Rate of Reaction: Change in amount of substance in a unit of time

Rate of Reaction in solutions: Change in concentration of substance in a unit of time

Unit of Rate of Reaction: moldm-3s-1
The initial rate is the tangent to the curve that goes through the origin. It is the gradient in concentration/time graphs.
Whenever this symbol is used: [ ], it means concentration of, hence the Rate of Reaction equation is:
Rate [A]m[B]n, A and B are the two reactants of the equation. m is the partial order of A or is also referred to as
order with respect to A, i.e. it tells you how the concentration of A affects the rate. n does the same for B.
Sometimes, the Rate is ZERO ORDER, i.e. Rate [A]0[B]0, i.e. a change in concentration of A or B, has no effect on
the rate. Therefore, in an actual reaction this would look like:
As you can see the gradient, which is the rate, in the second graph, does not change at all as time increases.

Sometimes, the Rate is FIRST ORDER,

i.e. Rate [A]1 OR Rate [B]1 , i.e. a
change in concentration of A or B, has
no effect on the rate. Therefore, in an actual reaction this would look like:
As you can see, the gradient, which is the rate, in the second graph, decreases as the concentration of A OR B
decreases

Sometimes the Rate is SECOND

ORDER, i.e. Rate [A]1[B]1 OR
Rate [A]2 OR Rate [B]2, i.e. a
change in concentration of A or B
has double the effect on the rate.
As you can see, in the second graph, as concentration decreases by 1, time increases by 1, as concentration
decreases by 2, time increases by 2, as concentration decreases by 3, time increases by 4, as concentration
decreases by 4, time increases by
8, as concentration decreases by
5, time increases by 16, and so on.
However instead of using Rate
[A]m[B]n, scientists replace with a
constant of proportionality K.
Hence it now equals: Rate=
K[A]m[B]n. The rate constant K in
cooperates all factors that affect
the rate other than concentration. It only changes if there is a change in temperature, pressure, etc.
The units of K vary; the units of Rate are moldm-3s-1, hence If the reaction is 0 order, then Rate= K therefore K has
units moldm-3s-1.
If the reaction is 1st order, then the unit of K is s-1 as Rate = moldm-3s-1, therefore the K has s-1 and the [A]1 has
moldm-3 .
If the reaction is 2nd order, then K = Rate [A]1[B]1, therefore (moldm-3 s-1) (moldm-3) (moldm-3), which means
s-1 1/moldm-3, therefore the units are mol-1dm3 s-1.
Orde
r
0
1

Unit of k
Moldm-3s-1
s-1

Mol-1 dm3s-1

3
4
5

Mol-2 dm6s-1
Mol-3 dm9s-1
Mol-4 dm12s-1

It is also important to
remember that the Rate
equation only involves those
reactants that are involved in
the slowest step of the
reaction. Therefore, the
Nucleophilic reaction of 2bromo-2-methylpropane has
the rate equation:
Rate= K [(CH3)3CBr],

so as we can see the OH:- is not in the rate of equation, telling us that this reaction follows Mechanism 2 as the
slowest step in Mechanism 2 does NOT involve OH:-.
Zero Order reactions are known as pseudo order reactions as they imply that nothing has collided. They can occur
in 3 ways:
1) The concentration of a reactant in the slow step is remaining constant
2) If one of the reactants is the solvent
3) One of the reactants is deliberately in EXCESS, therefore so less gets used up, we cant measure it
When the temperature is lowered:
The rate constant K is lowered, this is because the less reacting particles have the activation energy
How you can tell that a chemical is behaving as a catalyst:
1) It is in the Rate Equation
2) However it is not in the Stoichiometric Equation
Equilibrium constants K
It tells you the position of the equilibrium by measuring the relative amounts of products and reactants. Equilibrium
relates to a BALANCED WRITTEN equation. The number of moles of each chemical in the BALANCED WRITTEN
equation becomes the POWER in the Equilibrium expression. The value of K will change as temperature changes,
the value of K that you obtain will be at a specific temperature.
It is always K = [Products]/[Reactants]
K can never be zero as it is the number of moles.
Value of K
What it means
Never involve a Solid in an expression as its
K>>1
A lot more products than reactants
concentration remains constant.
K>1
More products than reactants
EXAMPLE: CaCO3(S) CaO(S) + CO2(g)
K=1
Equal amount of product and reactant
Therefore the equilibrium expression is: K = [CO2]
K<1
More reactants than products
K<<1
A lot more reactants than products
Also do not involve any Solvents in an Equilibrium expression, (Solvent is the Liquid substance in which you dissolve
something). This does not mean do not involve Liquids in the Equilibrium expression, it means that the Liquid
substance will not be involved in the Equilibrium expression if it also a Solvent.
EXAMPLE: CH3CO2CH3(aq) + H2O(l) CH3CO2H(aq) + CH3OH(aq) ;Therefore the Equilibrium expression will be
K = [CH3CO2H] [CH3OH]/ [CH3CO2CH3]
To work out the value of K, you ALWAYS need to know the concentration at EQUILIBRIUM, which is sometimes
given, and sometimes it must be worked out.
Example:
PCl5

PCl3
+
Cl2
Initial MOLES
5.0
0.0
0.0
Equilibrium
4.5
0.5
0.5
MOLES
Now in the exam, they will ask you at this point to work out the moles of PCl5, well you know that as PCl5 loses one
mole, PCl3 gains one mole and Cl2 gains one mole, therefore if PCl5 lost half a mole, PCl3 would gain half a mole Cl2
would gain half a mole. PCl5 lost half a mole from its original (5.0).
Hence K = (0.5/v)(0.5/v) (4.5/v)

Example:

