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Periodicity

All covalent oxides are acidic. WHY: MO(S) + H2O(l) MO(OH)-(aq)+ H+(aq)
All ionic oxides are alkaline. WHY: O2-(aq)+ H2O(l) 2OH-(aq)
Oxides
Bonding Type
Properties
Equations
of
Period 3
Ionic Bonding:
1) Solid
2Na + 1/2O2 Na2O(s)
large difference in 2) High melting point; to
Yellow flame is seen
Na2O
electronegativity.
strong electrostatic force of
Very exothermic reaction (H= - ) with water:attraction between negative Na2O(s) + H2O(l) 2NaOH(aq)
and positive ions.
O2-(s) + H2O(l) 2OH3) Conducts electricity when The O2- gains a proton (H+) and therefore it is:
molten.
Strongly alkaline (base); pH= 14.0
4 ) Brittle; different sized
Conducts electricity when molten as ions free
ions
to move
Ionic Bonding:
1) Solid with higher melting
2Mg +O2 2MgO(s)
MgO
large difference in point than Na2O.
Bright white light is seen and white fumes of
electronegativity.
WHY:
the oxide formed
a) Mg smaller ion
Almost totally insoluble in water (forms
b) Mg has higher charge
suspension in water):c) Stronger electrostatic
MgO(s) + H2O(l) Mg(OH)2(aq)
force of attraction.
O2-(s) + H2O(l) 2OHAlmost not feasible as reversible sign shows;
pH= 8.0
Ionic with
1) Solid; due to ionic
4Al + 3O2 2Al2O3
Al2O3
Covalent
bonding
Bright white light is seen and white fumes of
Character:
2) The fact that it has
the oxide formed
polarisation
covalent character makes it Totally insoluble in water or moist air as G is
introduces
amphoteric
very positive and lattice energy is large; pH=
covalence
7.0
Giant Molecular:
1) Very High melting point
Si + O2 SiO2
SiO2
Lots of strong
2) Very hard
Bright white light is seen and white fumes of
covalent bonds
3) Good insulator
the oxide formed
that require a lot
4) High melting point
Totally insoluble in water or moist air
of energy to
pH= 7.0
break
Molecular
1) Solid as the strongest
4P + 5O2 P4O10
P4O10
Covalent:
force is Van Der Waals, this Bright white light is seen and white fumes of
(It not
Phosphorus and
molecule is big therefore
the oxide formed
P4O10 as Oxygen have
Van Der Waals is higher
Very exothermic reaction (H= - ) with water
this is its similar
2) Van Der Waals increase (makes phosphoric acid) :most
electronegativity.
as surface area increases
P4O10(s) + 6H2O(l) 4H3PO4(l)
stable
3) Higher melting point than This dissolves again in water:form)
SO3
H3PO4(l) 3H+(aq) + PO43-(aq)
Strongly acidic; pH= 1-0
Molecular
1) Gas; Van Der Waals
S + O2 SO2(g) - colourless
SO2
Covalent: Sulphur forces BETWEEN
Blue flame is seen and pungent smell of gas is
and Oxygen have MOLECULES not high
observed.
similar
enough
Extremely soluble in water but endothermic
electronegativity.
reaction (H= + ) reaction (dissolves in watercolourless):SO2 SO2 H2SO3 H+ + HSO3- 2H+ +
SO32Weak acid; pH= 3-4
Molecular
1) Van Der Waals forces
S + 3/2O2 SO3 ; can also be made by
SO3
Covalent: Sulphur BETWEEN MOLECULES
reacting SO2 with O2 (Contact Process).
and Oxygen have very high as molecule is big Very exothermic reaction (H= - ) with water:similar
2) Melting point not as high
SO3 + H2O(l) H2SO4(l)
electronegativity.
as P4O10 as it is not as big
This dissolves again in water:H2SO4(l) 2H+(aq) + SO42-(aq)
Strongly acidic; pH= 1-0
Order of melting point:MgO > Al2O3 > SiO2 > Na2O > P4O10 > SO3 > SO2

Also remember that if we wanted to show that an oxide contained ions, we would heat it until it is molten,
and see whether it conducts electricity.
As you go down oxides of metal groups (group 1 and 2): melting point decreases as the ion gets bigger
and therefore there is less electrostatic force of attraction between the positive metal ion and negative
Oxygen ion. In a question such as this, never mention electro-negativity, nuclear force or shielding at all.
Melting point of MgO is higher than Na2O: Because Mg is a smaller ion with a more negative charge than
Na, Therefore stronger electrostatic force of attraction with negative Oxygen ion.
Also remember, that when it says aqueous in the question, it wants ions. So if it says: aqueous Sodium
Hydroxide, DO NOT write NaOH, write OH- or Na+.
Cations (+) form Acids. Anions (-) form Bases. As a general rule Acid + Base + (Water) Salt + (Water)
REMEMBER: Hydroxide (OH) is not the same as a substance being soluble. Aluminium is not soluble in
water; however it does form a hydroxide. Hydroxide involves the ion OH-.
Oxide
Contains
Equation as to how cation/anion
Salt formed
It is
Reacts
formed
with
Na2O(s) + 2H+(aq) 2Na+(aq) +
NaOH / Na2O
Na+ (cation)
Sodium salts
BASE
ACID
H2O(l)
Mg(OH)2 / MgO

Mg2+ (cation)

MgO(s) + 2H+(aq) Mg2+(aq) + H2O(l)

Al3+ (cation)

Al2O3(s) + 6H+(aq) 2Al3+(aq) +


3H2O(l)

Al(OH)4- (anion)

Al2O3 / Al(OH)3

Magnesium
salts
Aluminium salts

BASE

ACID

BASE

ACID

Al2O3(s) + 3H2O(l) + 2OH-(aq)


2Al(OH)4-(aq)
SiO2(s) + 2OH-(aq) SiO32-(aq) +
H2O(l)

Aluminate salts

ACID

BASE

Silicate salts

ACID

BASE

SiO2

SiO32- (anion)

P4O10 / H3PO4

PO43- (anion)

P4O10(s) + 12OH-(aq) 4PO43-(aq) +


6H2O(l)

Phosphate (II)
salts

ACID

BASE

SO2 / H2SO4

SO42- (anion)

SO3(g) + 2OH-(aq) SO42-(aq) + H2O(l)

ACID

BASE

SO3 / H2SO3

SO32- (anion)

SO2(g) + 2OH-(aq) SO32-(aq) + H2Ol)

Sulphate (VI)
salts
Sulphate (IV)
salts

ACID

BASE

Elemen
t
Na

Mg

Examples:1) NaOH + H3PO4 Na+ + PO433NaOH + H3PO4 Na 3PO4 + 3H2O


6Na2O + P4O10 4Na3PO4
2) NaOH + H2SO4 Na+ + SO422NaOH + H2SO4 Na 2SO4 + 2H2O
3) NaOH + Al2O3 Al(OH)-+ Na+
3H2O + 2NaOH + Al2O3 2NaAl(OH)4
The tip for this is to always draw the anion (negative ion) first such as Al(OH)4- SO42-, PO43-, then add the
cation. Also when a weak alkaline is used to neutralise a strong acid, we can use excess and no problems
will occur. However if a strong alkaline is used (NaOH), we must not use excess as we will create a strong
alkaline solution, and this as we know could cause environmental problems in lakes.
Equation
Properties
EXTREMELY EXOTHERMIC (H= - )
1) Sodium melts, we see fizzing
+
2Na(s) + H2O(l) 2Na (g) + 2OH (aq) +
2) Large lump explodes, due to Hydrogen gas, which burns
with a yellow flame
H2(g)
3) Low density metal, therefore floats on water
5) Sodium hydroxide forms in alkaline solution
DOES NOTHING
Mg(s) + H2O(g) MgO(s) + H2(g)
1) Mg sinks
(Originally Mg(OH)2 was made, but it
2) Very slow reaction giving small quantity of H2(g) after a
week
decomposed to MgO at the
temperature of the reaction.
3) HOWEVER, if steam is added, a very exothermic reaction
occurs because Mg melts into gas.
Also remember that Phosphorus is stored under water as it spontaneously ignites in air.

