Chem U5 A2 Edexcel

16.
Redox Equilibria
Electron
flow
Electrochemical cells
Salt bridge
•A cell has two half–cells. copper
•The two half cells have to be connected with a salt electrode
bridge. Zinc
•Simple half cells will consist of a metal (acts an electrode
electrode) and a solution of a compound containing
that metal (eg Cu and CuSO4). 1M
•These two half cells will produce a small voltage if 1M zinc copper
connected into a circuit. (i.e. become a Battery or sulphate sulphate
cell). solution solution
Why does a voltage form? Why use a High resistance

In the cell pictured above voltmeter?
When connected together the zinc half-cell has more of a tendency to The voltmeter needs to be of very
oxidise to the Zn2+ ion and release electrons than the copper half-cell. high resistance to stop the current
(Zn Zn2+ + 2e-) from flowing in the circuit. In this
More electrons will therefore build up on the zinc electrode than the state it is possible to measure the
copper electrode. maximum possible potential
A potential difference is created between the two electrodes. difference (E).
The zinc strip is the negative terminal and the copper strip is the The reactions will not be occurring
positive terminal. because the very high resistance
voltmeter stops the current from
This potential difference is measured with a high resistance voltmeter, flowing.
and is given the symbol E. The E for the above cell is E= +1.1V.
Salt Bridge
The salt bridge is used to connect up the circuit. The free moving ions conduct the charge.
A salt bridge is usually made from a piece of filter paper (or material) soaked in a salt solution, usually
Potassium Nitrate.
The salt should be unreactive with the electrodes and electrode solutions.. E.g. potassium chloride would not
be suitable for copper systems as Chloride ions can form complexes with copper ions.
A wire is not used because the metal wire would set up its own electrode system with the solutions.
What happens if current is allowed to flow?

If the voltmeter is removed and replaced with a bulb or if the circuit is short circuited, a current flows. The
reactions will then occur separately at each electrode. The voltage will fall to zero as the reactants are used up.
The most positive electrode will always undergo reduction.

Cu2+ (aq) + 2e-  Cu(s) (positive as electrons are used up)
The most negative electrode will always undergo oxidation.

Zn(s)  Zn2+ (aq) + 2e- (negative as electrons are given off)
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Cell Diagrams
• The solid vertical line represents the boundary
Electrochemical cells can be represented by a cell diagram:
between phases e.g. solid (electrode) and
solution (electrolyte)
Zn(s) | Zn2+ (aq) | | Cu2+ (aq) | Cu (s) E= +1.1V
•The double line represents the salt bridge
between the two half cells
Most oxidised form is put next to the double line
•the voltage produced is indicated
•the more positive half cell is written on the right
if possible (but this is not essential)
Systems that do not include metals.

If a system does not include a metal that can act as an electrode, then a platinum electrode must be used
and included in the cell diagram. It provides a conducting surface for electron transfer
A platinum electrode is used because it is unreactive and can conduct electricity.
e.g. for Fe2+ (aq)  Fe3+ (aq) + e- there is no If the system contains several species
solid conducting surface, a Pt electrode must be e.g. MnO4- + 8H+ + 5e- Mn2+ + 4H2O
used. then in the cell diagram the balancing numbers, H+
ions and H2O can be left out.
The cell diagram is drawn as:
| | Fe3+ (aq), Fe2+ (aq) |Pt | |MnO4- , Mn2+ |Pt
or if on left hand side
Still with more oxidised form near double line Pt | Mn2+ , MnO4- | |
A comma separates the oxidised from the reduced
species.
If a half equation has several physical states then the solid vertical
line should be used between each different state boundary.
4e- + 2H2O (l) +O2 (g) 4OH- (aq) | | O2 | H2O, OH- | Pt
Cl2 (g) + 2e-  2Cl- (aq) | | Cl2 | Cl- | Pt
As the phase line also separates the oxidised and

reduced terms a comma is not necessary here.
Measuring the electrode potential of a cell
• It is not possible to measure the absolute potential of a half electrode on its own. It is
only possible to measure the potential difference between two electrodes.
• To measure it, it has to be connected to another half-cell of known potential, and the
potential difference between the two half-cells measured.
• by convention we can assign a relative potential to each electrode by linking it to a
reference electrode (hydrogen electrode), which is given a potential of zero Volts
The standard hydrogen electrode
The potential of all electrodes are measured by comparing

their potential to that of the standard hydrogen electrode. Metal
Salt bridge
electrode
H2 gas at KNO3 (aq)
e.g. Fe
The standard hydrogen electrode (SHE) is assigned the 100kPa
potential of 0 volts.
Pt electrode
The hydrogen electrode equilibrium is:
H2 (g) 2H+ (aq) + 2e-
1M HCl
In a cell diagram the hydrogen electrode is
represented by: Pt |H2 (g) | H+ (aq)
Solution containing metal
ions (e.g. Fe2+) at 1 mol
Components of a standard hydrogen electrode. dm-3 concentration
To make the electrode a standard reference electrode
some conditions apply: Because the equilibrium does not include a
1. Hydrogen gas at pressure of 100 kPa conducting metal surface a platinum wire is used
2. Solution containing the hydrogen ion at 1.00 mol dm-3 which is coated in finely divided platinum. (The
(solution is usually 1M HCl) platinum black acts as a catalyst, because it is
3. Temperature at 298K porous and can absorb the hydrogen gas.)
Secondary standards
Standard conditions are needed because
The Standard Hydrogen Electrode is difficult to use, so often a
the position of the redox equilibrium will
different standard is used which is easier to use.
change with conditions.
These other standards are themselves calibrated against the SHE.
For example, in the equilibrium:
This is known as using a secondary standard - i.e. a standard
Mn+(aq) + n e- M(s)
electrode that has been calibrated against the primary standard.
The common ones are:
an increase in the concentration of Mn+
silver / silver chloride E = +0.22 V
would move the equilibrium to the right,
calomel electrode E = +0.27 V
so making the potential more positive.
Standard Electrode Potentials E

The standard conditions are :
When an electrode system is connected to the •All ion solutions at 1 1.00 mol dm-3
hydrogen electrode system, and standard conditions •temperature 298K
apply the potential difference measured is called the •gases at 100kPa pressure
standard electrode potential, •No current flowing
Salt bridge
Standard electrode potentials are found in KNO3 (aq)
data books and are quoted as H2 gas at
100kPa
Li+(aq) | Li (s) E= -3.03V Pt electrode
more oxidised form on left
They may also be quoted as half Pt electrode

equations
Li+ (aq) + e- Li (s) E= -3.03V
but again the more oxidised form is on 1M HCl
the left
Pt|H2|H+||Fe3+,Fe2+|Pt 1M Fe2+ and 1M Fe3+
Note: in the electrode system containing two solutions it is

necessary to use a platinum electrode and both solutions must
be of a 1M concentration.
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Calculating the EMF of a cell
In order to calculate the Ecell, we must use ‘standard
Mg(s) | Mg2+ (aq) | | Cu2+ (aq) | Cu (s) E= +1.1V electrode potentials’ for the half cells.
use the equation Ecell= Erhs - Elhs Each half cell has a standard
electrode potential value
For the cell diagram above Mg2+ (aq)| Mg(s) E= -2.37V
Ecell = 0.34 - -2.37 Cu2+ (aq) | Cu (s) E = +0.34V
= + 2.71 V
Using electrode potentials
The most useful application of electrode potentials is to show

the direction of spontaneous change for redox reactions
The easiest way to use electrode potentials is as follows:
For any two half equations The more negative half cell will
always oxidise (go backwards)
If we want to work out the Ecell
Mg2+ (aq) + 2e-  Mg(s) E= -2.37V that corresponds to this
Cu2+ (aq) + 2e-  Cu (s) E = +0.34V spontaneous change then use
The reaction would be Ecell = Ered – Eox
The more positive half cell will always Mg + Cu2+  Cu + Mg 2+ A spontaneous change will
reduce (go forwards) always have a positive Ecell
The most negative electrode will oxidise and go from right to left
Zn2+(aq) + 2e-  Zn(s) E= - 0.76V
The half equation is therefore Zn(s)  Zn2+ (aq) +2e-
Fe2+(aq) + 2e-  Fe(s) E= -0.44V
Electrons are given off (lost) and travel to positive electrode
To get the full equation of the reaction add the

The more positive electrode will reduce and go from left to
two half reactions together, cancelling out the
right Fe2+ (aq) +2e-  Fe(s)
electrons.
Electrons arrive at this electrode and are absorbed (gained)
Zn + Fe2+  Fe + Zn2+
Using series of standard electrode potentials

Most strong reducing
oxidation agents found here
As more +ve As more -ve

Li+ + e-  Li -3.03V
increasing increasing
Mn2+ + 2e-  Mn -1.19V
tendency for tendency for
species on left to species on right
reduce, and act to oxidise, and
2H+ + 2e-  H2 0V
as oxidising act as reducing
agents agents
Ag+ + e-  Ag +0.8V
F2 + 2e-  2F- +2.87
Most strong oxidising reduction If we want to work out the Ecell from two
agents found here standard electrode potentials then use
Ecell = Ered – Eox
The most powerful reducing agents will be found at the most negative end of the series
on the right (ie the one with the lower oxidation number)
The most powerful oxidising agents will be found at the most positive end of the series on
the left (ie the one with the higher oxidation number)
4
Example 1
Use electrode data to explain why fluorine reacts with water.

Write an equation for the reaction that occurs.
oxidise
O2(g) + 4H+(aq) + 4e– → 2H2O(I) Eo+1.23V
First apply idea that more positive Eo will reduce (go forward)
F2(g) + 2e– → 2F–(aq) Eo +2.87V
and more negative Eo will oxidise (go backwards)
reduce
Explanation to write
As Eo F2/F- > Eo O2/H2O, and Ecell is a positive work out Ecell and quote it as part of your
value of +1.64V, F2 will oxidise H2O to O2 answer
Ecell = Ered - Eox = 2.87-1.23 =1.64V
Equation Remember to cancel out electrons in full equation

2F2(g) + 2H2O(I) → 4F–(aq) + O2(g) + 4H+(aq)
Example 2
Cl2(aq) + 2e– → 2Cl–(aq) Eo+1.36V
Use data from the table to explain why chlorine
2HOCl(aq) + 2H (aq) + 2e → Cl2(aq) + 2H2O(I) Eo+1.64V
+ –
should undergo a redox reaction with water. Write
H2O2(aq) + 2H+(aq) + 2e– → 2H2O(I) Eo +1.77V
an equation for this reaction. + –
O2(g) + 4H (aq) + 4e → 2H2O(I) Eo +1.23V
reduce
First select relevant half equations by considering the Eo
values and applying the idea that more positive Eo will reduce Cl2(aq) + 2e– → 2Cl– (aq) Eo+1.36V
(go forward) and more negative Eo will oxidise (go backwards) O2(g) + 4H (aq) + 4e → 2H2O(I) Eo +1.23V
+ –
oxidise
Explanation to write
Equation
As Eo Cl2/Cl- > Eo O2/H2O, and Ecell is a positive
value of +0.13V, Cl2 will oxidise H2O to O2 2Cl2(g) + 2H2O(I) → 4Cl–(aq) + O2(g) + 4H+(aq)
Example 3
Suggest what reactions occur, if any, when hydrogen gas Fe3+ (aq) + e– → Fe2+ (aq) Eo +0.77V
is bubbled into a solution containing a mixture of iron(II) 2H+(aq) + 2e– → H2(g) Eo 0.00V
and iron(III) ions. Explain your answer. Fe2+ (aq) + 2e– → Fe(s) Eo–0.44V
reduce
First select relevant half equations by considering the Eo
values and applying the idea that more positive Eo will reduce Fe3+ (aq) + e– → Fe2+ (aq) Eo +0.77V
(go forward) and more negative Eo will oxidise (go backwards) 2H+(aq) + 2e– → H2(g) Eo 0.00V
Explanation to write oxidise

