaction is favoured.

"

Le Chateliers Principle:
This French principal is the basis to all theory surrounding changing the position of equilibrium and it
basically states that:
IF A CLOSED SYSTEM IS AT EQUILIBRIUM AND A CHANGE IS IMPOSED ON THAT
SYSTEM, THE SYSTEM ADJUSTS ITSELF TO RE-ESTABLISH EQUILIBRIUM
The best way of understanding this is by considering a seesaw:
Two people are on a seesaw perfectly balanced.
One of the people suddenly puts on all his body weight again having twice the mass of before.
THE ONLY WAY THE OTHER PERSON CAN BALANCE THE SEESAW AGAIN
WITHOUT BRINGING SOMEONE ELSE ON IS BY MOVING AWAY TO WARDS
THE END OF THE SEESAW.
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So the middle point between the two people is now over the side of the lighter person.
We will look at and explain this all much better as we look at the next section.

"

Factors Affecting the Position of Chemical Equilibrium:

We know that concentration, temperature and pressure affect the position of equilibrium how they do
that is far more complex, so lets look at each factor individually with a few examples and explain it:

"
"
"

CONCENTRATION

First lets consider the reaction of Iron III ions and thiocyanate ions (PUT ON CALCULATOR):

Fe3+ (aq ) + SCN (aq ) ! FeSCN 2 + (aq)

yellow
!!

colourless

de ep red

If this is initially at equilibrium, with all of the ions above present at a concentration we need to
investigate what happens to the equilibrium when the following changes take place:
ADDING Fe3+ IONS
As soon as the ion is added, the substances equilibrium will be disturbed and it will want to
somehow re-establish that equilibrium:
In this case we originally have a balanced seesaw:

!
Then when we add more Fe3+ and it becomes unbalanced:

!
To balance it the FeSCN2+ moves further away so the middle point between them is now
gone to the right.

"
That MIDDLE POINT is EQUILIBRIUM and the way it has moved.
"

NOW we need to look at what has happened in terms of chemical and not seesaws:
As Soon as you add the Fe3+ a reaction would occur.

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"

"

o You could consider it in terms of the reaction rate of the forward reaction
increasing but not that of the reverse reaction.
This reaction will try to USE UP the excess Fe3+ and re-establish equilibrium.
AS THE Fe3+ is reacted then it is also using up some of the SCN-.
IT IS ALSO PRODUCING MORE FeSCN2+.
SO, a reaction occurs using up the Fe3+ ions and producing more FeSCN2+ ions.
o The concentration of the Fe3+ and the SCN- ions has decreased.
o The concentration of the FeSCN2+ ions has increased.
o SO EQUILIBRIUM HAS MOVED TO THE RIGHT
i.e. the forward reaction is now more favoured than before.

! FeSCN 2 + #$ > !" Fe3+ #$

So we can say that now ! "
, and the solution has become red.
The new colour is constant so we have a new equilibrium just with different constant
concentrations.

"

REMOVING SOME SCN- VIA PRECIPITATION

Basically here the exact opposite happens than what happened before:
By removing the SCN- a reaction will again occur to re-establish equilibrium.
o This time you could consider it in terms of the reaction rate of the forward reaction
slowing down.
Basically a reaction occurs to REPLACE the SCN- which has been taken out.
So the FeSCN2+ will be breaking up into ions using up itself.
It will be producing MORE SCN- and MORE Fe3+.

"

"

SO, a reaction occurs to replace the SCN- ions by breaking up the FeSCN3+ ions:
o So the concentration of Fe3+ and SCN- will eventually increase.
o The concentration of the FeSCN2+ will decrease.
o SO EQUILIBRIUM HAS MOVED TO THE LEFT
i.e. the reverse reaction is now more favoured than before.

" SCN $% > "# FeSCN 2 + $%

We can say on relative terms than now compared to before ! #
and the solution is
more yellow than before.
Because we once again have a constant colour we can say we again have a new equilibrium with
different constant concentrations again.
THE BEST WAY to represent all of this so we can easily understand it is on a
CONCENTRATION versus TIME graph. This shows how the concentration of each of the ions in
the solution changes as we impose the changes on the system.
So if we were to look at a concentration time graph for the following situation we would get
something like:

By Josh Walker

"

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"

Now example two

To make sure we understand this consider the Chromate/Dichromate equilibrium

2CrO4 2 (aq) + 2H + (aq) ! Cr2O7 2 (aq) + H 2O(l )

yellow
!!

"

or ange

Now one of the important things we need to consider is which species is in greater concentration:
If the solution is YELLOW then it makes sense that the left hand side is in greater
concentration (i.e. reverse reaction favoured).
If the solution is ORANGE then it makes sense that the right hand side is in greater
concentration (i.e. forward reaction favoured).

"

So if this solution is orange at the start then it means the forward reaction is favroured but
what happens when we:
ADD NaOH
We can see that the NaOH would dissociate into ions and then the OH- would react with the hydrogen
ion i.e:

NaOH (s) Na + (aq ) + OH (aq)

!
Because of this some of the H+ ion would have been removed from the solution:
So a reaction occurs to REPLACE the H+ ions.
So concentration of right hand side will decrease whilst the concentration of the left hand
side will increase.
o EQUILIBRIUM WILL MOVE TO THE LEFT AND THE SOLUTION WILL
BECOME YELLOW.

"

ADD H2SO4 TO NEW SOLUTION

From our knowledge of chemistry we know that sulfuric acid (which is what we are adding) will ionise
to produce a proton.
+

! H 2 SO4 H + HSO4
So we are effectively ADDING more hydrogen ions to the solution:
So a reaction will occur to USE UP the H+ ions.
So the concentration of the right hand side will increase whilst the concentration of the left
hand side will decrease.
o EQUILIBRIUM MOVES TO RIGHT AND SOLUTION BECOMES ORANGE.
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"

So with two changes we are pretty much back to where we started which can be seen by the
concentration v time graph below:

"

Just one more example to show how the answers should be written
Consider the following reaction

Cu 2 + (aq) + 4NH 3(g) ! Cu (NH 3 )4

pale blue
!!

2+
(aq)

de ep blue

Simply fill in the table below:

What happened Equilibrium Moved

Concentration Cu(NH3)4

Why

Add NH3 gas

Right

Increase

Reaction occurs to use up

NH3 thus moving
equilibrium to the right

Add H2O

Left

Decrease

NH3 is soluble in H2O so

reaction occurs to replace it
moving equilibrium to left

Add Na2CO3

Left

Decrease

Cu2+ forms a precipitate

with the sodium carbonate
so a reaction occurs to
replace lost Cu2+ moving
equilibrium to the left.

"

To summarize concentration we can basically say:

WHEN THERE IS AN INCREASE IN CONCENTRATION OF A SUBSTANCE A REACTION
OCCURS ON THAT SIDE TO USE UP THE ADDED SUBSTANCE MOVING
EQUILIBRIUM TO THE OTHER SIDE
The reverse happens when you DECREASE the concentration of a substance.

"

Now lets move on

"
"

TEMPERATURE

The
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logic behind heat is basically exactly the same as that for

89 of 117
concentration except heat is actually easier and simpler to understand. Lets look at the logic behind it
first:

"

If we have the reaction !

! A + B + heat ! C + D then it makes sense to say:
If you raise the temperature then you are adding more heat to the reaction.
So therefore a reaction would occur to use up that extra heat.
o Basically the extra heat energy means that more bonds would be broken on the side
of the equation with the heat in it.
o So that reaction would occur faster.
o Moving the equilibrium to the other side.