If you want to know whether something basic (alkali) or acidic, add it to water, if you get H+ its acidic, if you
get OH- its basic (alkali)
If in the exam, the word moist is used, it is a reference to water (H2O(l)).Sometimes, to prevent corrosion in
moist air, aluminium oxide is coated over a metal, this is because aluminium oxide is insoluble.
Thermodynamics
Bonds being broken = Endothermic (+)
S

What happens
Reaction
reversible
as
H
is
going
to
reactants but S is going to products. Hence if you
+ +
increase the temperature H moves to products (LCP), as does S. This tells us that a
reaction of this sort is only feasible (i.e. will go to products) at very high temperatures.
- Reaction reversible as H is going to products but S is going to reactants. Hence if you
increase the temperature H moves to reactants (LCP), as does S. This tells us that a
reaction of this sort is only feasible (i.e. will go to products) at very low temperatures.
Type of Enthalpy
Information Regarding It
is never feasible at any temperature (i.e. will never go to products) as H is
+
- This reaction
Endothermic
(+);isyou
make
one
of gaseous atoms. Remember you make
going to reactants
but S
also
going
to mole
reactants.
EnthalpyThis
of reaction
one is
mole
of
atoms,
not
ions
just
yet.
In
bond
enthalpy
make atoms
feasible at all temperatures (i.e. will
always
go toyou
products)as
H of
is that
going
- Atomisation
+
element
but
it
is
not
one
mole,
it
is
two.
Therefore
you
multiply
this
number
by
to products but S is also going to products.
two. For example: Cl2 will have a bond enthalpy twice the enthalpy of
atomisation of chlorine as breaking Cl2 gives you 2Cl.
Endothermic (+); each ionisation more endothermic (+) than the other. WHY?
Enthalpy of
Ion is gaining more charge; therefore the outer-electron is closer to the nucleus,
Ionisation
and the ion is smaller, therefore it becomes more difficult to remove the outerelectron. Here, we make ions.
1st Electron Affinity: Exothermic (-) WHY? Electrons lose energy as they fall into
orbitals.
Electron Affinity
Attractive force between nucleus and
external electron.
Remaining are: Endothermic (+) WHY? Repulsion between negative ion and
negative electron
Lattice Enthalpy Exothermic (-) as you make bonds to form ionic lattice from gaseous ions.
of Formation
Endothermic (+) as you break an ionic lattice to form gaseous ions. Complete
Lattice Enthalpy/ opposite of Lattice Enthalpy of Formation. It will usually be the same number as
Lattice
Lattice Enthalpy of Formation but it will have a + in front of it instead. It
Disassociation
increases as the force between the lattice increases. Hence smaller, higher
Enthalpy
charged ions will be harder to pull apart and therefore will have a higher Lattice
Enthalpy. Size decreases across a period, and increases down a group. Charge
increases across a period and stays the same down a group.
You make one mole of aqueous ions from one mole of gaseous ions. Hence if
Enthalpy of
you are making 2 moles of aqueous ions from 2 moles of gaseous ions, then
Hydration
multiply this number by 2. When the aqueous ion is in the water, e.g. Na+, it will
have dipole with the O-- of H2O, or if it is F-, it will have a dipole with the H+ of
H2O. Hydrogen bonding will ONLY take place between molecules.
You dissolve the ionic lattice in water and this gives you aqueous ions. It is
Enthalpy of
worked by first doing the Lattice enthalpy of the ionic lattice, this will give you
Solution
gaseous ions, now use Enthalpy of hydration to work out aqueous ions. Add
them together to give you the Enthalpy of solution.
You work out enthalpy of breaking (+)/ making (-) each bond in a compound.
However, all products and reactants must be in the gas state. To work it out:
Bond Enthalpy
Bonds broken - Bonds made. Bond Enthalpy differs from Enthalpy of
formation in 2 ways:
1) Enthalpy of Formation has products and reactants in
standard states, bond enthalpy has them in gas state
2) Bond Enthalpy considers mean values of enthalpy for that bond
Bonds being made = Exothermic (-)
Things you should know about S and H:
H: 1) If it is (exothermic), then it is going to products, but increase the temperature and it will move to
reactants due to Le Chatelliers principle.
2) If it is + (endothermic), then it is going to reactants, but increase the temperature and it will move to
products due to Le Chatelliers principle.
S: 1) If it is + (endothermic), then it is going to products, and if you increase the temperature it will be even
more powerful towards products. (La Chatelliers principle ineffective)
2) If it is - (exothermic), then it is going to reactants, and if you increase the temperature it will be even
more powerful towards reactants. (La Chatelliers principle ineffective)

Always remember, when drawing Born-Haber Cycles, is for endothermic (+) is for exothermic (-).
Examinations also tend to as to why the enthalpy of hydration or lattice disassociation is higher for a certain
molecule or atom than another molecule or atom, the answer should always mention the SIZE of the ion
involved and its charge and how this will affect its force of attraction.
For example, the enthalpy of lattice disassociation of Calcium Fluoride is greater than that for Calcium
Chloride because Fluoride ions are smaller, therefore they form a stronger electrostatic force of attraction
with positive ion (Ca2+), and therefore more energy is required to break them.
Also for example, the enthalpy of hydration of Aluminium ions is much higher than enthalpy of hydration of
magnesium ions because Al3+ is more polarising (higher charge density/size to charge ratio), and therefore
attracts water more strongly.
It is also important to remember rather more confusing question such as why HF(l) has a higher enthalpy of
vaporisation (turn substance to gas) than NH3. Well this is because although BOTH have hydrogen
bonding, the hydrogen bonding in HF(l) is stronger because H-F is more polar than H-N, therefore more
energy required to separate it.
Entropy is the colleague of Enthalpy. It explains as to how endothermic reactions take place, if you think
about it, in endothermic reactions (+), enthalpy is pushing to reactants, so how does the reaction even take
place? Its because Entropy is pushing to products. However, entropy is very weak (compared to enthalpy),
hence endothermic reactions that are feasible (i.e. go to products) are very rare).

Entropy is defined as randomness. Gases have the highest


entropy. Liquids have the second highest entropy. Solids have
the least entropy. At 0K, there is no entropy as there is no
randomness. Then entropy increases as the temperature
increases as particles vibrate more. At Tm, the melting point
(solid to liquid) takes place and entropy jumps as the particles
become even more random. At Tb, the boiling point (liquid to
gas) takes and entropy jumps higher than it did for Tm, this is
because there is more randomness in a higher volume, there
bigger increase in disorder.
In solids: particles vibrating in small volume
In liquids: particles moving in small volume
In gases: particles moving in large volume
Entropy is worked out by: Entropy products - Entropy reactants
We can tell if the entropy is going to be positive by looking at the states of the reactants and products.
Hence, if a mole of solid is converted into two moles of gas, then entropy is most definitely positive. WHY?
Two big numbers (gas) one small number (solid)
Entropy is measured in Joules. Hence Enthalpy is measured in Kilojoules. Therefore Entropy is divided by
1000 to make it into Kilojoules when required.
Feasible: Thermodynamically possible
Spontaneous: takes place without any energy input
All spontaneous reactions are obviously feasible. However a feasible reaction may not be spontaneous,
maybe because it has very high activation energy.
Also remember that the enthalpy of solution (dissolve in water) is at times exothermic too, but when it is
endothermic (+) we should be providing energy, then the reason for the reaction taking place
SPONTANEOUSLY (it happens without us giving it energy) is because entropy is highly positive, pushing
the reaction to products.

Free Energy is known as G. It is measured in Kilojoules. It tells us whether a reaction is feasible or not,
i.e. will it take place or not. For a reaction to take place:- G0.
Hence, this is how we work it out:
G = H T (S/1000)
We can conclude a couple of things:
1) As S gets more positive, G becomes more negative
2) At equilibrium, when the products and reactants are EXACTLY the same amount, G = 0. When a liquid
boils G = 0, this is because boiling is a spontaneous change and mainly because water and water
vapour are in equilibrium.
3) When G = 0, the reaction is just about feasible. You can work out this temperature by re-arranging the
equation to: T = H/ (S/1000). This will tell you when G = 0 (i.e. when the reaction is just about
feasible)
4) In reversible reactions, G = 0 when the reaction has no tendency to move spontaneously in one
direction or the other. At G = 0, you can work out the temperature, if this temperature is
increased/decreased the reaction will no longer remain spontaneous in that direction. Hence yield in that
direction would decrease. This is why when a liquid boils (reversible reaction) G = 0, because the water
and water vapour are at equilibrium and the reaction has no tendency to move spontaneously in one
direction or the other.
5) When moles on both sides are equal and phase is also the same, entropy is close to zero; hence as long
as H is constant, G will remain constant at any temperature.

When H and S are both negative, we must use a low temperature (above), hence such a reaction if
carried out will not be feasible, i.e. will not produce products in an internal combustion engine as this type of
engine uses very high temperatures.
Industrialists however sometimes break this feasibility rule and do the reaction at a temperature higher than
the limit of the feasible temperature that we have calculated. But we dont need to know at this point much
about this; all we need to know is that they do this because the reaction may have high activation energy or
they need the reaction to speed up.
In the exam, a common question is one wherein two equations are given, and we must work out the
temperature at which both reactions will have the SAME VALUE for G. Hence we do it like this:
G (reaction A) = G (reaction B)
T = [H (reaction A) - H (reaction B)] [S (reaction A) - S (reaction B)]
Also, in the exam, when it gives you a Born-Haber cycle of a reaction, and asks you to name the
enthalpies, do not just write enthalpy of atomisation or enthalpy of ionisation, ensure to write what the
enthalpies are of. I.e. write enthalpy of atomisation of... (chemical) and enthalpy of ionisation of ...
(chemical).
A key reaction in enthalpy is the reaction in which NO is produced. In an internal engine, it is made in the
following way: N2 + O2 2NO, then the NO is turned into NO2. The temperature in an internal combustion
is above 794k, therefore this reaction does not take place: NO + 1/2O2 NO2 as it is not feasible above
794K.
As a general rule, whenever something does not form, which according to enthalpy and entropy, should
form, it is due to high activation energy.
Also remember that melting points and boiling points in molecular covalent structures have nothing to do
with the breaking of bonds, it is always about the intermolecular forces, and these intermolecular forces
(mainly H-Bonding) only arise between two molecules, NOT between two ions. There are no H-Bonds
between H2O molecules and F- ions.
Sometimes a graph that is presented in the exam is a graph which shows how the free-energy change for a
reaction varies with temperature above a certain temperature, such as:
Here, the value of the slope is known as the gradient which is S. The reason the graph stops to slope, is
because at this point there is a phase change, hence the graph moves vertically upwards. The units of the
SLOPE are KJmol-1K-1. Where the graph crosses the x-axis, G becomes 0 and hence the reaction at this
temperature is now feasible.