2SO3
8.0

2SO2

O2
0.0
1.4

Initial MOLES
0.0
Equilibrium
2.8
MOLES
Hence, you know that as SO3 loses one male, SO2 gains one mole and O2 gains half a mole. Therefore, if at
equilibrium, Oxygen has 1.4 moles, SO2 must have 1.4 x 2 = 2.8, therefore SO3 lost 2.8 moles as it loses the same
amount of moles that SO2 gains (because of 1:1 ratio), therefore 8.0 2.8 = 5.2.
If we have the following reaction:
A+BC
K = [C] [A][B]
Therefore if the moles of C were 24 and the moles of A were 3 and the moles of B were 4, and the volume was
2dm-3 then this would equal:
K = (24/2) (4/2)(3/2) = 4
But now if we add an inert gas (does not affect equilibrium reaction) at constant pressure, then this would increase
the volume, lets say that the volume increased to 4dm-3, hence K (24/4) (4/4)(3/4) = 8, this means that K has been
changed by volume change which as we know is not possible as only temperature and pressure can change K.
Therefore the equilibrium moves so as to make the K value back to 4, and therefore moves to reactants as
K = Products Reactants = 8, therefore if reactants are doubled, then K would become 4 again.
The value of Kc of the reversed reaction is simply 1/Kc of the forward reaction.
Units of K
Units of K also vary, but it is basically:
(mol dm-3)Sum of Powers of Products Sum of Powers of Reactant
Hence the K value for the following is:
K = (SO3)2/(SO2)2(O2)
Hence Powers of Products Powers of Reactants = 2 3 = -1, therefore (mol dm-3)-1 = mol-1 dm3
Sometimes K may not even have any units, such as the following:
K = (H2)(I2)/(HI)2
Hence Powers of Products Powers of Reactants = 2 2 = 0, therefore (mol dm-3)0 = NO UNITS
The value of K will increase: if the PRODUCTS increase due to a change in temperature

Brownstead Lowry Base: Proton acceptor/Electron pair donor

Brownstead Lowry Acid: Proton donor/Electron pair acceptor

pH = -log10[H+], it is a measure of the concentration of H3O+(aq) ions
p means log10
H means [H+]/[H3O+]
Water can act as a base and an acid. H2O(l) H+(aq) + OH-(aq), this is an ENDOTHERMIC REACTION (+)
The equilibrium constant is called Kw and it is Kw = [H+][OH-], at 25oC (298K), the value of Kw is 1.00 x 10-14
In pure water at ANY TEMPERATURE, [H+] = [OH-], therefore Kw = [H+]2, therefore [H+] = KW, therefore pH =
-logKW
Strong Base: Fully ionised in aqueous solution (no reversible equation)
NaOH(s) Na+ + OHFor example if [NaOH] is 1 x 10-3, then [OH-] = 1 x 10-3, therefore log10[OH-] + log10[H+] = 14, therefore pOH + pH =
14 at 25oC
Therefore pOH = 3.00, hence pH = 14 3.
Ba(OH)2 Ba2+ + 2OHFor example if [Ba(OH)2] is 1 x 10-3, then [OH-] = 1 x 10-3 X 2, therefore log10[OH-] + log10[H+] = 14, therefore pOH +
pH = 14
Therefore pOH = 3.00, hence pH = 14 3.
Strong Acid: Fully ionised in aqueous solution (no reversible equation)
HCl + H2O Cl- + H3O+
For example if [HCl] is 1 x 10-2, then [H+] = 1 x 10-2, therefore pH = 2.00
H2SO4 SO42- + 2H+
For example if [H2SO4] is 1 x 10-3, then [H+] = 1 x 10-3 X 2, therefore pH =
Weak Base: Partially ionised in aqueous solution (reversible equation)
NH3 + H2O NH4+ + OHTHE GENRAL FORMULA IS: B + H2O BH+ + OH- (BH+ is the salt of a weak base, in the above example CH3COOis the salt)
Weak Acid: Partially ionised in aqueous solution (reversible equation)
CH3COOH + H2O CH3COO- + H3O+
THE GENRAL FORMULA IS: HA H+ + A- (A- is the salt of a weak acid, in the above example CH3COO- is the salt)
How to work out the pH of a weak acid:
The equilibrium constant of a weak acid is called Ka, it generally equals Ka = [H+][A-] [HA]
Well as we know [H+]= [A-], therefore Ka = [H+]2 [HA]
Hence [H+] = (Ka X [HA]), another way of writing this is pH = (pKa log10[HA])/2 (Pka = -log(Ka), pKa just helps to
make the rather small numbers of Kainto larger numbers so that comparison can be made.
When you have a mixture of a weak acid (such as CH3COOH) and a strong base (NaOH):
NaOH + CH3COOH CH3COO- + Na+ + H+ + OHBut the CH3COO- can ACCEPT a proton, therefore it is a base, hence SALTS OF WEAK ACIDS ARE BASIC
The overall general equation would be:
Hence you get: NaOH + CH3COOH

NaCH3COO+
H2O
Base + Weak Acid
Salt of Weak Acid + Water
When you have a mixture of a weak base (such as NH3) and a strong acid (HCl):
NH3 + HCl Cl- + NH4+ + H+ + OHBut the NH4+ can DONATE a proton, therefore it is an acid, hence SALTS OF WEAK BASES ARE ACIDIC
The overall general equation would be:
Hence you get:
NH3
+
HCl
NH4Cl
+
H2O
Weak Base + Strong Acid
Salt of Weak Acid + Water
When in a solution you have a mixture of a weak acid and its salt OR a weak base and its salt, then it is known as a
BUFFER SOLUTION as it will resist a change in pH.
Buffer Solution: A solution that resists changes in pH on addition of small amounts of acid or base or on dilution
Uses of Buffer Solutions:
1)

Buffer

Equation

Acidic
Buffer

HA H+ + A-

Add little bit of Acid (H+)

H+ concentration
increases, thus it is
reduced by Le Chatelliers
Principle by combining
with A-:
H+ + A- HA

H+ concentration
increases, H+ reacts with
the OH- forming H2O, thus
reducing the concentration
Basic
B + H2O BH+ + of OH-, hence Le
Buffer
OHChatelliers Principle will
ensure the reaction
increases the
concentration of OH- by
moving to the left.
In each this is what we will be doing:
As you can see there is no buffer as

Add a little bit of Base (OH-)

The OH- concentration increases, the OH- reacts
with the H+ in the solution forming H2O, thus
reducing the concentration of H+, hence Le
Chatelliers Principle will ensure that the
reaction increases the concentration of H+ by
moving to the left:
OH- + H+ H2O
HA H+ + ATHEREFORE OVERALL REACTION:
OH- + HA H+ + H2O
The OH- concentration increases, thus it is
reduced by Le Chatelliers principle by
combining with BH+ forming H2O and B.

there is no weak acid and its salt or weak base and its salt in the
solution.