"

We can make two statements about the effect of heat in changing equilibrium but it is better to
UNDERSTAND and not to memorise:
A + B + heat ! C + D
ENDOTHERMIC REACTION !!

Adding Heat:
Causes forward reaction to be favoured.
Produces more C and D.
MOVES EQUILIBRIUM TO THE RIGHT.

W + X ! Y + Z + heat
EXOTHERMIC REACTION !!
Adding Heat:
Causes REVERE reaction to be favoured.
Produces more W and X.
MOVES EQUILIBRIUM TO THE LEFT.

"

"
Now lets look at two examples to make sure we understand this:
"

The first one

Consider a mixture of brown nitrogen dioxide gas yellow dinitrogen tetraoxide gas in a sealed
glass tube:

N2O4( g) + 27kJ ! 2NO2(g)

What will happen if we:

! Yellow
!

B rown

INCREASE TEMPERATURE OF TUBE

"

Basically:
The extra heat will break up more bonds of N2O4 causing more NO2 to be produced.

"

But we would correctly write it as:

Reaction occurs to use up the extra heat moving equilibrium to the right.
o The gas will turn brown.

"

LOWER TEMPERATURE OF TUBE

"

Basically:
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There is a decrease in heat so the N2O4 bonds are not broken as fast so the NO2 reverse
reaction will happen faster producing N2O4.

"

But we would correctly write it as:

Reaction occurs to replace the lost heat moving equilibrium to the left.
o The gas will turn yellow.

"

Once again you can represent this on a concentration versus time graph:
NOTE: On these graphs you can see the steady concentration at the beginning is indicating
equilibrium has been reached. When the concentration is again constant this shows you that the
equilibrium has been re-established.

"

Now for our second example:

Consider the following reaction of Hydrogen and chlorine gas reacting explosively when mixed
together in a sealed container then reaching equilibrium:
H + Cl2(g) ! 2HCl(g) + 257kJ
! 2(g)
!
A standard question what happens to the concentration of the hydrogen gas, chlorine gas and
hydrogen chloride gas when the temperature is increased explain your answer:
If we break it into three stages:
H2 increase.
Cl2 increase.
HCl decrease.
Because a reaction will occur to use up the extra heat the extra heat will break more
bonds of the HCl causing the equilibrium to move to the left so more H2 and Cl2 are
produced whilst HCl is used up in the reaction.

"

Now we have finished that lets move on again to the final thing that affects equilibrium.

"
"

PRESSURE

We need to consider pressure in two sections partial pressure and total pressure:
PARTIAL PRESSURE
When you increase the partial pressure of one of the gasses in the reaction at equilibrium you can
only be:
ADDING MORE OF THAT GAS!!!
So therefore PARTIAL PRESSURE follows the exact same idea as concentratioin because that
is what you are doing, increasing the concentration.
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So if we consider the following system at equilibrium:
N + O2(g) ! 2NO(g)
! 2(g)
!
What happens when we:
INCREASE PARTIAL PRESSURE OF N2(g)
So you are ADDING N2 or INCREASING CONCENTRATION of N2.
So a reaction will occur to use up this N2 and equilibrium will move to the right.

"

DECREASE PARTIAL PRESSURE OF NO(g)

So you are TAKING AWAY NO or DECREASING CONCENTRATION of NO.
So a reaction will occur to replace this NO and equilibrium will move to the right.
Pressure gets more complicated though when we look at total pressure.

"

TOTAL PRESSURE
The best way to understand this is to look at an example the reaction system below:

N2(g) + 3H 2(g) ! 2NH 3(g)

1 mole

3 moles

2 m oles

+
! Total: 4 Moles
!

2 M oles

In the reaction above:

There are four moles of GAS on the left hand side.
There are two moles of GAS on the right hand side.
We use this information to determine what happens when the total pressure is changed, but first lets
look at pressure:
Pressure is due to the collisions of particles.
If the number of collisions increases then the pressure increases.
If the number of collisions decreases then the pressure decreases.
o So adding there will be a higher pressure in a jar with 2 moles rather than the same
jar with only 1 mole of that gas because of more collisions

"

This last part in green is the important part because:

WHEN YOU INCREASE PRESSURE YOU INCREASE THE NUMBER OF
COLLISIONS.
BUT THE SYSTEM WILL WANT TO RE-ESTABLISH EQUILIBRIUM, and thus
decrease the pressure by REDUCING the number of collisions.
o So the EQUILIBRIUM WOULD MOVE TOWARDS THE SIDE OF THE
REACTION THAT HAD THE LEAST NUMBER OF MOLES.
o Equilibrium moves to the side of the reaction that gives the least pressure.

"

So if we were to look at the above reaction:

INCREASING PRESSURE would move it to the right

"

Now if we were to REDUCE the pressure then the opposite would happen:
The reaction would move towards the side that had morels and hence gave it more
collision and thus increased the pressure.
o So above equilibrium would move to the left.

"

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This idea is reasonably self-explanatory buts lets just look at one more example:

H 2(g) + Cl2(g) ! 2HCl(g)

"

! Total: 2 Moles
!

2 M oles

Here if we were to increase or decrease pressure there would be NO CHANGE.

This is because there is the same number of moles on both sides of the reaction so moving to
one side would not decrease or increase the pressure to counteract at all it would just give the
same.
Those are the basics to total pressure but there are a few other things we need to consider:

"

IMPORTANT NOTES ON PRESSURE

There are three important notes, which are common mistakes, related to pressure and which we will
ensure in this section are not common mistakes with us.
1. WHEN COUNTING MOLES OF GAS ONLY COUNT MOLES OF GAS:
If we get the reaction:
Ca(HCO3 )2(s) + 77kJ ! CaO(s) + 2CO2(g) + H 2O(l )
!
!
It is important that you note:
When you count the moles of gas to work out which way equilibrium will move
when total pressure is change only count gas and not solid and liquid.
This is because GAS IS THE ONLY STATE THAT AFFECTS PRESSURE.
So in the example above we would say:
Two moles of gas on the right hand side.
Zero moles of gas on the left hand side.
Then you can work with this.

"

2. ADDITION OF INERT GAS DOES NOT ALTER PRESSURE:

If we get the question:
Helium inert gas is added without causing a change in volume which was does equilibrium
move?
The initial response would be to count the moles of gas, because adding something without a
change in the volume would increase the pressure:

BUT THIS IS WRONG

What we need to say is:
The Helium is an INERT gas so it does not react with anything.
The total volume of the container does not change.
Since the helium is not mixing with the substance in the reaction then the respective
partial pressures of the substances in the reaction and hence total pressure of reaction
does not change.
ONLY the partial pressure of the helium is changing.
o SO THERE IS NO CHANGE TO EQUILIBRIUM.
This leads on to the final important point.

"

3. TOTAL PRESSURE IS ONLY ALTERED PHYSICALLY:

If we get the question:
Inert Neon gas is added and the volume of the container increases in compensation which
was does equilibrium move?
Then you may think that because it is an inert gas there would be no change
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BUT THIS IS WRONG

THE KEY POINT IS:

THE VOLUME OF THE CONTAINER HAS INCREASED.
So the molecules in the reaction will have more room to spread out and thus pressure will
DECREASE.
o WHICH WILL CAUSE EQUILIBRIUM TO MOVE left or right depending on the
equation

"

So basically unless you are adding more of a gas (which would increase partial pressure) the only
way you can change the total pressure of a system at equilibrium to cause a change is through
physical means:
INCREASING VOLUME decrease pressure
DECREASING VOLUME increase pressure
INCREASING TEMPERATURE increase pressure
DECREASING TEMPERATURE decrease pressure

"
And that is all for pressure and equilibrium.
"

IMPORTANT POINT IN EQUILIBRIUM:

This idea is such a common mistake that it gets its whole own section to itself:
IF A SOLID IS PRESENT AT EQUILIBRIUM THE ADDITION OF MORE OF THE SAME
SOLID TO A SYSTEM AT EQUILIBRIUM HAS NO EFFECT ON EQUILIBRIUM
This is simply because of surface area:
If there is already that solid in the solution then the solution is saturated so it will not
dissolve any more of that solid.
So by adding some more you are only increasing surface area, which does not change the
position of equilibrium.
IF HOWEVER you were to add a solid which DID DISSOLVE, THEN, it could alter one of the
factors effecting equilibrium and thus cause a change in equilibrium.