Fe3+ will be reduced to Fe2+ by H2 oxidising to H+
Equation
because Eo Fe3+ /Fe2+ > Eo H+/H2 and Ecell is a
positive value of +0.77V 2Fe3+ (aq) + H2(g) → 2Fe2+ (aq) + 2H+(aq)
Example 4 Disproportionation
Use the half-equations to explain in terms of oxidation states what
happens to hydrogen peroxide when it is reduced.
reduce
Explanation to write H2O2(aq) + 2H+(aq) + 2e– → 2H2O(I) Eo+1.77V
O2(g) + 2H+(aq) + 2e– → H2O2(aq) Eo +0.68V
As Eo H2O2/H2O > Eo O2/H2O2 and Ecell is a positive
value of +1.09V , H2O2 disproportionates from -1 oxidise
oxidation state to 0 in O2 and -2 in H2O Equation
2H2O2(aq) → O2 + 2H2O(I)
Disproportionation of copper(I) iodide
Copper(I) iodide when reacting with sulphuric acid will disproportionate to Cu2+ and Cu metal
2Cu+  Cu + Cu2+
Cu+(aq) + e−  Cu(s) Eo = +0.52 V As Eo Cu+/Cu > Eo Cu2+/Cu+ and Ecell has a positive
Cu2+(aq) + e−  Cu+(aq) Eo = +0.15 V value of +0.37V , Cu+ disproportionates from +1
So Eo cell = 0.52 − 0.15 = +0.37 V oxidation state to 0 in Cu and +2 in Cu2+
Ecell is directly proportional to the total entropy change

and to lnK (where K is equilibrium constant)for a reaction
A positive Ecell will lead to a positive total entropy change
Effect of conditions on Cell voltage Ecell
The effects of changing conditions on E cell can be Ecell is a measure of how far from equilibrium the
made by applying le Chatelier’s principle. cell reaction lies. The more positive the Ecell the
more likely the reaction is to occur.
If current is allowed to flow, the cell reaction will occur
and the Ecell will fall to zero as the reaction proceeds
and the reactant concentrations drop.
Zn2+(aq) + 2e-  Zn(s) E= - 0.76V
Effect of concentration on Ecell Fe2+(aq) + 2e-  Fe(s) E= -0.44V
Looking at cell reactions is a straight forward Zn + Fe2+  Fe + Zn2+ E= +0.32

application of le Chatelier. So increasing
Increasing the concentration of Fe2+ and
concentration of ‘reactants’ would increase Ecell and
decreasing the concentration of Zn2+ would
decreasing them would cause Ecell to decrease.
cause Ecell to increase.
Effect of temperature on Ecell
Most cells are exothermic in the spontaneous direction so applying Le Chatelier to a temperature rise to these
would result in a decrease in Ecell because the equilibrium reactions would shift backwards.
If the Ecell positive it indicates a reaction might occur. There is still a possibility, however, that the reaction will
not occur or will occur so slowly that effectively it does not happen.
If the reaction has a high activation energy the reaction will not occur.
Also if the reaction is carried out at non-standard conditions the Ecell using standard conditions may deviate
Fuel cell
A fuel cell uses the energy from the reaction of
a fuel with oxygen to create a voltage
Hydrogen Fuel cell (potassium hydroxide electrolyte)
4e- + 4H2O  2H2 +4OH- E=-0.83V H2 O2

4e- + 2H2O +O2  4OH- E=+0.4V from from air
fuel
Overall reaction 2H2 + O2  2H2O E=1.23V
2e- + 2H+ H2 E=0V In acidic conditions these are the

electrode potentials. The Ecell is H2O
4e- + 4H+ +O2  2H2O E=1.23V
the same as alkaline conditions as +heat
Overall 2H2 + O2  2H2O E=1.23V the overall equation is the same
Using standard conditions: The rate is too
slow to produce an appreciable current.
Fuel cells will maintain a constant voltage over time as they are Higher temperatures are therefore used to
continuously fed with fresh O2 and H2 so maintaining constant increase rate but the reaction is exothermic
so by applying le chatelier would mean the
concentration of reactants. This differs from ordinary cells where
emf falls.
the voltage drops over time as the reactant concentrations drop A higher pressure can help counteract this
Advantages of Fuel cells over conventional Limitations of hydrogen fuel cells

petrol or diesel-powered vehicles (i) expensive
(i) less pollution and less CO2. (Pure hydrogen (ii) storing and transporting hydrogen, in terms of
emits only water whilst hydrogen-rich fuels safety, feasibility of a pressurised liquid and a limited
produce only small amounts of air pollutants and life cycle of a solid ‘adsorber’ or ‘absorber’
CO2). (iii) limited lifetime (requiring regular replacement and
(ii) greater efficiency; disposal) and high production costs,
(iv) use of toxic chemicals in their production
Hydrogen is readily available by the

Hydrogen can be stored in fuel cells
electrolysis of water, but this is
(i) as a liquid under pressure,
expensive. To be a green fuel the
(ii) adsorbed on the surface of a solid material,
electricity needed would need to be
(iii) absorbed within a solid material;
produced from renewable resources
Ethanol fuel cells
Ethanol fuel cells have also been developed. Compared to

Equation that occurs at oxygen electrode
hydrogen fuel cells they have certain advantages including.
4e- + 4H+ +O2  2H2O E=1.23V
Ethanol can be made from renewable sources in a carbon
neutral way Equation that occurs at ethanol electrode
Raw materials to produce ethanol by fermentation are C2H5OH + 3H2O → 2CO2 + 12H+ + 12e-
abundant
Ethanol is less explosive and easier to store than hydrogen. Overall equation
New petrol stations would not be required as ethanol is a C2H5OH + 3O2 → 2CO2 + 3H2O
liquid fuel.
Methanol can also be used in fuel cells
Redox titrations
Manganate redox titration
The purple colour of manganate can make it
The redox titration between Fe2+ with MnO4– (purple) is a very
difficult to see the bottom of meniscus in
common exercise. This titration is self indicating because of the
the burette
significant colour change from reactant to product
If the manganate is in the burette then the
MnO4-(aq) + 8H+ (aq) + 5Fe2+ (aq)  Mn2+ (aq) + 4H2O (l) + 5Fe3+ (aq) end point of the titration will be the first
Purple colourless permanent pink colour
Colourless  purple
Choosing correct acid for manganate titrations.
The acid is needed to supply the 8H+ ions. Some acids are not suitable as they set up alternative redox
reactions and hence make the titration readings inaccurate.
Only use dilute sulphuric acid for manganate titration
Insufficient volumes of sulphuric acid will mean the solution is not acidic enough and MnO2 will be produced
instead of Mn2+
MnO4-(aq) + 4H+(aq) + 3e-  MnO2 (s) + 2H2O
The brown MnO2 will mask the colour change and lead to a greater (inaccurate) volume of Manganate being
used in the titration
Using a weak acid like ethanoic acid would have the same effect as it cannot supply the large amount of
hydrogen ions needed (8H+)
It cannot be conc HCl as the Cl- ions would be oxidised to Cl2 by MnO4- as the Eo MnO4-/Mn2+ > Eo Cl2/Cl-
MnO4-(aq) + 8H+(aq) + 5e–  Mn2+ (aq) + 4H2O(l) E+1.51V
Cl2(aq) +2e–  2Cl–(aq) E +1.36V
This would lead to a greater volume of manganate being used and poisonous Cl2 being produced
It cannot be nitric acid as it is an oxidising agent. It oxidises Fe2+ to Fe3+ as Eo NO3-/HNO2> Eo Fe3+/Fe2+
NO3- (aq) + 3H+(aq) + 2e–  HNO2(aq) + H2O(l) Eo +0.94V
Fe3+ (aq)+e–  Fe2+ (aq) Eo +0.77 V
This would lead to a smaller volume of manganate being used
be able to perform calculations for these titrations and for

others when the reductant and its oxidation product are given.
Manganate titration example Step1 : find moles of KMnO4
A 2.41g nail made from an alloy containing iron is moles = conc x vol
dissolved in 100cm3 acid. The solution formed 0.02 x 9.8/1000
contains Fe(II) ions. = 1.96x10-4 mol
10cm3 portions of this solution are titrated with Step 2 : using balanced equation find moles Fe 2+ in 10cm3
potassium manganate (VII) solution of 0.02M. = moles of KMnO4 x 5
9.80cm3 of KMnO4 were needed to react with the
= 9.8x10-4 mol
solution containing the iron.
Step 3 : find moles Fe2+ in 100cm3
What is the percentage of Iron by mass in the nail?
= 9.8x10-4 mol x 10
MnO4-(aq) + 8H+(aq) + 5Fe2+  Mn2+(aq) + 4H2O + 5Fe3+ = 9.8x10-3 mol
Step 4 : find mass of Fe in 9.8x10 -3 mol
mass= moles x RAM = 9.8x10-3 x 55.8 = 0.547g
Step 5 ; find % mass
%mass = 0.547/2.41 x100
= 22.6%
8
Other useful manganate titrations
With hydrogen peroxide
Ox H2O2  O2 + 2H+ + 2e-
Red MnO4-(aq) + 8H+(aq) + 5e-  Mn2+ (aq) + 4H2O The reaction between MnO4- and
Overall 2MnO4-(aq) + 6H+(aq) + 5H2O2  5O2 + 2Mn2+ (aq) + 8H2O C2O42- is slow to begin with (as
With ethanedioate the reaction is between two
negative ions) To do as a titration
Ox C2O42-  2CO2 + 2e-
the conical flask can be heated to
Red MnO4-(aq) + 8H+(aq) + 5e-  Mn2+ (aq) + 4H2O
60o C to speed up the initial
Overall 2MnO4-(aq) + 16H+(aq) + 5C2O42-(aq)  10CO2(g) + 2Mn2+(aq) + 8H2O(l)
reaction.
With Iron (II) ethanedioate both the Fe2+ and the C2O42- react with the MnO4-
1MnO4- reacts with 5Fe2+ and 2 MnO4- reacts with 5C2O42-
MnO4-(aq) + 8H+(aq) + 5Fe2+  Mn2+ (aq) + 4H2O + 5Fe3+

2MnO4-(aq) + 16H+(aq) + 5C2O42-  10CO2 + 2Mn2+ (aq) + 8H2O
So overall
3MnO4-(aq) + 24H+(aq) + 5FeC2O4  10CO2 + 3Mn2+ (aq) + 5Fe3+ + 12H2O
So overall the ratio is 3 MnO4- to 5 FeC2O4
Step1 : find moles of KMnO4

A 1.412 g sample of impure FeC2O4.2H2O
moles = conc x vol
was dissolved in an excess of dilute
sulphuric acid and made up to 250 cm3 of 0.0189 x 23.45/1000
solution. 25.0 cm3 of this solution = 4.43x10-4 mol
decolourised 23.45 cm3 of a 0.0189 mol Step 2 : using balanced equation find moles FeC 2O4.2H2O in 25cm3
dm–3 solution of potassium = moles of KMnO4 x 5/3 (see above for ratio)
manganate(VII). = 7.39x10-4 mol
What is the percentage by mass of Step 3 : find moles FeC2O4.2H2O in 250 cm3
FeC2O4.2H2O in the original sample? = 7.39x10-4 mol x 10
= 7.39x10-3 mol
Step 4 : find mass of FeC2O4.2H2O in 7.39x10-3 mol
mass= moles x Mr = 7.39x10-3 x 179.8 = 1.33g
Step 5 ; find % mass
%mass = 1.33/1.412 x100
= 94.1%
Thiosulphate redox titration A starch indicator is added near the end

The redox titration between I2 and thiosulphate S2O32- is a point when the iodine fades a pale yellow
common exercise. to emphasise it.
With starch added the colour change is
2S2O32-(aq) + I2 (aq)  2I- (aq) + S4O62-(aq) from blue/black to colourless
yellow/brown sol colourless sol
The starch should not be added until nearly all the iodine has
reacted because the blue complex formed with high
concentrations of iodine is insoluble and does not re-dissolve as
more thiosulfate is added
Uncertainty
Readings and Measurements
Readings Measurements The uncertainty of a reading (one judgement) is at

the values found from a the values taken as the least ±0.5 of the smallest scale reading.
single judgement when difference between the The uncertainty of a measurement (two
using a piece of equipment judgements of two judgements) is at least ±1 of the smallest scale
values (e.g. using a reading.
burette in a titration)
Calculating Apparatus Uncertainties

Each type of apparatus has a sensitivity uncertainty To decrease the apparatus uncertainties
you can either decrease the sensitivity
•balance  0.001 g uncertainty by using apparatus with a
•volumetric flask  0.1 cm3 greater resolution (finer scale divisions )
•25 cm3 pipette  0.1 cm3 or you can increase the size of the
•burette  0.05 cm3 measurement made.
Calculate the percentage error for each piece of equipment used by Uncertainty of a measurement using
a burette. If the burette used in the
% uncertainty =  uncertainty x 100 titration had an uncertainty for each
Measurement made on apparatus reading of +/– 0.05 cm3 then during a
titration two readings would be taken
e.g. for pipette so the uncertainty on the titre volume
% uncertainty = 0.05/ 25 x100 would be +/– 0.10 cm3 .
To calculate the maximum percentage apparatus uncertainty in the

final result add all the individual equipment uncertainties together.
Reducing uncertainties in a titration If looking at a series of measurements

in an investigation the experiments
Replacing measuring cylinders with pipettes or burettes which have with the smallest readings will have
lower apparatus uncertainty will lower the error the highest experimental uncertainties.
To reduce the uncertainty in a burette reading it is necessary to

make the titre a larger volume. This could be done by: increasing
the volume and concentration of the substance in the conical flask
or by decreasing the concentration of the substance in the burette.
Reducing uncertainties in measuring mass

Using a more accurate balance or a larger mass will
reduce the uncertainty in weighing a solid
Weighing sample before and after addition and then
calculating difference will ensure a more accurate
measurement of the mass added.
If the %uncertainty due to the apparatus <

percentage difference between the actual value
Calculating the percentage difference between the
and the calculated value then there is a
actual value and the calculated value
discrepancy in the result due to other errors.
If we calculated an Mr of 203 and the real value is 214,
then the calculation is as follows: If the %uncertainty due to the apparatus >
Calculate difference 214-203 = 11 percentage difference between the actual value
% = 11/214 x100 and the calculated value then there is no
=5.41% discrepancy and all errors in the results can be
explained by the sensitivity of the equipment.
17. Transition Metals
Sc 1s22s22p63s23p6 4s23d1 Sc 3+ [Ar] 4s03d0
General properties of transition metals
Ti 1s22s22p63s23p6 4s23d2 Ti 3+ [Ar] 4s03d1
V 1s22s22p63s23p6 4s23d3 V 3+ [Ar] 4s03d2
transition metal characteristics of elements Sc 
Cu arise from an incomplete d sub-level in ions Cr 1s22s22p63s23p6 4s13d5 Cr 3+ [Ar] 4s03d3
Mn 1s22s22p63s23p6 4s23d5 Mn 2+ [Ar] 4s03d5
Fe 1s22s22p63s23p6 4s23d6 When Fe 3+ [Ar] 4s03d5
these characteristics include Co 1s22s22p63s23p6 4s23d7 forming Co 2+ [Ar] 4s03d7
•complex formation, ions lose
Ni 1s22s22p63s23p6 4s23d8 4s before Ni 2+ [Ar] 4s03d8
•formation of coloured ions, Cu 1s22s22p63s23p6 4s13d10 Cu 2+ [Ar] 4s03d9
3d
•variable oxidation state
Zn 1s22s22p63s23p6 4s23d10 Zn 2+ [Ar] 4s03d10
•catalytic activity.
Why is Zn not a transition metal?