As you can see, in the first graph, there is a

buffer at the start as at the beginning you have
a weak acid and as you add a strong base, the
weak acid is being converted to its salt, hence
you have a mixture of a weak acid and its salt,
and this can act as a buffer. Also notice how the
equivalence point is above 7 as salts of weak
acids (which is what in the end, all the acid is
converted to) are BASIC.
The reverse is taking place in the second
graph.
As you can see, in the first graph, at the
beginning there is no buffer as there is a strong
acid to which a weak base is being added, the
weak base is converting the strong acid to its
salt, hence you have a mixture of a strong acid
and its salt, and this is not a buffer. However at
the end point, all the strong acid
Has been converted to the salt (which is also
the salt of the weak base which was being
added), hence after this, when you add further
weak base, you have a mixture of a weak
base and its salt, which is a buffer, the reverse
is taking place in the second graph.

Calculation method for Strong Acid/Strong Base calculation:

1) Work out moles of H+ using the formula: Volume 1000 x concentration of ACID
NOTE: If it is a DIPROTIC ACID, multiply this answer by two as you make 2 moles of H+ in diprotic acids
2) Work out moles of OH- using the formula: Volume 1000 x concentration of BASE
3) After deducting which one is bigger take away the smaller number from the bigger number
If the bigger one is OH-, then do moles of OH- - moles of H+,
If the bigger one is H+, then do moles of H+ - moles of OH4) Now work out the concentration of the remaining moles of OH-/H+ (whichever one is remaining)
5) Use the formula: Concentration (mol dm-3) = (Moles (mol) x 1000) TOTAL VOLUME
Remember by total volume it means, the volume of the H+ and OH- combined
6) After working out the concentration, work out the pH or pOH by doing log10 of the concentration
7) If it was pOH you worked out (because OH- had the higher number of moles), then do 14 ANSWER to get
pH
Calculation method for Strong Base and Weak Acid
1) Work out the moles of ACID in flask
2) Work out the moles of OH- added
3) Moles of OH- added = moles of salt (A-) formed
4) Moles of ACID remaining = moles of ACID in flask - moles of salt (A-) formed
5) Work out the concentration of both the moles of ACID remaining and the moles of the salt formed
8) To do this, use the formula: Concentration (mol dm-3) = (Moles (mol) x 1000) TOTAL VOLUME
Remember by total volume it means, the volume of the ACID and OH- added combined
6) Once you have the concentration of ACID concentration of A-, use the following formula:
pH = pKa log10([ACID] [salt])
NOTE: In this above situation (Strong Base and Weak Acid), if a lot of the Strong Base has been added, then the
moles of OH- added will be greater than the moles of ACID in flask, therefore just follow the routine for the Strong
Acid and Strong Base calculation, i.e. moles of OH- - moles of ACID.
Calculation method when a buffer is made:
1) Calculate concentration of HA
2) Calculate concentration of A3) Rearrange the formula Ka = [H+][A-] [HA] to find [H+]
4) Do log10(answer)
You make a buffer by the following formulas: HA H+ + A- and NaA Na+ + A-, hence you have a solution of HA
and its salt, A-.
Calculation method when a Strong Acid is added to a buffer:
1) Moles of Strong Acid added is now added to the moles of weak acid because: H+ + A- HA
2) Therefore the moles of A- remaining are: moles of A- - moles of Strong Acid added
3) From this point on, you have the moles of HA and moles of A-, simply work out pH using:
pH = pKa log10([ACID] [salt])
Calculation method when a Strong Base is added to a buffer:
1) Moles of Strong Base is now added to the moles of salt A- because: OH- + H+ A- + H2O
2) Therefore the moles of HA remaining are: moles of HA moles of Strong Base added
3) From this point on, you have the moles of HA and moles of A-, simply work out pH using:
pH = pKa log10([ACID] [salt])
Indicators are weak acids, hence they disassociate in aqueous solution in the following way:
HIn H+ + InHence HIn has a colour different to the colour of In-. Hence at a low pH, when the H+ are abundant, i.e. you are
adding H+, the H+ will react with In- and form HIn, and hence you will see the colour of HIn. At High pH, when the OHis abundant, i.e. you are adding OH-, the OH- reacts with the H+ in the above equilibrium, thus reducing
concentration of H+, therefore Le Chatelliers Principle tells us that the equilibrium will displace to the right forming Inand H+, hence you will see the colour of In-. It is important that when the equilibrium displaces to the right or left in
the indicator equilibrium it happens in a flash, i.e. just one drop of extra H+ or OH- pushes the equilibrium left or right
respectively.

GIVE ALL pH ANSWERS TO 2 DECIMAL PLACES!

If you are asked to name the chemical that needs to be added to a Weak Acid or a Weak Base to make it a buffer
solution, ensure that it is the salt of the Weak Acid or Weak Base, i.e. if you have a Weak Acid such as Ethanoic
Acid, then the chemical you will add will be Sodium Ethanoate, if you a Weak Base such as CH3CH2NH2
(ethylamine), then you will add the salt of ethylamine which is CH3CH2NH3Cl.
In a Diprotic Acid such as Sulphuric acid, there will be two equivalence points; each one will be where each H from
H2SO4 was lost. The moles of H+ will be 2 x the moles of H2SO4. (Bog off!)

OPTICAL ISOMERS
A Chiral Centre will give 2 optical isomers; R/S
(enantiomers).
Most common way to make a Chiral Centre:

4 different groups attached to the same

carbon atom, it is said to possess an
ASYMMETRIC CARBON ATOM.
The isomers are MIRROR IMAGE MOLECULES that are NON-SUPERIMPOSABLE.
We indicate Chiral Centres with:
Properties of Optical Isomers:
Same colour
Same melting point
Same boiling point
Same density
Reason: same atoms with the same bonds between them.
Only difference between Optical Isomers: their effect on the plane of Plane Polarised Light; isomers will rotate the
plane of plane polarised light by equal amounts but in opposite directions,
one isomer will rotate the plane clockwise, this is known as the + isomer
(dextrorotary), whilst the other isomer will rotate it counter clockwise.
Plane Polarised Light: light made up of waves vibrating in one plane only
Racemic Mixture: a
50:50 mixture of the
two isomers, therefore
NO EFFECT ON
PLANE POLARISED
LIGHT as directions
cancels out. Aracemic
mixtures have different
properties to the
individual isomers, for example the melting point is lower than individual isomers: WHY: Impurities
lower the melting point, impure because one isomer is left-handed whilst the other is right-handed.
CHIRAL CENTRES are made from planar molecules such as Ethanal.
Hence, both attacks take place, resulting in a Racemic Mixture, with a mixture of both enantiomers taking place.