"

Industrial Processes:
There are two important industrial process that we need to put on the calculator. There is no point in
memorising the effect of certain things on them in terms of equilibrium as it is best to work that out
but there are a few points from each process that should be committed to memory:
Industrial Preparation of Ammonia HABER PROCESS
Basically in a large closed reaction chamber atmospheric nitrogen is reacted with hydrogen in the
reaction:

N + 3H 2(g) ! 2NH 3(g) + 93kJ

!!2(g)

There are few things that we need to understand about how this is reacted:
Ammonia is periodically removed:
Basically we want to always INCREASE the yield of ammonia so by periodically removing it:
A reaction must occur to replace that lost.
So equilibrium moves to the right.
And thus more ammonia is produced.

"

Reaction is carried out at high pressure:

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Once again by increasing the pressure we cause the equilibrium to move to the right where there are
less moles of gas and so more ammonia is produced.

"

Reaction is carried out at high temperatures:

EQUILIBRIUM FAVOURS LOW TEMPERATURE, but we use a high temperature because of
ACTIVATION ENERGY:
If we have a low temperature there would be a too low a percentage of molecules for a
reaction to occur.
Therefore we need to have a high temperature so the activation energy can be provided
and the reaction can occur.
This is all really just logical.

"

Industrial Preparation of Sulfuric Acid CONTACT PROCESS

This is a multistage reaction:

S( s) + O2(g) SO2(g)
V2 O5
!!
!
!
2SO2(g) + O2(g) !
!
!
!
!2SO3(g) + 192kJ

SO3(g) + H 2 SO4(l ) H 2 S2O7(l )

H S O + H 2O 2H 2 SO4(l )
!!2 2 7(l )

The important part of this process is:

V2 O5
!!
!
!
2SO2(g) + O2(g) !
!
!
!
!2SO3(g) + 192kJ
!!

What we need to understand is pretty much the same as the Haber process:
It Is produced at High Pressure:
Because equilibrium will move to the right there are less moles of gas on that side so the reaction
will adjust itself, favouring the forward reaction to reduce pressure. And as a result we will produce
more SO3.

"

It is produced at a reasonably low temperature:

This is all about again finding the compensation point remembering we want to produce MORE
SO3:
Therefore a low temperature would favour this, moving equilibrium to the right.
HOWEVER IF THE TEMPERATURE IS TOO LOW THE ACTIVATION ENERGY
WILL NOT BE FOR THE REACTION TO OCCUR.
o So we want the LOWEST POSSIBLE TEMPERATURE, for a reaction to still
efficiently occur.

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Reacted with a catalyst:

This does not change the position of equilibrium but IT SPEEDS UP THE REACTION. So the
Reaction will reach equilibrium faster and you can start extracting the SO3 quicker.

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If you can get these basic points and memorize the equations then industrial processes are easy as pie.
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Equilibrium Constant:
The Equilibrium Constant K is simply and INDICATION of whether at equilibrium the forward
(right) reaction or reverse (left reaction) is FAVOURED.
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aA + bB ! cC + dD
!

If we have the reaction: !

K=

[C ] [D ]
[A] [B]

Then the equilibrium constant is: !

Note: a, b, c and d are the number of moles of the reactants A and B and products C and D.
[ ] is concentration in mol L-1
K = equilibrium constant

"

A LARGE VALUE FOR K indicates the right hand reaction (formation of products) is
favoured and at equilibrium small maounts of the reactans remain
i.e. [products] > [reactants]
e.g.

H + Cl2(g) ! 2HCl(g)
!!2(g)

"

K = 7.5 10 5

A LOW VALUE FOR K indicates a left biased reaction (formation of reactants is

favoured) and at equilibrium very little product is formed.
i.e. [reactants] > [products]
e.g.

H 2O(l ) ! H + (aq ) + OH (aq)

!!

"

K = 1.0 10 14

Now we can find K values in tables however these are not in the course.
It is important you remember that the value of K is usually given at room temperature (298K)
so therefore A CHANGE IN TEMPERATURE AT EQUILIBRIUM WILL CHANGE THE
VALUE FOR K.

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However you also need to note that it is the EQUILIBRIUM CONSTANT so as long as you
dont change the temperature K WILL NOT CHANGE WHEN EQUILIBRIUM MOVES.

"

It is important to remember about the equilibrium constant that when you are calculating it:
K only takes into account species in GAS (g) phase or in SOLUTION (aq).
Concentrations of liquids and solids are constant and not included in the K expression.

"

TO FIND EXPRESSIONS FOR K SIMPLY SUB IN THE VALUES WHEN GIVEN A

FORMULA:

"

2I O + 5SF4(g) ! 4IF5(g) + 5SO2(g)

!!2 5(g)
4
5
IF5 ] [SO2 ]
[
K=
[I 2O5 ]2 [SF4 ]5
!
Here we are simply following the formula given before.

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H 2O(l ) ! H + (aq ) + OH (aq)

!!
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96 of 117
K = !" H + #$ !"OH #$
!
We leave out the liquid in the equation as told so by the formula.

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CH
+ Br2(g) ! C6 H 12 Br2(l )
!!6 12(l )
1
K=
[Br2 ]
!
Because the concentration of the liquid is constant we can simply
express it as one on the top line

"

6H + (aq) + 2Al (s) ! 2Al 3+ (aq) + 3H 2(g)

!!

!" Al 3+ #$ [H 2 ]
K=
6
!" H + #$

Once again we leave out the solid in the expression.

"
And that is pretty much all you need to know.
"
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NOTE: THERE ARE NO CALCULATIONS INVOLVING K OR EQUILIBRIUM

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Redox Basic:
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Redox

REDOX:
A redox reaction is the combined process of OXIDATION AND REDUCTION. So before we look at a
redox reaction we need to define oxidation and reduction:
o Both Oxidation and Reduction are defined in terms of ELECTRON TRANSFER.
OXIDATION: The loss of electrons during a chemical reaction
LEO
REDUCTION: The gain of electrons during a chemical reaction
GER
So we would say:
o A substance that looses electrons is oxidised.
o A substance that gains electrons is reduced.
The most important point about a redox reaction is that:
Oxidation and reduction occur SIMULTANEOUSLY as a reduction-oxidation (REDOX) reaction

"

What we do:
o Express reduction as half equation.
o Express Oxidation as half equation.
o Equate number of electrons:
o i.e. if reduction gains two electrons and oxidation only looses one, then multiply the
entire oxidation equation by two.
o Add together.

"

It is worth noting:
o METALS: Have one or two valence electrons, and low ionisation energy therefore they
want to loose them easier.
o Hence they Oxidise easily.
o NON-METALS: Have a larger number of valence electrons (close to eight) and high ionisation
energy so they want to gain electrons.
o Hence they can be reduced easily.
Knowing these very basic ideas is essential to understanding redox.