Zn can only form a +2 ion. In this ion the Zn2+ has a complete d orbital and so does
not meet the criteria of having an incomplete d orbital in one of its compounds.
Why is Sc not a transition metal?

Sc can only form a +3 ion. In this ion the Sc3+ has an empty d orbital and so
does not meet the criteria of having an incomplete d orbital in one of its ions.
The successive ionization energies for the elements Sc to Zn show a gradual increase in ionisation
energy until all the 4s and 3d electrons have been removed. There is then a big jump as electrons start
to be removed from the inner core electrons
Complex formation
2+
complex :is a central metal ion surrounded by ligands. OH2
H2O OH2
ligand.: An atom, ion or molecule which can donate a lone electron pair
Cu
H2O OH2
Co-ordinate bonding is involved in complex formation.
Co-ordinate bonding is when the shared pair of electrons in the covalent bond OH2
come from only one of the bonding atoms.
Co-ordination number: The number of co-ordinate bonds formed to a central
metal ion
ligands can be monodentate (e.g. H2O, NH3 and Cl- 3+

A complex with bidentate
CH2
) which can form one coordinate bond per ligand or NH2
ligands e.g.
H2 C [Cr(NH2CH2CH2NH2)3]3+
bidentate (e.g. NH2CH2CH2NH2 and ethanedioate NH2 NH2 CH2
ion C2O4 2- ) which have two atoms with lone pairs Cr
CH2 There are 3 bidentate
and can form two coordinate bonds per ligand NH2 NH2
ligands in this complex
or multidentate (e.g. EDTA4- which can form six NH2
H2 C each bonding in twice
coordinate bonds per ligand). CH2 to the metal ion
The EDTA4- anion has the formula
It has a coordination number of 6
O O
O
-O C CH2 CH2 C O- C 3-
O O
N CH2 CH2 N C
O O A complex with
-O C CH2 CH2 C O- O
C
Cr
bidentate ethanedioate
C
ligands e.g. [Cr(C2O4)3]3-
O O O O O
with six donor sites(4O and 2N) and forms a 1:1 O C O

C
complex with metal(II) ions O
Formation of coloured ions
Colour changes arise from changes in

1. oxidation state, O2 In this
2. co-ordination number [Co(NH3)6]2+ (aq)  [Co(NH3)6]3+ (aq) +e- equation only
3. ligand. yellow brown oxidation state
is changing
Cu(H2O)62+ + 4Cl-  [CuCl4]2- + 6H2O

blue greem
Co(H2O)62+ + 6 NH3  Co(NH3)62+ + 6H2O
In this equation both ligand and co-
Pink yellow brown
ordination number are changing
In this equation only the ligand is changing
How colour arises

dz2 dx2- y 2
Colour arises from electronic transitions from the
E
ground state to excited states: between different d
orbitals Average energy of
A portion of visible light is absorbed to promote d d orbitals in field of
electrons to higher energy levels. The light that is not ligands dxy dxz dyz
absorbed is transmitted to give the substance colour.
Octahedral complex ion
A solution will appear blue if it absorbs orange light.
Ligands cause 5 d orbitals to
split into two energy levels
Changing colour
Changing a ligand or changing the coordination number will alter the energy split between the d- orbitals,
changing E and hence change the frequency of light absorbed.
Compounds without colour
Scandium is a member of the d block, its ion In the case of Zn2+ ions and Cu+ ions the d shell is full
(Sc3+) hasn't got any d electrons left to move e.g.3d10 so here there is no space for electrons to
around. So there is not an energy transfer equal to transfer. So there is not an energy transfer equal to that
that of visible light of visible light
Spectrophotometry
Absorption of visible light is used in spectrometry to
If visible light of increasing frequency is passed through a
determine the concentration of coloured ions.
sample of a coloured complex ion, some of the light is
absorbed. method
The amount of light absorbed is proportional to the •Add an appropriate ligand to intensify colour
concentration of the absorbing species. •Make up solutions of known concentration
Some complexes have only pale colours and do not •Measure absorption or transmission
absorb light strongly. In these cases a suitable ligand is •Plot graph of results or calibration curve
added to intensify the colour. •Measure absorption of unknown and compare
Shapes of complex ions
transition metal ions
transition metal ions commonly form square planar Ag+ commonly forms
commonly form octahedral tetrahedral complexes complexes are also linear complexes
complexes with small with larger ligands formed, e.g. e.g. [Ag(NH3)2]+,
ligands (e.g. H2O and NH3). (e.g.Cl- ). cisplatin [Ag(S2O3)2]3- and
[Ag(CN)2]- (all
2+ Cl 2- colourless).
NH3 H 3N Cl
H3 N NH3 Pt +
Ni Cu H 3N H3 N Ag NH3
H3 N Cl
NH3
NH3 Cl Cl
Cl
Platin binds to DNA of cancer cells and

Cisplatin
stops cancer cells dividing
The Pt(II) complex cisplatin is used as an anticancer drug.
H 3N Cl Cl NH3
The cisplatin version only works as two chloride ions are displaced and the
molecule joins on to the DNA. In doing this it stops the replication of Pt Pt
cancerous cells. H 3N Cl H 3N Cl
In the body one Cl ligand is subsituted by a water molecule
Pt(NH3)2Cl2 + H2O  [Pt(NH3)2Cl(H2O)]+ + Cl– cisplatin transplatin
It can also prevent the replication of
Be able to apply your knowledge of bonding to given information in the
healthy cells by bonding on to
question to explain how it bonds to DNA molecule- generally a
healthy DNA which may lead to
combination of dative covalent bonding and hydrogen bonding
unwanted side effects like hair loss
Fe(II) in haemoglobin enables oxygen to be transported in the blood. Haem is an iron(II) complex with a multidentate ligand.
CO is toxic to humans as CO can from a strong coordinate bond with haemoglobin and replaces oxygen in a ligand
exchange reaction. This is a stronger bond than that made with oxygen and so it prevents the oxygen attaching to the
haemoglobin.
3
Variable oxidation states
When transition metals form ions they
Transition elements show variable oxidation states lose the 4s electrons before the 3d
Transition metals form various oxidation states. They are able to donate and receive electrons and are
able to oxidize and reduce. This is because the ions contain partially filled sub-shells of d electrons that
can easily lose or gain electrons. The energy differences between the oxidation states are small.
General trends
•Relative stability of +2 state with respect to +3 state increases across the period
•Compounds with high oxidation states tend to be oxidising agents e.g MnO4-
•Compounds with low oxidation states are often reducing agents e.g V2+ & Fe2+
Vanadium
Vanadium has four main oxidation states The ion with the V at oxidation state +5 exists as a solid
compound in the form of a VO3- ion, usually as NH4VO3
VO2+ Oxidation state +5 ( a yellow solution) (ammonium vanadate (V). It is a reasonably strong
oxidising agent. Addition of acid to the solid will turn into
VO2+ Oxidation state + 4 (a blue solution) the yellow solution containing the VO2+ ion.
V3+ Oxidation state + 3 (a green solution)
V2+ Oxidation state + 2 (a violet solution)
Addition of zinc to the vanadium (V) in acidic solution will reduce the vanadium down through each successive
oxidation state, and the colour would successively change from yellow to blue to green to violet
Redox Equation Eo Values

VO2+(aq) + 2H+(aq) + e-  VO2+(aq) + H2O +1.00 V
VO2+(aq + 2H+(aq) +e-  V3+(aq) + H2O +0.34 V
- 0.26 V
V3+(aq) + e-  V2+(aq)
Zn2+ + 2e-  Zn E=-0.76V

As zinc has a more negative electrode potential than all the vanadium half equations, zinc will
reduce down to V2+
Sn2+ + 2e-  Sn E=-0.136V
Tin metal will only reduce the vanadium to the +3 state
Chromium Reactions
Reducing Chromium Cr2O72- + 14H+ + 3Zn  2Cr3+ + 7H2O + 3 Zn2+

Cr3+ (green) and then Cr2+ (blue) are formed by reduction of Cr2O72- + 14H+ + 4Zn  2Cr2+ + 7H2O + 4 Zn2+
Cr2O72- (orange) by the strong reducing agent zinc in (HCl) acid
solution. Fe2+ is a less strong reducing agent and will only reduce Keeping the zinc/dichromate under a
the dichromate to Cr3+ hydrogen atmosphere is needed to reduce it
to Cr2+, because O2 in air will oxidise Cr2+
up to Cr3+
The Cr2+ state can be stabilised by forming a stable complex ion with a ligand such as the ethanoate
ion. If the blue Cr2+ ions are bubbled through sodium ethanoate, a stable red precipitate of chromium(II)
ethanoate is formed.
The Fe2+ and Cr2O7 2- in acid solution reaction can be used Cr2O72- + 14H+ + 6Fe2+  2Cr3+ + 7H2O + 6 Fe3+
as a quantitative redox titration. This does not need an Orange green
indicator
Redox Potentials
Cr2O72- + 14H+ + 6e-  2Cr3+ + 7H2O E +1.33V

The electrode potential of Iron(II) is in between
Fe3+(aq) + e–  Fe2+(aq) E +0.75V the two chromium half equations, so Fe2+ will
reduce chromium down to Cr3+
Cr3+(aq) + e–  Cr2+(aq) E -0.41V

As zinc has a more negative electrode potential
Zn2+ + 2e-  Zn E=-0.76V than all the chromium half equations, zinc will
reduce chromium down to Cr2+
Oxidising Chromium
When transition metals in low oxidation states are in alkaline It is easier to remove an electron
solution they are more easily oxidised than when in acidic solution from a negatively charged ion
excessNaOH
[Cr(H2O)6]3+ (aq) [Cr(OH)6]3- (aq) The metal ions can be oxidised by using
Acidified alkaline oxidising agents such as hydrogen peroxide
Not easy to oxidise easier to oxidise
H2O2 Reduction :H2O2 + 2e-  2OH-

Cr(OH)63- (aq) CrO42- (aq) Oxidation: [Cr(OH)6]3- + 2OH- CrO42- + 3e- + 4H2O
Green solution yellow solution 2 [Cr(OH)6]3- + 3H2O2 2CrO42- +2OH- + 8H2O
Half equations in alkaline conditions: For change Cr(OH)63- CrO42-

These are more difficult to do than half
equations under acidic conditions. The
Add H2O to balance O: [Cr(OH)6]3- CrO42- + 2H2O + 3e-
easiest way of doing it is to balance as Add H+ to balance H: [Cr(OH)6]3- CrO42- + 2H2O + 2H+ + 3e-
if under acidic conditions then add OH-
Add OH- to both sides
ions to both sides to convert to [Cr(OH)6]3- +2OH-  CrO42- + 2H2O + 2H+ +2OH- + 3e-
to cancel out H+:
alkaline.
[Cr(OH)6]3- + 2OH- CrO42- + 3e- + 4H2O
Chromate/ dichromate equilibrium
The chromate CrO42- and dichromate Cr2O72- ions can be converted This is not a redox reaction as both
from one to the other by the following equilibrium reaction. the chromate and dichromate ions
have an oxidation number of +6. This
2 CrO42- + 2H+ Cr2O72- + H2O is an acid base reaction.
Yellow solution orange solution
Addition of acid will by application of le chatelier push the equilibrium to the dichromate.
Addition of alkali will remove the H+ ions and, by application of le chatelier, push the equilibrium to
the chromate.
Chromium Summary
acid
+6 Orange
Cr2O72- (aq) solution CrO42- (aq) Yellow
solution
alkali
Zinc and HCl

H2O2
Or Fe2+
acidified
with HCl
Excess Limited
NaOH Excess
NH3 NaOH
or NH3
[Cr(NH3)6]3+ [Cr(H2O)6]3+ (aq) green [Cr(OH)6]3-
+3 Cr(H2O)3(OH)3 s)
purple solution Green
Green
solution solution
Zinc and HCl precipitate
O2 Hydrogen atmosphere
+2 [Cr(H2O)6]2+ (aq) blue

solution
Reactions of Inorganic Compounds in Aqueous Solution
Lewis acids and bases
In the formation of complex ions the ligand is the Lewis
Definitions: Lewis acid: electron pair acceptor base because it is donating a pair of electrons in the
Lewis base: electron pair donator dative covalent bond and the metal ion is the Lewis acid.
Metal-aqua ions
Metal aqua ions are formed in aqueous solution. In solution Cr(III) often appears green and
Fe(III) appears yellow/brown due to
[M(H2O)6]2+, limited to M = Fe (green) , Co(pink) and Cu (blue); hydrolysis reactions. The ruby and violet
[M(H2O)6]3+, limited to M = Cr (ruby) and Fe (violet) colour is only really seen in solid hydrated
salts that contain these complexes.
Acidity or hydrolysis reactions
The following equilibria happen in aqueous solutions of metal ions.