How a racemic mixture is formed:

1) A planar molecules is used
2) Hence EQUAL probability of attack by nucleophile, etc. from above and below
Most Optical Isomers have the same properties, with exceptions such as when optically active molecules interact
with other optically active molecules (enzymes), enzymes are stereospecific, and they can distinguish between
enantiomers and catalyse reactions of only one of a pair of enantiomers, the other enantiomers could fit into a
different enzyme and cause harmful effects. For example: Thalidomide is a racemate of the R isomer and the S
isomer, the R isomer relieves morning sickness in pregnant women, however, the S isomer causes birth defects. To
the point that even if the safe isomer, R, is given, the body will convert some of it to the harmful isomer.
In these optical isomers, if asked to draw them, then draw the compound in a tetrahedral shape with the CHIRAL
CENTRE in the middle.
Advantage of using a racemate rather than a single enantiomer in medicine:
Cheaper medicine as there is no need to separate mixture
Disadvantage of using a racemate rather than a single enantiomer in medicine:
May be side effects from one enantiomer in the mixture
One enantiomers may be ineffective

Double dose is required

Functional
Group

Ending

Aldehyde

R-al

Ketones

R-one

Amides

Esters

Carboxylic
Acid

Anhydrides

Acid
Chlorides

Amines

N-yl R-amide

R(Alcohol)-yl
R(Carboxylic
Acid)-oate

R-noic acid

R-oic
Anhydride

R-oyl Chloride

-Amine or
begin with
Amino

Feature

Condition
1) It is always at the rear end of a
chain.
2) Numbers begin from butanal
3) The C-H bond never breaks
NUCLEOPHILIC ADDITION
1) Isomer will be in the middle of a
chain
2) The C-R bond never breaks
NUCLEOPHILIC ADDITION
1) The N-C bond never breaks
NUCLEOPHILIC ADDITION
ELIMINATION
WITH CATALYST H+ OR OH-

1) The R-O bond never breaks

NUCLEOPHILIC ADDITION
ELIMINATION WITH CATALYST H+
OR OH1) It is always at the rear end of a
chain.
2) The R-C rarely breaks
3) Therefore very weak acid
NUCLEOPHILIC ADDITION
ELIMINATION WITH CATALYST H+
OR OH1) The C-O bond EASILY breaks
2) Therefore the O:- is a GOOD
LEAVING GROUP
3) Therefore weak acids
4) The two R-Group HAVE to be the
same, and name will be
R+C Anhydride
NUCLEOPHILIC ADDITION
ELIMINATION
1) The C-Cl bond EASILY breaks,
2) Therefore Cl:- is a GOOD LEAVING
GROUP
3) It fully ionises, therefore it is a
strong acid
NUCLEOPHILIC ADDITION
ELIMINATION
1) The difference with the amide is
that the amide has a C=O next to
the Nitrogen

R-Ol
Alcohol
Nitriles

R-nitrile

Remember the following Curly Arrow Rules:

1) DO NOT DISCRIMINATE
AGAISNT THE e

1)
2)
3)
4)

Curly Arrow starts at a bond or lone pair

Curly Arrow arrives, one unit more negative
Curly Arrow leaves, one unit more positive
A charged substance (ions) will not stay in a bottle, take curly arrows to ensure no charges are left

In alkenes, as the length of the chain increases, the melting point and boiling point increases.

Bifunctional Molecules:
In naming, usually the Carboxylic Acids will have the greatest right to take the main name, then the Ketones and
then the alcohols.
When asked to write the formulas of an organic chemical ensure to not discriminate against the e!
For example: DO NOT write methyl propanoate X, instead you must write: methyl propanEoate,
DO NOT write 2-hydroxybutanitrile X, instead you must write: 2-hydroxybutanEnitrile
1)
2)
3)
4)
5)

When there are two Carboxylic Acids on a carbon chain, then the name will involve DIOIC ACID.
When there are two Ketones on a carbon chain, then the name will involve DIONE.
When there are two Esters on a carbon chain, then the name will involve DIOATE.
When there are two Alcohols on a carbon chain, then the name will involve DIOL.

When a COOH group is attached as well as an OH group, the COOH Carbon will be where the carbon chain begins,
whichever carbon number the OH is attached to will be labelled with Hydroxy, for example: the chemical
HOCH2CH2COOH will be called 3-Hydroxypropanoic Acid.
Aldehydes must always be written as CHO not COH.
Do not be confused by formulas such as (CH3CH2)2NH, this is simply Diethylamine.

NUCELOPHILIC ADDITION:

Aldehydes & Ketones:

Nucelophil
e

Product for Aldehyde and Ketone

Comment
HydroxyNitriles are made.
The picture shown in Aldehydes is of
2-Hydroxy R-Nitrile
The picture shown in Ketones is of
2-Hydroxy R-yl R-Nitrile

-:

CN

Aldehydes:
Ketones:

The aldehyde reacts faster, this is because of the

inductive effects of alkyl groups, i.e. the C=O is
more +

For
example: Aldehydes:
CH3CH
2CHO + HCN
CH3CH2CH(OH)CN, Propanal to 2-hydroxybutanenitrile
Hydroxy Nitriles can be converted into 2-HydroxyCarboxylic Acids via Hydrolysis using H+ OR OH-:

Hydroxy Nitriles can be converted into 1-AminoAlcohols via Reduction using H2 OR Pd:

Nucleophile
BH4- / H:But we are
allowed to use
the symbol
[H]

Product for Aldehyde & Ketone

Comment
Alcohols are made.
The Aldehydes make
PRIMARY ALCOHOLS.