"

Good Example:
Consider the following example:
A piece of copper metal is placed in a silver nitrate solution, and it is observed that the pink Cu
metal is coated silver in some places whilst the solution goes from colourless to blue:
1.) IDENTIFY
We know:
o Cu metal must go to Cu2+ ions to make the solution blue:
o Therefore the Cu must loose electrons.
o Oxidised.
o Ag+ ions must go to Ag metal to coat the copper in silver:
o Therefore the Ag+ ions must gain electrons.
o Reduced.
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98 of 117
2.) REDUCTION
Writing the reduction HALF equation:

Ag+

+ e Ag

(aq )
(s)
o !
3.) OXIDATION
Writing the oxidation HALF equation:

Cu Cu 2 +

+ 2e

Cu + 2Ag+

Cu 2 +

(aq)
o ! (s)
4.) REDOX
Because there are two electrons produced in oxidation and only one in reduction multiply
reduction by two then combineand we get the redox equation.

+ 2Ag

(aq )
(aq )
(s)
o ! (s)
It is important to note:
In redox reactions the following substance do not normally enter the reaction:
Water H2O.
NO3 SO42 OH NH4+
This is the bare basics of a redox equation you cannot expect something this simple.

"

Agents:
It is important that we understand the following agents in redox:
OXIDISING AGENTS:
o Substance that cause OXIDATION.
o Therefore this substance will be reduced.
Because by being reduced it will gain electrons, causing another substance to
loose them and THUS causing oxidation.
O2 oxygen.
Cl2 chlorine.
MnO4- - Permanganate ion.
Cr2O72- - dichromate ion.
REDUCING AGENTS:
o Substance that cause REDUCTION.
o Therefore this substance will be oxidised
Because by being oxidised it will loose electrons which will allow another
substance to gain them, THUS causing reduction.
C Carbon.
H2 Hydrogen.
Reactive Metals such as Zn, Mg, Na.
We can use the E0 Table to identify common oxidation and reduction agents as well as finding
oxidation/reduction half equations.
That is as simple as the oxidising/reducing agents identification is.

"

THE RULE:
One of the most useful rules in chemistry is an unofficial one, which basically states:

ALL CHEMICAL REACTIONS OF ELEMENTS ARE REDOX REACTIONS

This comes forth from simple logic:
For an element to react with anything it must exchange electrons (therefore must be redox)
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99 of 117
Oxidation number of an element is 0 oxidation number of compound is also 0 so for
the two to combine then the element must have a change in oxidation number to make it
equal to zero (we will look at oxidation numbers in a minute).
This rule is to be memorised and understood, as it is a godsend when we come to multiple chocie.

"

Types of Redox Reactions:

There are a few standard types of redox reactions that we should consider:
Metal Metal Ion Displacement:
This is where metal ions from a solution displace the metal from a solid:
1) Zinc Metal in Copper II Nitrate Solution:
Reduction: Cu 2 + (aq) + 2e Cu(s)
!

Oxidation: Zn(s) Zn2+ (aq) + 2e

!

Redox: Zn(s) + Cu 2+ (aq) Cu(s) + Zn2 + (aq)

2) Tin Metal and Silver Nitrate Solution:

Reduction: Ag+ (aq ) + e Ag(s)
2

Oxidation: Sn(s) Sn 2 + (aq) + 2e

!

Redox: Sn(s) + 2Ag+ (aq) 2Ag(s) + Sn 2+ (aq)

"

Dilute Acid on Metals:

This where an acid acts on a metal to produce hydrogen gas:
1.) Dilute Sulfuric Acid on Magnesium Metal:
Reduction: 2H + (aq) + 2e H 2(g)

Oxidation: Mg(s) Mg2+ (aq) + 2e

!

Redox: Mg + 2H +

+ Mg2+

(s)
(aq )
2(g)
(aq)
!
2.) Dilute hydrochloric acid reacting with aluminium metal:
Reduction: 2H + (aq) + 2e H 2(g)
3

"

Oxidation: Al (s) Al 3+ (aq) + 3e

!

Redox: 2Al (s) + 6H + (aq) 3H 2(g) + 2Al 3+ (aq)

Halogen Halide Ion Displacement:

It Is important to know the halogens:
F2 a pale yellow as.
Cl2 a yellow green gas.
Br2 a red-brown liquid.
I2 a purple black solid that goes brown in water.

"
The halide ions are colourless
"

Also when reacted they are often reacted in terms of saturated solutions in water for safety
purposes:
1.) Chlorine reacting with sodium bromide solution:

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100 of 117

Reduction: Cl2( g) + 2e 2Cl (aq )

Oxidation: 2Br (aq ) Br2(l ) + 2e
!

Redox: Cl

+ 2Br

Br

+ 2Cl

2(g)
(aq)
2(l )
(aq )
!
2.) Bromine reacting with potassium iodide solution:
Reduction: Br2(l ) + 2e 2Br (aq )

Oxidation: 2I (aq) I 2(s) + 2e

!

Redox: Br2(l ) + 2I (aq ) I 2(s) + 2Br (aq)

Common Oxidising Agents:

There are certain common oxidising agents that need to be recognised and easily used below are two
examples.
1.) Acidified potassium permanganate solution reacting with Iron II Sulfate:
Reduction: MnO4 (aq ) + 8H + (aq) + 5e Mn2 + (aq) + 4H 2O(l )
1

Oxidation: Fe2 + (aq) Fe3+ (aq) + e

!

Redox: MnO

+ 8H +

+ 5Fe2+

5Fe3+

+ Mn2 +

+ 4H O

4 (aq)
(aq)
(aq)
(aq )
(aq )
2 (l )
!
2.) Acidified potassium dichromate solution reaction with hydrogen peroxide:
Reduction: Cr2O7 2 (aq) + 14 H + (aq) + 6e 2Cr 3+ (aq ) + 7H 2O(l )
1

Oxidation: H 2O2(aq) O2(g) + 2H + (aq) + 2e

Redox: Cr2O7 2 (aq) + 8H + (aq) + 3H 2O2 2Cr 3+ (aq) + 7H 2O(l ) + 3O2(g)

!
And that is basically all of them.
If you have a good grasp on these concepts AND you are able to use the E0 table effectively, then you
are well on your way to succeeding in redox chemistry.

"

Constructing Half Equations:

When we do not have the half equation we are looking for on the E0 table we have to construct our
ownwhich we do simply using the WHE method:
BALANCE: Everything other than Oxygen, Hydrogen and Charges.
W: WATER added to balance Oxygen.
H: H+ ions added to balance hydrogens.
E: ELECTRONS e- added to balance charges.

"

It is worth looking at a simple example of how this works:

We start with the skeleton:

V O 2

V 3+

V O 2

2V 3+

V O 2

2V 3+

(aq)
! 2 7 (aq)
First balance elements within it:
(aq)
! 2 7 (aq)
Now add water to balance oxygens on each side:

+ 7H O

(aq)
2
! 2 7 (aq)
We must now add hydrogen ions to balance hydrogens:

14H + (aq) + V2O7 2 (aq ) 2V 3+ (aq) + 7H 2O

Finally add electrons to balance the charges:

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101 of 117

+ V O 2

6e + 14H +

2V 3+

+ 7H O

(aq)
2 7 (aq)
(aq)
2
!
We can see from this equation that the reaction is a reduction half equation.