Redox Equilibria
General Rule:
Reducing agents lose electrons as they themselves are oxidised.
Oxidising agents gain electrons as they themselves are reduced.

Electrochemical cells contain two electrodes (electrical conductors) immersed in an electrolyte (ionic
conductor). The electrolyte can be an aqueous solution (the solution cannot be due to dissolving in water is
SOME cells, because water could SOMETIMES react with very reactive metals such as Lithium) or a
molten salt. An electrode with its electrolyte is called an electrode compartment. If two compartments are
used, then a salt bridge is used to connect the two compartments (cells).
The salt bridge allows the flow of ions (in this case: M+ and H+) and the electrode allows the flow of
electrons (current).
As you can see, in one cell there
is an oxidation process and in the
other, there is a reduction
process.
SALT BRIDGE (needed to join
two half-cells and complete
circuit whilst preventing phase
change, this is because every
phase change causes a change
in voltage): Contains the salt KCl
which is unreactive and allows
ions to move.
In a cell that involves a reactive
metal such as Lithium, water is
never used as a solvent as it will
react with the reactive metal.
Sometimes, in batteries a Porous
Separator is used, it has the
same function as a salt bridge.
ELECTRODE: Platinum as it is unreactive, it is a good conductor (can carry electrons) and allows
equilibrium to be established. It is also a good catalyst and therefore Platinum Rods are made by coating
ceramic material with Platinum so as to increase the surface area. The purpose of the electrode is to carry
electrons.
The representation of the cell is this: Reducing agent I Oxidising agent II Oxidising agent I Reducing agent
The double line (II) separates the two half-cells. The single line (I) separates a phase change- i.e. solid,
liquid and gas.
The metal electrode is the actual metal in equilibrium with a solution of its ions (left hand side). For
example: Cu2+(s) I Cu(s). In this cell, the Cu(s) will be the actual electrode.
The gas electrode is a platinum electrode surrounded by a gas in equilibrium with a solution of its ions, the
gas and its ions are obviously in a different phase, but the platinum electrode is needed as the gas cannot
CARRY ELECTRONS to the other cell as an electrode is supposed to do, also the platinum acts as a
catalyst for the gas and its ions to reach equilibrium. For example: H+(aq) I H2(g). The H2(g) gas will be bubbled
in.
The redox electrode is the platinum electrode surrounded by a solution in which the phase (state-solid,
liquid, and gas) is the same, but the oxidation number is different. For example: Fe3+(aq) , Fe2+(aq)
Every half-cell has an electrode potential (E-00; we work out this potential by joining it with the half-cell of
Hydrogen as seen in the picture above. The Standard Hydrogen Electrode (SHE) is assigned the electrode
potential 0; this is by definition so that we can use it as a reference for all other half-cell electrode
potentials.
SHE: Hydrogen gas is bubbled into a 1.00 moldm-3 solution of HCl (contains H+) at 298K, with a Platinum
electrode.
The positive electrode will be considered to be the one with the more positive electro potential, by
convention the positive electrode is placed on the right.
N.B. Always remember we cannot have a solution of ions alone, therefore when we say a metal in
equilibrium with a solution of its ions, we dont mean for example Mg and Mg2+, we mean Mg and MgCl2,
however, when in solution the MgCl2 becomes Mg2+. Basically it is not possible to have a jar of Mg2+ on your
shelf.

A voltage (measure of flow of electrons) is set up between the two half-cells. Each half-cell has an
electrode potential as discussed in the paragraph above, the difference between these two potential is
called the voltage/e.m.f. It is worked out by:
Electrode Potential of right hand cell Electrode potential of left hand cell
The following shows the conditions needed in order to get the correct e.m.f of a cell, any changes with the
below and the e.m.f will change.
Standard Conditions of half-cell:
Zero-current conditions (not when ions are both aqueous)
Concentration must be 1.00 moldm-3
Temperature must be 298K
Pressure must be 100kPa (in gases only)
The most powerful reducing agent (gives away most amount of electrons) is the product (right-hand side) of
the most negative/least positive electro potential half-cell.
The most powerful oxidising agent (takes away from others the most amount of electrons) is the reactant
(left-hand side) of the most positive/least negative electro potential half-cell.
This is because the best oxidising agent has the highest E-00
The worst oxidising agent has the lowest E-00
Therefore as the Electro potential decreases, the reducing power of the substance on the right (product)
increases and it will be able to reduce everything to the left (reactant) that is above it.
In the same way as the Electro potential increases, the oxidising power of the substance on the left
(reactant) increases and it will be able to oxidise everything to the right (product) that is above it.

1
2
3
4

Equation

E-00

Cl(aq) + 2e- 2ClH2O2(I) + 2H+(aq+ 2e- 2H2O(I)


O2(g) + 4H+(aq) + 4e 2H2O(I)
O2(g) + 2H+(aq) + 2e- H2O2(aq)

+1.36
+1.77
+1.23
+0.68

Most powerful reducing agent: H2O2(aq)


Most powerful oxidising agent: Cl(aq)
Hence when the most powerful reducing agent is at the bottom right and the most powerful oxidising agent
is at the top left. The reactions occur as:
Bottom Right + Top Left Bottom Left + Top Right
(Ensuring the electrons are balanced)
For example: when 2 and 4 discharge (react):H2O2(aq) (Bottom Right) + H2O2(I) + 2H+(aq+ 2e- (Top Left ) 2H2O(I) (Top Right) + O2(g) + 2H+(aq) + 2e- (Bottom
Left)
Similarly when the most powerful reducing agent is at the top right and the most powerful oxidising agent is
at the bottom left. The reactions occur as:
Bottom Left + Top Right Bottom Right + Top Left
(Ensuring the electrons are balanced)
When these reactions are shown, remember that a reaction in alkaline conditions will contain OH- in the
equation, whereas a reaction under acidic conditions will contain H+ in the equation.
Also remember that the concentrations must be constant (no increase or decrease) for our worked out
e.m.f to be correct. But if we DID change the concentration of a substance how would that affect e.m.f?
For example: we have two half cells:
Mg2+(aq) + 2e- Mg(s) = -2.37
Fe2+(aq) + 2e- Fe(s) = -0.44
Now, the e.m.f is right left. Therefore, the e.m.f is -0.44 (-2.37) = 1.93. But if we increased the
concentration of Mg2+ions, by Le Chatelliers Principle the half-cell equilibrium will reduce it by moving
towards Mg, Mg is a reducing agent and as we know if were making more reducing agent, the Electro
potential of that cell becomes MORE NEGATIVE. So lets just say it now goes from -2.37 all the way down
to -4.37, now lets look at our e.m.f, it will be -0.44 (-4.37) = 3.93. Hence you see how our e.m.f increased.
In the exam they will ask about this. Always remember, if you increase the concentration of a weak
oxidising agent such as Mg2+, the half cell reaction gets MORE NEGATIVE, if you increase the
concentration of a strong oxidising agent such as O2, the half cell reaction gets MORE POSITIVE.

Also remember any time when a metal is being converted into its ions in the overall reaction, then that
metal electrode will be corroding away.
Batteries that are not re-chargeable only discharge in the way shown above, hence their e.m.f will
eventually decrease and go down to zero, and if the voltmeter were replaced by an ammeter, the ammeter
would read zero, as the ions/elements/molecules reacting are used up (H+ will not get used up as constant
supply of H2 that is being oxidised, however reactants in the other half-cell will get used up) and because
the reaction is not reversible, the battery cant be re-charged either.
However, in re-chargeable batteries, such as Lead-acid batteries, this does not happen, because as soon
as reactants are used up, the reverse reaction begins to take place. Hence, first the discharge reaction
takes place (as shown above), then when it wishes to re-charge the reaction will turn itself around, hence in
the exam, just turn the discharge reaction the other way round to show that the battery is now re-charging.
This is similar to a reversible reaction (). The advantage of re-chargeable batteries is that it reduces
landfill.
N.B. When working out oxidation states (oxidation numbers), always remember that in H2O2, Oxygen has
oxidation state -1, not -2 as it usually has.
Fuel cells convert stored chemical energy directly into chemical energy.
Fuel cells have a constant e.m.f. WHY? 1) Constant supply of external fuel
2) Constant concentration of reagents
In a hydrogen/oxygen fuel cell, H2 and O2 are added to a cell in which there is a platinum electrode with a
cathode and anode. It releases H2O. It has advantages such as: 1) H2 is easy to make
2) No pollution
It is not carbon-neutral as making H2 does release CO2. How? Electrolysis of water produces H2.
Their advantage over a re-chargeable battery is that they have a constant supply of external fuel and do not
need to re-charge.