Aldehyde:

Ketone:

The Ketones make

SECONDARY
ALCOHOLS

This process is also

referred to as
REDUCTION OF
ALDEHYDES &
KETONES
For Aldehydes: R CO - H + 2[H] R CHOH H
For Ketones: R CO R + 2[H] R CHOH R
EXAMPLE: CH3 CO - CH3 + 2[H] CH3 CHOH CH3

NUCELOPHILIC ADDITION ELIMINATION (ACYLATION):

Acyl Chlorides:
They are extremely reactive as the Cl:- is a good leaving group, therefore it is a hazardous chemical and it is safer to
use other alternatives if possible.
Nucleophile

Products

Comment
The product is a Carboxylic Acid.
The lone pair on O: forms a bond
with C, however this makes O+,
hence the O+ loses one of its 2 H to
return to O:.
This reaction is of no value, it just
happens when you open a bottle.

H2O
(Water)

So for example, if
you were asked to form Ethanoic Acid from
Water and an Acyl Chloride, then you would
know that it was made from Ethanoyl
Chloride and Water; hence you would end
with Ethanoic Acid and HCl (shown in blue
diagram above).
The product is an Ester.
:

R - OH
(Alcohol)

The lone pair on :O The lone pair on

O: forms a bond with C, however
this makes O+, hence the O+ loses
its 1 H to return to O:.
This is a good way to make esters
on a small scale
The product is an Amide.

NH3
(Ammonia)

The lone pair on :N forms a bond

with C, however this makes N+,
hence the N+ loses one of its 3 H to
return to N:.

This is a good way to make Amides

on a small scale.

The product is an N-Ryl Amide.

:

H2N - R
(Amines)

For exampl
e: The
reaction between Ethanoyl Chloride
(CH3COCl) and Methlyamine (CH3NH2)
forms N-methylethanamide (CH3CONHCH3).
Why Acyl Chlorides react readily with Nucleophiles:
1) Large charge in Carbonyl Carbon atom due to bonding with O and Cl
2) Nucleophiles have electron pairs which can be donated

The lone pair on :N forms a bond

with C, however this makes N+,
hence the N+ loses one of its 2 H to
return to N:.

Acid Anhydrides:
They are also reactive but safer than Acid Chlorides. They are safer because:
1) Less corrosive 2) less vulnerable to hydrolysis 3) less violent 4) do not produce HCl
Nucleophile

Products

Comment
The product is 2 Exactly the same
Carboxylic acids; one is with the R
group, whilst the other is with the
other R group.

H2O:
(Water)

The lone pair on O: forms a bond

with C, however this makes O+,
hence the O+ loses one of its 2 H to
return to O:.
This reaction is of no value, it just
happens when you open a bottle.

For Example,
the reaction of Propanoic Anhydride with Water
would give 2 Propanoic acids, the equation would
be:
(CH3CH2CO)2O + H2O 2CH3CH2COOH
This reaction is also called addition and Hydrolysis.

The product is an Ester with the R

group, whilst the other is with the
other R group.

R - :OH
(Alcohol)

The lone pair on :O The lone pair on

O: forms a bond with C, however this
makes O+, hence the O+ loses its 1
H to return to O:.
This is the main industrial way of
making esters.
The reaction of alcohol with
Anhydrides is the best way to make
Esters because:
Not reversible
Not as hazardous as Acid Chloride
No HCl as by product

So for
example, if you were asked to form Butyl
Ethanoate from an Alcohol and Acid Anhydride,
then you would know that it was made from
Butanol (CH3CH2CH2CH2-:OH) and Ethanoic
Anhydride (CH3-COOCO-CH3), hence you would
end up with Butyl Ethanoate and Ethanoic Acid (the
blue diagram above). The equation would be:
CH3CH2CH2CH2-:OH + CH3-COOCO-CH3
CH3CH2CH2CH2-OCO-CH3 + CH3COOH
MANUFACTURE OF ASPIRIN from reaction of Alcohol and Anhydride:

The product is an Amide.

:

NH3
(Ammonia)

The lone pair on :N forms a bond

with C, however this makes N+,
hence the N+ loses one of its 3 H to
return to N:.
The product is an N-Ryl Amide.
The lone pair on :N forms a bond
with C, however this makes N+,
hence the N+ loses one of its 2 H to
return to N:.

H2N - R
(Amines)

One of the key molecules formed by our body is through the reaction of an Amine (H2N: - R) and Anhydride in the
box shown above:
This molecule is known as ANTIFEBRIN, it is an AMIDE and it is used to prevent blood clotting.

Amides:
Amides also carry out NUCLEOPHILIC ADDITION ELIMINATION; however, they require a CATALYST such as
H+(aq) or OH-(aq).
Hydrolysis of Amides:
The water breaks the C-N bond.
H+(aq) + R-CO-NH2 R-CO-OH + H4N+
This produces a Carboxylic Acid.
OH-(aq) + R-CO-NH2 R-CO-O- + H3N:
This produces a Carboxylate Ion
Carboxylic Acids:
They are weak acids, this is because in water, they partially dissociate into a Carboxylate ion and an H+ ion,
therefore a Carboxylic Acid lowers pH and also has a sour taste.
Carboxylic Acids react with Carbonates (CO32-) OR Hydrogen Carbonates (HCO3-) to form a SALT, CARBON
DIOXIDE and WATER:
2CH3COOH(aq) + CO32-(s) 2CH3COO-(aq) + H2O(l) + CO2(g)
Ethanoic Acid + Carbonate Ethanoate Ion + Water+ Carbon Dioxide
OR
CH3COOH(aq) + HCO3-(s) CH3COO-(aq) + H2O(l) + CO2(g)
Another way of writing this is:
2H+ + CO32- CO2 + H2O
OR
H+ + HCO3- CO2 + H2O
A Carboxylic Acid can react with an Amine to form an Amide:
EXAMPLE: CH3COOH + NH3 CH3CONH2 + H2O
The Amide formed can be converted BACK to Carboxlic Acid using H+ in a Hydrolysis reaction:
CH3CONH2 + HCl + H2O CH3COOH + NH4Cl
Esterification of Carboxylic Acid:

If you heat a Carboxylic Acid with an Alcohol in the presence of a Strong Acid Catalyst (H+), (hence you could use
concentrated H2SO4), you get an ester, and this is known as esterification. Esterification is actually any reaction that
forms an ester.
CARBOXYLIC ACID + ALCOHOL ESTER + H2O
In the ester, the R-C=O part comes from the Carboxylic acid (the R-oate), whereas the O-R, comes from the alcohol
(The R-yl). So for example, in a reaction between Ethanoic Acid and Ethanol, you will get Ethyl Ethanoate.
Esters
Esters also carry out NUCLEOPHILIC ADDITION ELIMINATION; however, they require a CATALYST such as
H+(aq) or OH-(aq).
Hydrolysis of Esters:
The water breaks the O-R bond. The requirement is of temperature to be less than 1000C.