The equilibria lead to generation of acidic
[M(H2O)6]2+ + H2O [M(H2O)5(OH)]+ + H3O+ solutions with M3+ ions, and very weakly
acidic solutions with M2+ ions. The 3+ ions
[M(H2O)6]3+ + H2O [M(H2O)5(OH)]2+ + H3O+ are noticeably more acidic.
The acidity of [M(H2O)6]3+ is greater than that of [M(H2O)6]2+ in terms of the greater polarising power
(charge/size ratio) of the 3+ metal ion. The greater the polarising power, the more strongly it attracts the water
molecule. This weakens the O-H bond so it breaks more easily.
Reaction with limited OH- and limited NH3

M(OH)2(H2O)4 (s) : Cu blue ppt, Co blue ppt, Fe (II) green ppt,
The bases OH- and ammonia when in limited
Ni green ppt, Zn white ppt, Mn pale brown ppt
amounts form the same hydroxide
M(OH)3(H2O)3 (s) :Cr (III) green ppt, Fe(III) brown ppt,
precipitates. They form in deprotonation
acid base reactions
[Cu(H2O)6]2+ (aq) + 2OH- (aq)  Cu(H2O)4(OH)2 (s) + 2H2O (l) [Co(H2O)6]2+ (aq) + 2NH3 (aq)  Co(H2O)4(OH)2 (s) + 2NH4+ (aq)
[Cr(H2O)6]3+(aq) + 3OH- (aq)  Cr(H2O)3(OH)3 (s) + 3H2O (l) [Fe(H2O)6]3+ (aq) + 3NH3 (aq)  Fe(H2O)3(OH)3 (s) + 3NH4+ (aq)
This process can happen step wise removing one proton at a time. Be able to write equations for this too.
e.g. [Cr(H2O)6]3+ (aq) + OH- (aq)  [Cr(H2O)5(OH)]2+ (aq) + H2O (l)
Here the NH3 and OH- ions are acting as
[Cr(H2O)5(OH)]2+ (aq) + OH- (aq)  [Cr(H2O)4(OH)2]+ (aq) + H2O (l) Bronsted-Lowry bases accepting a proton
Reaction with excess OH-

With excess NaOH, the Cr and Zn hydroxides dissolve. •These hydroxides are classed as amphoteric
Cr becomes [Cr(OH)6]3- (aq) green solution because they react with alkali to give a solution
Zn becomes [Zn(OH)4]2- (aq) colourless solution and react with acid to form the aqueous salt
Cr(H2O)3(OH)3 (s) + 3OH- (aq ) [Cr(OH)6]3- (aq) + 3H2O(l) Cr(H2O)3(OH)3 (s) + 3H+ (aq ) [Cr(H2O)6]3+(aq)
Zn(H2O)4(OH)2 (s) + 2OH- (aq ) [Zn(OH)4]2- (aq) + 4H2O (l) Zn(H2O)4(OH)2 (s) + 2H+ (aq ) [Zn(H2O)6]2+ (aq)
Reaction with excess NH3

With excess NH3 ligand exchange reactions occur with Cu, Zn,Ni and Cr and their precipitates dissolve
Cr becomes [Cr(NH3)6]3+ purple solution
The ligands NH3 and H2O are similar in size and are
uncharged. Ligand exchange occurs without change of Zn becomes [Zn(NH3)4]2+ colourless solution
co-ordination number for Co and Cr Ni becomes [Ni(NH3)6]2+ blue solution
This substitution may, however, be incomplete Co becomes [Co(NH3)6]2+ pale yellow solution
as in the case with Cu Cu becomes [Cu(NH3)4(H2O)2]2+ deep blue solution
Cr(OH)3(H2O)3(s) + 6NH3 (aq)  [Cr(NH3)6]3+(aq) + 3H2O(l) + 3OH- (aq)
Cu(OH)2(H2O)4(s) + 4NH3 (aq)  [Cu(NH3)4(H2O)2]2+ (aq) + 2H2O (l) + 2OH- (aq)

Ni(OH)2(H2O)4(s) + 6NH3 (aq)  [Ni(NH3)6]2+(aq) + 4H2O (l) + 2OH- (aq)
7
2+ Ion Summary
[MCl4]2-
[Zn(OH)4]2- colourless sol
[CuCl4]2- green sol
[CoCl4]2- blue sol
excess OH-
water Conc Cl-
Few drops OH -
or NH3 excess NH3 [Cu(NH3)4(H2O)2]2+
[M(H2O)6]2+ M(OH)2 (H2O)4 deep blue solution
H+ [Co(NH3)6]2+
[Cu(H2O)6]2+ blue sol Cu(OH)2(H2O)4 blue ppt yellow/light brown solution
[Co(H2O)6]2+ pink sol Co(OH)2(H2O)4 blue ppt [Ni(NH3)6]2+ blue sol
[Fe(H2O)6]2+ green sol Fe(OH)2(H2O)4 green ppt [Zn(NH3)4]2+ colourless sol
[Ni(H2O)6]2+ green sol Ni(OH)2(H2O)4 green ppt
[Mn(H2O)6]2+ very pale pink sol Mn(OH)2(H2O)4 light brown ppt
[Zn(H2O)6]2+ colourless sol Zn(OH)2(H2O)4 white ppt Air or H2O2
Air or H2O2 [Co(NH3)6]3+ brown sol
M(OH)3 (H2O)3
Fe(OH)3(H2O)3 brown ppt

Co(OH)3(H2O)3 brown ppt
Mn(OH)3(H2O)3 dark brown ppt
3+ Ion Summary Cr2O72- orange sol
H+ OH-
H2O2
[Cr(OH)6]3- green sol CrO42- yellow sol
excess OH-
Few drops
OH- or NH3 excess NH3
[M(H2O)6]3+ M(OH)3 (H2O)3 [Cr(NH3)6]3+ violet sol
H+
[Cr(H2O)6]3+ green sol
[Fe(H2O)6]3+ yellow sol Cr(OH)3(H2O)3 green ppt
Fe(OH)3(H2O)3 brown ppt
8
Ligand exchange reactions with chloride ions
Addition of conc HCl to aqueous ions of Cu
Addition of a high concentration of chloride ions (from conc HCl or and Co lead to a change in coordination
saturated NaCl) to an aqueous ion leads to a ligand substitution number from 6 to 4
reaction. [CuCl4]2- yellow/green solution
[CoCl4]2- blue solution
The Cl- ligand is larger than the uncharged H2O and NH3
These are tetrahedral in shape
ligands so therefore ligand exchange can involve a
change of co-ordination number.
[Cu(H2O)6]2+ + 4Cl-  [CuCl4]2- + 6H2O
Be careful: If solid copper chloride (or any other metal )is
dissolved in water it forms the aqueous [Cu(H2O)6]2+ complex [Co(H2O)6]2+ + 4Cl-  [CoCl4]2- + 6H2O
and not the chloride [CuCl4]2- complex
Stability of complexes
The substitution of monodentate ligand with a bidentate or a multidentate ligand leads to a more stable complex.
This chelate effect can be explained in terms of a positive entropy change in these reactions as more
molecules of products than reactants
[Cu(H2O)6]2+ (aq) + EDTA4- (aq)  [Cu (EDTA)]2- (aq) + 6H2O (l)

The copper complex ion has changed from having monodentate ligands to a multidentate ligand
In this reaction there is an increase in the entropy of the system because there are more moles of
products than reactants (from 2 to 7), creating more disorder.
The stability of the EDTA complexes has many applications. It can be added to rivers to remove
poisonous heavy metal ions as the EDTA complexes are not toxic. It is in many shampoos to remove
calcium ions present in hard water, so helping lathering.
Ethane-1-2-diamine
Ethane-1-2-diamine is a common bidentate ligand.

There are 3 bidentate ligands in this
Cu(H2O)62+ + 3NH2CH2CH2NH2  [Cu(NH2CH2CH2NH2)3]2+ + 6H2O complex each bonding in twice to the
metal ion
CH2 3+
[Co(NH3)6]2+ + 3NH2CH2CH2NH2  [Co(NH2CH2CH2NH2)3]2+ + 6NH3 H2 C
NH2
NH2 NH2 CH2

This reaction has an increase in entropy because of in the increase
Cr
in moles from 4 to 7 in the reaction. ΔSsystem is positive. NH2 NH2
CH2
Its enthalpy change ΔH (and ΔSsurroundings) is close to zero as the
NH2
number of dative covalent and type (N to metal coordinate bond) H2 C
CH2
are the same so the energy required to break and make bonds will
be the same.
It has a coordination number of 6
Therefore ΔSTotal will be positive and the complex formed is stable Octahedral shape
Bond angle around Cr 90o
Ethane-1-2-diamine, as a base, can also carry out the deprotonation reactions

(similar to those of ammonia) forming hydroxide precipitates.
2[Al(H2O)6]3+ (aq) + 3 H2NCH2CH2NH2 (aq)  2Al(H2O)3(OH)3 (s) + 3 [H3NCH2CH2NH3 ]2+ (aq)
Note small molecules such as NH2NH2 cannot act as bidentate ligands because even though they have two
lone pairs they are too close together and would not be able to fit around the metal ion
9
More on some common ligands
O
Ethanedioate C2O42- C 3-
O O A 6 coordination number
C
complex with bidentate
O
O O
C ethanedioate ligands e.g.
Cu(H2O)62+ + 3C2O42- [Cu(C2O4)3]4- + 6H2O Cr [Cr(C2O4)3]3-
C
O O O
Cr(H2O)63+ + 3C2O42- [Cr(C2O4)3]3- + 6H2O O C O Octahedral shape with