"

Now another question you may get asked is to balance the half reactions in OH- solution:
BALANCE: Everything other than Oxygen, Hydrogen and Charges.
WHE: Perform this as usual.
ADD OH-: Add on THE SAME NUMBER of OH- ions as H+ Ions.
CANCEL: OH- and H+ combine to
Once again, consider the following example to make sure you understand this idea:
We start with the skeleton:

Br

BrO

Br

2BrO

3 (aq )
! 2(l )
First balance elements within it:
3 (aq)
! 2(l )
Now add water to balance oxygens on each side:

6H O + Br

2BrO

6H O + Br

2BrO

+ 12H +

6H O + Br

2BrO

+ 12H + (aq ) + 10e

2
2(l )
3 (aq)
!
We must now add hydrogen ions to balance hydrogens:
2
2(l )
3 (aq)
(aq )
!
Next add electrons to balance the charges:
2
2(l )
3 (aq)
!
Now add 12OH ions too each side:

12OH

+ 6H O + Br

2BrO3 (aq ) + 12H + (aq ) + 10e + 12OH (aq)

(aq)
2
2(l )
!
Combine OH- and H+ to make water:

12OH (aq) + 6H 2O + Br2(l ) 2BrO3 (aq ) + 12H 2O + 10e

!
Cancel waters to get answer:

"

12OH (aq) + Br2(l ) 2BrO3 (aq) + 6H 2O + 10e

When you get a full redox equation:

Break it up into two half equations.
Perform WHE and if necessary react for Base.
Add two half equations together.

"

So if we now consider this final example:

First we start with the whole equation:

HCHO(l ) + Cr2O7 2 (aq ) HCOOH (l ) + Cr 2 + (aq )

!
Now pull it out into two parts:
OXIDATION:

By Josh Walker

REDUCTION:

102 of 117
Perform WHE on both Sides:
Add together as normal:
Reduction: 10e + 14 H + + Cr2O7 2 (aq) 2Cr 2 + + 7H 2O
!

Oxidation: H 2O + HCHO(l ) HCOOH (l ) + 2H + + 2e

OXIDATION:

REDUCTION:

4H +

+ Cr O 2

+ 5HCHO Cr 2 +

+ 5HCOOH + 2H O

(aq)
2 7 (aq )
(l )
(aq )
(l )
2 (l )
!
If you understand all of this then you should be okay no matter what redox equation you are given
just beware that the equations may get more complex and you may not have a lot of time to answer the
question.

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Oxidation Number:
An oxidation number is an arbitrary number assigned to atoms to help identify reduction and
oxidation.
Therefore we need to assign some rules to these oxidation numbers:

"

Rule

Examples

Oxidation number of an element is always zero (0)

Fe = 0
O2 = 0

Oxidation number of oxygen when combined is negative two (-2)

H2O
MnO4-

Oxidation number of hydrogen when combined is positive one

(+1)

NaOH
HCO3-

Total oxidation number of a compound is always zero (0)

KNO3 = 0
Al2(SO4)3 =
0

Oxidation number of an ion in an ionic compound is the valency

of that ion!

FeCl3
Fe = +3
Cl = -1

Total oxidation number of an ion is always the charge on that ion

NO3- = -1
PO43- = -3

EXCEPTION Oxygen in the PEROXIDE ion (O22-) is negative 1 (-1) not -2

S
Hydrogen in the HYDRIDE ion (H-) is negative 1 (-1) not +1
By Josh Walker

H2O2
NaH

103 of 117
It is important and useful to note:
When you get a complex equation look at sections of it you know to identify oxidation
number:
o i.e. Oxidation number of Nitrogen in !

"

Cu (NH 3 )4 SO4 .5H 2O

SIMPLY LOOK AT THE ! NH 3 COMPOUND:

3 x (+1) = +3
So therefore N = -3 To Make NH3 = 0
This is far simpler than looking at the entire equation.

Because oxidation numbers are designed to make it easy to identify redox reactions we need to know
how that works:
OXIDATION
Identified by an INCREASE in oxidation number.
2+

! Zn Zn + 2e
Zn goes from 0 to +2 which indicates oxidation (LEO)
REDUCTION
Identified by a DECREASE in oxidation number.

! Cl2 + 2e 2Cl
Cl goes from 0 to -2 which indicates reduction (GER)
That is all there is to oxidation numbers.

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Concentrated Acids:
We know that dilute acids react with metals to produce hydrogen gas.
However what we need to look at now is how concentrated oxyacids such as sulfuric and
nitric acid are oxidising agents:

"

There are two reactions we need to know and understand for concentrated oxyacids (acids containing
oxygen):
Concentrated H2SO4 reacts to produce colourless, pungent sulfur dioxide gas, SO2:

SO

+ 4H +

+ 2e SO

+ 2H +

+ e NO

+ 2H O

(aq )
2(g)
2 (l )
o ! 4 (aq)
Concentrated HNO3 reacts to produce brown pungent Nitrogen dioxide gas NO2.

NO

+H O

3 (aq)
(aq )
2(g)
2 (l )
o !
These need to be on your calculator and accessible at al times.

"

Disproportionation:
Disproportionation (or self reduction oxidation) is where the same species both oxidises and
reduces itself.

"

An example of this is the Cu+ ion:

i.e. if you place a solution of red CuCl in water then both pink solid copper will form and also t
he solution will turn blue:
!

Cu + (aq) + Cu + (aq) Cu(s) + Cu 2 + (aq)

or

2Cu

Cu(s) + Cu 2 + (aq)

!
if we consider the oxidation numbers above:
By Josh Walker

(aq)

104 of 117

Cu goes from +1 to 0 = reduced.

Cu goes from +1 to +2 = oxidised
So using oxidation numbers we have proved that the reaction is disproportionation.

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Another example of disporportionation is hydrogen peroxide:

2H 2O2(aq ) 2H 2O + O2(g)
!
And a final example is that of bromine below:

Br

+ 6OH

5Br

+ BrO

+ 3H O

(aq)
(aq)
3 (aq)
2 (l )
! 2(l )
As long as you can use oxidation numbers to identify whether the reaction is disproportionation then
you should be okay.

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Titrations

Acids Base Volumetric Analysis 1:

Titrations are an application of the acid base chemistry we have learnt already this year. They are also
one of the most logical processes as one of the oldest processes in chemistry. Firstly we are looking at
ACID BASE VOLUMETRIC ANALYSIS that basically involves titrating and acid into a base (or
base into an acid) and using that to work out different quantities.

"

Introduction Terms:
Before we begin to look at the methods of titration we need to understand some terms and definitions
so lets consider these under two categories processes and equipment:
PROCESSES
VOLUMETRIC ANALYSIS is a technique where a solution of known concentration is titrated
against a solution of unknown concentration and from the results analysis can be made to:
Concentration of unknown solution.
Percentage composition of unknown solution.

"
STANDARD SOLUTION this is a solution with a known concentration.
"

PRIMARY STANDARDS this is what you use to establish a standardised solution. It must have
the characteristics of:
High purity and known chemical formula.
Does not react with water or oxygen, or carbon dioxide or
other substance commonly found in the air.
Has a reasonably high molar mass.
Is soluble in water.
Two good examples of primary standards are:
Sodium Carbonate.
Oxalic Acid.
You will often use both of these in titrations.

"
"

EQUIPMENT
VOLUMETRIC FLASK this is flask, which holds an accurately known volume of solution.
There is a line on its neck that indicates the volume. It is used when preparing standard solution.

"

PIPETTE this is used to accurately deliver a specific volume of solution. So you use this to take
some of the standard solution into the conical flask

"

BURETTE This delivers variable volumes of solution into the conical flask. So you put what you
want to titrate in here and add it to the known solution drop by drop.

"

CONICAL FLASK This is used to keep the known solution (or unknown if you are going opposite
way around) during titration.

"

BEAKER you initially dissolve your primary standard in here at the start. You would the
transfer it to a volumetric flask and work from there.