Fats and Oils are esters of Propan-1,2,3-triol (glycerol) and long carboxylic acid chains.

The diagram shows the general structure of fats and oils. However, fats mainly have R-Chains, with saturated
hydrocarbons, hence increasing their melting point; hence they are solid at room
temperature.
Whereas, oils mainly have R-Chains, with unsaturated hydrocarbons, hence decreasing
their melting point; hence they are liquid at room temperature.

Soaponification of Esters:
If you heat an ester with an alkali, it is hydrolysed to an alcohol and a Carboxylate salt.

The actual alkali would be NaOH, and hence the Soap would be 3(NaOCO-R). Also not that the R-CO-O- salt can be
returned to its long carboxylic acid chain by reacting with a Strong Acid (H+), the H+ ions would attach to the Oforming R-CO-OH, hence this is a long chain carboxylic acid, also known as FATTY ACID.
Transesterification of Esters:
This is when one ester is converted into another ester. I.e. fat/oil is converted to a methyl ester.

Hence Bio Diesel is a mixture of methyl esters of long chain carboxylic acids.
Uses of Esters:
1) Perfumes
2) Plasticisers

3) Solvents
4) Artificial food flavours

Benzene Ring:
1)
2)
3)
4)

Symmetrical
All 6 C-H bonds are normal single bonds
All 6 C-C bonds are one single bond and one half a bond, therefore 11/2 bonds
It is a flat molecule with bond angle of 120, whilst Cyclohexane has bond angle
1091/2

The bonding in benzene ring is delocalised around the benzene, hence it is displayed as a
ring. Originally, each Carbon atom has 11/2 bonds, however, it is easier to just draw this as a ring.
Benzene Rings are unusually stable because:
1) Delocalisation provides stability
2) Benzene rings form hydrogenation reactions; bond energy fails to calculate correct answer
This is what this means:

3)
Lack of chemical reactivity with electrophiles
4) When it does react with electrophiles, it only does Electrophilic Substitution
BENEZENE DOES NOT DO ADDITION (losing double bond).
Also substances such as Chlorobenzene will not react with Ammonia because: Electron rich benzene repels
nucleophile

ELECTROPHILIC SUBSTITUTION:
There are 2 types:1) Nitration 2) Acylation
Nitration:
Reagents: Concentrated H2SO4 AND Concentrated HNO3
Electrophile: +NO2
Conditions: Temperature less than 10
The Reagents first actually make the Electrophile through the following reaction:
HNO3 + H2SO4 HSO4- + +NO2 + H2O
Now this Electrophile carries out Electrophilic Substitution with the Benzene Ring.
This is how the mechanism takes place:

We can ignore the 5 other H present on the Benzene ring.

Now if this molecule, nitrobenzene, further reacted with +NO2, it would form 1,3dinitrobenzene, then if
1,3-dinitrobenzene reacted with +NO2, you would make 1,3,6-trinitrobenze (TNT).
Hence there would be an explosion and you would die. This is because nitro
compounds are good explosives.
Reduction of NitroBenzene:

When Nitrobenzene is reduced using a catalyst such as Tin (Sn) or concentrated HCl, it forms an AMINE.

Friedel Crafts Acylation:

Reagent: Acid Chloride
Electrophile: R-+CO
Condition: Lewis Acid (electron pair donor) Catalyst such as AlCl3, FeBr3, AlBr3, etc.
The Reagent first actually makes the Electrophile through the following reaction:
R-CO-Cl + AlCl3 R-+CO + AlCl4This is how the mechanism takes place:
Notice, in the above equations product, the main functional group is actually ketone, the Phenyl is a side-chain, and

therefore you may have a number before the phenyl, e.g. 2-Phenyl Pentan-3-one.
In the above Acylation, if instead of Benzene, there was MethylBenzene or another chain attached to the Benzene,
then Acylation would be faster, this is because:
1) The Carbon chain group increases electron density of Benzene
2) Therefore electrophile attracted more to Benzene
In Acylation, you could also use an alkene, with first reacting it with HBr in an electrophilic addition reaction and then
reacting with AlCl3 in the example reaction: H2C=CH2 + HCl + AlCl3 CH3+CH2 + AlCl4-, the alkene can even by
Cyclohexene, hence you could get:

Amines:
They are Bronstead Lowry Bases,
i.e. they are proton acceptors and electron pair donors.
:
NH3, R-:NH2 Primary amine, R2 -:NH Secondary amine, R3 -:N Tertiary amine, Phenyl-:NH2 Aromatic amine
R4-N+ Quaternary ammonium ion
They react as bases in the following way:
Hence the Basic Strength of an amine depends on the availability of the lone pair on Nitrogen, the lone pair will be
more available if its electron density is
higher, if the lone pair is available
readily then there is an increase in the
stability of the Quaternary Ammonium
ion as the lone pair was ready for the
reaction to take place.
The Trend in Basic Strength is:
Phenyl-:NH2 <<<:NH3 < R-:NH2 < R2
-:NH

These are small but measurable/significant increases in Basic Strength

REASON: Alkyl Groups are electron releasing, therefore increasing electron density of Nitrogen
With the aromatic amine, the lone pair interacts with the benzene giving double bond character to the C-N bond and
thus utilising the vital lone pair needed, therefore the basic strength is significantly reduced. Of course, it can still act
as a Base and accept a proton, however, now you would need to break that C=N.
In the exam, write this: Lone pair on Nitrogen in benzene delocalised into ring, therefore benzene is of high electron
density, therefore lone pair on Nitrogen less available for protonation
AMIDES ARE NOT BASES. I.e. they cannot accept a proton/donate an electron pair, this is why:
In amides, the C-N bond has significant double bond character; therefore the C-N bond does not rotate.