C 90o bond angles
O
Partial substitution of ethanedioate ions may 2-

occur when a dilute aqueous solution containing OH2
ethanedioate ions is added to a solution O O O O
C
containing aqueous copper(II) ions. In this C
Cu
reaction four water molecules are replaced and C C
O O O O
a new complex is formed.
OH2
Cu(H2O)62+ + 2C2O42- [Cu(C2O4)2(H2O)2]2- + 4H2O
Using Silver nitrate to work out formulae of chloride containing complexes
Sometimes a compound containing a complex may have Cl- ions acting as ligands inside the complex and
Cl- ions outside the complex attracted ionically to it. If silver nitrate is added to such a compound it will only
form the silver chloride precipitate with the free chloride ions outside of the complex.
e.g. Co(NH3)6Cl3 reacts on a 1:3 e.g. Cr(NH3)5Cl3 reacts on a 1:2 e.g. Cr(NH3)4Cl3 reacts on a
mole ratio with silver nitrate as mole ratio with silver nitrate as 1:1 mole ratio with silver
there are three free Cl- ions. So there are two free Cl- ions. So 1 nitrate as there is one free
all 3 Cls are outside the complex Cl is a ligand and 2 are outside Cl- ion. So 2 Cl’s are ligands
the complex and 1 is outside the complex
NH3
3+ +
H3N NH3 - NH3
2+ NH3
Co 3Cl H3N NH3 -
H3N NH3 -
Cr Cl
H3N NH3 Cr 2Cl -
- H3N Cl
NH3 H3N Cl -
Cl
NH3
10
Catalysis
Catalysts increase reaction rates without getting used up. They do this by providing an
alternative route with a lower activation energy
Transition metals and their compounds can A heterogeneous catalyst is in a different phase from the reactants
act as heterogeneous and homogeneous A homogeneous catalyst is in the same phase as the reactants
catalysts.
Heterogeneous catalysis
Adsorption of reactants at active sites on the surface
Heterogeneous catalysts are usually solids may lead to catalytic action. The active site is the place
whereas the reactants are gaseous or in solution. where the reactants adsorb on to the surface of the
The reaction occurs at the surface of the catalyst. catalyst. This can result in the bonds within the reactant
molecules becoming weaker, or the molecules being held in
a more reactive configuration. There will also be a higher
concentration of reactants at the solid surface so leading to
Strength of adsorption a higher collision frequency
The strength of adsorption helps to determine the
effectiveness of the catalytic activity Transition Metals can use the 3d and 4s e- of atoms on the
Some metals e.g. W have too strong adsorption and metal surface to form weak bonds to the reactants.
so the products cannot be released
Some metals e.g. Ag have too weak adsorption, and
the reactants do not adsorb in high enough
concentration
Advantages of Heterogeneous catalysts
Ni and Pt have about the right strength and are most
Heterogeneous catalysts can be filtered off and are
useful as catalysts
easy to separate from any liquid or gaseous
products. They are also suited to continuous
Surface area: processes rather than batch processes
Increasing the surface area of a solid catalyst will
improve its effectiveness. A support medium is often
used to maximise the surface area and minimise the
cost (e.g. Rh on a ceramic support in catalytic
converters).
Example of heterogeneous catalysts
V2O5 is used as a catalyst in the Contact Process. Note the oxidation number of the vanadium changes and then
Overall equation : 2SO2 + O2  2SO3 changes back. It is still classed as a catalyst as it returns to its
step 1 SO2 + V2O5  SO3 + V2O4 original form
step 2 2V2O4 + O2  2V2O5
Catalytic converters
These remove CO, NOx and unburned Steps in Heterogeneous Catalysis in catalytic
hydrocarbons (e.g. octane, C8H18) from the converter
exhaust gases, turning them into ‘harmless’ CO2,
1. CO and NO molecules form bonds with atoms at
N2 and H2O.
active sites on the surface of the catalyst -
adsorbed onto the surface
2 CO + 2 NO  2 CO2 + N2
2. As a result bonds in the reactants are weakened
C8H18 + 25 NO  8 CO2 + 12½ N2 + 9 H2O and break
3. New bonds form between the reactants held close
Converters have a ceramic honeycomb together on catalyst surface
coated with a thin layer of catalyst metals 4. Desorption of CO2 and N2 product molecules from
Platinum, Palladium, Rhodium – to give the surface of the catalyst
a large surface area.
Developing New Catalysts
Over the years the catalyst used for this
Making ethanoic acid from methanol and carbon monoxide is a reaction has been developed using different
preferable industrial production method because it has a high transition metal catalysts.
atom economy. This has lead to greater selectivity of the
catalysts, cheaper catalysts, milder conditions
CH3OH + CO  CH3COOH being used and improved separation processes.
A iridium/iodine based catalyst is currently used.
The scientific community reports and validates new discoveries by publishing new discoveries in scientific journals
that are peer reviewed.
Homogeneous catalysis
When catalysts and reactants are in the same The intermediate will have a different oxidation state to the
phase, the reaction proceeds through an original transition metal. At the end of the reaction the original
intermediate species oxidation state will reoccur. This illustrates importance of
variable oxidation states of transition metals in catalysis
Transition metals can act as homogeneous catalysts because they can form various oxidation states. They are able to donate
and receive electrons and are able to oxidize and reduce. This is because the ions contain partially filled sub-shells of d
electrons that can easily lose or gain electrons.
Example of homogeneous catalysts
Reaction between iodide and persulphate ions

The uncatalysed reaction is very slow because the reaction
The reaction between I- and S2O82- catalysed by Fe2+ needs a collision between two negative ions. Repulsion
overall S2O82- + 2I-  2SO42- + I2 between the ions is going to hinder this – meaning high
activation energy
S2O82- +2e-  2SO42- Eo+2.01V For a substance to act as a homogenous catalyst its electrode
potential must lie in between the electrode potentials of the two
Fe3+ + e-  Fe2+ Eo+0.77V
reactants, so it can first reduce the reactant with the more positive
electrode potential and then in the second step oxidize the
I2 + 2e-  2I- Eo+0.54V reactant with the more negative electrode potential
Catalysed alternative route Both of the individual stages in the catalysed mechanism
stage 1 S2O82- + 2Fe2+  2SO42- + 2Fe3+ involve collision between positive and negative ions and will
stage2 2I- + 2Fe3+  2Fe2+ + I2 have lower activation energies.
Using E values to find a catalyst only shows that catalysis is possible. It does not guarantee that the rate of
reaction will be increased
Fe3+ ions can also act as the catalyst because the two steps in the catalysed mechanism can occur in any order
Constructing a catalysed mechanism for a reaction Example

The following reaction is catalysed by Co2+ ions in an acidic solution. SO32– + ½ O2  SO4 2–.
Write a mechanism for the catalysed reaction by writing two equations involving Co 2+ and Co3+ ions
Split full equation into its two ½ O2 + 2H+ + 2e-  H2O

half equations SO32– + ½ O2  SO4 2–
SO32– + H2O  SO4 2– + 2H+ + 2e-
Add in cobalt to make two
new redox equations.
Making sure the oxidised Co2+  Co3+ + e- ½ O2 + 2H+ + 2Co2+  H2O + 2Co3+
cobalt equation is combined
with the original reduced half
Co3+ + e-  Co2+ 2Co3+ + SO32– + H2O  SO4 2– + 2H+ + 2Co2+
equation and vice versa
Check your two mechanism equations add up to
the original full non catalysed equation
Autocatalytic Reaction between Ethanedioate and Manganate ions
The autocatalysis by Mn2+ in titrations of C2O4 2- with MnO4- This is an example of autocatalysis where one of the
products of the reaction can catalyse the reaction.
overall - 2-
2 MnO4 + 5 C2O4 + 16 H+  2Mn2+ + 10 CO2 + 8 H2O
Catalysed alternative route Mixture with only

reactants showing
Step 1 4Mn2+ + MnO4- + 8 H+  5Mn3+ + 4 H2O
effect of
Step 2 2Mn3+ + C2O42-  2Mn2+ + 2 CO2 autocatalysis
The initial uncatalysed reaction is slow because the reaction is a
collision between two negative ions which repel each other
leading to a high activation energy.
The Mn2+ ions produced act as an autocatalyst and therefore the Mixture with
reaction starts to speed up because they bring about the alternative added
reaction route with lower activation energy. catalyst Mn2+
The reaction eventually slows as the MnO4- concentration drops. at start
Following the reaction rate

This can be done by removing samples at set times and titrating to work out the concentration of MnO 4- .
It could also be done by use of a spectrometer measuring the intensity of the purple colour. This method has the
advantage that it does not disrupt the reaction mixture, using up the reactants and it leads to a much quicker
determination of concentration.
18. Arenes
There are two major classes of organic chemicals All of the organic substances we have
aliphatic : straight or branched chain organic substances looked at so far have been aliphatic
aromatic or arene: includes one or more ring of six carbon
atoms with delocalised bonding. Benzene belongs to the aromatic class.
Benzene’s Structure In 1865 Kekule suggested the following

The simplest arene is benzene. It has the molecular formula C6H6 structure for Benzene consisting of
Its basic structure is six C atoms in a hexagonal ring, with one H alternate single and double covalent
atom bonded to each C atom bonds between the carbon atoms
Each C atom is bonded to two other C atoms and one H atom by H
single covalent σ-bonds. This leaves one unused electron on each
C atom in a p orbital, perpendicular to the plane of the ring. H C H
The Six p electrons are delocalised in a ring structure above and C C
below the plane of carbon atoms
C C
H C H
H H H H
H
H H H H
This structure is not correct. Evidence
suggests that all the C-C bonds are the
H H H H
same length.
In formulae we draw a circle to show

this delocalised system The six electrons in the pi bonds are delocalised and spread out
over the whole ring. Delocalised means not attached to a particular
atom.
Benzene is a planar molecule.The evidence suggests all the C-C

Abbreviated bonds are the same and have a length and bond energy between a
formula C-C single and C=C double bond
Displayed formula The H-C-C bond angle is 120o in Benzene
Enthalpies of Hydrogenation
Theoretically because there
+ H2  H = -120 kJ/mol are 3 double bonds one might
enthalpy
expect the amount of energy H = -152kJ/mol

cyclohexene cyclohexane x3 to be 3 times as much. delocalisation
energy
-360 kJ/mol
+ 3H2  H = -360 kJ/mol Theoretical
However, the real amount of value
Non delocalised energy is less. The 6 pi
structure electrons are delocalised and H = -208kJ/mol
not arranged in 3 double bonds actual value
+ 3H2  H = -208kJ/mol
This when represented on an energy level
delocalised diagram shows that the delocalised benzene
structure is more thermodynamically stable.
The increase in stability connected to delocalisation is called

the delocalisation energy
Reactions of Benzene
Benzene does not generally undergo addition reactions because these would involve breaking up the delocalised
system. Most of Benzene’s reactions involve substituting one H for another atom or group of atoms. Benzene has
a high electron density and so attracts electrophiles. It reactions are usually electrophilic substitutions
Naming aromatic molecules
Naming aromatic compounds can be complicated. The simplest molecules are derivatives of benzene and have
benzene at the root of the name
CH3 C2H5 Cl Br NO 2 CO2H CHO
Methylbenzene ethylbenzene chlorobenzene bromobenzene nitrobenzene benzenecarboxylic benzaldehyde

acid
If two or more substituents are present on the benzene ring, their positions must be indicated by the use of
numbers. This should be done to give the lowest possible numbers to the substituents. When two or more
different substituents are present, they are listed in alphabetical order and di, tri prefixes should be used.
CH3 CH3
CH3
COOH
O 2N NO2
CH3
Cl NO2
OH
1,3-dimethylbenzene
1-chloro- 4-methylbenzene 4-hydroxybenzenecarboxylic acid 2,4,6-trinitromethylbenzene
In other molecules the benzene ring can be regarded as a substituent side group on another molecule, like
alkyl groups are. The C6H5- group is known as the phenyl group.
O
NH2 CH CH2 CH3
H3C CH CH2 CH3 O
C
H3C C O
phenylamine phenylethene
2-phenylbutane
phenylethanone phenylethanoate
Toxicity of Benzene
Benzene is a carcinogen (cancers causing molecule) and is banned for use in schools.
Methylbenzene is less toxic and also reacts more readily than benzene as the methyl side group releases
electrons into the delocalised system making it more attractive to electrophiles
Reactions of Benzene
Combustion
Benzene will combust with a very sooty flame.
Benzene + oxygen  carbon dioxide + water The lower the carbon to hydrogen ratio the
C6H6 (l) + 7.5 O2  6 CO2 + 3 H20 sootier the flame.
Halogenation of Benzene
Change in functional group: benzene  Bromobenzene This reaction can be done with chlorine.
Reagents: Bromine The catalyst can be AlCl3 or FeCl3
Conditions: iron(III) bromide catalyst FeBr3
It is possible to create the iron(III)
Mechanism: Electrophillic Substitution
bromide in situ by reacting iron with
bromine
Overall Equation for reaction Br
Equation for Formation of electrophiles:
+ HBr (Learn!)
+ Br2  AlCl3 + Cl2  AlCl4– + Cl+
FeBr3 + Br2  FeBr4– + Br+
Mechanism Cl
Cl+
H Cl
+
The H+ ion reacts with the AlCl4- to H+ + AlCl4-  AlCl3 + HCl

reform AlCl3 catalyst and HCl.
Nitration of Benzene
Change in functional group: benzene  nitrobenzene
Reagents: conc nitric acid in the presence of concentrated Importance of this reaction
sulphuric acid (catalyst) Nitration of benzene and other arenes is
Mechanism: Electrophilic Substitution an important step in synthesising useful
Electrophile: NO2+ compounds
e.g. explosive manufacture (like TNT,
Overall Equation for reaction trinitrotoluene/ 2,4,6-
NO2
trinitromethylbenzene)
+ NO2 +  + H+ and formation of amines from which
dyestuffs are manufactured. (The reaction
for this is covered in the amines section.)
Equation for Formation of electrophile: (Learn!)
HNO3 + 2H2SO4  NO2+ + 2HSO4- + H3O+
Mechanism This reaction is done at 60oC.

NO 2 On using higher temperatures
HSO4-
NO2+ NO 2 a second nitro group can be
H substituted onto different
+ positions on the ring
If the benzene ring already has

The horseshoe shape of the a side group e.g. methyl then
intermediate must not extend the Nitro group can also join on
beyond C’s 2 to 6 different positions. A-level does
not require knowledge of what
The H+ ion rejoins with the HSO4- to H+ + HSO4-  H2SO4 positions the groups go on.
reform H2SO4 catalyst.
3
Hydrogenation of Benzene
Reaction: benzene  cyclohexane Ni

Reagents: Hydrogen Catalyst
+ 3H2
Conditons: Nickel catalyst at 200C and 30 atm
Type of reaction: Addition and reduction
Sulphonation of Benzene
The sulfur trioxide can act as an
Change of functional group: benzene  sulphonated benzene
electrophile because it can accept a
Reagents: Fuming concentrated Sulphuric acid
Conditions: heat under reflux for several hours pair of electrons
Mechanism: Electrophillic Substitution
Electrophile : SO3 (fuming sulphuric acid is SO3 dissolved in The three oxygen atoms on the
concentrated sulphuric acid) sulfur give it a large δ+ charge
SO 3H
+ SO3
sulphur trioxide
Sulphonated arenes are used in Benzenesulphonic acid

drugs, detergents and dyestuffs
Friedel Crafts Alkylation
Change in functional group: benzene  alkylbenzene

Reagents: chloroalkane in the presence of anhydrous Any chloroalkane can be used RCl where
aluminium chloride catalyst R is any alkyl group Eg –CH3 , -C2H5.
Conditions: heat under reflux The electrophile is the R+.
Mechanism: Electrophilic Substitution
Formation of the electrophile.