You
can also get
an ethanol-oxygen fuel cell, wherein ethanol is oxidised to CO2 and O2 is reduced as above to H2O.
However Ethanol CAN be considered a carbon-neutral fuel because the number of moles in photosynthesis
and fermentation are equal (6:6) UNIT 2.
Also remember that half-cells use chemical change to produce electricity.
However electrolysis uses electricity to bring about a chemical change.

Transition Metals
Transition metals have incompletely occupied d-orbitals. This means any ion/element with a d0 or d10 will
not be a transition metal ion/transition metal. Look at electronic structures of the d-block elements to see
which ones are transition metals and which ones are not.
They have 4 main characteristics: 1) Complex formation: due to incompletely occupied d-orbital
Sc

3+

Ti

3+
4+

3+
4+

Cr

Mn

Fe

Co

Ni

2+
3+

2+

2+
3+

2+
3+

2+
3+

Cu

Zn

1+
2+

2+

Al

3+

4+

5+
(VO2+)
6+
(CrO42-, Cr2O72-)

6+

6+

7+
(MnO4-)
2) Coloured Ions: due to complex formation
3) Catalysts: due to variable oxidation states
4) Variable Oxidation numbers/states
In transition metal elements the 4s orbital is before the 3d orbital, however in transition metal ions the 3d
orbital is before the 4s orbital as the 4s orbital in a transition metal ion is empty.
So as you can see CrO42-, Cr2O72-, MnO4-, VO2+ are good oxidising agents, i.e. they gain electrons. However
Zn2+, Cu+, Cu2+ are good reducing agents, i.e. they lose electrons.

1) Complex formation; this is done by the metal forming dative covalent bonds with a molecule/ion. This
molecule/ion is called a ligand. Hence all the hard work is done by the ligands as they provide both the
electrons in the each bond.
2) Obviously, the fact that ligands form dative covalent bonds with metal ions, tell us that the ligand must
have a lone pair/s.
3) Depending on the size of the ligand, the metal ion can form 2, 4 or 6 coordinate bonds with a ligand.
Therefore you may get a complex that is linear (2 coordinate bonds), Tetrahedral (4 coordinate bonds with a
big ligand), square planar (4 coordinate bonds with big ligands) or octahedral (6 coordinate bonds with a
small ligand)
The coordination number is the number of coordinate bonds formed. This is not always the same number
as the number of ligands as some ligands form 2 or more coordinate bonds.
Unidentate Ligands form one coordinate bond a metal ion, Multidentate Ligands form 2 or more coordinate
bonds with a metal ion (obviously they must have 2 lone pairs).
Common ligands are:
:NH3 = Ammonia (unidentate)
-:OH = Hydroxide(unidentate)
NC-: = Cyanide(unidentate)
Cl-: = Chloride (unidentate)
H2O: = Water (unidentate)
:O2 = Oxygen
H3N:-CH2-CH2-:NH3 = 1,2 Diaminoethane (en) (multidentate - 2 coordinate bonds)
-:OOC-COO-: = Ethanedioate Ion (C2O42-) (multidentate - 2 coordinate bonds)
EDTA4Notice that Chlorine is NOT a ligand, a chloride is. Also as you can see, some ligands have charges, and
some dont.
The ligands form different shapes with the metal ions, the ones that are most common and ones we are
required to know are: Linear, Tetrahedral, Square Planar and Octahedral.
Just as a side note, when excess Hydrochloric Acid is added to H3N:-CH2-CH2-:NH3 = 1,2 Diaminoethane
(en), it becomes ClH3N-CH2-CH2-NH3Cl, the Chloride (Cl-) bonds with the Nitrogen.

UNIDENTATE LIGANDS: The ligand is forming only 1 coordinate bond with the metal ion.
Linear Complexes: Formed by Cu+ and Ag+ (remember that neither are transition
metals; complete d-shell)
Ligand in use: Cl-:
[CuCl2]- The Cu has charge +1; the 2Cl- has charge -2, therefore -2+1 = -1
It is colourless.
Ligand in use: :NH3
[Ag(NH3)2] The Ag has charge +1; the NH3 has no charge, therefore = +1
This complex is known as Tollens Reagent (Unit 2) and is reduced by Aldehydes. Also, it is colourless, but
when added to Aldehyde such as Ethanal, we get a silver mirror
colour, which is the colour of Ag(s). The reduction reaction is:
[Ag(NH3)2]2+ + 2e- Ag + 2NH3
As a side note, you can also get [AgCl2]- as you did with the Cu.
+

Square Planar Complexes: Formed by Pt2+

Ligand/s in use: Cl- and NH3


It called Cis Platin and it forms 4 coordinate bonds only (instead of 6) as the Cl- ligand is a
very big ligand big ligands are caused by the negative charge, as you should know by
now, negative charges are quite big in size.
Cis Platin is a cancer drug that has one risk-you could die, as it is toxic.
Ligand/s in use: :Cl- and :NH3
This is called Trans Platin, it is much like Cis Platin but the Cl- and the NH3 arranged
differently.

Octahedral Complexes: Formed by Fe2+, Co2+, and all other transition metals.
Ligand in use: H2O:
[Fe(H2O)6]2+ The H2O: has charge 0, the Fe has charge +2, therefore = +2
It is called hexa aqua Iron (II)
Hexa because of the 6 ligands, Aqau because of the ligands being water and Iron (II) because of the
Fe2+
This is known as the Aqua Complex, we will discuss regarding this later on.
However, as mentioned above, some ligands form more than one coordinate bond with the metal ion.
Obviously this is only possible if the ligand has more than 1 lone pair.
MULTIDENTATE LIGANDS: The ligand is forming
more coordinate bonds with the metal ion.
Examples of BIIDENTATE LIGAND (2 coordinate
bonds with metal ion) COMPLEXES:
Octahedral Complexes: Formed by Co2+, Fe2+, and couple others
Ligand in use: H3N:-CH2-CH2-:NH3 = 1, 2 Diaminoethane (en)
The NH3 has no charge, the Co has charge +2, therefore = +2
There is a shorter way of drawing it (easy peasy):

2 or

Ligand in use: -:OOC-COO-: = Ethanedioate Ion (C2O42-) and H2O:


The O has no charge, the Fe has charge +2, therefore = +2

Example of QUADRIDENTATE LIGANDS (4 coordinate bonds with metal ion)


COMPLEXES:
Octahedral: Formed by Fe2+ (Haemoglobin), Mg2+ (Chloroplast), Co2+ (Vitamin B12)
Ligand in use: Porphyrin Ring (PR)
The N has no charge, the Fe has charge +2, therefore = +2
If youre wondering why we have said octahedral whereas you can only see 4 coordinate bonds of N to Fe,
it is because there are two more ligands above and below Fe that are difficult to draw.
The object of this structure is to carry oxygen. (Biology)

Example of HEXADENTATE LIGANDS (6 coordinate bonds with metal


ion) COMPLEXES:
Octahedral:
Formed by EDTA4-. However, it is important to understand that although the shape is octahedral, the ligand
is only one; this is because EDTA4- looks like this:
Fear not, they will not ask you to draw this ligand in a complex, it would be very difficult. However, they
could ask you about it, especially in Ligand Substitution.
N.B. The picture is not a complex, its just a ligand. A mighty bigun.

Ligand Substitution
Ligand Substitution: A ligand is attached to a metal ion, it is then chucked out and replaced by another
stronger ligand
EXAMPLE:
[Co(H2O)6]2+ + EDTA4- [CoEDTA]2- + 6H2O
Can you see how the EDTA4- chucked out the 6H2O ligands and joined the Co2+? This is why we see 6H2O
in the products. However [CoEDTA]2- is still octahedral because although now only 1 ligand is attached to
the Co2+, this ligand is a Hexadentate ligand, which means that it is forming 6 coordinate bonds with the
Co2+.
The [CoEDTA]2- is a very stable complex as there has been an increase in Entropy, from 2 moles you
created 7, and you replaced 6 ligands of water with 1 ligand of EDTA4-. G for this reaction is very negative
as Enthalpy is close to zero. WHY? Same number and same type of bonds broken and made, but Entropy
is very positive making G very negative.
Its also important that you notice how ligand substitution will always involve the sign.
Ligand Substitution can be very dangerous too. This is because Haemoglobin (red blood cells) contains
Fe2+ with :O2 ligands, however CO: is a stronger ligand, so ligand substitution would occur and the O2 would
be chucked out and replaced by CO:, which would obviously kill you. Thats why you shouldnt breathe in
Carbon Monoxide (CO:), ever. It will kill you.
However, Oxygen being a weak ligand is actually rather important as it allows Oxygen to be carried by the
Haem and then removed from the Haem so that it may be used inside the body. If it was a strong ligand, it
would forever remain attached to the Haem and the body would be deprived of Oxygen.
A common ligand substitution question involves HCl, where 4Cl- ions replace the water molecules in a
complex.
FOR EXAMPLE:
[Cu(H2O)6]2+ + 4Cl- [CuCl4]2- + 6H2O
The product [CuCl4]2- is a yellow-green colour, It will be asked regarding the colour too in the exam.
Also ensure that you do not write HCl as a reactant, when added to water HCl becomes Cl- and H+, by
writing HCl, you are implying that Cl- is using up its lone pair to bond with the H+ and make HCl hence no
longer remaining a ligand. (The [CuCl4]2- can become [CuCl4]3-, wherein the oxidation state of Cu is +1, and
Cu metal acts as a reducing agent
In Vitamin B12, Co2+ is co-ordinately bonded to a porphyrin ring (above) and 2 other ligands, one above Co2+
and one below that are difficult to draw. One of these ligands is CN:- (Cyanide if it is on its own in the
body, it is toxic), but yet Vitamin B12 is not toxic, this is because CN:- (Cyanide) is strongly bonded to Co,
and therefore does not separate from it.
Different types of Ligand Substitution:
Type of Ligand Substitution
[Co(H2O)6]2+ + 6NH3 [Co(NH3)6]2+ + 6H2O
[Co(H2O)6]2+ + 4Cl- [CoCl4]2- + 6H2O
[Co(H2O)6]2+ + 3C2O42- [Co(C2O4)3]4- + 6H2O

CHANGE IN
Co-ordination Number

Charge

Notice how [CoCl4]2- is formed, the Cl- is a big ligand, therefore it has coordination number 4 (tetrahedral).
We can ascertain an important fact here; this is that H2O and NH3 are similar in size.

Colourimetry
Ligands are only one of many ways a substance receives colour, for example pure ice is pale blue when
illuminated by white light because ice absorbs frequencies from light spectrum and transmits the colour it
has not absorbed which is blue. But in transition metals, colour is transmitted due to the ligands. A metal
that is not transition metal and is in solution may form a ligand, but not a colour = [Al(OH4)]- is colourless.
How Ligands cause colour in TRANSITION METALS (must be transition metal):
White light is directed at a transition metal complex, the d-orbital electrons absorb certain frequencies from
the visible light spectrum that are equal to hf and move from a ground state to an excited state (i.e. the dorbital splits into 2 levels, an excited state and a ground state). Hence the change in energy of the electrons
is equal to: E = hf (sometimes they write it as E = hv, theres no difference, v is frequency (f)). Frequency
of the wave of light that it absorbs = f, Planks Constant = h. The colour that we see is the colour of that
frequency of light that the electrons did not absorb. Hence its like this:
Although it is important to understand that the electrons
will only absorb the frequency they need to move from
the ground state to the excited state, no MORE, no
LESS. Hence the thing that defines just how far the
distance is between the ground state and the excited
state is the complex ion itself. This difference between
the ground state and excited state is known as the d-d
transition and changes as charge, oxidation state and
ligand change, therefore different complexes have
different colours.

By finding out the frequency of light that gave maximum absorption of energy (we focus on maximum
absorption so as to reduce percentage error); we can determine the concentration of a transition metal
complex.
Hence as you can see, the amount of
maximum absorbance at a certain frequency
tells you the concentration of complex. Hence,
the higher the maximum absorbance is, the
higher the concentration of the transition metal
it is. This is similar to how a spectrophotometer
works. It measures light transmission (opposite
of absorbance). The higher the transmission is,
the lower the concentration. However, all
OTHER products must be not be coloured.
But it is important to remember that ligands are only one of many ways for a chemical to gain colour. But it
is always caused by electrons absorbing a frequency of light and moving to a higher energy level,
sometimes, such as in Fluorescence, electrons absorb ultra-violet light frequency and yet these electrons
give out the energy they have gained in the form VISIBLE LIGHT. How is this possible? This is because
after gaining energy from the frequency of Ultra-Violet light, the electrons get excited and move to a higher
energy level, however, they then de-excite and move back down to a slightly lower energy level, which is in
the visible light range.
A change in any of the following can cause a complex ion to change colour:
a) Ligand (always remember ligands intensify colour, which helps a spectrophotometer a lot)
b) Coordination Number
c) Oxidation State
Overall, the meaning of the colour of transition-metal complexes is that electrons get excited in the d-shell
by ABSORBING ENERGY that is in the VISIBLE LIGHT RANGE.

Lewis Base and Bronstead Lowry Base


There are 6 metals whose aqua complexes you must remember and the reaction of these aqua complexes with three different reagents. These 6 metals are:
Cu2+, Co2+, Fe2+, Fe3+, Cr3+, Al3+
Always remember these General Rules:
Lewis Base = Electron Pair Donor = Ligand Substitution
Bronstead Lowry Base = Proton (usually H+) Acceptor = Acidity Reaction = Hydrated Hydroxide
If it has a [ ] around the complex, it is a solution, if it does not have a [ ], then it is a precipitate.
Any mention of the word AQUEOUS (in water), should automatically tell you that the aqua complex for that metal is present as metals form complex ions (make
dative covalent bonds) with water as soon as they fall into water. Even if it says aqueous Cobalt Sulphate, it will still be [Cu(H2O)]2+. Do NOT write CoSO4.
In these reactions, when we are making a hydrated hydroxide, we must ensure that the hydrated hydroxide has charge 0. Hence when a 3+ such as Fe3+ ion reacts
with a 2- Bronstead Lowry Base such as CO32-, we must ensure that 2Fe3+ reacts with 3CO32-. This will make a 0 charge hydrated hydroxide. Think about it, a
Bronstead Lowry Base accepts protons, hence 3 x (-2) = -6, therefore CO32- has 6 extra electrons (-), however 2 x (+3) = +6, therefore Fe3+ has 6 extra protons (+),
hence the CO32- accepts the 6 protons, making the overall charge zero and creating a hydrating hydroxide.
Polarisation: It is the distortion of positive charge by a negative charge. Hence a small negative ion is more polarising than a larger negative ion. It is the size to
charge ratio, i.e. something that is very small but has a high charge is very polarising (has a very high charge density). This strengthens lattices but in
transition metals it weakens the complex. This means that the compound becomes weaker. It is through polarisation that we can explain that M3+ ions are
more acidic than M2+ ions. HOW?
Well, if we added Fe3+ ions and Fe2+ ions to water, we would get the complexes [Fe(H2O)6]3+ and [Fe(H2O)6]2+. However, when added to water the Fe3+
distorts the H2O bounds surrounding it as does Fe2+. This is because the Fe3+ and Fe2+ are small ions with a charge greater than +1.
In the Fe2+, the ligands around it (H2O) are being squeezed a little around it, hence
M2+ ions such as Fe2+ are a little polarising and when added to water the
distorted bond between O-H breaks and a H+ is released, this H+ does not sit
around, it attaches itself via a co ordinate bond to the H2O of water and forms
H3O+. Hence the H3O+ is the actual way of writing H+. Hence H+ is an acid and
therefore M2+ ions when dissolved in water are slightly acidic.
(pH =
3.5-4.5)
In the Fe3+, the ligands around it (H2O) are being squeezed A LOT around it, hence
M3+ ions such as Fe3+ are a VERY polarising and when added to water the
EXTREMELY DISTORTED bond between O-H breaks and a H+ is released, this
H+ does not sit around, it attaches itself via a co ordinate bond to the H2O of
water and forms H3O+. Hence the H3O+ is the actual way of writing H+. Hence H+
is an acid and therefore M3+ ions when dissolved in water are VERY acidic due
to high polarisation producing higher concentration of H3O+. (pH = 3.5-4.5)
NOTE: Fe3+ and Fe2+ were just examples. All M2+ and M3+ will follow the same procedure, for example Cr3+/ [Cr(H2O)6]3+ is also highly acidic for the above reasons.
So overall why are M3+ ions more acidic than M2+ ions?
M3+ ions are smaller and are therefore more polarising and therefore more O-H bonds are broken, making more H+.
But always remember, in lattices, a high charge density strengthen the lattice, such as Sodium Chloride (Na+) being weaker than Aluminium Chloride (Al3+).

As a general rule: remember H+ is acid, hence if a substance is added to water and it gives you H+ as a product, then it is an acid.
remember OH- is alkali, hence if a substance is added to water and it gives you OH- as a product, then it is an alkali.
Always remember, complexes without charge such as hydrated hydroxides are insoluble in water.
The idea is that add OH- (alkali) to a metal aqua complex such as adding 2OH- [Fe(H2O)]2+ and you will get a hydrated hydroxide as the 2OH- will take one H+ each
resulting in: Fe(H2O)4(OH)2, now if we add 2H3O+ (acid) to this Fe(H2O)4(OH)2 it will go back to [Fe(H2O)]2+ as the 2H3O+ will give back a H+ each to Fe(H2O)4(OH)2.
Hence hydrated hydroxides are bases. However Al and Cr are amphoteric, this means that their hydrated hydroxide reacts with acid (as all others do) and bases too.
If the hydrated hydroxide Al(H2O)3(OH)3 is reacted with a base again, we would get [Al(OH)4]- (in exam they may present this as [Al(OH)6]3- and [Cr(OH)6]3-.
Our first reagent: NaOH (Sodium Hydroxide); so we add our metal ion into water and this forms the aqua complex shown in the first box below, then we add NaOH
into the water and this reaction takes place: NaOH + H2O Na+ + OH- , hence it is fully ionised and we get a strong concentration (amount) of OH- ions and hence
these ions form the following complexes with the Aqua Complexes.
Complex
[Cu(H2O)6]2+
Blue
Octahedral
[Co(H2O)6]2+
Pink
Octahedral
[Fe(H2O)6]2+
Green
Octahedral
[Fe(H2O)6]3+
Orange/Violet
Octahedral
[Cr(H2O)6]3+
Green (Ruby)
Octahedral
[Al(H2O)6]3+
Colourless
Octahedral

pH
6.5

6.5

6.5

3.5 to 4.5

3.5 to 4.5

3.5 to 4.5

Few Drops of Sodium Hydroxide (OH-)


Cu(H2O)4(OH)2 Acidity Reaction (Bronstead Lowry Base)
Pale Blue precipitate (Octahedral)
[Cu(H2O)6]2+ + 2OH- Cu(H2O)4(OH)2 + 2H2O
Co(H2O)4(OH)2 Acidity Reaction (Bronstead Lowry Base)
Pink/Blue precipitate (Octahedral)
[Co(H2O)6]2+ + 2OH- Co(H2O)4(OH)2 + 2H2O
Fe(H2O)4(OH)2 Acidity Reaction (Bronstead Lowry Base)
Green precipitate (Octahedral)
[Fe(H2O)6]2+ + 2OH- Fe(H2O)4(OH)2 + 2H2O
Fe(H2O)3(OH)3 Acidity Reaction (Bronstead Lowry Base)
Orange/Brown precipitate (Octahedral)
[Fe(H2O)6]3+ + 3OH- Fe(H2O)3(OH)3 + 3H2O
Cr(H2O)3(OH)3 Acidity Reaction (Bronstead Lowry Base)
Green/Grey precipitate (Octahedral)
[Cr(H2O)6]3+ + 3OH- Cr(H2O)3(OH)3 + 3H2O
Al(H2O)3(OH)3 Acidity Reaction (Bronstead Lowry Base)
White precipitate (Octahedral)
[Al(H2O)6]3+ + 3OH- Al(H2O)3(OH)3 + 3H2O

Excess Sodium Hydroxide (OH-)


NO FURTHER CHANGE SAME PRODUCTS

NO FURTHER CHANGE SAME PRODUCTS


NO FURTHER CHANGE SAME PRODUCTS
But when left standing, it is oxidised (loses electrons) by air to
Fe3+, and therefore turns dark brown.
NO FURTHER CHANGE SAME PRODUCTS
[Cr(OH)4]- Acidity Reaction (Lewis Base)
Green Solution (Tetrahedral because OH- is a big ligand)
Cr(H2O)3(OH)3 + OH- [Cr(OH)4]- + 3H2O
[Al(OH)4]- Acidity Reaction (Lewis Base)
Colourless Solution (Tetrahedral because OH- is a big ligand)
Al(H2O)3(OH)3 + OH- [Al(OH)4]- + 3H2O

Every time a precipitate becomes a solution, we say that it is because it dissolved in that reagent, for example Al(H2O)3(OH)3 becomes [Al(OH)4]- because it
DISSOLVED in excess Sodium Hydroxide

N.B.

Our second reagent: NH3 (Ammonia); so we add our metal ion into water and this forms the aqua complex shown in the first box below, then we add NH3 into the
water and this reaction takes place: NH3 + H2O NH4+ + OH-. Hence this tells us that as OH- is produced, the same reactions will occur when a few drops are added
to the solution of water containing metal aqua complexes, so again with the OH- acting as a Bronstead Lowry Base (H+ acceptor) but well also get NH4+ as each NH3
molecule accepts a proton (H+) and becomes NH4+. Except, the difference, is that when excess NH3 is added, the NH3 begins to react with the complexes acting as a
Lewis Base and causes Ligand Substitution. Also notice that Aluminium now has no difference when excess reagent is added, this is because NH3 produces a low
concentration of OH- ions in comparison to NaOH, and the evidence for this is that this reaction has a , whereas NaOH has . (Any reaction with goes to
completion which is an advantage; any reaction with does not go to completion which is not advantageous.
Complex
[Cu(H2O)6]2+
Blue
Octahedral

pH
6.5

Few Drops of Ammonia (NH3)


Cu(H2O)4(OH)2 Acidity Reaction (Bronstead Lowry Base)
Pale Blue precipitate (Octahedral)
[Cu(H2O)6]2+ + 2NH3 Cu(H2O)4(OH)2 + 2NH4+

Excess Ammonia (NH3)


[Cu(H2O)2(NH3)4] Ligand Substitution (Lewis Base) as you
can see, not complete ligand substitution this ones a bit weird.
Deep Blue Solution (Octahedral)
Cu(H2O)4(OH)2 + 4NH3 [Cu(H2O)2(NH3)4]2+ + 2H2O + 2OH[Co(NH3)6]2+ Ligand Substitution (Lewis Base)
Straw/Yellow solution (Octahedral)
Co(H2O)4(OH)2 + 6NH3 [Co(NH3)6]2+ + 4H2O + 2OH2+

[Co(H2O)6]2+
Co(H2O)4(OH)2 Acidity Reaction (Bronstead Lowry Base)
Pink
6.5
Pink/Blue precipitate (Octahedral)
Octahedral
[Co(H2O)6]2+ + 2NH3 Co(H2O)4(OH)2 + 2NH4+
2+
[Fe(H2O)6]
Fe(H2O)4(OH)2 Acidity Reaction (Bronstead Lowry Base)
Green
6.5
Green precipitate (Octahedral)
NO FURTHER CHANGE SAME PRODUCTS
2+
+
Octahedral
[Fe(H2O)6] + 2NH3 Fe(H2O)4(OH)2 + 2NH4
[Fe(H2O)6]3+
Fe(H2O)3(OH)3 Acidity Reaction (Bronstead Lowry Base)
Orange/Violet 3.5 to 4.5 Orange/Brown precipitate (Octahedral)
NO FURTHER CHANGE SAME PRODUCTS
Octahedral
[Fe(H2O)6]3+ + 3NH3 Fe(H2O)3(OH)3 + 3NH4+
[Cr(H2O)6]3+
Cr(H2O)3(OH)3 Acidity Reaction (Bronstead Lowry Base)
[Cr(NH3)6]3+ Ligand Substitution (Lewis Base)
Green (Ruby) 3.5 to 4.5 Green/Grey precipitate (Octahedral)
Purple SLOWLY (Octahedral)
3+
+
Octahedral
[Cr(H2O)6] + 3NH3 Cr(H2O)3(OH)3 + 3NH4
Cr(H2O)3(OH)3 + 6NH3 [Cr(NH3)6]3+ + 3H2O + 3OH3+
[Al(H2O)6]
Al(H2O)3(OH)3 Acidity Reaction (Bronstead Lowry Base)
Colourless
3.5 to 4.5 White precipitate (Octahedral)
NO FURTHER CHANGE SAME PRODUCTS
Octahedral
[Al(H2O)6]3+ + 3NH3 Al(H2O)3(OH)3 + 3NH4+
Once the [Co(NH3)6]2+ is formed, when left on standing it gets oxidised (loses electron) and turns to [Co(NH3)6]3+ which is brown. The Oxidising agent (gains electron)
is obviously O2 (oxygen).
This is how it happens:
[Co(NH3)6]2+ [Co(NH3)6]3+ + e(x4)
4e- + O2 + 4H+ 2H2O
(x1)
OVERALL EQUATION: 4[Co(NH3)6]2+ + O2 + 4H+ [Co(NH3)6]3+ + 2H2O
However this reaction took place in alkaline solution, (can you not see when we put NH3 in water you get OH- and OH- is alkali), therefore we should have no H+, but
instead OH-. So we do this be putting the same amount of OH- as there are H+ on the opposite side of the H+
Hence: 4[Co(NH3)6]2+ + O2 [Co(NH3)6]3+ + 2H2O + 4OHThen balance by adding H2O molecules wherever necessary; 4[Co(NH3)6]2+ + O2 + 4H2O [Co(NH3)6]3+ + 2H2O + 4OHThen by cancelling the H2O molecules in the product and H2O molecules in reactant we get: 4[Co(NH3)6]2+ + O2 + 2H2O [Co(NH3)6]3+ + 4OHAlso remember that this [Co(NH3)6]3+ is a very powerful oxidising agent and can take electrons very easily, for example it will easily turn 2I- to I2 and become Co2+
again. Ironically by adding H+ to [Co(NH3)6]3+ which will turn it into [Co(H2O)6]3+, and as mentioned this is a powerful oxidising agent and will turn back to [Co(H2O)]2+.

Our third reagent: Na2CO3; so we add our metal ion into water and this forms the aqua complex shown in the first box below, then we add Na2CO3 into the water and
this reaction takes place: CO32- + H2O HCO3- + OH- (dont think where did the Na2 go? remember its an ionic compound, add it to water and it fully ionises). Hence
this tells us that as OH- is produced, the same reactions will occur when a few drops are added to the solution of water containing metal aqua complexes, so again
with the OH- acting as a Bronstead Lowry Base (H+ acceptor) but well also get HCO3- as each CO32- molecule accepts a proton (H+) and becomes HCO3-.
However, a more major product is made in these reactions that involve a 2+ metal ion, a metal carbonate. This is because the 2+ metal ions react with the CO 32- to
make MCO3. This does happen with 3+ metal ions, this is because in acidic conditions, CO32- becomes CO2, and as we earlier mentioned 3+ metal ions are HIGHLY
ACIDIC due to being very polarising.
Complex
[Cu(H2O)6]2+
Blue
Octahedral

pH

Few Drops of Sodium Carbonate


Excess Sodium Carbonate
Cu(H2O)4(OH)2 Acidity Reaction (Bronstead Lowry Base)
6.5
Pale green precipitate, this is the CuCO3
NO FURTHER CHANGE SAME PRODUCTS
2+
2[Cu(H2O)6] + 2CO3 Cu(H2O)4(OH)2 + 2HCO3
Cu2+ + CO32- CuCO3 = MAJOR PRODUCT
2+
[Co(H2O)6]
Co(H2O)4(OH)2 Acidity Reaction (Bronstead Lowry Base)
Pink
6.5
Purple precipitate, this is the CoCO3
NO FURTHER CHANGE SAME PRODUCTS
Octahedral
[Co(H2O)6]2+ + 2CO32- Co(H2O)4(OH)2 + 2HCO3Co2+ + CO32- CoCO3 = MAJOR PRODUCT
2+
[Fe(H2O)6]
Fe(H2O)4(OH)2 Acidity Reaction (Bronstead Lowry Base)
Green
6.5
Green precipitate, this is the FeCO3
NO FURTHER CHANGE SAME PRODUCTS
Octahedral
[Fe(H2O)6]2+ + 2CO32- Fe(H2O)4(OH)2 + 2HCO3Fe2+ + CO32- FeCO3 = MAJOR PRODUCT
3+
[Fe(H2O)6]
Fe(H2O)3(OH)3 Acidity Reaction (Bronstead Lowry Base)
Orange/Violet 3.5 to 4.5 Orange/Brown precipitate and fizzing (CO2)
NO FURTHER CHANGE SAME PRODUCTS
3+
2Octahedral
2[Fe(H2O)6] + 3CO3 2Fe(H2O)3(OH)3 + 3CO2 +3H2O
[Cr(H2O)6]3+
Cr(H2O)3(OH)3 Acidity Reaction (Bronstead Lowry Base)
NO FURTHER CHANGE SAME PRODUCTS
Green (Ruby) 3.5 to 4.5 Green/Grey precipitate and fizzing (CO2)
But if you added some NaOH, it can become
Octahedral
2[Cr(H2O)6]3+ + 3CO32- 2Cr(H2O)3(OH)3 + 3CO2 + 3H2O
3+
[Al(H2O)6]
Al(H2O)3(OH)3 Acidity Reaction (Bronstead Lowry Base)
Colourless
3.5 to 4.5 White precipitate and fizzing (CO2)
NO FURTHER CHANGE SAME PRODUCTS
N.B. Octahedral
3+
22[Al(H2O)6] + 3CO3 2Al(H2O)3(OH)3 + 3CO2 + 3H2O
Always remember that in the examination they may give you a different reagent but tell you that it reacts just like one of the above reagents, hence you will use the
same method as you would for the above reagent, i.e. same type of products and observations, etc.
We can use these laws and apply it to metal extraction of Cu from Cu2+ using scrap Fe. Cu2+(aq) + Fe Cu + Fe2+(aq), this is better than extraction of Cu from CuO using
CO (Carbon Monoxide. WHY? There is a low energy requirement, CO2 harmful gas not produced and scrap iron is cheap.
N.B. In all these reactions we have used transition metal aqua complexes as [M(H2O)6]2+/3+, whereas really it should really be [M(OH2)6]2+/3+ because remember, it is
the Oxygen that forms a coordinate bond to the metal, not the Hydrogen.
There is one more reagent: HCl, but we only need to know it for two transition metals: Co2+, Cu2+
[Cu(H2O)6]2+ + 4Cl- [CuCl4]2- + 6H2O
[Co(H2O)6]2+ + 4Cl- [CoCl4]2- + 6H2O

Catalysts
Transition metals can also act as catalysts; this is due to the fact that they can change their oxidation states.
This is different from other blocks such as the S block that have only one oxidation state.
They act as catalyst intermediates. They speed up the reaction but have no effect on the position of the
equilibrium, this is because forward and backward rate changes by the same amount, hence concentration of
reactants and products remain constant and therefore yield does not change. These catalysts are made
more efficient by increasing their surface area; therefore they are placed over a coated mesh or made into a
powder or placed on a ceramic support, doing this also reduces the cost of the catalyst. ONLY transition
metals can be catalysts.
A + catalyst Y + reactive intermediate
Reactive intermediate + B catalyst + Z
A+BY+Z
Homogenous Catalyst is when the catalyst is in the same phase (solid, liquid, gas) as the reactants. They
form an intermediate.
EXAMPLE 1: Catalyst: Fe3+(aq)
I-(aq) + S2O82-(aq) has very high activation energy; this is because they are both negatively charged, therefore
repulsion, but when they do react, the products are I2 and 2SO42- . Hence we use Fe3+ as an intermediate and
this lowers the activation energy
1) 2Fe3+ + 2I- 2Fe2+ + I2
2) 2Fe2+ + S2O82- 2Fe3+ + 2SO422I- + S2O82- I2 + 2SO42P.S. We can also use Fe2+ as the catalyst and react with S2O82- first, hence equation 1 and 2 can occur in any
order. The fact that equation 1 and 2 can occur in any order is evidence that Fe2+ and Fe3+ are equally
effective as the catalyst here.
EXAMPLE 2: Catalyst: Mn2+
MnO4-(aq) + C2O42- has very high activation energy; this is because they are both negatively charged, therefore
repulsion, but when they do react, the products are CO2 and Mn2+. Hence we use a Mn2+(aq) catalyst as then
activation energy would be low as a positively charged ion would be reacting with a negatively charged ion.
But Mn2+(aq) is also a products of the reaction, therefore autocatalysis takes place where the product of the
reaction was the catalyst for the reaction.
HENCE THE REACTION THAT TAKES PLACE IS:
1) 8H+ + 5e- + MnO4- Mn2+ + 4H2O (x2)
2) C2O42- 2CO2 + 2e(x5)
16H+ + 2MnO4- + 5C2O42- 10CO2 + 2Mn2+ + 8H2O
But the real reaction that has happened with the catalyst is:
1) 4Mn2+ + 8H+ + MnO4- 5Mn3+ + 4H2O
2) 2Mn3+ + C2O42- 2CO2 + 2Mn2+
Hence MnO4- is purple coloured, so we can track its progress in becoming Mn2+ (colourless) via a
spectrophotometer, this is because all other substances in the above reactions are colourless. Hence our
spectrometer would turn from purple (MnO4-) to colourless (Mn2+). Also remember that a spectrophotometer is
the best method to measure the concentration of coloured ions as it gives you a rapid determination of
concentration and does not interfere with the reaction.

This is a very important graph that appears


frequently in examinations.
Therefore as you can see, the reaction is
slow at first, but then speeds up as more of
Mn2+ is made.

EXAMPLE 3: Catalyst Co2+


SO32- is turned into SO42- in the process of flue-gas desulphurisation. The oxidising agent (takes electrons) is
Oxygen.
HENCE THE REACTION THAT TAKES PLACE:
1) SO32-

Heterogeneous Catalyst is when the catalyst is in a different phase (solid, liquid, gas) to the reactants. Their
catalytic action occurs on the surface. They lower the activation energy by forming bonds between the
molecule and the surface whilst breaking them, hence they make bonds whilst breaking them, balancing out
the enthalpies.
The strength of adsorption helps to determine the activity of the catalyst. If adsorption (bringing reactants
together at the surface and orientating them) is too weak, the reactants are not brought together at the
surface (e.g. silver).
If adsorption is too strong, products cannot move around the surface and block the active sites, also they
cannot be desorbed from the surface (e.g. tungsten).
EXAMPLE 1: Haber Process; Catalyst: Fe (Iron)
N2(g) + 3H2(g) 2NH3 (g)
H = S = EXAMPLE 2: The Contact Process ; Catalyst: V2O5 (gains electrons/reduced as V has oxidation state +5)
1) V2O5 + SO2 V2O4 + SO3
2) V2O4 + 1/2O2 V2O5
H = S = SO2 + 1/2O2 SO3
The Sulphur Trioxide is converted to Sulphuric Acid
EXAMPLE 3: Making Methanol from CO and H2; Catalyst: Cr2O3
CO + H2 CH3OH
H = S = Sometimes, we use a weak catalyst (such as Silver which is a weak catalyst as reactants are adsorbed very
weakly) even though we know that a more powerful catalyst could be used, this is because the reaction is
very exothermic and using a better catalyst may cause an explosion.
On the surface of the catalyst, there are active sites and particles migrate to and from the active site. If there
is some sort of impurity inside the catalyst, POISON could attach to the active sites irreversibly. To ensure
this does not happen, the catalyst must be purified properly. The poison will reduce the effectiveness of the
catalyst as it attaches to the surface. However Catalyst Poisoning does happen, such as lead in petrol will
poison the Catalytic Converter. This is extremely dangerous as if the Catalytic Converter is not working, then
more harmful gases would be produced by the car.
Just to recap Unit 1, the reaction in the Catalytic Converter is: 2NO + 2CO N2 + 2CO2
The reducing agent in this reaction is CO (Carbon Monoxide). The catalyst is Platinum which is coated over a
mesh.
Usually all sulphur compounds are excellent poisons, sulphur actually poisons the iron catalyst in the Haber
Process, this is why sulphur compounds must be removed from oil/gas before catalytic reactions.
Always remember, adsorption is fuelled by enthalpy, but desorption is fuelled by entropy.

Reactions Involving Changing Valency

The most important reactions you must remember showing the changing of valency for transition metals
involve the reduction (gain electrons) of the transition metals: Chromium and Vanadium.
The reducing agents (lose electrons) are: Zinc (Zn) and Hydrochloric Acid (HCl)/Sulphuric Acid (H2SO4)
For Chromium reduction, it goes like this:
Cr6+ (Cr2O72-/CrO42-) = orange Cr3+ ([Cr(H2O)6]3+) = green Cr2+ = blue
The first reaction:
Cr2O72- + 6e- +14H+ 2Cr3+ + 7H2O
The second reaction:
Cr3+ + e- Cr2+
The Zinc (Zn) and Hydrochloric Acid (HCl) oxidation reaction will be:
Zn Zn2+ + 2eFor Vanadium reduction, it goes like this:
V5+ (VO2+) = yellow V4+ (VO2+) = blue V3+ = green V2+ = violet
The first reaction:
VO2+ + 2H+ + e- VO2+ + H2O
The second reaction:
VO2+ + e- + 2H+ V3+ + H2O
The third reaction:
V3+ V2+ + eThe Zinc (Zn) and Hydrochloric Acid (HCl) reaction oxidation will be:
Zn Zn2+ + 2eBe wary though, because at times they can ask you to go from V5+ straight to V2+ or from Cr6+ straight to Cr2+.
Now, in the above, the species which had metals in them were all gaining electrons (e.g. Cr3+ to Cr2+).
However, there is one special case that we are required to learn that involves oxidation (lose electrons) of the
transition metals Cr3+ and Co2+ to Cr6+ and Co3+ respectively.
The oxidising agents (gain electrons) will be H2O2 and NaOH
For Chromium oxidation it goes like this:
4H2O + Cr3+ CrO42- + 3e- +8H+
The H2O2 and NaOH will be:
H2O2 + 2e- + 2H+ 2H2O
But remember, that once again, this reaction will be in alkaline conditions, therefore, in the overall reaction,
you must replace the H+ with OH-.
Also remember the following equilibrium:
2CrO42- + 2H+ Cr2O72- + H2O
yellow
orange
Hence in alkaline conditions, you will get CrO42-, and hence you get a yellow colour, but when in acid
conditions, you will get Cr2O72-, and hence you get an orange colour.
For Cobalt oxidation it goes like this:
Co2+ Co3+ +eThe H2O2 and NaOH will be:
H2O2 + 2e- + 2H+ 2H2O

Titrations
The main titrations the examination will ask are (i.e. the questions regarding moles the examination will ask):
1) Fe2+ (after acidification) with Cr2O72- (oxidation number of Cr is +6)
2) Fe2+ (after acidification) with MnO4- (oxidation number of Mn is +7)
Above, we have mentioned that Fe2+ is acidified first, but with MnO4-, the acidification should not be done with
Hydrochloric Acid, this is because MnO4- is a powerful oxidising agent and therefore would oxidise the 2Cl- to
Cl2(aq). The acidification should also not be done with Nitric Acid as NO3- can oxidise Fe2+ to Fe3+.
Always remember in both of these, you should write the half-equations first, this will gain you a mark.
The fact that Fe2+ is acidifies tells us that this reaction takes place in acidic conditions, therefore H+ in
equations.
1) Half-equations of the first reaction:
Fe2+ Fe3+ + eCr2O72- + 6e- +14H+ 2Cr3+ + 7H2O

(x6)
(x1)

Therefore, overall reaction: 6Fe2+ + Cr2O72- +14H+ 2Cr3+ + 7H2O + 6Fe3+


2) Half-equations of the second reaction:
Fe2+ Fe3+ + eMnO4- + 5e- + 8H+ Mn2+ + 4H2O

(x5)
(x1)

Therefore, overall equation reaction: 5Fe2+ + MnO4- + 8H+ Mn2+ + 4H2O Fe3+
But beware as they may at times ask the titrations of Cr2O72-, MnO4- with H2O2 instead of Fe2+. You should
then use the same procedure of using half-equations, but this time involving H2O2.
Now as we know H2O2 can be oxidised (gives electrons) to form Oxygen, and H2O2 can also be reduced
(takes electrons) to form Hydrogen. Here we will have to use the oxidation version as reduction is already
happening to the Cr2O72-, MnO4- (theyre both gaining electrons). Hence, our product will be Oxygen.
The half-equation for H2O2 is:
H2O2 O2 + 2e- + 2H+
Therefore from above we know the half equations for both Cr2O72-, MnO4-. Hence we balance electrons in the
same way that we did for Fe2+.
Remember the following for titrations:
SOLID
Moles=Mass/Mr

SOLUTION

Moles=(Concentration x volume)/1000

GAS
Moles=Volume/24000

Moles= Particles/6.02 1023


Atom Economy: Mr of wanted product/Mr of total product
If atom economy is very low, the company tries to sell the unwanted product to gain financially.
Percentage Yield: (Mass of actual yield/Mass of theoretical yield) 100
Theoretical yield done like this: Mass/Mr=Mass/Mr
Ideal Gas Equation: pV=nRT
P must be in Pa, not KPa
V must be in m3, (if in cm3 multiple by 10-6 or divide by 1000000) (if in dm3 multiply by 10-3 or divide by 1000)
N will be in Mol
R will be 8.31
T will always be in K (Kelvin), if not, add 273 to the oC.
If ever asked for the concentration in g dm-3, work out the concentration in mol dm-3 like normal and then
multiply by the Mr.

A FEW TIPS:

Remember HCl(g) is corrosive


Remember reactions that are highly exothermic are vigorous and therefore could be dangerous
Hydrogen gas is collected with a gas syringe
Remember AgCl is a white precipitate, AgBr is a cream precipitate and AgI is a yellow precipitate.
In every J = m x 4.18 x T equation, remember that when an enthalpy is given it is given per mol, hence
when you attempt to get your J value, work out the moles of the reactant, multiply it by the enthalpy of the
reactant (as enthalpy is KJmol-1), then multiply by 1000 (to get it into Joules (J)).
In the same way remember when it is mentioned that 3.49kJ of heat energy to convert to 1.53g of liquid
water into steam, hence work out enthalpy. Now, first work out the moles of water, then remember that
enthalpy is kJ per mole (kJ moles), therefore now you will do 3.49 moles of liquid water.
Remember simple reactions such as Fe + 2HCl FeCl2 + H2
FeC2O4 Fe3+ + 2CO2 + 3e- can be separated into two equations:
Fe2+ Fe3+ + eC2O42- 2CO2 + 2eRemember, oxidation of alcohols is alcohol aldehyde carboxylic acid
Also aldehydes have a low boiling point and can be distilled readily
In metal extraction, you can only separate it a substance via electrolysis if it is able to conduct electricity, i.e.
if the substance is a molecular covalent structure, you cannot use electrolysis.
Finally, read up on all AS notes, especially metal extraction (unit 2), alcohols (unit 2) and bonding (unit 1)