Reactions of Amines:
Nucleophilic Substitution
Substrate: Haloalkane.
Condition: Excess Ammonia if you want a high yield of Primary Amine (because it reduces probability of further
substitutions) and Excess Haloalkane if you want a high yield of Quaternary Ammonium Ion (as it
increases the probability of further substitutions).
The Quaternary Ammonium Ion and Tertiary Amine are considered to be organic impurities, however they form
easily as each time the Nitrogen gets an alkyl group and hence a lone a pair, it becomes a better nucleophile as the

alkyl groups are electron releasing, therefore increasing probability of further reactions.
Another way that Primary amines can be made is by a two step reaction:
In the first step, ALCOHOLIC AQUEOUS Potassium Cyanide reacts with a Haloalkane in a Nucleophilic Substitution
reaction, just like above, this obviously forms a Nitrile.
In the second step is known as CATALYTIC HYDROGENATION, the Nitrile formed is reacted with H2 with Nickel as
a catalyst and under high temperature and high pressure, the H2 reduces the CN group into an Amine group
1) RCl + -:CN RCN + Br2) RCN + 2H2 RCH2NH2
Notice how in the second step, due to the CN containing a Carbon already, the R group alkyl has increased by
another carbon when the RCN was reduced
The second way in which Primary Amines are made by the reduction of a Nitrile is by using the strong reducing
agent LiAlH4 (Lithium Aluminium Hydride) followed by some DILLUTE acid such as H2SO4.
The following reaction shows how this can be done: RCN + 4[H] RCH2NH2
As you can remember from above, Aromatic Amines are produced by the reduction of nitro compounds such as
Nitrobenzene.

Amino Acids have the general structure:

Physical Properties of naturally occurring amino acids:
1) Soluble in Water; H bonding to Nitrogen
2) Solubility changes at high or low pH
3) Considerably high melting points due to Ionic Bonding
through Zwitter Ion
The general name is 2-amino carboxylic acid. The carbon
chain starts with the Carboxylic Carbon.
Formation of Zwitter ion:
Some amino acids have an acidic R group whilst others have a basic R group; pH affects each in a different way.
Condensation of Proteins:

Proteins are polymers made from Amino Acids via Peptide Bonds/Amide Groups being formed.

The reaction is known as a condensation reaction wherein we remove water, 2 products can be formed:

Hydrolysis of Proteins:
The amide group is easily hydrolysed.
Hydrolysis: A reaction with water that breaks up the molecule
Requirement: A strong acid (H+) or a strong base (OH-)
If we use strong acid, the reaction is:

If we use a strong base (OH-), the reaction is:

In the same way, if a dipeptide is converted into an ester, it may still not be used as a sweetener in cooking; this is
because when you heat it, it will break up into the amino acids which are not sweet.
Zwitterions:
1) They are solids due to the ionic bonding
2) They are usually formed when the amino acid is dissolved in water
Hence amino acids are Carboxylic Acids and therefore if reacted with an alcohol such as Methanol it will from an
ester and the alcohol (R-OH) will become: Amino Acid-CO-R

ADDITION POLYMERISATION:
Addition Polymers work in the following way:
X
H
Cl
Ph
CH3

Monomer
Ethene
Chloroethene
Phenylethene
Propene

Polymer
Polyethene
Polychloroethene
Polyphenylethene
Polypropene

Common Name
Polythene
PVC
Polystyrene
Polypropylene

Use
Plastic bags
Building materials e.g. gutters
Packaging
Plastic bottles

As the chain length of Alkenes increase: 1) Melting Point increases 2) Density increases 3) Viscosity increases
IMPORTANT: Polyalkenes are inert, therefore they are non-degradable; this is a disadvantage of Polyalkenes.
Advantages of plastics over traditional materials:
1) Cheap
2) Easy to make into any shape
3) Easy to make into any colour
4) Resist corrosion
5) Good water insulators
6) Good electricity insulators
Disadvantages of plastics over traditional materials:
1) Flammable
2) Very hard to recycle
3) Non-Biodegradable
Monomers

Repeating Unit after the removal of H2O

Monomer 1

Monomer 2

Monomer 1

Monomer 2

Nylon 6:6

Kevlar

As you can see, the above polymers are POLYAMIDES, as we know polyamides are easily hydrolysed.
Hence these Polyamides (Kevlar/Nylon 6:6) hold the following advantages over Polyalkenes:
1) Polyamides are degradable and Polyalkenes are not degradable
2) Polyamides can be hydrolysed easily by OH:- and H+ and Polyalkenes cannot be hydrolysed as
Carbon-Carbon bonds are hard to break
Why Polyamides make stronger fibres than Polyalkenes:
1) In Polyamides, there is Hydrogen Bonding
2) In Polyalkenes, there is only Van Der Waals forces
3) Hydrogen Bonding is stronger than Van Der Waals forces

But you can also get Polyesters, in which monomers when joint, produce polymers containing the ester group.
Monomers
Repeating Unit after the removal of H2O
Monomer 1
Monomer 2

Terylene

Polyesters can also be easily hydrolysed by alkali unlike Polyalkenes and are therefore degradable.
Polyesters are Degradable:
1) They can be hydrolysed
2) This is because polyesters have a +C
3) Therefore reacts with OH:-, the OH:- would break the Ester bond and combine with O to make OH (alcohol)
Advantages of recycling objects made from Terylene:
1) Reduces landfill
2) Saves raw materials
3) Lower cost for recycling than making from scratch
4) Reduces CO2 emissions by not being incinerated
Disadvantages of recycling object made from Terylene:
1) Cost of collecting and sorting
2) Product not suitable for original purpose as it is easily contaminated
Difference between an Addition Polymer and Condensation Polymer:
Addition Polymerisation is the joining together of monomers with a double bond and therefore one product
only, but condensation also involves the elimination of a small molecule such as H2O, HCl, etc.
Chromatography: Separation technique
There are two phases:
1) Stationary Phase
2) Moving Phase
Separation occurs as different substances have different affinities for the 2 phases. Therefore separation depends
on the solubility in the moving phase and the retention in the stationary phase.
For example: Gas-Liquid Chromatography
Retention time: The time from being in ejected into the tube to being recorded at the other ened
For example, if you wished to separate Propan-1-ol from Propanone, then Propan-1-ol is more polar as it has
Hydrogen Bonds, etc. Therefore it has a higher affinity for the stationary phase, whereas Propanone is more
SOLUBLE, therefore it has a higher affinity for the moving phase and therefore, the Propanone will have a shorter
retention time, i.e. will appear quicker
out at the other end.
Why Chromatography is able to
separate a mixture of compounds:
1) There is a moving phase and a
stationary phase
2) Separation depends on
balance between solubility or
affinity in each phase
Mass Spectrometry
Base Peak: tallest peak, it is the peak
caused by the most stable ion/isotope
Mass Peak: furthest peak on the x-axis, it is the peak caused by the entire molecule