AlCl3 + CH3CH2Cl  CH3CH2+ AlCl4-
Overall Equation for reaction

CH2CH3
CH3CH2+ AlCl4- + + AlCl3 + HCl
ethylbenzene
Mechanism
+CH CH
2 3 CH 2CH 3
CH2CH3
H
+
The H+ ion reacts with the AlCl4- to

H+ + AlCl4-  AlCl3 + HCl
Friedel Crafts Acylation
Change in functional group: benzene  phenyl ketone
Reagents: acyl chloride in the presence of anhydrous Any acyl chloride can be used RCOCl where
aluminium chloride catalyst R is any alkyl group e.g. –CH3 , -C2H5. The
Conditions: heat under reflux (50OC) electrophile is the RCO+.
Mechanism: Electrophilic Substitution
Equation for Formation of the electrophile.

AlCl3 + CH3COCl  CH3CO+ AlCl4-
Overall Equation for reaction These are important

O
reactions in organic
C synthesis because they
CH3CO+ AlCl4- + CH3 + AlCl3 + HCl introduce a reactive
functional group on to the
benzene ring
phenylethanone
Mechanism O O
+ O
C CH3 C CH3
C
CH3
H
+
The H+ ion reacts with the AlCl4- to
H+ + AlCl4-  AlCl3 + HCl
Effect of side groups on benzene ring
Electron releasing side groups such as alkyl groups, phenols and amines releases electrons into the
delocalised system making a higher electron density in the ring and it more attractive to electrophiles.
They will therefore carry out the substitution reactions more readily with milder conditions
Effect of delocalisation on side groups with lone pairs
If a –OH group, a Cl atom or an NH2 group is directly attached to a benzene ring the
delocalisation in the benzene ring will extend to include the lone pairs on the N,O and Cl. This
changes the properties and reactions of the side group
Cl NH2
OH
chlorobenzene
phenylamine
phenol
The C-Cl bond is made stronger.
Typical halogenoalkane Delocalisation makes the C-O Less basic than aliphatic
substitution and elimination bond stronger and the O-H bond amines as lone pair is
reactions do not occur. Also the weaker. Phenol does not act like delocalised and less
electron rich benzene ring will an alcohol- it is more acidic and available for accepting a
repel nucleophiles does not oxidise proton
Phenols
In a phenol the OH group is directly attached to the CH2OH

benzene ring.
OH
In a phenol the lone pair of electrons on the
oxygen is delocalised with the electron
charge cloud of the arene ring.
The delocalised bonding changes the
This is not a phenol, but is
reactivity of the OH group and the arene ring.
an alcohol because the
OH group is attached to an
alkyl group rather than the
Phenols are very weakly acidic. They are weaker acids than carboxylic acids. benzene ring.
Both phenols and carboxylic acids will react with sodium metal and sodium
hydroxide. Only carboxylic acids will react with sodium carbonate as a phenol
is not strong enough an acid to react.
-
OH + Na O Na+ + ½ H2
The sodium phenoxide

- compound is more soluble
OH + NaOH O Na+ + H2O
than the original phenol. So
the solid phenol dissolves on
sodium phenoxide addition of NaOH
Reaction of phenol with Bromine
Reagents: Bromine water

Conditions: room temp
OH Phenol does not need a FeBr3
OH
catalyst like benzene and
Br Br undergoes multiple
substitution whereas benzene
+ 3 Br2 + 3 HBr will only add one Br.
The product in this reaction is a

Br white solid
2,4,6 –tribromophenol
In phenol the lone pair of electrons on the oxygen (p- orbital) is

partially delocalised into the ring. The electron density increases
and the Br2 is more polarised
Phenols are used in the production of plastics,

antiseptics, disinfectants and resins for paints.
19. Amines, Amides , Amino Acids and proteins
Naming
H H H
Amines H2N O
These end in –amine. H C C C NH2 If there is another
There is, however, rather confusingly CH C
priority functional group
two ways of using this suffix. H H H
as well as the amine H3C O H
The exam board tend to use the propylamine group then the prefix
common version where the name Or propan-1-amine 2-aminopropanoic acid.
amino is used.
stem ends in -yl propylamine.
The IUPAC version of the same
chemical is propan-1-amine. (This is
used in the same way as naming
alcohols)
If the amine is secondary and has two alkyl CH3CH2CH2NHCH3

groups attached to the nitrogen, then each N-methylpropylamine (common name)
chain is named and the smaller alkyl group N-methylpropan-1-amine (IUPAC name)
is preceded by an –N which plays the same
role as a number in positioning a side alkyl CH2 CH2
chain H3C NH CH3
Diethylamine (common name- does not use N if

In the common naming version if the chains are same length)
chain lengths are the same an –N is N-ethylethanamine (IUPAC name does still use N)
not used
CH3CH2 CH2 N CH3

If a tertiary amine similar rules apply,
and each alkyl side group is given an CH3
N N,N-dimethylpropylamine (common name)
N,N-dimethylpropan-1-amine (IUPAC name)
H H
N (CH2)6 N It could also be named
1,6-diaminohexane
H H
hexane-1,6-diamine
Amides
O Secondary and tertiary amides

Add –amide to the stem are named differently to show the O
name CH3 C two (or three) carbon chains.
NH2 The smaller alkyl group is
preceded by an –N which plays H3C CH2 C NH CH3
ethanamide the same role as a number in
N-methylpropanamide
positioning a side alkyl chain
O CH3
CH3 O CH3
H3C CH2 C N CH3
H3C CH C N CH3
N,N-dimethylpropanamide N,N,2-trimethylpropanamide
Properties of Amines
Amines have a characteristic fishy smell H δ+
δ- δ+ δ-
Small amines can form hydrogen bonds with water and CH3 N H O
δ+
therefore can dissolve readily in water.
H
Base Properties
H δ+
Primary aliphatic amines act as Bronsted-Lowry Bases because the lone
pair of electrons on the nitrogen is readily available for forming a dative CH3NH2 +H2O  CH3NH3+ +OH-
covalent bond with a H+ and so accepting a proton.
Primary aliphatic amines are stronger bases than ammonia as the alkyl
groups are electron releasing and push electrons towards the nitrogen NH3 (aq) +H2O (l)  NH4+(aq) +OH-(aq)
atom and so make it a stronger base.
Secondary amines are stronger bases than primary amines because they have more alkyl groups that are substituted onto
the N atom in place of H atoms. Therefore more electron density is pushed onto the N atom (as the inductive effect of alkyl
groups is greater than that of H atoms).
One might expect using the same trend that tertiary amine would be the strongest amine base but the trend does not hold.
The tertiary amines and corresponding ammonium salts are less soluble in water and this makes them less strong bases
than the secondary amines. (This point will not be examined)
Base strength of aromatic amines NH2

Primary aromatic amines such as Phenylamine do not form basic solutions because the lone
pair of electrons on the nitrogen delocalise with the ring of electrons in the benzene ring. This
means the N is less able to accept protons. phenylamine
Reactions with acids
Amines as bases react with acids to form ammonium salts.

CH3NH2 (aq) +HCl (aq)  CH3NH3+Cl-(aq) Addition of NaOH to an ammonium salt
Methylamine methylammonium chloride will convert it back to the amine
2CH3NH2 (aq) +H2SO4 (aq)  (CH3NH3+)2 SO42- (aq)
These ionic salts will be solid crystals, if the
water is evaporated, because of the strong
The ionic salts formed in this reaction means that the ionic interactions.
compounds are soluble in the acid.
e.g. Phenylamine is not very soluble in water but
phenylammonium chloride is soluble
Making a basic buffer from an amine

Basic buffers can be made from combining a weak base with a salt of that weak base
e.g. Ammonia and ammonium chloride
Methylamine and methylammonium chloride
Ethylamine and ethylammonium chloride
Formation of complex ions
The lone pair of electrons on the nitrogen enable amines to act as ligands and form dative covalent bonds into
transition metal ions to form coloured complex ions.
4 CH3CH2NH2 + Cu(H2O)62+ [Cu(CH3CH2NH2)4(H2O)2] 2+ +4H2O
This is a similar ligand exchange reaction to the one where ammonia acts as the ligand
4NH3 + Cu(H2O)62+ [Cu(NH3)4(H2O)2] 2+ + 4H2O

light blue solution deep blue solution
Reaction of primary Amines with halogenoalkanes forming secondary amines
Amines will react with halogenoalkanes in a similar way to the reaction of ammonia with
halogenoalkanes via a nucleophilic substitution reaction
2CH3CH2NH2+ CH3CH2Br CH3CH2NH2CH2CH3+ CH3CH2NH3Br
H
+
H3C C Br H3C CH2 NH2 CH2 CH3 Br -
H
:
CH3CH2NH2
+
H3C CH2 NH CH2 CH3 H3C CH2 NH CH2 CH3 + CH3CH2NH3Br
:NH2CH2CH3
Diethylamine
H
The secondary amine formed can also then react with more halogenoalkane to form a tertiary amine
and subsequently on to what is called a quaternary ammonium salt
Where RX is the haloalkane
H R R
H RX
RX RX
+
H N: R N: R N: R N R
R R R R
Reaction with primary amines with acyl chlorides
Change in functional group: acyl chloride  secondary amide

Reagent: primary amine
Forming Amides
Conditions: room temp.
Aliphatic amines and
RCOCl +2CH3NH2  RCONHCH3 + CH3NH3+Cl- phenylamine can react
with acyl chlorides to
form amides in a
O O
nucleophilic addition-
CH 3 + CH3NH3 Cl
+ -
CH3 C + 2CH3NH2  CH 3 C NH elimination reaction- see
chapter 15C for more
Cl N-methylethanamide details.
Paracetamol is made by the reaction of an aromatic amine with an

acyl chloride to produce an amide
O
CH3 C
Cl O
HO NH2 HO NH C CH3
Paracetamol
The preparation of primary aliphatic amines
1. Forming a primary amine in a one step reaction of halogenoalkanes with ammonia
Primary amines can be formed by the nucleophilic substitution reaction between halogenoalkanes and ammonia in
a one step reaction. However, as the lone pair of electrons is still available on the N in the amine formed, the
primary amine can react in the same nucleophilic way in a successive series of reactions forming secondary, tertiary
amines and quaternary ammonium salts.
This is therefore not a good method for making a primary amine because of the further reactions. It would mean the
desired product would have to be separated from the other products.
CH3CH2Br + 2NH3  CH3CH2NH2 + NH4Br Ammonia dissolved in ethanol is the initial nucleophile
H H
+ In the first step of the mechanism the nucleophile
H3C C Br H3C C NH3 Br -
attacks the halogenoalkane to form an intermediate
H
3HN:
H
H H
+ In the second step of the mechanism a second
H3C C NH2 H3C C NH2 + NH4Br ammonia removes a proton from the
:NH3 intermediate (acts as base) to form the amine
H H H
Using an excess of Ammonia can limit the further

subsequent reactions and will maximise the amount of
primary amine formed
2. Preparing Amines from Nitriles

Using the method above of reacting halogenoalkanes and ammonia is not an efficient method for preparing a
high yield of the primary amine because of the further substitution reactions that occur.
A better method is to use the following reactions
Step 1. convert halogenoalkane to nitrile by using KCN in ethanol (heat under reflux)
CH3CH2Br + CN-  CH3CH2CN + Br -

Step 2. reduce nitrile to amine by using LiAlH4 in ether or by reducing with H2 using a Ni catalyst
CH3CH2CN + 4[H] CH3CH2CH2NH2
A disadvantage of this method is that it is a two step reaction that may therefore have a low yield. Also
KCN is toxic.
Reducing nitroarenes to aromatic amines
The nitro group on an arene can be reduced an amine group as follows
Reagent: Sn and HCl or Fe and HCl NO 2 NH2

Conditions: Heating + 6[H] + 2H2O
Mechanism:reduction
phenylamine
nitrobenzene
As the reaction is carried out in HCl the salt C6H5NH3+Cl- will be formed.
Reacting this salt with NaOH will give phenylamine.
The phenylamine formed in this reaction is best

separated from the reaction mixture by steam distillation.
Synthesis of azo dyes
Step 1: reaction of an aromatic amine with nitrous acid at Nitrous acid is generated in
<10 °C, forming a diazonium ion, situ from NaNO2/HCl.
NH2 NaNO2 + HCl <10oC Below 0oC the temperature is

+ too low and the reaction would
N N be too slow
diazonium ion If the diazonium ion is allowed to

heat above 10oC it reacts with water
to form phenol and N2 gas
C6H5NH2 + HNO2 + HCl C6H5N2+ Cl− + 2H2O
C6H5N2+ + H2O  C6H5OH + N2 + H+
Step 2: coupling of diazonium ion with a phenol under

alkaline conditions;
NaOH
+
N N + OH N N OH
4-hydroxyazobenzene
C6H5N2+ Cl− +C6H5OH  C6H5N2C6H4OH +HCl
Azo dyes are used for dyes, pigments and

colourings
Addition Polymerisation
An addition polymer forms when unsaturated Poly(alkenes) are chemically inert due to the strong C-C
monomers react to form a polymer and C-H bonds and non-polar nature of the bonds and
Monomers contain C=C bonds therefore are non-biodegradable.
It is best to first draw out

O O O
the monomer with groups
of atoms arranged around H C NH2
C H C NH2
the double bond
H2C CH NH2
C C H C C H
e.g. For propenamide n
H H H H
Poly(ethenol) poly(propenamide)
H OH H OH
n C C H C C H The addition polymer poly(ethenol) has good solubility in
n water because it can form many strong hydrogen bonds
H H H H with water. The makes it a useful polymer for uses such
poly(ethenol) as soluble laundry bags and liquid detergent capsules
(liquitabs) .
Condensation Polymerisation
In condensation polymerisation there are two different monomers
The two most common types of that add together and a small molecule is usually given off as a
condensation polymers are side-product e.g. H2O or HCl.
polyesters and polyamides which
involve the formation of an ester The monomers usually have the same functional group on both ends
linkage or an amide linkage. of the molecule e.g. di-amine, di carboxylic acid, diacyl chloride.
Forming polyamide uses these reactions we met earlier in the course
Acyl chloride + Amine  amide + HCl Carboxylic Acid + Amine  amide + water
If we have the same functional group on each end of molecule we can make polymers so we have the
analogous equations:
diacyl dichloride + diamine  poly(amide) + HCl dicarboxylic acid + diamine  poly(amide) + water
Nylon 6,6 - a common polyamide

O O
O O H H
N (CH2)6 N
n C (CH2)4 C +n C (CH2)4 C N (CH2)6 N + 2n-1 H2O
H H
HO OH
hexanedioic acid Hexane-1,6-diamine H H
n
The 6,6 stands for 6 carbons in each of the monomers. Different length carbon chains produce different
polyamides
Kevlar- a common polyamide
O O
n HO2C CO2H + n H2N NH2 + 2n-1 H2O
N N C C
H H n
Note on classification for condensation polymers
If asked for type of polymer: It is polyamide or polyester
Whereas type of polymerisation is condensation
It is also possible for polyamides and polyesters to form from one monomer, if that monomer
contains both the functional groups needed to react
O O O O
HO (CH2)3 C O (CH2)3 C O (CH2)3 C O (CH2)3 C
Cl
3 repeating units
O O O O
H2N C
N C N C N C
OH
H H H
3 repeating units
Chemical reactivity of condensation polymers The reactivity can be explained by the presence of
polyesters and polyamides can be broken down by polar bonds which can attract attacking species
hydrolysis and are, therefore, biodegradable such as nucleophiles and acids
Hydrolysis
Polyesters and polyamides can be hydrolysed by acid and alkali
The hydrolysis will result in the original monomers forming- although the carboxylic acid or amine group
will be in salt form depending on whether the conditions are alkaline or acidic
O O
O
+
HCl OH H 3N +
C (CH2)4 C N (CH2)6 N
HO
+ NH 3
H H O
n
NaOH O
-
-CO(CH2)4CONHC(CH3)2CH2O- - O
O + H2N
This polymer has both an amide and O
OH
ester link
Intermolecular bonding between condensation polymers chains

Polyesters have permanent dipole forces between the Cδ+=Oδ- groups in the different chains in
addition to the London forces between the chains.
Polyamides (and proteins) have hydrogen δ-

:
O Oδ- O
bonding between the lone pairs on oxygen in δ-
N C N C Nδ- C
Cδ+=Oδ- groups and the H in the Nδ- —Hδ+ δ+ δ+
H H δ+ H δ+
groups in the different chains.
There are also Permanent dipole-permanent
dipole forces because the polar C=O
:
O δ- Oδ- O
bond and polar C-N bond δ- δ-
N C N C N C
There are also London forces which are large δ+ δ+
because there are many electrons in the H H Hδ+
δ+
molecule
Polyamides will therefore have higher melting
points than polyesters.
Amino Acids
The simplest amino acid is

General structure of an amino acid NH2 CH2 CO2H
glycine, where the R is an H
NH2 CH CO2H
R
The R group can be a variety of
different things depending on what
amino acid it is.
Naming amino acids

CO2H Some amino acids have an extra CO2H
You do not need to know any carboxylic acid or an amine
CH2 CH2
common names for the 20 group on the R group. These are
essential amino acids. We NH2 C CO2H classed as acidic or basic NH2 C CO2H
should, however, be able to H 2-aminobutanedioic acid (respectively) amino acids H
name given amino acids using Aspartic acid
IUPAC organic naming OH
CO2H
CH2
H C (CH2)4 NH2
NH2 CH2 CO2H NH2 C CO2H Lycine (basic)
H 2-amino-3-
H2N 2,6-diaminohexanoic acid
(2-)aminoethanoic acid
hydroxypropanoic acid
Zwitterions
R R
The no charge form of an amino acid never occurs. + -
The amino acid exists as a dipolar zwitterion. H2N C CO2H H3N C CO2
H H
Amino acids are often solids Zwitterion
The ionic interaction between zwitterions explains the relatively high melting points of amino acids as
opposed to the weaker hydrogen bonding that would occur in the no charge form.
Acidity and Basicity

The amine group is basic and the carboxylic acid group is acidic. Amino acids act as weak buffers and will
only gradually change pH if small
R OH- R H+ R amounts of acid or alkali are added to the
- + - +
H2N C CO2 H3N C CO2 H3N C CO2H amino acids.
+NH -CH -CO - + HCl  Cl- NH3+-CH2-CO2H
H H H 3 2 2
H+ OH-
+NH -CH -CO - + NaOH  NH2-CH2-CO2-Na+ +H2O
Species in Species in Species in 3 2 2
alkaline solution neutral solution acidic solution
High pH Low pH
-
The extra carboxylic acid or amine groups COO
on the R group will also react and change CH2 Aspartic acid in high pH
form in alkaline and acid conditions -
NH 2 C COO
H
Optical Activity Optical isomers have similar
All amino acids, except H H
physical and chemical
glycine, are chiral because properties, but they rotate
there are four different groups C C
H2N CO2H HO2C plane polarised light in
around the C NH2 different directions.
CH3 CH3
They rotate plane polarised light.
Proteins CH3
Proteins are polymers made from H3C CH3 S

combinations of amino acids. CH HS CH2
The amino acids are linked by peptide links,
CH3 O CH2 O CH2 O CH2 O
which are the amide functional group.
H N CH C N CH C N CH C N CH C O H
O O O H H H H
NH CH C NH CH C NH CH C
R R R
Dipeptides
Dipeptides are simple combination molecules of For any two different amino acids there are two possible
two amino acids with one amide (peptide) link. combinations of the amino acids in the dipeptide.
HO HO
HO
CH3 H
Can make CH3 H CH2 CH2 CH3
CH2 or
H2N C CO2H +
H2N C C N C CO2H H2N C C N C CO2H
H H2N C CO2H
H H H O H
O
H
O δ- O
Importance of hydrogen bonding in proteins
:
δ-
N CH C N CH C
The 3D arrangement of amino acids with the δ+
polypeptide chain in a corkscrew shape is held in δ+
H R H R
place by Hydrogen bonds between the H of –Nδ-
:
—Hδ+ group and the –O of Cδ+=Oδ- δ-

O O
δ-
N CH δ+ C N CH C
H R H R
Other reactions of amino acids

The carboxylic acid group and amine group in amino acids can undergo the usual reactions of these functional groups met
in earlier topics. Sometimes questions refer to these.
e.g. Esterification reaction
CH3 CH3 O
H+ +
H2N C CO2H + CH3OH H3N C C O CH3 + H2O
H H
20 Synthetic Routes
KOH aqueous
dihalogenoalkane heat under reflux
Nucleophilic substitution
poly(alkene) diol
Br2, Cl2 KMnO4
room temp oxidation
Electrophilic addition
high pressure
alkane
Catalyst Br2, Cl2
H2, Nickel Catalyst
polymerization UV light
addition/reduction
alkene HBr, HCl
Free radical Substitution
room temp
Electrophilic addition
KOH alcoholic heat
halogenoalkane
conc. H3PO4 under reflux
H2O (g) Elimination
Catalyst: Elimination,
dehydration
Conc H3PO4 CN– and
PCl5, NaBr/H2SO4 P + I2
,
ethanol
Heat under reflux Nucleophilic
substitution KOH aqueous Alcoholic NH3 substitution
heat under reflux heat under pressure
Nucleophilic substitution Nucleophilic
LiAlH4
alcohol substitution
Reduction Caboxylic acid + H2SO4

heat amine LiAlH4
nitrile
LiAlH4 K2Cr2O7/H+ esterification
Reduction
Reduction
LiAlH4
If primary If secondary Reduction haloalkane
heat gently and distill heat under reflux NuSub
partial oxidation oxidation
Acyl chloride
2o amine room temp
3o amine Nu add/elim
aldehyde ketone
HCN + KCN secondary
Nucleophilic addition amide
K2Cr2O7/H+
heat under reflux + Esters and amides
excess oxidising agent can be hydrolysed
Oxidation hydroxynitrile by NaOH and acids
1o amine
Alcohol + H2SO4 room temp Primary
heat ester amide
carboxylic acid esterification
Alcohol
PCl5 room temp NH3 room temp
H2O room
temp Acyl chloride
Acid hydrolysis
Heat with HCl
Aromatic synthetic routes
Br N N OH
CH2CH3
chloroalkane and
+ OH
NaOH
anhydrous AlC3
Hydrogen Electrophilic catalyst
Nickel substitution
catalyst Br2 SO 3H
FeBr3
+
N N
SO3
conc nitric acid +

conc sulphuric acid NaNO2 + HCl <10oC
Electrophilic NO2
substitution
Sn and HCl NH2
NH CH3
reduction CH3Cl
Nu sub
acyl chloride in the presence
of anhydrous aluminium
chloride catalyst
Electrophilic substitution
O CH3COCl
C
CH3 O
NaCN + H2SO4 NH C CH3
Nu Add
LiAlH4 H
Red Nu Add
O
H
C CN
O
CH CH 3
CH3
HCl/heat
H
O O
CH3CO2H + H2SO4
heat C C
esterification OH
CH3
O
H3C CH O C CH3
Grignard Reactions
Grignard Reagent is used to increase the length of the carbon chain in a molecule
Preparing Grignard Reagent

A halogenoalkane is dissolved in dry ether and reacted with magnesium to
produce the reactive Grignard Reagent
This Grignard reagent is highly reactive and the

CH3CH2I + Mg  CH3CH2MgI
alkyl group can be considered to have a
Ethyl magnesium iodide negative charge. The R- [+MgI] and so contains
Grignard Reagent
a nucleophilic carbon atom
Reactions of Grignard Reagent
Reactions with carbonyls

With methanal will produce a primary alcohol
H2O
CH3CH2MgI + HCHO  CH3CH2CH2OH + Mg(OH)I
RMgI + HCHO  RCH2OH + Mg(OH)I
With other aldehydes will produce secondary alcohols

CH3
H2O
CH3CH2MgI + CH3CHO  H3C CH2 C OH + Mg(OH)I
H
H2O
RMgI + R’CHO  RCH(OH)R’ + Mg(OH)I
With ketones will produce tertiary alcohols

CH3
H3C CH3 H2O
CH3CH2MgI + C  H3C CH2 C OH + Mg(OH)I
O CH3
H2O
RMgI + R’COR”  RR’C(OH)R” + Mg(OH)I
Reaction with carbon dioxide

With CO2 will produce a carboxylic acid
H2O
CH3CH2MgI + CO2  CH3CH2CO2H + Mg(OH)I
The carbon chain can also be increased by the introduction of a nitrile group into a compound by either
reacting a halogenoalkane with KCN (see chapter 6D) or producing hydroxynitriles from carbonyls (see
chapter 17B)
Organic techniques
It’s important to be able to
draw and label this
Distillation apparatus accurately.
thermometer Don’t draw lines between
In general used as separation technique to separate an flask, adaptor and
organic product from its reacting mixture. Need to condenser.
collect the distillate of the approximate boiling point
range of the desired liquid.
Classic AS reaction using distillation Liebig condenser

Reaction: primary alcohol  aldehyde
Reagent: potassium dichromate (VI) solution and
dilute sulphuric acid.
Conditions: use a limited amount of dichromate
and warm gently and distil out the aldehyde as it
forms [This prevents further oxidation to the Water
carboxylic acid] out
CH3CH2CH2OH + [O]  CH3CH2CHO + H2O
Round Water in
Observation
bottomed
Orange dichromate solution changes to green
flask
colour of Cr3+ ions
Heat
Reflux
Reflux is used when heating organic reaction mixtures for long Water out
periods. The condenser prevents organic vapours from escaping
by condensing them back to liquids.
condenser
Never seal the end of the condenser as the build up of gas
pressure could cause the apparatus to explode. This is true of any
apparatus where volatile liquids are heated
Classic AS reaction using reflux

Reaction: primary alcohol  carboxylic acid Water in
Reagent: potassium dichromate(VI) solution and dilute
sulphuric acid
Conditions: use an excess of dichromate, and heat
under reflux: (distill off product after the reaction Round
has finished using distillation set up) bottomed
CH3CH2CH2OH + 2[O]  CH3CH2CO2H + H2O flask
Observation
Orange dichromate solution changes to green colour of
Cr3+ ions
Heat
Anti-bumping granules are added to the flask in both distillation and reflux to prevent vigorous,
uneven boiling by making small bubbles form instead of large bubbles
It’s important to be able to draw and label this apparatus accurately.

• Don’t draw lines between flask and condenser.
• Don’t have top of condenser sealed
• Condenser must have outer tube for water that is sealed at top and bottom
• Condenser must have two openings for water in and out that are open
Purifying an organic liquid General method
• Put the distillate of impure product into a separating

funnel
• wash product by adding either Sodium hydrogencarbonate will
• sodium hydrogencarbonate solution , shaking neutralise any remaining reactant acid.
and releasing the pressure from CO2 produced. Sodium chloride will help separate the
• Saturated sodium chloride solution organic layer from the aqueous layer
•Allow the layers to separate in the funnel, and then run and The layer with lower density will Separating
discard the aqueous layer. be the upper layer. This is usually funnel
the organic layer
•Run the organic layer into a clean, dry conical flask and add
three spatula loads of drying agent (e.g. anhydrous sodium
The drying agent should
sulphate, calcium chloride) to dry the organic liquid. When
•be insoluble in the organic liquid
dry the organic liquid should appear clear.
• not react with the organic liquid
• Carefully decant the liquid into the distillation flask
Decant means carefully pour off organic liquid
•Distill to collect pure product leaving the drying agent in the conical flask
Purifying an organic solid: Recrystallisation Used for purifying aspirin
Step Reason
1. Dissolve the impure compound in a minimum An appropriate solvent is one which will dissolve both
volume of hot (near boiling) solvent. compound and impurities when hot and one in which
the compound itself does not dissolve well when cold.
The minimum volume is used to obtain saturated
solution and to enable crystallisation on cooling (If
excess (solvent) is used, crystals might not form on
cooling)
2. Hot filter solution through (fluted) filter paper This step will remove any insoluble impurities and
quickly. heat will prevent crystals reforming during filtration
3. Cool the filtered solution by inserting beaker in ice Crystals will reform but soluble impurities will remain
in solution form because they are present in small
quantities so the solution is not saturated with the
impurities. Ice will increase the yield of crystals
4. Suction filtrate with a buchner flask to separate The water pump connected to the Buchner flask
out crystals reduces the pressure and speeds up the filtration.
5 Wash the crystals with distilled water To remove soluble impurities
6. Dry the crystals between absorbent paper
Loss of yield in this process

• Crystals lost when filtering or washing
• Some product stays in solution after recrystallisation
• other side reactions occurring Buchner flask
If the crystals are not dried properly the mass will be larger
than expected which can lead to a percentage yield >100%
Steam distillation steam
in
In steam distillation steam is passed into

the mixture and the product vapour is
distilled off with the water and condensed
Advantage of steam distillation:

The product distils at a lower temperature
which can prevents decomposition of the
product if it has a high boiling point
Water
out
Water
in
Solvent extraction
Mix organic solvent and oil-water mixture in a

separating funnel then separate the oil layer.
Distil to separate oil from organic solvent
Add anhydrous CaCl2 to clove oil to dry oil
Decant to remove CaCl2
Separating funnel
Safety and hazards
A hazard is a substance or procedure that can has the RISK: This is the probability or chance that
potential to do harm. harm will result from the use of a
Typical hazards are toxic/flammable /harmful/ hazardous substance or a procedure
irritant /corrosive /oxidizing/ carcinogenic
Irritant - dilute acid and alkalis- wear googles Hazardous substances in low
Corrosive- stronger acids and alkalis wear goggles concentrations or amounts
Flammable – keep away from naked flames will not pose the same risks
Toxic – wear gloves- avoid skin contact- wash hands after use as the pure substance.
Oxidising- Keep away from flammable / easily oxidised materials
Measuring melting point
One way of testing for the degree of purity is to determine the melting
“point”, or melting range, of the sample.
Thermometer with
If the sample is very pure then the melting point will be a capillary tube
sharp one, at the same value as quoted in data books. strapped to it
containing sample
If impurities are present (and this can include solvent from the
recrystallisation process) the melting point will be lowered and Heating oil- needs
the sample will melt over a range of several degrees Celsius to have boiling point
higher than samples
melting point and
Melting point can be measured in an electronic melting point low flammability
machine or by using a practical set up where the capillary tube is
strapped to a thermometer immersed in some heating oil.
In both cases a small amount of the salt is put into a capillary tube.
Heat
Comparing an experimentally determined melting point
value with one quoted in a data source will verify the
degree of purity.
Sometimes an error may occur if the temperature on the thermometer is not the same as the temperature in
the actual sample tube.
Measuring boiling point

Purity of liquid can be determined by measuring a boiling point. This can be
done in a distillation set up or by simply boiling a tube of the sample in an To get a correct measure
heating oil bath. of boiling point the
thermometer should be
Pressure should be noted as changing pressure can change the boiling above the level of the
point of a liquid surface of the boiling liquid
and be measuring the
temperature of the
Measuring boiling point is not the most accurate method of identifying a saturated vapour.
substance as several substances may have the same boiling point.
Combustion Analysis
0.328 g of a compound containing C,H and O was burnt completely in excess oxygen,
producing 0.880 g of carbon dioxide and 0.216 g of water. Use these data to calculate
the empirical formula of the compound.
Work out moles of CO2 = Mass of CO2/Mr of CO2

= 0.88/44
=0.02mol
Moles of C in compound = moles of CO2 Mass of C in = mol of C x 12
= 0.02 mol compound =0.02 x12
=0.24g
Work out moles of H2O = Mass of H2O /Mr of H2O
= 0.216/18
=0.012mol
Moles of H in compound = 2 x moles of H2O Mass of H in = mol of H x 1

= 0.024 mol compound =0.024 x1
=0.024g
Work out mass of O = mass of compound – mass of C – mass of H

in compound = 0.328 – 0.24 -0.024
=0.064
Work out moles of O = Mass of O /Ar of O

in compound = 0.064/16
= mol 0.004
Work out molar ratio

of 3 elements (divide C = 0.02/0.004 H = 0.024/0.004 O = 0.004/0.004
by smallest moles) =5 =6 =1
empirical formula = C5H6O
See notes in chapter 10 and 15E on spectroscopy for mass spec, IR, and NMR
Bringing it all together
C H O
1. Work out empirical formula
66.63/12 11.18/1 22.19/16
Elemental analysis C 66.63% H 11.18% O 22.19%
=5.5525 =11.18 =1.386875
=4 =8 =1
2. Using molecular ion peak m/z value from mass

spectrum calculate Molecular formula Mr empirical formula C4H8O = 72
molecular ion peak m/z value= 144 If Mr molecular formula 144 then
compound is C8H16O2
3. Use IR spectra or functional group C8H16O2 could be an ester, carboxylic acid or combination of
chemical tests to identify main alcohol and carbonyl. Look for IR spectra for C=O and O-H
bonds/functional group bonds
There is a C=O but no

O-H absorptions, so
must be an ester.
C-H
C=O
CH3
4. Use NMR spectra to give details of carbon chain singlet of area 9 H3C C H
At δ =0.9 CH3
4 peaks – only 4 different environments. Means 3 CH3 groups
9
Peak at δ 4 shows H–C–O Peak at δ 1.2

Peak at δ 2.2 shows H–C=O
shows R-CH3
Area 2 suggests CH2 Area 2 suggests CH2 Area 3 means CH3
Quartet means next to a Singlet means adjacent to Triplet means next
CH3 C with no hydrogens to a CH2
H H3C CH3
H O
H3C O C H
H3C O C C H 2
2 3
H
H
5 4 δ ppm 3 2 1
Put all together to give final structure
CH3 O
H3C C CH2 C O CH2 CH3
CH3
Testing for Organic Functional Groups
Functional group Reagent Result
Alkene Bromine water Orange colour

decolourises
Alcohols + carboxylic acids PCl5 Misty fumes of HCl
produced
Alcohols, phenols, Sodium metal Effervescence due to H2
carboxylic acids gas
Carbonyls 2,4,DNP Orange/red crystals
produced
Aldehyde Fehlings solution Blue solution to red
precipitate
Aldehyde Tollens Reagent Silver mirror formed
Carboxylic acid Sodium carbonate Effervescence of CO2

evolved
1o 2o alcohol and Sodium dichromate and Orange to green colour
aldehyde sulphuric acid change
chloroalkane Warm with silver nitrate Slow formation of white
precipitate of AgCl
Acyl chloride Silver nitrate Vigorous reaction- steamy
fumes of HCl- rapid white
precipitate of AgCl
Tollen’s Reagent Fehling’s solution

Reagent: Tollen’s Reagent formed by mixing aqueous Reagent: Fehling’s Solution containing blue Cu 2+ ions.
ammonia and silver nitrate. The active substance Conditions: heat gently
is the complex ion of [Ag(NH3)2]+ . Reaction: aldehydes only are oxidised by Fehling’s
Conditions: heat gently Solution into a carboxylic acid and the copper ions
are reduced to copper(I) oxide .
Reaction: aldehydes only are oxidised by Tollen’s
reagent into a carboxylic acid and the silver(I) Observation: Aldehydes :Blue Cu 2+ ions in solution
change to a red precipitate of Cu 2O. Ketones do
ions are reduced to silver atoms not react
Observation: with aldehydes, a silver mirror forms
coating the inside of the test tube. Ketones result CH3CHO + 2Cu2+ + 2H2O  CH3COOH + Cu2O + 4H+
in no change.
CH3CHO + 2Ag+ + H2O  CH3COOH + 2Ag + 2H+
The presence of a carboxylic acid can be tested by

addition of sodium carbonate. It will fizz and produce
carbon dioxide
2CH3CO2H + Na2CO3  2CH3CO2-Na+ + H2O + CO2

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16.

Why does a voltage form? Why use a High resistance

What happens if current is allowed to flow?

The most positive electrode will always undergo reduction.

The most negative electrode will always undergo oxidation.

Systems that do not include metals.

Cl2 (g) + 2e-  2Cl- (aq) | | Cl2 | Cl- | Pt

As the phase line also separates the oxidised and

Measuring the electrode potential of a cell

The potential of all electrodes are measured by comparing

Standard Electrode Potentials E

They may also be quoted as half Pt electrode

Pt|H2|H+||Fe3+,Fe2+|Pt 1M Fe2+ and 1M Fe3+

Note: in the electrode system containing two solutions it is

Using electrode potentials

The most useful application of electrode potentials is to show

The easiest way to use electrode potentials is as follows:

To get the full equation of the reaction add the

Using series of standard electrode potentials

As more +ve As more -ve

Use electrode data to explain why fluorine reacts with water.

Equation Remember to cancel out electrons in full equation

Explanation to write oxidise

Ecell is directly proportional to the total entropy change

A positive Ecell will lead to a positive total entropy change

Effect of conditions on Cell voltage Ecell

Looking at cell reactions is a straight forward Zn + Fe2+  Fe + Zn2+ E= +0.32

Hydrogen Fuel cell (potassium hydroxide electrolyte)

4e- + 4H2O  2H2 +4OH- E=-0.83V H2 O2

2e- + 2H+ H2 E=0V In acidic conditions these are the

Advantages of Fuel cells over conventional Limitations of hydrogen fuel cells

Hydrogen is readily available by the

Ethanol fuel cells

Ethanol fuel cells have also been developed. Compared to

Methanol can also be used in fuel cells

be able to perform calculations for these titrations and for

MnO4-(aq) + 8H+(aq) + 5Fe2+  Mn2+ (aq) + 4H2O + 5Fe3+

So overall the ratio is 3 MnO4- to 5 FeC2O4

Step1 : find moles of KMnO4

Thiosulphate redox titration A starch indicator is added near the end

Readings Measurements The uncertainty of a reading (one judgement) is at

Calculating Apparatus Uncertainties

To calculate the maximum percentage apparatus uncertainty in the

Reducing uncertainties in a titration If looking at a series of measurements

To reduce the uncertainty in a burette reading it is necessary to

Reducing uncertainties in measuring mass

If the %uncertainty due to the apparatus <

Why is Zn not a transition metal?

Why is Sc not a transition metal?

ligands can be monodentate (e.g. H2O, NH3 and Cl- 3+

with six donor sites(4O and 2N) and forms a 1:1 O C O

Colour changes arise from changes in

Cu(H2O)62+ + 4Cl-  [CuCl4]2- + 6H2O

How colour arises

Compounds without colour

Platin binds to DNA of cancer cells and

Redox Equation Eo Values

Zn2+ + 2e-  Zn E=-0.76V

Sn2+ + 2e-  Sn E=-0.136V