"

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106 of 117
General Method:
It is worthwhile gathering an understanding of the basic method of titration and why it works before we
look at specifics with worked examples below so here we look at each step in the titration process:
FIRST OBTAIN A STANDARD SOLUTION
You do this by dissolving:
A known mass of a substance to which you know the molar mass in water.
Since you know molar mass and mass you can work out number of moles of substance.
If you then put it in a certain amount of water (e.g. 500mL) you know:
Moles.
Volume.
So you can find the concentration.
NOW FIND AN EXACT VOLUME OF YOUR UNKNOWN
Basically you take a pipette and measure a certain amount (5.g 5mL) into a conical flask:
You know volume taken.
You know concentration.
So you can find the number of moles of the standard solution in the conical flask.

"

ALTERNATIVELY YOU COULD INITIALLY PLACE THE KNOWN SOLUTION IN THE

BURETTE!!

"

TITRATE TOGETHER AND FIND AVERAGE VOLUME OF SUBSTANCE USED

Basically you then add in your unknown, which is in the burette until you observe a colour
change (NOTE YOU MUST PUT AN INDICATOR IN YOUR KNOW SOLUTION)
Your first titration is a rough one you do not bother measuring it accurately just let the
substance flow through until you see a colour change.
o THIS GIVES YOU AND IDEA OF WHEN IT WILL CHANGE.
Your second third and fourth titrations should be accurate.
o If they differ my more than 0.3 then you are off.

"

IF YOU PUT THE KNOWN SUBSTANCE IN THE BURETTE

Then you will follow the exact same process as above (for now)

"

SOLVE FOR WHAT YOU NEED

Now since you know how much of the unknown has been added.
And you also know chemically (via equations) the mole ratio between that and the known
solution.
You can work out the concentration of the unknown solution and then go from there.

"

IF YOU PUT THE KNOWN SUBSTANCE IN THE BURETTE

You know the concentration and the volume of it added to the other solution so you can work
out the number of moles added:
Chemically you know how these two substances would combine.
You also know the volume of the unknown in the conical flask.
So once again you can work out the concentration of the unknown and go from
there.
Understanding this very basic idea will make titrations all that much easier.

"

What to Rinse with What:

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107 of 117
One of the most important aspects in a titration is rinsing so we need to know what to rinse with what
so below is a list you need to remember or better understand:
BEAKER you need to rinse this with water and distilled water so there is NOTHING in
it at the start.
VOLUMETRIC FLASK you need to rinse this with water and distilled water also so
there is NOTHING in it at the start.
PIPETTE you need to rinse this with the SOLUTION FROM VOLUMETRIC FLASK
so that there is no other solution to mess up measurements.
CONICAL FLASK you need to rinse this with water so there is NOTHING in there
when you start.
BURETTE you need to rinse this with the solution that you are running through it so
there is nothing else in there to disrupt measurements.
Remember the general rinsing method after you have a finished a titration is:
TWICE with tap water.
TWICE with distilled water.
IN THAT ORDER.
These rinsing ideas or not important in understanding titrations but they are likely to come up in
multiple choice tests so make sure you understand them.

"

Worked Example Preparing Standard Solution of Na2CO3:

Now lets look at applying the theory we have learnt to actually do things, below is the process of
preparing a 500mL standard solution of Na2CO3 of concentration around 0.05mol L-1.
FIRSTLY FIND MOLES REQUIRED
We know concentration and we know volume so we can say:
n = cv

n = 0.050 0.5
! n = 0.0250mol
THEREFORE CALCULATE MASS OF Na2CO3 REQUIRED:
Now we know the molar mass of Na2CO3 so we can say:
m = nM
m = 0.0250 106.0
! n = 2.65g
THEN YOU CREATE IT
So basically:
Weight out 2.65g of sodium carbonate.
Dissolve it in a beaker.
Transfer it to a volumetric flask making sure you rinse all of solution into it.
Make up to 500mL.
It is very important that in an experiment:
YOU WOULD NOT AIM TO GET EXACTLY 2.65g to MAKE KNOWN CONCENTRATION
What you would want to do is:

Measure accurately an amount CLOSE to this (if you get it exact then its a bonus)

You then use THIS MASS to calculate number of moles and concentration.
As long as you KNOW the concentration what it IS does not matter.

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Worked Example Standardisation of Hydrochloric Acid Solution:

Basically HCl cannot exist in a pure form so we need to STANDARDISE IT AGAINST A
SOLUTION OF KNOW CONCENTRATE.
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108 of 117
Let consider a solution of 20mL of 0.051mol L-1 Na2CO3 in a conical flask. The ALIQUOT.
You would:
You would then place HCl in the beaker and titrate it into the sodium carbonate solution
until you reached the end point.
o REMEMBER THE END POINT is the point where the colour of the indicator
begins to change. Methyl orange will go peachy if it goes to red then you have
gone too far.
SO the first thing you do is calculate the average volume of HCl needed:
Rough Titration

Titration 1

Titration 2

Titration 3

Initial Volume

0.00mL

19.5mL

0.02mL

17.59mL

Final Volume

19.5mL

37.1mL

17.59mL

35.13mL

Volume Added

19.5mL

17.6mL

17.57mL

17.54mL

So ignoring initial rough titration:

17.6 + 17.57 + 17.54
V(average) =
= 17.57mL
3
!

"

Now look at the chemical equation between these two substances (USE MOLECULAR
EQUATIONS)

2HCl

"

+ Na CO

CO

+ H O + 2NaCl(aq)

(aq)
2
3(aq)
2(g)
2 (l )
!
Now calculate the moles of Na2CO3 in standard solution.
We know concentration and volume so:
! n = cv = 0.051 0.02 = 0.00102mol

"

So because of the chemical equation there must be twice this moles of HCl to complete
reaction (i.e. reach end point)
! n (HCl ) = 2 0.00102mol = 0.00204 mol

Now we can use the idea that n=cv and rearrange to find concentration of unknown
Basically there have been 0.00204mol HCl added
In 17.57mL of water so we can say
!

c=

n 0.00204
=
= 0.166mol L1
v 0.01757

"
That is the basics for what you need to know in every titration.
"

Worked Example Standardisation of Sodium Hydroxide Solution:

This is an example of having the known solution in the burette.
Once again we cannot obtain NaOH in its pure state because it observes water and carbon
dioxide in the air.
But we can find the concentration of it by using a solution of known concentration of HCl.
So consider 20mL of NaOH pipetted into a conical flask with phenolphthalein indicator added.
If put 0.166mol L-1 HCl in the burette and titrate it against NaOH the end point is reached after an
average volume of 18.95mL of HCl has been added.
So to calculate the concentration of NaOH.
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109 of 117
SOMETIMES IT IS USEFUL TO DRAW A DIAGRAM TO REPRESENT THE
SITUATION

!
CONSIDER CHEMICAL EQUATION

HCl

"

+ NaOH

H O + NaCl

(aq)
aq)
2 (l )
(aq)
!
CALCULATE MOLES OF HCl IN BURETTE
We know concentration and we know volume so:
! n = cv = 0.166 0.01895 = 0.0022mol

"

USE CHEMICAL EQUATION TO WORK OUT MOLES OF NaOH PRESENT

We know the are equal so there are 0.0022mol of NaOH present

SINCE YOU KNOW VOLUME OF NaOH CALCULATE CONCENTRATION

Volume is 20mL
Moles present are 0.0022mol
!

c=

n 0.0022
=
= 0.110mol L1
v 0.020

"
Now we have seen the two basic forms of titrations you will encounter.
"

Percentage Composition:
Often, in practical applications and in real life you will need to find the percentage composition of
something:
For example, percentage of acetic acid in vinegar.
Percentage of NaOH in oven cleaner.
In titrations we do this as percentage via mass. And the method is not hard but lets look at an
example with explanations before we move on:
To determine the PERCENTAGE OF AMMONIA in a floor cleaner 6.54g of the floor cleaner
is weighed out.
It is then dissolved in water and transferred to a volumetric flask and made up to exactly
250mL.
20.0mL samples are pipetted to conical flasks and indicator added.
The solution Is then titrated against 0.1M HCl and average volume required for the end point
found to be 17.80mL.
Hence, calculate the percentage of ammonia in the floor cleaner:
STEP ONE: DRAW A DIAGRAM

By Josh Walker

110 of 117

!
STEP TWO: LOOK AT REACTION EQUATION
!

NH 3 + HCl NH 4 + + Cl

STEP THREE: USE THIS TO CALCULATE MOLES OF AMMONIA IN 20.0mL

We can see the above equation is all 1:1 so therefore in 20mL
! n (HCl ) = n(NH 3 ) = 0.1 0.01780 = 0.00178mol
STEP FOUR: USE RATIOS TO FIND MOLES OF AMMONIA IN 250mL
We have 20mL and we want 250mL so
250
n (NH 3 in 250ml ) =
0.00178 = 0.02225mol
20
!
STEP FIVE: FIND MASS OF THIS MANY MOLES OF AMMONIA:
Molar mass of ammonia is 17 so
m = Mn
! m = 0.0225 17 = 0.37825g
STEP SIX: LOOK AT THIS AS PERCENTAGE OF FLOOR CLEANER ADDED:
We originally had 6.54g of floor cleaner so:
0.37825
percentage =
100
6.54
! = 5.78%

"

It is imperative you understand this as it is the basis to calculating percentage of acetic acid in
vinegar which is one of the most common questions.

"

Worked Example Percentage Composition (Other Way Around):

This is a slightly more complicated example because it involves ratios between the reactions it is not
all 1:1 as above. Also it is different because the unknown substance is in the burette, but anyway here it
is:
To determine the percentage of sulfuric acid in a car battery 12.5g sample of the acid is
weighed out from the battery.
The acid is then dilated in a 500mL flask and added to a burette.
20.0mL samples of standardised 0.195mol L-1 sodium hydroxide solution are pipetted into
conical flasks.
The average volume required to neutralise the sodium hydroxide is 17.5mL
Knowing this find percentage of sulfuric acid in the battery acid:
STEP ONE: DRAW A DIAGRAM

By Josh Walker

111 of 117

!
STEP TWO: LOOK AT REACTION EQUATION

2NaOH + H SO Na SO + 2H O

2
4
2
4
2
!
STEP THREE: USE THIS TO CALCULATE MOLES OF SULFURIC ACID IN 17.5mL:
1
We can see from equation above moles of sulfuric acid in 17.5mL is ! 2 moles of NaOH:
1
1
n (H 2 SO4 ) = n(NaOH ) = [0.02 0.195 ] = 0.00195mol
2
2
!
STEP FOUR: USE RATIOS TO FIND MOLES OF SULFURIC ACID IN 500mL:
We have 17.5mL and we want 500mL so:
500
n (H 2 SO4 in 500ml ) =
0.00195 = 0.055714 mol
17.5
!
STEP FIVE: FIND MASS OF THIS MANY MOLES OF SULFURIC ACID:
Molar mass of sulfuric acid is 98.1g

! m = 0.055714 98.1 = 5.46g

STEP SIX: LOOK AT THIS AS PERCENTAGE OF THE BATTERY ACID SAMPLE:
We originally had 12.5g so:
5.46
percentage =
100
12.5
! = 43.7%
It is very important you understand the small differences when the unknown is in the burette.

"

Colours of Indicators:
When titrating you need to know what colour change you are looking for, so below is a table which you
need to memorise and probably put on your calculator:

"

Litmus

Universal
Indicator

Phenolphthalein

Methyl
Orange

Bromothymol
Blue

ACID

BlueRed

Red

Clear

Red

Orange

BASE

RedBlue

Purple/Blue

Pink/Purple

Orange

Blue

"
"

Acids Base Volumetric Analysis 2:

We have gleaned a basic knowledge of the theory and ideas behind titrations and most of all we
should now understand the LOGIC. But titrations are in reality more complex than that so we need to
look at a few of the more complex situations now:

"

Analysis of Vinegar Percentage of Acetic Acid in Vinegar:

This Is almost a standard percentage composition question however:
YOU NEED TO USE THE DENSITY OF VINEGAR TO WORK OUT THE MASS.
By Josh Walker

112 of 117
So probably the best way to understand how to do it is to look at an example:
A 25mL sample of vinegar is diluted to 250mL in a volumetric flask.
20mL samples of this diluted solution are placed in conical flasks and phnolphtalien
indicator is added.
Standardised 0.103M sodium hydroxide solution is placed in the burette and titrated against
the acetic acid.
The average volume of NaOH to reach end point (THE TITRE) was 13.05mL.
If the vinegar has an original density of 1.05g mL-1 calculate the percentage of acetic acid in
the vinegar:
STEP ONE: DRAW A DIAGRAM

!
STEP TWO: CONSIDER THE REACTION EQUATION:
! CH 3COOH + NaOH CH 3COONa + H 2O
STEP THREE: USE EQUATION TO WORK OUT MOLES OF ACETIC ACID IN 20mL:
We can see that moles of NaOH equals the moles of acetic acid so:
! n (NaOH ) = n(CH 3COOH ) = 0.103 0.01305 = 0.00134 mol
STEP FOUR: USE RATIOS TO FIND MOLES OF ACETIC ACID IN 250mL:
We have 20mL and we want 250mL so:
250
n (CH 3COOH in 250ml ) =
0.00134 = 0.0168mol
20
!
STEP FIVE: CONNECT SAMPLE TO ORIGINAL AND WORK OUT MASS
So therefore in the 25mL of acetic acid that was diluted there was 0.0168 moles of acetic acid
So the mass of this would be (knowing M acetic acid = 60.2)
! m = 0.0168 60.2 = 1.0081125 g
STEP SIX: USE DENSITY TO FIND MASS OF SAMPLE AND THEN FIND PERCENTAGE
Using density we can say the mass of 25mL of vinegar is:

"
"

Analysis of Unknowns:
By Josh Walker

! m = 25 1.05 = 26.25g
Therefore the percentage of acetic acid in vinegar is:
1.0081125
percentage =
100
26.25
! = 3.84%

113 of 117
We can also use this exact same procedure to work out what something is and so once again by
looking at an example:
An unknown monoprotic acid HX (either HF, HCl, HBr or HI) was analysed using
volumetric analysis.
1.62g of HX was dissolved in 100mL of distilled water which was placed in a burette.
20.0mL of 0,10M NaOH was placed in a flask, indicator added, and titrated against HX.
The average volume of acid required for neutralisation was 10.0mL.
Identify HX:
STEP ONE: DRAW A DIAGRAM

!
STEP TWO: CONSIDER CHEMICAL EQUATION
Because it is a monoprotic acid we can consider the ionic equation:

H + + OH H O

2
!
STEP THREE: USING EQUATION WORK OUT MOLES OF HX IN 10mL:
It is a one to one ratio so:
! n (NaOH ) = n(HX ) = 0.02 0.1 = 0.002mol

STEP FOUR: USE RATIOS TO WORK OUT MOLES OF HX IN 100mL:

We have 10mL and we want 100mL so:
1000
n (HX in 100ml ) =
0.002 = 0.02mol
10
!
STEP FIVE: FIND MOLAR MASS AND MATCH UP TO IDENTIFY
From this and knowing original mass added was 1.62g we can find Molar Mass:
n=

m
M

M =

m 1.62
=
= 81g
n 0.02

!
Now from inspection with the molar masses of acids we could consider we can see Molar Mass of
HBr=81
So therefore the unknown acid is HBr.

"
"
"

Percentage Composition- Advanced:

This is simply an example of how you can work out percentages even when you are given information
and compounds that you have never seen in your life:
Aspirin is a natural compound that acts as an analgesic (pain relief).
Aspirin was isolated from willow tree bark 120 years ago an analysed as
acetylsalicyclic acid C9H8O4.
750g of willow tree bark were ground up and stirred in water, the mixture was filtered
and placed in a volumetric flask and made up to 100mL with distilled water.
10ml samples were pipetted into conical flasks and phenolphthalein indicator was
added.
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114 of 117
Standardised 0.0775M NaOH was placed into the burette and titrated against the acid
solution the average volume for the end point was 6.33mL.
Given acetylsalicyclic acid reacts with sodium hydroxide according to:

!
Find percentage of C9H8O4 in willow bark:
STEP ONE: DRAW DIAGRAM

!
STEP TWO: USING GIVEN EQUATION WORK OUT MASS OF C9H8O4 IN BARK
There are 2 moles of NaOH to every one mole of acid so:
1
1
1
n (C9 H 8O4 ) = n (NaOH ) = [0.0755 0.00633 ] = 0.0004779 = 0.00023895 mol
2
2
2
!
But there are 100mL of solution so therefore:
100
n (C9 H 8O4 in 100mL ) =
0.00023895 = 0.002389mol
10
!
Molar mass of the acid is 180g so mass in willow bark solution is:
! m = 180 0.002389 = 0.430g
STEP THREE: USE THIS TO FIND PERCENTAGE
The mass of willow bark added was 750g so therefore
0.430
percentage =
100
750
! = 0.057%
This is the standard of percentage composition questions you can expect.

"

Back Titrations:
A back titration is usually classified by the following situation:
An acid or base has been contaminated with something and some of it has reacted.
Therefore a titration occurs on that acid or base to find the exact concentration.
By subtracting this from the original concentration before contamination you can work out who
many moles have reacted.
So the best way is to understand this is to look at two examples, an easy one and then a slightly
more complex one:

"

Example 1 all one-one ratios:

A bottle containing 500.0mL of HCl has the label 0.25M.
A small amount of solid potassium hydroxide is accidentally added to the bottle of HCl.
In Order to find the moles of acid that reacted a 20.00mL sample of HCl was pipetted into a
conical flask and phenolphthalein added.
This is titrated against a 0.110M NaOH solution with an average volume of 17.50mL being
By Josh Walker

115 of 117
required to reach end point.
Find mass of KOH that reacted:

"

STEP ONE: DRAW DIAGRAM

!
STEP TWO: CALCULATE MOLES OF HCl IN BOTTLE AFTER REACTION

HCl + NaOH NaCl + H O

2
!
So moles of HCl equal moles of HCl in 20mL:
! n (HCl ) = n(NaOH ) = 0.11 0.0173 = 0.001925mol

Therefore in the 500mL of HCl there would be:

500
n (HCl in 500mL ) =
0.001925 = 0.048125mol
20
!
STEP THREE: WORK OUT HOW MANY MOLES OF HCl ORIGINALLY IN BOTTLE
We know volume and concentration so we can say:
! n (HCl originally) = 0.5 0.25 = 0.125mol
STEP FOUR: WORK OUT MOLES OF HCl THAT REACTED WITH KOH, & MASS KOH:
The change in moles is:
0.125
0.048125 = 0.077mol
!
If we look at the reaction between KOH and HCl:
! HCl + KOH KCl + H 2O
You can see it is all one to one ratio so therefore 0.077mol of KOH has reacted meaning the mass
is (given molar mass of KOH is 56.01g):
m = 0.077 56.01
!

mass = 4.32g

Now something more challenging

"

Example 2 what you can expect:

A small amount of sodium carbonate is dissolved into 200mL of 0.5M HCl solution.
To find out exact moles left in HCl solution 25.0mL of contaminated acid was pipetted into
conical flasks with an average volume of 20.50mL of 0.50M NaOH solution required for
neutralisation.
Calculate the mass of sodium carbonated dissolved in the hydrochloric acid:

"

STEP ONE: DRAW DIAGRAM

By Josh Walker

116 of 117

!
STEP TWO: CALCULATE MOLES OF HCl IN AFTER REACTION

HCl + NaOH NaCl + H O

2
!
So moles of HCl equal moles of HCl in 25mL:
! n (HCl ) = n(NaOH ) = 0.0205 0.5 = 0.01025mol

Therefore in the 200mL of HCl there would be:

200
n (HCl in 200mL ) =
0.01025 = 0.082mol
25
!
STEP THREE: WORK OUT HOW MANY MOLES OF HCl ORIGINALLY IN BOTTLE
We know volume and concentration so we can say:
! n (HCl originally) = 0.2 0.5 = 0.1mol
STEP FOUR: WORK OUT MOLES OF HCl THAT REACTED WITH Na2CO3:
The change in moles is:
! 0.1 0.082 = 0.018mol
If we look at the reaction between Na2CO3 and HCl:
! 2HCl + Na2 CO3 2NaCl + H 2O
We can see for every mole of sodium carbonate reacted there are two moles of HCl reacted.
So in order to find moles of sodium carbonate reacted we say:
1
n(Na2CO3 ) = n(HCl )
2
1
= 0.018
2
= 0.009mol
!
STEP FIVE: FIND MASS OF SODIUM CARBONATE:
Now we know the moles of Sodium carbonate that react.
And we also know molar mass of sodium carbonate is 105.98 we can say:
m = 0.009 105.98

"
"

mass = 0.954 g

Empirical Formula Example:

This is once again the easiest form of calculation and one of the easies forms you will see a titration
question in, but lets just look at one example to make sure we understand it clearly:
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117 of 117
An organic compound contains C,H,N, and O. Upon analysis 0.3g of the compound produced
0.180g of water and 220.0mL of CO2 at pressure of 105.352kPa and 75C. The Nitrogen was
converted to NH3 gas and dissolved in water, this was titrated and required 40.0mL of 0.10M HCl
solution for neutralisation find empirical formula:
HYDROGEN WATER
We can say:
2H H 2O

n(H 2O) =

0.18
18

= 0.01mol
n (H ) = 0.02mol
m(H ) = 0.02g
!

CARBON CARBON DIOXIDE

C CO2

n(CO2 ) : PV = nrt
n(CO2 ) =

105.352 0.22
8.315 348

= 0.008mol
n (C ) = 0.008mol
m(C) = 0.096g
!

NITROGEN AMMONIA
N NH 3

Then Titrated In: NH 3 + H + NH 4 +

n(HCl ) = n(NH 3 ) = 0.04 0.1
= 0.004 mol
n (N ) = 0.004mol
m(N) = 0.056g
!

OXYGEN IS LEFT OVER MASS

m(O) = 0.3 0.096 0.02 0.056 = 0.116

n(O) =
!

0.128
= 0.008moll
16
n (O) = 0.008mol

NOW USE RATIOS TO SOLVE

0.02
0.008
H=
C=
0.004
0.004
!= 5
!= 2
So the empirical formula is C2H5NO2.

"

By Josh Walker

N=
!=1

0.004
0.004

O=
!= 2

0.008
0.004