If the Mass Peak is ODD: Assume Nitrogen is present

If Mass Peak is EVEN: Assume Hydrocarbon or Oxygen present
When an element has two isotopes, and you have a molecule that has only one atom of this element in its structure
then both isotopes will appear on the Mass Spectrum, according to each of their relative abundances.

Hence 35Cl has a relative abundance of 75% whereas 37Cl has a relative abundance of 25%, hence in the Mass
Spectrum; you would get 2 major peaks, with the ratio 3:1.
If there was a molecule with 2 atoms of Chlorine, then you would have 3 peaks, this is because one peak is when
both are Chlorine are 35Cl, another peak is when both are 37Cl, and the final peak is when 1 is 37Cl and 1 is 35Cl. But
how do we know the relative ratios of each peak? This is when we use a BOX METHOD:
Hence the ratios are:
35
35
35
37
Both 35Cl: Both 37Cl: 1 is 37Cl and 1 is 35Cl
35
70
70
70
72
9: 6: 1
35
70
70
70
72
35

70

70

70

72

37

72

72

72

74

Bromine also has two isotopes and both like Chlorine are M+2 Peaks, i.e.
it has an isotope of 79 and 81. However, both isotopes have a relative
abundance of 50%. Hence in the Mass Spectrum; you would get 2 major

peaks, with the ratio 1:1.

If there was a molecule with 2 atoms of Bromine, then you would have 3 peaks, this is because one peak is when
both are Chlorine are 79Br, another peak is when both are 81Br, and the final peak is when 1 is 79Br and 1 is 81Br. But
how do we know the relative ratios of each peak? This is when we use a BOX METHOD:
Hence the ratios are;
79
81
Both 79Br: Both 81Br: 1 is 79Br and 1 is 81Br
79
158
160
1: 1: 2
81
160
162
if we use very high energy electrons in the ionisation process, the impact can even result in BOND BREAKING.
Ionisation: M M+. + eFragmentation: M+. A+ + B.
Aldehydes and Ketones have the most common fragment:

N.M.R (Proton and Carbon n.m.r) are run as solutions as it is better to run the N.M.R. as a dissolved substance
rather than solid, etc. however, there cannot be any 1H atoms in the solvent, i.e. solvent MUST BE PROTON FREE.
Therefore as a Solvent, we can use:
1) CCl4
2) D2O (this is known as deuterated water/heavy water,
this does not absorb radiation,
hence good solvent)
3) CDCl3; this solvent is more effective than CCl4 for polar
molecules as CDCl3 is polar, a polar
solute is more likely to dissolve in a polar solvent

As a standard for the values, we use a sample that will give us a large singlet peak which we can drag to the 0
value and use as a standard for all other values of spectrum.
This sample is known as Tetramethylsilane:
Hence as you can see, it has 12 Hydrogen in one environment, and therefore gives a large singlet peak.
There are other reasons why Tetramethylsilane is preferred, these include:
Unreactive/ Inert
Soluble in N.M.R. solvent
It can be easily removed from sample if necessary
Only shows one singlet peak on spectrum, therefore can be distinguished and
used as a standard

Functional Group

Test

Observation

Alkenes

Add bromine water

Brown colour becomes Colourless

Haloalkanes R X

Warm with NaOH(aq), acidify with

HNO3 and AgNO3(aq)

Precipitate of AgX

Add ACIDIFIED K2Cr2O7

Alcohols R OH
Aldehydes R COH
Carboxylic Acids R - COOH
Acyl Chlorides R - COCl

Warm with CH3COOH and a little

concentrated H2SO4
Add ACIDIFIED K2Cr2O7
Warm with Tollens Reagent
Warm with Fehlings Reagent
Add NaHCO3(aq) at room
temperature
Add AgNO3

Orange Colour turns Green for primary and

secondary alcohols
Sweet smell of Ester
Orange Colour turns Green
Silver Mirror
Red Precipitate of Cu2O
Effervescence of CO2
Vigorous reaction and White Precipitate of
AgCl
REACTION: HCl + AgNO3 AgCl + HNO3
No Reaction

Benzene
Add bromine water
What scientists can do to make a research reliable:
1) Carry out experiment and repeat experiment as well as keeping the study over a long period
2) Ensure qualified chemists carry out experiment

Remember simple things such as why alkenes do not react with nucleophiles such as OH:-, simply because the
double bond has high electron density and therefore repels the OH:Any time you see COCH3, think acyl chlorides.
ANY TIME you see Nitrogen with only 3 bonds, know that it has a lone pair and in the question, it may well be
behaving as a nucleophile.
REMEMBER:
Atom Economy: Mr of wanted product/Mr of total product
Percentage Yield: (Mass of actual yield/Mass of theoretical yield) X 100
Theoretical yield done like this:Mass/Mr=Mass/Mr
To find out from an infrared spectrum whether an unknown chemical is what we think it is, we should look at the
FINGERPRINT REGION.
Remember, even Phenyl Ketones can undergo Nucleophilic Addition and become Phenyl Alcohols.
Remember the Reagent -:CN can be used when you can see that the carbon length is increasing, HOWEVER -:CN is
toxic.
With Ammonia (NH3), the main disadvantage is that further substitution reactions can occur.
Acid Elimination which is sometimes referred to as DEHYDRATION is done using concentrated acid, for example: