Rate of reaction: change in the concentration of either reactants or

products at a given time.

Rate of reaction is altered when the concentration of reactants or
products is changed.
Rate equation shows this effect mathematically.
A + B ---- C + D
For this equation:
Rate is directly proportional to [A]

Rate is directly proportional to [B] y

Therefore rate is directly proportional to [A] x [B] y

Rate equation

A and B are concentrations and x and y are the orders respectively.

K is the rate constant.
Order of reaction with respect to one of the substance is the power to
which the concentration of that substance is raised.
Eg: order with respect to A is x and with respect to B is y.
Overall order of reaction is the sum of all the orders in a rate
equation.
Eg: for the equation above, the overall order of reaction is x+y
Provided that reactant B is kept constant in all these cases below:
If the order with respect to a reactant A is 1, then if concentration of
A is doubled, rate will also double.
Half-life will be a constant for first order reactions.
If the order with respect to reactant A is 2, then if the concentration
of A is doubled, rate increases by 4 times.
Half-life will double with time.
If the order with respect to reactant A is 0, then its change in
concentration doesnt have an effect on the rate since any number to
the power 0 is one. And A will not be involved in the rate determining
step.

Suggesting orders Initial Rate Method

A + B ---- P
trial
1
2
3

[A]
0.001
0.002
0.001

[B]
0.001
0.001
0.002

Initial rate
1 x 10-2
2 x 10-2
4 x 10-2

Choose two trials where one reactant is kept constant.

To find order of [A]: select 1 and 2 since [B] is constant.
A increased by factor 2
B constant
Rate increased by factor 2
2=2
So order 1
To find order of [B]: select 1 and 3 since A is constant.
B increased by 2
A constant
Rate increased by 4
2=4
2 = 22
So order is 2Rate equation: rate = k [A]1 [B]2

Rate determining step (RDS): this is the slowest step of a mechanism.

The rate depends on this step. This requires very high Ea.
The identity and number of reactants involved in the rate
determining step can be identified from a rate equation.
A + 3B ---- AB3
Rate = k [A] [B]2
According to the chemical equation 1 molecule of A and 3
molecules of B react.
But according to the rate equation 1 molecule of A and 2
molecules of B react.
Rate equation shows the molecules involved in the rate
determining step.
This means that only 2 molecules of B are involved in the rate
determining step. The other molecule will also react but thats a
faster reaction.
A + 2B ---slow-- AB2 RDS
AB2 + B ----fast--- AB3
Identifying the mechanism using rate equation
For SN1, rate equation will be:
Rate = [halogenoalkane] 1
The order with respect to the other reactant (OH-) is zero hence
that will not be present in the rate equation.
Mechanism will have two steps.
If its SN1 we can also conclude that the halogenoalkane is
tertiary/secondary.

For SN2 the rate equation will be:

Rate = [halogenoalkane] 1 [OH-] 1
Both reactants take part in RDS.
Mechanism will have minimum one step.
If its SN2 we can also conclude that the halogenoalkane is
primary/secondary.

Rate constant is the constant proportionality of a reaction. Its value

depends on:
1. Temperature
2. Activation energy
K is directly proportional to temperature
K is inversely proportional to activation energy.
Unit of K depends on the overall order of reaction.

Activation energy is the energy required by the reactants to start a

reaction.
It can also be said that its the energy required to form the transition
state. The transition state is a condition where old bonds are half
broken and new bonds are half formed.
Activation energy and temperature are not considered in the rate
equation.
The effect of activation energy and temperature on the rate is
shown mathematically in the Arrhenius equation.

K = Ae-Ea/RT
K is the rate constant.
A is the pre-exponential factor. This includes frequency and
orientation of collisions. It varies slightly with change in
temperature.
e is a mathematical quantity.
Ea is the activation energy.
R is the gas constant.
T is the temperature in Kelvin.
If the Activation energy is increased, the power to which e is
raised increases, so the value of k decreases hence rate
decreases.
If the temperature is increased, the power to which e is raised
decreases, so the value of k increases hence rate increases.

Half-life of a reaction is the amount of time required for the

concentration of the reactants to decrease by half of its initial
amount.

Homogeneous and Heterogeneous catalysts

1. Homogeneous catalyst
Catalyst which has the same physical state as the reactants.
Transition metals can be homogeneous catalysts since they
exhibit variable oxidation states.
In presence of catalyst, reaction proceeds through a number of
intermediates.

 Catalyst is regenerated at the end of reaction

2. Heterogeneous catalyst
Catalyst that are not in the same physical state as the reactants.
Heterogeneous catalysis occurs on the surface of the catalyst.
There are active sites on the surface of the catalyst.
When the catalyst is introduced, reactant molecules move into
the active sites.
The surface of catalyst attracts reactant molecules by
intermolecular forces and form dative covalent bonds.
Due to formation of temporary dative covalent bonds, bonds in
reactant molecules get weaker so less energy is required to break
them.
New bonds are formed on the surface of the catalysts and the
products move away.

If a product produced has a colour, for example, Bromine, then

the intensity of the reaction mixture can be found using a
colorimeter at regular intervals to calculate rate.
In some of the reactions, some molecules may escape reaction
mixture as by-products for example decomposition of CaCO3
releases CO2. This causes a loss in mass. The mass can be
measured at regular intervals to measure the rate.

 In some reactions gases are produced. The gas can be collected

using a syringe and the volume of gas released can be checked at
regular intervals to find the rate.
Quenching and then titration is done when all the reactants and
products are in aqueous state.

CH3COCH3 + I2 + H+ ------- CH3COCH2I + HI

Mix the propanone and iodine solution both of known
concentrations. The moment you mix, start the stop watch.
Remove known volumes of the reaction mixture at regular
intervals.
Each time, pour the volume of reaction mixture to a constant
volume of NaHCO3. This neutralizes the acid in the reaction so
the reaction stops. This is called quenching.
Then the reaction mixture is titrated against a known
concentration of sodium thiosulfate with starch solution as the
indicator.

This procedure is repeated every time a volume of reaction

mixture is removed at regular intervals.
A graph of volume of sodium thiosulfate against time is plotted.
Since volume of thiosulfate is directly proportional to the
concentration of iodine, the graph can be used to determine the
order with respect to iodine.
Graph will be:

We know that the order with respect to iodine is zero by the

trend in the graph. This means that the iodine will not take part
in RDS.
So the rate equation will be:
Rate = [CH3COCH3] [H+]
The order with respect to propanone can be found out using initial
rate method.

This mechanism will have at least 2 steps since iodine is not

taking part in the RDS. So there will be one more step where
iodine reacts.
At first the starch solution is not added to the iodine to prevent
formation of a starch-iodide complex.
The sodium thiosulfate is added before starch so that the
thiosulfate rapidly reduces I2 to I-. The blue black color can only
be seen after the reaction between thiosulfate and I- is
complete.

For a concentration-time graph the gradient would be rate.

FOR ZERO ORDER REACTIONS

Gradient is constant which means the rate is constant. There is

no effect on rate by the change in [A].
So the reactant doesnt take part in the RDS. But its
concentration decreases with time since it does take part in the
other steps of the reaction and gets used up.

FOR FIRST ORDER REACTIONS

Changing [A] changes rate (gradient).

So [A] is involved in RDS.
Half-life is constant so we know that its first order.

Rate directly proportional to [A] since:

Rate = k [A]
Rate/ [A] = k
FOR SECOND ORDER REACTIONS

Change in [A] changes rate.

So [A] involved in RDS.
Half-life not constant so must be second order.

When [A] is doubles, rate increases by four times so the increase

in not linear.

Identifying the mechanism using rate equation

For SN1, rate equation will be:

 Rate = [halogenoalkane] 1
The order with respect to the other reactant (OH-) is zero
hence that will not be present in the rate equation.
So there will be at least two steps since OH- doesnt take
part in RDS hence there has to be another step where it
reacts.
If its SN1 we can also conclude that the halogenoalkane is
tertiary/secondary.
For SN2 the rate equation will be:
Rate = [halogenoalkane] 1 [OH-] 1
Both reactants take part in RDS.
So there is only one step.
If its SN2 we can also conclude that the halogenoalkane is
primary/secondary.
For reaction between propanone and iodine:
Rate = [propanone] [H+]
Iodine doesnt take part in RDS.
So there should be at least two steps since iodine has to
react in another step.

 Spontaneous reactions are reactions that occur on their own.

Very small activation energy is required for these reactions.
Ex: combustion of petrol.
It is commonly known that most exothermic reactions are
spontaneous and endothermic reactions are not.
But there are exothermic reactions that are not spontaneous and
endothermic reactions that are spontaneous.
So enthalpy changes alone do not give us an idea of the feasibility
of a reaction.

Entropy is a measure of randomness or disorder of a system.

Electrons occupy fixed energy levels in atoms.
When electrons gain energy they move from a lower energy level
to a higher one.

Atoms and molecules change their energy states by vibrational,

rotational and translational movements.

 Energy comes in quanta for these changes.

Molecules moving from low energy state to higher energy states
increase the number of ways which the molecules can move and
therefore increase entropy.

As temperature increases, molecules move from lower energy

level to higher energy level.
So number of ways in which they can move increases.
Therefore entropy increases.
Entropy increases from solid to liquid to gas.
At zero Kelvin, the perfect crystals will have zero entropy since
they are not moving at all.

From solid to liquid to gas, the entropy increases since the

molecules are gaining more energy and they are moving more
randomly.
Entropy mainly depends on physical state.
However, it also depends on the complexity of a molecule.
As a molecule becomes more complex, the entropy increases.
Ex: H2 and N2 have lower entropy than NH3.

Stotal = Ssys + Ssurrounding.

When a reaction is occurring in a system, some energy will be
released (if exothermic reaction) or absorbed (if endothermic
reaction).
This will affect the temperature of the surrounding.
So if the energy is released into the surrounding, the entropy of
the surrounding will increase.
If the energy is energy is absorbed from the surrounding, the
entropy of the surrounding will decrease.
Hence the total entropy change of any reaction is the sum of the
change in entropy of the system and the change in entropy of the
surrounding.

Ssys = Sproducts - Sreactants

Ssurrounding = -H x 1000/T
Where T is the room temperature in Kelvin. (298 K)

Reactions occur due to chance collisions.

One possible ordered arrangement can be rearranged for greater
entropy.
For example a crystalline solid can be dissolved to a solution or it
can be heated to a gas. The probability of disorder is greater in
solution and in gas than in solid state.

Natural direction of change is the direction of increasing total

entropy.

For example when a potassium permanganate crystal in kept in

water its color spread so entropy increased.

When the lid of the jar containing bromine gas is taken the gas
spreads spontaneously in the room.

Stotal = Ssystem + Ssurr

Positive= positive + positive
Positive = positive > negative
Positive = negative < positive
All these reactions can occur since S total is positive.
In surroundings at higher temperatures Ssurr is less since
molecules have very high entropy and are in a disordered motion.
So at higher temperatures the contribution of Ssurr to the
total entropy is less.
For endothermic reactions entropy of surrounding will decrease
since heat is absorbed from surrounding.
For exothermic reactions entropy of surrounding will increase
since heat is released and molecules gain more energy and become
more disordered.

 Thermodynamic stability is related with energy.

For exothermic reactions, reactants have more energy than
products so reactants are thermodynamically unstable compared
to products.

For endothermic reactions, reactants have less energy than

products so reactants are thermodynamically stable compared to
products.

Kinetic stability is related with activation energy.

If the activation energy is high, the reactants are kinetically
stable.

In combustion of petrol, petrol is thermodynamically unstable

since it has more energy than products.

But petrol is kinetically stable since and ignition is required for

its combustion.

Hydration enthalpy is the energy change that occurs when one

mole of gaseous ions is completely dissolved in excess of water to
form one mole of aqueous ions under standard conditions of 298K
and 1 atm. Its usually a negative value.
To calculate enthalpy of solution:

Hsol = Hhyd + (-HLE)

Factors affecting enthalpy of Hydration.

The attraction of smaller ions with the dipoles of water is much
stronger.
So for smaller ions, enthalpy of hydration is greater.
The attractions are greater when the ions have a greater charge.
So for ions with greater charges, enthalpy of hydration is
greater.

Factors affecting lattice enthalpy

The greater the total charge of the compound, the greater the
lattice energy.

The smaller the size of the ion, the greater the lattice energy.

 If the total entropy change of a solution is positive when a

compound is mixed with it, the compound will be soluble.
If enthalpy of solution is negative then the compound is soluble at
a given temperature.

 A reaction is said to be in equilibrium if the rate of forward

reaction is equal to the rate of backward reaction and the
concentration of reactants and products remain constant.

Haber process:
3H2 + N2 -- 2NH3
Contact process:
2SO2 + O2 -- 2SO3

For any reaction at equilibrium at a constant temperature the

ratio of concentration of products to reactants will be equal to a
constant.

 Example:

3H2 + N2 <--- 2NH3

[NH3]2/ [N2] [H2]3 = Kc

This constant Kc is called equilibrium constant.
When equilibrium is not attained, the constant is called
reaction quotient.

Q: 5 moles PCl3 and 10 moles Cl2 are allowed to attain equilibrium at

298K. At equilibrium 8 moles of Cl2 are found to be present. If the
total volume of the container is 20cm3 calculate value of Kc
PCl3

Cl2

PCl5

Initial

10

Change

Equilibrium

Equilibrium

150

400

2
100

Concentration
Initially there will be zero moles of PCl5 since no product formed.
If there are 8 moles of Cl2 at equilibrium, 2 moles must have reacted
hence the change in mole is 2.
If two moles of Cl2 reacted, then 2 moles of PCl3 must be used up since
they have a ratio of 1:1. So change in mole for PCl3 is 3.
Equilibrium mole = initial mole change in mole

Concentration can be found by ratio method.

Kc = [PCl5]/ [PCl3][Cl2]
= 100/150 x 400
= 1.67 x 10-3 mol-1dm3

For the reaction: H2 + I2 -- 2HI

Kc = [HI]2/[I2][H2]
Kp = P2HI/PH2PI2
Temperature is the only factor that affects Kc/Kp
Kc is the equilibrium constant found in terms of concentration.
Kp is the equilibrium constant found in terms of partial pressures.
In this case, changing pressure will not alter Kp or the equilibrium
position since number of moles on both side are same.
Calculating Kp
Q: one stage of manufacturing sulfuric acid is 2SO2 + O2 2SO3.
Calculate Kp if 5 moles of SO2 and 5 moles of O2 were allowed to reach
equilibrium and about 12% of SO2 was converted to SO3 given that the
equilibrium total pressure is 2.5 atm.

2SO2 + O2 2SO3

Initial
Equilibrium
Mole
Change in
Mole
Mole fraction
Partial P

5
4.4

5
4.7

0
0.6

0.6

0.3

0.6

44/97
1.13

47/97
1.21

6/97
0.15

(0.15)2/ (1.13)2(1.21)
= 0.0146 atm-1
Mole fraction= constituent equilib. Mole/ total equilib. Mole
Partial pressure = mole fraction x equilibrium total pressure
The unit depends on the number of moles of the reactants and
products.

At equilibrium Stotal is zero since entropy change of forward

reaction is equal to the entropy change of backward reaction.
The total standard entropy is related to equilibrium constant as:
Stotal = RlnK
This equation gives an idea of Stotal at equilibrium.

 K can be Kc or Kp and R is the gas constant.

So as Stotal increases the equilibrium constant increases.

For the reaction: CaCO3 CaO + CO2

H +ve

When temperature increased:

Forward reaction is endothermic.
Ssurr is negative. It decreases since T increases.
Ssys constant at equilibrium.
Stotal increases since it becomes less negative.
Stotal is directly proportional to Keq
Hence Keq increases.
So reaction quotient K should also increase.
K = [CaO][CO2]/[CaCO3]
For K to remain same, the yield of products should increase so
this favours forward reaction.
We should not include solids in Kc equations since it is assumed
that concentration of solids remains constant.
For the reaction:

2NO + O2 2NO2

When temperature is increased:

Forward reaction is exothermic.
Ssurr positive. It decreases since T increases.
Ssys remains constant at equilibrium.

H ve

 Stotal decreases since it becomes less positive.

Stotal is directly proportional to Keq
Hence Keq decreases.
So the reaction quotient k should also decrease.
K = [NO2]2/[NO]2[O2]
For K to remain same, yield of products must decrease so the
backward reaction is favoured.
Pressure changes:
For the reaction:

2NO + O2 2NO2

Kp remains constant as pressure is increased.

But when pressure is increased, equilibrium position changes.
Kp = X2NO2 Ptotal/X2NO XO2 Ptotal
There are more P total terms in denominator.
So more NO2 should be produced for the Kp value to be same.
So forward reaction is favored and equilibrium shifts to right.
For the reaction:

2NO2 2NO + O2

Kp remains constant as pressure is increased.

But when pressure changes the equilibrium position changes.
Kp = X2NO XO2 P3/X2NO2 P2
Increasing pressure increases the value of this fraction.
So to keep it same as Kp the reactants should increase.
So backward reaction is favoured and equilibrium shifts to left.

 Only the temperature can have an effect on the equilibrium

constant.

Changing pressure wont change the equilibrium constant but will

change the equilibrium composition according to a given situation
(discussed in previous topic)

If temperature is increased for an exothermic reaction it will

favour the endothermic reaction and vice versa.

If the pressure is increased for a gaseous mixture, equilibrium

will move to the side with less number of gaseous molecules and
vice versa.

 In the Haber process, the temperature affects both the rate and
yield since the reaction is exothermic and when the temperature
is low, the forward reaction is favored. This in turn increases the
yield. However at lower temperatures the rate is slow.

The process is heterogeneously catalyzed so pressure has little

or no effect on the rate. This is because pressure only helps the
active sites of the catalysts to be occupied faster.

The industrial processes usually cannot remain in equilibrium since

the products are continuously removed and reactants are
continuously added.

Capturing and recycling any unused products.

Using more efficient alternate reactions in the process.
Consider both thermodynamic and kinetic factors.
Recycling unreacted reactants.
Converting by-product into desired product by alternate reaction
pathways.

 Its important to control reactions because:

If the reaction is too slow, the system has to be run for a
longer time to produce less yield therefore this will cause a
loss.
If the reaction is too fast, it will go out of hand and if its an
exothermic reaction, it may even cause an explosion.
We have seen how entropy has an effect on the equilibrium
constant and how the concentration of reactants and products
alter to keep the equilibrium constant same under spec 6 of
equilibria.
Using that knowledge, we would know whether to increase or
decrease temperature/pressure for a particular reaction to get
the maximum yield within less time and with low cost.
For this, industries have to resort to compromise conditions
An example of a compromise condition is as follows:
An exothermic reaction may require a very low temperature
for maximum yield.
However the rate of reaction is very slow at low temperatures.

 An endothermic reaction may require a very high temperature

for maximum yield and rate.
However high temperatures use a lot of energy and are
expensive.
So a temperature is chosen which is not so low and not so high.
Likewise, a reaction may require a very high pressure for
maximum yield and high rate.
However high pressure requires expensive reaction vessels
that are difficult to maintain.
So a pressure is used which is not so high and not so low.
Industries use catalysts wherever possible to increase reaction
rates.
Some reactions go because the Ea required is low and total
change in entropy is positive.
Some reactions never occur because Ea required is too high and
total change in entropy is negative.

 In the early days, acids were thought to be substances that have

a sour taste.
And later they were thought to be substances that produce an
excess of hydrogen ions. (Arrhenius theory)
After that and till now, acids are known to be substances that
can donate protons. (Bronsted-Lowry theory)

Spec 2: demonstrate an understanding that a

BrnstedLowry acid is a proton donor and a base a
proton acceptor and that acid-base equilibria involve
transfer of protons
A Bronsted-Lowry acid is one which is a proton donor.
And a base a proton acceptor.
Acid base equilibria involve transfer of protons.

Spec 3: demonstrate understanding of the Brnsted

Lowry theory of acid-base behaviour, and use it to
identify conjugate acid-base pairs
CONJUGATE ACID-BASE PAIRS
HCl + H2O H3O+ + ClWhen a species loses a proton, the product has to be a base.
In the reaction above, HCl donates a proton to H2O and the base
formed is Cl-.
Cl- is said to be the conjugate base of HCl and HCl is the
conjugate acid of Cl-.
When a species gains a proton, the product has to be an acid.
In the reaction above, H2O accepts a proton and the acid formed
is H3O+.
H2O is the conjugate base of H3O+ and H3O+ is the conjugate acid
of H2O.
Conjugate Acid: the one which can donate a proton to form the base.
Conjugate Base: the one which can accept a proton to form the acid.
Acid-base reactions are reversible since the conjugate acid can
donate the proton to form the original base and the conjugate
base can accept a proton to form the original acid.

Spec 4: define the terms pH, Ka and Kw, pKa and

pKw, and be able to carry out calculations relating
the pH of strong acids and bases to their
concentrations in mol dm-3

Acid dissociation constant (Ka)

When a monoprotic acid, HA dissociates in water:
HA + H2O H3O+ + AKc can be written as:
Kc = [H3O+][A-]/[HA][H2O]
For a dilute weak acid the concentration of water is effectively
constant since it is in large excess.
Kc[H2O] = [H3O+][A-]/[HA]
The new constant is called Ka
Ka = [H3O+][A-]/[HA]
All the concentrations in the final equation are the
concentrations at equilibrium.
If Ka is larger the position of equilibrium is more towards the
right.
Ka is larger for strong acids.
The extent of dissociation of an acid will be different in
different solvents.
H+ ions can be in the form H3O+.

Assumptions
No self ionization of water so all H+ ions are from the acid.
Therefore: [H3O+]eq = [partially ionized acid]eq
A weak acids ionization is negligible.

Therefore: [Acid]eq = [Acid]initial

Ka = [H3O+]2/[Acid]initial
Note: Since Ka values can be extremely large for strong acids and
extremely small for weak acids, it is more convenient to compare acid
strength using pKa values.
pKa = -log10 Ka
Ionic Product of Water (Kw)
Water ionizes to a small extent.
2H2O H3O+ + OH The Kc can be written as:
Kc = [H3O+][OH-]/[H2O]2
The concentration of water is constant since it is in excess.
Kc[H2O]2 = [H3O+][OH-]
The new constant is called the ionic product of water.
Kw = [H3O+][OH-]
Note: There can be H+ instead of H3O+
For pure water, [H3O+] = [OH-]
When an acid or alkali is dissolved in water there will be different
concentrations of H3O+ and OH- ions but the product of these two will
be equal to value of Kw at a given temperature.
pKw = -log10 Kw
pH
pH is the acidity or alkalinity of a substance.

 pH can be calculated by:

pH = -log [H3O+]
If the concentration of H3O+ is to be found and the pH is given:
[H3O+] = 10-pH
Calculating pH of strong base
Strong base is completely ionized so concentration of OH- is
directly obtained from concentration of the base.
Eg: NaOH = 0.1 mol/dm3 = [OH-]
Kw = 1 x 10-14
Ans: Kw = [H3O+][OH-]
10-14 = [H3O+][0.1]
[H3O+] = 10-13
pH = -log [10-13]
= 13
Calculating pH of a strong acid
Strong acids are completely ionized so the concentration of
[H3O+] is obtained directly from concentration of acid.
[HCl] = 0.10 moldm-3 = [H3O+]
Ans: pH = -log [0.1]
pH = 1

 Weak acids and weak bases dissociate only partially in aqueous

solution so it can be assumed that the base/acid doesnt
dissociate at all.
Equilibrium law applied in a previous spec.

Assumptions
Self ionization of water does not occur so all H3O+ ions are from
the acid.
[H3O+]eq = [partially ionized acid]
Dissociation of acid is negligible.
[Acid]initial = [Acid]equilibrium
Ka = [H3O+]2/[Acid]initial

Buffer solutions are used to keep the pH constant.

 They always maintain the pH within a range.

Basically they are solutions of known pH which have the ability to
resist change in pH when a small amount of acid or alkali is added.

To make acidic buffer we can use a weak acid and its conjugate
base or the salt. (ex: ethanoic acid and sodium ethanoate)

To make alkaline buffer we can use a weak base and its salt (ex:
ammonia and ammonium chloride)
Action of Acidic Buffer Solution (Weak acid and Salt)
A buffer solution containing ethanoic acid and sodium ethanoate.
The weak acid is partially ionized.
CH3COOH + H2O H3O+ + CH3COOThe salt is fully ionized.
CH3COONa -- CH3COO- + Na+
A large excess of CH3COO- ions forms. This suppresses the
ionization of the weak acid.
Calculation of pH of acidic buffer
Excess of CH3COO- forces equilibrium to shift to left. So we
assume that CH3COO- is only from CH3COONa.
[CH3COO-]eq = [CH3COONa]initial
We can assume that CH3COOH is not even ionizing.
[CH3COOH]eq = [CH3COOH]initial
Ka = [CH3COONa]initial[H3O+]/[CH3COOH]initial
Ka = [Salt]in [H3O+]/[Acid]in
[H3O+] = Ka [Acid]in/[Salt]in

pH = -log [H3O+]
Adding an Acid to the Buffer
When an acid is added, most of the H+ ions are removed by the
reaction with the large reservoir of CH3COO- ions.
H+ ions are removed by the conjugate base which are the
CH3COO- ions.
[H+] remains constant.
So pH remains unchanged.
H3O+ + CH3COO- H2O + CH3COOH
Adding an alkali to the Buffer
When an alkali is added most of the OH- ions are removed by the
large excess of CH3COOH.
[OH-] remain constant.
So pH remains unchanged.
OH- + CH3COOH CH3COO- + H2O

Example question
Q:a) Calculate pH of the buffer solution formed by mixing 50cm3 of
0.9moldm-3 HCOOH and 70cm3 of 0.95 moldm-3 HCOONa
Ka = 1.6x10-4

number of moles:
For HCOOH:- 0.045 moles
For HCOONa :- 0.0665 moles
[H3O+] = 1.6x10-4 x 0.045 / 0.0665
= 1.08x10-4
pH = -log [1.08x10-4]
=4
Q b) 20cm3 of 0.5moldm-3 of NaOH is added to above solution.
Calculate the pH of the resulting solution.
Moles of NaOH:- 0.01 moles
NaOH : HCOOH
1:1
:- 0.01 moles of HCOOH reacted with NaOH
Acid remaining: 0.045 0.01 = 0.035 moles acid
HCOOH : HCOONa
1:1
:- 0.01 moles of salt formed after adding NaOH
Total salt now: 0.01 + 0.0665 moles salt
New concentrations
Acid: 0.035 mol 140 cm3

1000cm3

X = 0.25 moldm-3
Salt: 0.546 moldm-3
[H3O+] = 1.6x10-4x 0.25 / 0.546
= 7.33x10-5 moldm-3
pH = -log [7.33x10-5]
= 4.1

Titration Curves
There are few things we need to take into consideration while drawing
a pH curve which are:
1. Initial pH: always equal to the pH in the conical flask.
2. Final pH: always equal to the pH in the burette.
3. Equivalence point (end point): the point at which the (acid/base)
in the burette neutralizes the (base/acid) in the conical flask.
Its the middle of the vertical range.
4. pH range of equivalence: sudden change in pH when the acid/base
in the conical flask is neutralized
There are 3 types of titration curves which are:
Strong acid strong base

 Weak acid strong base

Strong acid weak base
Strong Acid Strong Base
a) Conical flask: HCl

burette: NaOH

The curve starts with the pH of the acid.

As NaOH is added the pH increases.
A buffer does not form in this titration since both the strong
acid and strong base completely dissociate in water.
At equivalence point, there is NaCl and water.
Hydrolysis of NaCl will produce strong base NaOH and strong
acid HCl.
Both of them dissociate completely in water.
[H+] = [OH-]
So pH is 7 at equivalence point.
Curve ends with the pH of NaOH.
b) Conical flask: NaOH

burette: HCl

 Curve starts with the pH of NaOH in the flask.

As the acid is added, the pH decreases.
At equivalence point, there is NaCl and water in the conical flask.
Hydrolysis of NaCl will produce strong base NaOH and strong
acid HCl.
Both of them dissociate completely in water.
[H+] = [OH-]
So pH is 7 at equivalence point.
Curve ends with the pH of HCl.

Weak Acid Strong Base

a) Conical flask: CH3COOH

Burette: NaOH

At half equivalence point, a buffer is formed since a mixture of

the acid and its salt(conjugate base) maintains the pH.
At half equivalence point:
pKa = pH of buffer solution
Therefore Ka can be obtained by 10-pH of solution
The pH then increases when more and more NaOH is added.
When all of the acid is neutralized, volume of equivalence point is
reached.
pH at end point is greater than seven since the strong conjugate
base forces the water to donate protons.
There is a sudden change in pH of about 4-6 units. (vertical pH
range.

 The pH keeps on increasing as the acid is neutralized and the

NaOH is further added.
b) Conical flask: NaOH

Burette: CH3COOH

pH starts with 13.

It decreases as the acid is added.
A buffer is not formed at half equivalence point since at that
instant there will be the salt and NaOH.
NaOH is a strong alkali so it dissociates completely.
Salt alone cant form a buffer.
At equivalence point, pH is greater than 7 since the weak acid will
form a strong conjugate base which will force the water to
donate protons.
The pH further decreases when all of the base is neutralized and
acid is in excess.
Towards the end of the titration a buffer region is formed.
This is because there is the acid and the salt.

 When more and more acid is added, the buffer becomes

ineffective hence the pH decreases.

Strong Acid Weak Base

a) Conical flask: HCl

Burette: NH4OH

As NH4OH is added, the pH starts increasing.

At half equivalence point, there is no buffer region since at that
point there is the acid and the salt.
Since HCl is a strong acid it dissociates completely and the salt
by itself cant form a buffer.
At equivalence point pH is lower than 7 since the weak base forms
a strong conjugate acid which forces water to accept protons.
When the acid is neutralized, there is a sudden increase in pH of
about 4-6 units.
After neutralization, when about half the amount of NH4OH
remaining is added, a buffer is formed.

 At that point there will be the salt and excess of the weak base.
A weak base and its salt will form a buffer.
When more and more NH4OH is added the buffer becomes
ineffective and hence pH increases.
b) Conical flask: NH4OH

Burette: HCl

pH starts decreasing when acid is added.

A buffer region is formed at half equivalence point.
At that point, there will be the salt and the weak base.
A weak base and its salt will form buffer.
When more and more acid is added, the buffer will become
ineffective and the pH decreases.
At equivalence point, the pH is lower than 7 since the weak base
produces a strong conjugate acid that forces water to accept
protons.
There is a sharp change in pH of about 4-6 units during
neutralization.
After that the pH further decreases as more acid is added.

Weak Acid Weak Base

There is a buffer before the end point and after end point.
Thus a sudden change in pH will not occur (no vertical range)
Therefore visual indicators cannot be used to detect end point.

Indicators are weak organic acids that have different colours in the
undissociated acid and the dissociated base.
In representing the indicator:
HIn

H2O

Color 1

In- +

H3O+

color 2

When an acid is added, equilibrium is pushed to left as H3O+

concentration will increase and color 1 will be seen.
When an alkali is added, it reacts with H3O+ ions and hence
equilibrium shifts to right so color 2 is seen.
Color change requires a change of about 1.5-2 units.
For a particular titration, a suitable indicator can be chosen by
checking the pKIn value.
pKin value should be within the vertical range.

 In the body, enzymes work best at a certain pH. Buffers help to

keep the pH in a certain range.
Changes in pH may also cause change in protein structures so its
important for buffers to be present.
Buffers are added to foods to prevent deterioration due to pH
change caused by bacterial or fungal activity

 Isomers are divided into 2 groups which are:

1. Structural Isomerism
2. Stereo Isomerism
Structural Isomerism
Divided into 3 which are chain, functional and position isomerism.
Structural isomers arise because of the possibility of branching
in carbon chains.
Functional isomers can have different functional groups. For
example a ketone is a functional isomer of the respective
aldehyde.
In position isomerism, carbon skeleton remains same but
important groups move. For example but-1-ene and but-2-ene.
Stereo Isomerism
Isomers have the same molecular formula.
Isomers have the same bonding arrangement.
They are arranged differently in 3D space.
Divided into 2 which are geometrical isomerism and optical
isomerism.

Geometrical Isomerism
Molecules that have C=C with each carbon bonded to 2 different
atoms/molecules can exhibit geometrical isomerism.
Pi bonding electron cloud prevents free rotation of C=C.
Isomers have similar chemical properties but different physical
properties.
If same atoms on same side: Z/cis
If same atoms on opposite sides: E/trans

Terminologies
chiral centre: a carbon atom bonded to 4 different atoms/molecules
asymmetric carbon: a carbon atom bonded to 4 different
atoms/molecules
non-superimposable: cannot overlap one another completely. For
example left and right hand.
Optical isomers are molecules that have a chiral center and form 2
different molecules which are non-superimposable.
Optical isomers have the same bonding arrangement in 3D space.

For optical isomerism there must be a chiral center.

Optical activity is the ability of a single isomer to rotate the

plane of polarization of plane-polarized monochromatic light.

The isomers that rotate the light clockwise are +ve

The isomers that rotate light anticlockwise are ve.
Optical activity can only be found in optical isomers and those
molecules have a chiral center.

An equamolar mixture of optical isomers is called a racemic

mixture.

Racemic mixture will have 50% positive and 50% negative optical
isomers.

So the optical activity cancels out.

Mixture is said to be optically inactive even though molecules
have a chiral center.

.
SN1 Mechanism

 If it is SN1 mechanism, the product will be optically inactive.

This is because the carbocation formed after RDS has a trigonal
planar shape.
Therefore the nucleophile can attack the carbocation from either
side.
This will form a racemic mixture.
Hence there will be no optical activity in the product.
SN2 Mechanism
Proceeds through a single step via a transition state.
So only one product is formed.
No racemic mixture forms.
Therefore the product is optically active.
Product can only be optically active if the halogenoalkane we are
starting with has a chiral center.
Nucleophilic Addition to Carbonyl Compounds
When hydrogen cyanide is added to an aldehyde:
The cyanide ion can attack the carbonyl carbon from any side
since the compound is planar.
As a result product will have same amount of negative and
positive optical isomers (racemic mixture)
Therefore the optical activity cancels out and the product is said
to be optically inactive.
All aldehydes will give a racemic mixture with this reaction
except methanal.
Thats because methanal doesnt have a chiral center.
When hydrogen cyanide is added to a ketone:
If the ketone is asymmetric, then it will give a racemic mixture.

 If the ketone is symmetric, then it wont give a racemic mixture

since symmetric ketones dont have a chiral center.

Any molecule having C=O like above are called carbonyl

compounds.

Short chain carbonyl compounds are completely soluble in water

due to formation of hydrogen bonds with water.
Solubility decreases with increasing carbon chain since carbon
chain is non-polar.
Methanal is a gas at room temperature while all the other
aldehydes and ketones are liquids.
Carbonyl compounds usually have a pleasant smell.

Carbonyl group is strongly polar dipole-dipole force between

molecules is very strong. Therefore carbonyl compounds have high
boiling points.

Tollens Reagent (oxidation)

o This reagent is made by adding a few drops of dilute NaOH to
AgNO3. This would form a brown ppt. Add ammonia until the ppt
dissolves.
o Mixture should be warmed gently when aldehyde/ketone is added.
o Aldehydes react with the reagent and reduce Ag+ to Ag resulting
in a silver mirror on the wall of the apparatus.
o Ketones do not react with the reagent and hence no observation.
Fehlings Reagent (oxidation)
o Reagent is a mixture of aq CuSO4 and alkaline sodium tartarate
solution. Cu2+ ions give the reagent its blue color.
o Aldehydes can reduce Cu2+ ions to Cu2O on warming. This will give
a reddish brown precipitate.
o Ketones will not react with the reagent hence no observation.
Benedicts Reagent (oxidation)

o Aldehydes will give a brick-red ppt.

o Ketones will give no observation.
Acidified dichromate (vi) ions (oxidation)
o Reagent: dil. H2SO4 and K2Cr2O7
o Conditions: heat under reflux
o Aldehydes oxidize to carboxylic acids.
o Ketones do not oxidize.
o This is because in ketones, the carbonyl carbon has C-C bonds.
o The reagent is not strong enough to oxidize C-C
o However it can oxidize the weaker C-H bonds on the carbonyl
carbon of aldehydes.

LiAlH4 in ether
o reagent and condition: LiAlH4 in dry ether
o We use dry ether because if water is present, it hydrolyze
LiAlH4.
o Reaction is nucleophilic addition.
o Nucleophile: :H- ion
o Ketones will give secondary alcohols.
o Aldehydes will give primary alcohols.

o reagent: KCN with dilute H2SO4

o conditions: room temperature
o type of reaction: nucleophilic addition
o mechanism: heterolytic nucleophilic addition
o product: 2-hydroxynitrile

Since the aldehyde is planar, :CN- can attack from either side
equally. The reaction will form a racemic mixture.

o Both aldehydes and ketones react with 2,4dinitrophenylhydrazine.

o Its a test for carbonyl group.
o Its an addition elimination reaction.
o Example:
2,4 dinitrophenylhydrazine + ethanal --- ethanol-2,4dinitrophenylhydrazone
Mechanism:

H2O is formed by taking an O from the ketone/aldehyde and taking H

from NH2.
Identifying unknown Carbonyl Compound
o Make a solution out of the unknown substance.
o Add 0.5cm3 solution into a beaker.
o Add 5 cm3 of 2, 4 dinitrophenylhydrazine solution and stir.
o Filter the ppt using suction filtration.
o Recrystallize the derivative (ppt)

Recrystallization:
Dissolve the derivative in minimum amount of hot solvent.
Minimum: to make a saturated solution.
Hot solvent: to dissolve it and not dissolve solid impurities
Filter the solution in hot condition by using a pre-heated Buchner
funnel.
Filter: to remove impurities.
Cool the filtrate in ice until crystals reappear.
Filter the crystals by using a Buchner funnel. This will remove
soluble impurities in the derivative.
Wash the crystals with little amount of cold solvent.

 Wash: to remove impurities

Little amount: or else the crystals will dissolve.
Dry the crystals with filter paper.
Determine melting point of crystals to check purity.
If melting point not sharp, repeat recrystallization until sharp
melting point is obtained.
Then compare the melting temperature of the derivative with
known melting temperature in data booklet.

Iodoform Test (oxidation)

o A compound can only react with iodine and NaOH(aq) if it has the
group CH3CO
o It would produce a yellow ppt of triodomethane
o Example:
CH3CO + 3I2 + 4NaOH -- CHI3 + HCOONa+ + 3NaI + 3H2O
CH3COCH2CH3 + 3I2 + 4NaOH -- CHI3 + C2H5COONa+ + 3NaI
+ 3H2O

Spec 8: give some examples of molecules that contain

the carboxylic acid functional group
Any compound with the COOH group will be a carboxylic acid.
Ex: ethanoic acid, propanoic acid..

 Carboxylic acids with low molecular mass are liquids at rtp while
those with high molecules are solids at rtp.

Since the electronegative oxygen attracts the bonding electrons

towards it, the carboxylic acid is polar.

It can form hydrogen bonds with water and hence is soluble in

water.

Boiling temperature of carboxylic acids is higher than alkanes due

to strong hydrogen bonding. Adjacent carboxylic acids can bond
to one another by hydrogen bonds in solid and gaseous state and
also when dissolved in non-polar solvent.

Because of that, carboxylic acids have a higher melting

temperature than alcohols.

Oxidation of Alcohols
Reagent: dilute H2SO4 and K2Cr2O7
Condition: heat under reflux.
When primary alcohols are allowed to completely oxidize, they
form carboxylic acids.
They will fully oxidize with heat under reflux.
If heat and distillation used, an aldehyde will form.

Oxidation of Carbonyl Compounds

Reagent: dilute H2SO4 and K2Cr2O7
Condition: heat under reflux
And aldehyde will further oxidize with heat under reflux to give a
carboxylic acid.
Hydrolysis of Nitriles
Reagent: dilute H2SO4
Condition: heat under reflux
Nitriles can be hydrolyzed to the corresponding carboxylic acids
with the conditions above.
Example:
CH3CH2CN + H2O -- CH3CH2COOH
Propanenitrile + water -- propanoic acid

Reagent: LiAlH4
Condition: dry ether followed by acid hydrolysis
This is a reduction reaction.
Carboxylic acids undergo nucleophilic addition.
The reduction will give a primary alcohol.

ii)

Carboxylic acids react with alkali to form carboxylic acid salts

and water.

Observation: system gets hot since this is an exothermic reaction

Example:
CH3COOH + KOH -- CH3COOK + H2O

A titration of fruit juice against NaOH can be carried out to

determine the amount of citric acid in fruit.

A solution of NaOH of known concentration can be added to the

fruit juice by titration.

The volume of NaOH required to react with all the acid will
enable us to calculate the concentration of acid.

iii)
Reagent: PCl5 (s)
Condition: room temperature and pressure
Type of reaction: nucleophilic substitution
Observation: misty fumes which turn damp blue litmus red due to
formation of HCl
CH3COOH + PCl5 ---- CH3COCl + POCl3 + HCl

iv)

 Reagent: Alcohol
Condition: conc. H2SO4 as catalyst and heat under reflux.
Type of reaction: addition-elimination
Example:
C2H5OH + CH3COOH ----- CH3COOC2H5 + H2O

In the ester, after COO would be the alcohol part.

Acyl chlorides and esters are carboxylic acid derivatives.

Functional group of esters:

Example methyl methanoate, ethyl ethanoate etc.

Functional group of acyl chlorides:

Example propanoyl chloride, ethanoyl chloride, propane dioyl

chloride.

Reagent: water
Condition: room temperature
Type of reaction: hydrolysis
Observation: misty fumes due to formation of HCl
Example:
Acid chloride + water ---- carboxylic acid + HCl
Ethanoyl chloride + water --- ethanoic acid + HCl

Reagent: alcohol
Condition: room temperature
Type of reaction: condensation
Example:
Propanoyl chloride + propanol ---- propane propanoate + HCl

Alcohol part would be after C=O

Reagent: concentrated ammonia/ammonia gas

Condition: room temperature
Type of reaction: nucleophilic substitution
Example:
Ethanoyl chloride + ammonia ---- ethane amine + HCl

Reagent: primary amine

Condition: room temperature
Type of reaction: nucleophilic substitution
Example:
Ethanoyl chloride + methyl amine ---- methyl ethanamide + HCl

acid chloride part should be at the end.

reagent: dilute HCl

conditions: heat under reflux
type of reaction: hydrolysis
general equation:
ester alcohol + carboxylic acid

reagent: dilute NaOH

conditions: heat under reflux

 general equation:
ester ----- sodium salt + methanol

Trans-esterification
It is the process by which the R group of an ester is replaced by
the R group of alcohol/acid its reacted with.

Manufacture of low fat spreads

Previously hydrogenation was used to produce margarine.
Hydrogenation produces saturated fatty acids by adding
hydrogen across C=C bonds.
Saturated fatty acids can be harmful to health.
Therefore trans-esterification is used to produce the healthier
alternative, unsaturated fatty acids.
The process is shown below.

Unsaturated fatty acid

Catalyst: sodium methoxide and enzyme lipase.

Esters in Biodiesel
Biodiesel is a renewable fuel.
The need for biodiesel is increasing with the urgency to reduce
carbon emissions.
Generally biodiesel is considered to be carbon neutral.
However this may not be true because more energy is released
during:
Manufacture of fertilizers.
Plant cultivation.
Harvesting
Extraction of oil.
Processing of oil into fuel
All of these are steps involved in the production of biodiesel.
All CO2 released during these steps may not be absorbed by the
plants cultivated to produce the fuel.
Trans-esterification is used to produce biodiesel.

 Triglyceride is reacted with methanol or ethanol.

A strong base like sodium hydroxide is used as a catalyst.
At the end of reaction, fatty acids are converted to methyl or
ethyl esters.
Glycerol is a by-product.
Ethyl propanoate + methanol ----- methyl propanoate + ethanol

Importance of Polyesters
Polyesters are polymers made of monomers linked by ester
groups.
Terylene is a polyester which has a number of uses like:
Clothing fabric
Packing goods and soft drink bottles.
Used in audio and video tapes
Net curtains
Conveyor
Ropes, safety belts

Condensation polymerization of ethane-1,2-diol & benzene 1,4

dicarboxylic acid
Ethane- 1,2-diol + benzene 1,4 dicarboxylic acid ----- terylene
2 Hs taken from the diol
2 OHs taken from the acid
2 H2O as the by-product

Condensation polymerization of ethane-1,2-diol & benzene 1,4,

dioyl dichloride
Ethane-1,2-diol + benzene 1,4 dioyl dichloride ----- terylene
2 Hs taken from diol
2 Cls taken from dioyl dichloride.
2 HCls are the by-products

Spec 1: explain the effect of different types of radiation

on molecules and how the principles of this are used in
chemical analysis and in reactions, limited to:
i)

infrared in analysis
Molecules vibrate when they absorb infrared radiation.
Only the molecules that can absorb infrared radiation are the
ones that change polarity as they vibrate.
When infrared radiation is absorbed, the bonds within the
molecule can either stretch or bend.
An infrared spectrum will show peaks for bonds that vibrate in
different ways.
The spectrum will also show the peaks for the functional groups
of organic compounds.

Application
In wine production, oxidation of wine can occur through contact
with oxygen.
Partial oxidation of ethanol will produce ethanol.
Complete oxidation will produce carboxylic acid.
Oxidation of wine will cause alterations in taste and color of wine.
Therefore this oxidation needs to be monitored.
Infrared spectroscopy can be used to trace progress of this
reaction.
If the spectrum shows a peak at C=O bond absorption, they will
know that wine is partially oxidized.

If the spectrum shows a peak at COOH bond absorption, they will

know that wine is completely oxidized.
So wine makers can work accordingly.

ii)

Microwaves for heating

In a microwave oven, microwave radiation sets up an electric
field.
Water molecules (dipolar) in the food try to be in line with the
field.
But just as they do, the field switches and the water molecules
continue to vibrate.
This causes energy in the oven to be converted to thermal energy
heating up the food.
Microwaves can also speed up reactions.
To extract an organic compound from tetrachloromethane, water
can be added to it.
Shake the mixture so that the organic compound gets distributed
fairly equally to both solvents.
If the mixture is then subjected to microwave radiation, water
(polar) gets heated up faster than the non-polar
tetrachloromethane.
Therefore more of the organic compound will dissolve in aqueous
layer giving a better separation.

iii) Radio waves in nmr

Nmr spectroscopy will be studied in detail in the specs to follow.

iv) Ultraviolet in initiation of reactions

In the Earths atmosphere, when oxygen is subjected to
ultraviolet radiation, they split into free radicals by homolytic
fission

Then each of the very reactive radical will react with an oxygen
molecule to form ozone (O3)
Ultraviolet radiation is needed to break the strong bonds within
halogens for free radical substitution reaction of halogens.

Spec 2: explain the use of high resolution NMR spectra

to identify the structure of a molecule:
i)

based on the different types of proton present

from chemical shift values
Number of peaks: number of different proton environments.
Ratio of area/integration ratio: number of hydrogen atoms.
Chemical shift: gives an idea of the sort of proton environment.
Integration ratio can be found by dividing all the integration
trace values by the smallest number.

ii)

by using the spin-spin coupling pattern to

identify the number of protons adjacent to a
given proton

Low resolution NMR spectrum only shows peaks which indicate

the different groups of protons.
In high resolution NMR spectrum, those peaks are split to give
clearer idea about the structure of a molecule.
The splitting occurs due to the interaction between the protons
and the neighboring atoms. This interaction is called spin-spin
coupling.
To find the number of neighboring protons, we use the n+1 rule.
For example, if the peak is split into a triplet, it is the number of
neighboring protons with an addition of 1. So a triplet would mean
that there are 2 neighboring protons.

 Likewise a quartet would mean that there are 3 neighboring

protons and a singlet would mean that there are no neighboring
protons.

iii) the effect of radio waves on proton spin in nmr,

limited to 1H nuclei
H nuclei have a property called spin.
H nucleus behaves like a magnet.
When it is placed in a magnetic field, it can either be aligned with
that magnetic field or against it.
When it is aligned with the magnetic field it is more stable and
this is a low energy state.
When it is aligned against the magnetic field, it is less stable
and this is a high energy state.
The energy required to change the state of the H proton is
provided by radio waves.
Radio wave must be of a certain frequency to change the state of
H proton.

iv) the use of magnetic resonance imaging as a noninvasive technique, eg scanning for brain
disorders, or the use of nmr to check the purity
of a compound in the pharmaceutical industry
Scanning for Brain Disorders
Using NMR, doctors can rapidly check the growth of a tumour in
brain.
If high levels of a substance called choline is detected, that
would mean that growth of tumour is rapid.

 If low levels of choline are detected, that would mean growth of

tumour has slowed down.
Therefore by using NMR, doctors can keep a close check on the
tumor without surgery.
They can work accordingly to treat the patient.
In the Pharmaceutical Industry
When producing nicotine synthetically, its oxidation forms a
product called cotinine.
Cotinine has a very similar structure to nicotine but has
undesirable properties.
NMR spectroscopy can be used to measure the purity of the
sample of nicotine.
If the spectrum shows that cotinine is present in one of the
batches, it can be isolated and removed before nicotine is used.

Spec 3: demonstrate an understanding of the use of IR

spectra to follow the progress of a reaction involving
change of functional groups, eg in the chemical
industry to determine the extent of the reaction
In wine production, oxidation of wine can occur through contact
with oxygen.
Partial oxidation of ethanol will produce ethanol.
Complete oxidation will produce carboxylic acid.
Oxidation of wine will cause alterations in taste and color of wine.
Therefore this oxidation needs to be monitored.
Infrared spectroscopy can be used to trace progress of this
reaction.

 If the spectrum shows a peak at C=O bond absorption, they will

know that wine is partially oxidized.
If the spectrum shows a peak at COOH bond absorption, they will
know that wine is completely oxidized.
So wine makers can work accordingly.

Spec 4: interpret simple mass spectra to suggest

possible structures of a simple compound from the m/e
of the molecular ion and fragmentation patterns

The final peak is the molecular ion peak. It shows the molecular
mass of the compound.
Therefore subtracting that with the other m/e ratios would give
the mass of the other fragments produced.
72-57= 15
The species that would give 15 is CH3+
72-43= 29
The species that would give 29 is CH3CH2+
72-29 = 43
The species that would give 43 is CH3CH2CH2+

Therefore the compound is: CH3CH2CH2CH2CH3

Pentane

Spec 5: describe the principles of gas chromatography

and HPLC as used as methods of separation of
mixtures, prior to further analysis (theory of Rf
values not required), and also to determine if
substances are present in industrial chemical processes

The sample to be tested is injected to the port using a micro

syringe.
The column contains liquid adsorbed onto the surface of an inert
solid. (Stationary phase).
The sample is heated 50oC higher than the boiling point of the
least volatile component in the sample.
As the sample is heated, the components are carried through the
column by the flow of an inert gas (mobile phase).
As the sample passes through the column, the components
separate because they move at different rates.

 This is similar to column chromatography.

In column chromatography, the column is packed with a solid
stationary phase.
The solution to be tested is added to the column.
The solvent is added which acts as the mobile phase.
The tap of the column is opened so that the solvent flows.
The components in the test solution separate in the process.
As soon as one component has flown out completely, a new beaker
is kept below the column for the next component to flow into.
In HPLC, instead of allowing the solvent to flow under force of
gravity, it is forced through the column under high pressure.
This makes the process faster. (merit)
Size of particles with which the column is packed with can be
made smaller for better separation of components.
Advantage of this method over column chromatography is that
this uses a more sensitive detector.
There are 2 type of HPLC which are:

 The column is filled with silica (polar)

The solvent used is non-polar (eg: hexane)
The polar components stick to the silica more than the non-polar
components
Therefore the non-polar components leave more quickly.
The column is filled with silica that is made non-polar with long
hydrocarbon chains.
The solvent is polar.
The polar components wont stick to the non-polar silica.
They would stick to the polar solvent and move out more quickly.
Retention time: the time taken for a particular component to move
through the column and reach the detector.
Retention time depends on:
o Pressure used effects flow of solvent
o Nature of stationary phase particle size, material
o The exact composition of solvent.
o The temperature of column.
To find whether a compound P is present in a sample:
Inject a small amount of P into the apparatus and record the time
taken for its peak to be formed. This is called calibration peak.
Then test the sample which might contain P.
If a peak forms with the same retention time as P, then the
sample contains P.

 Comparing the size of the peak with same retention time with the
calibration peak will allow us to calculate the concentration of P.
Note: you cannot compare the concentrations of different components
in one sample by comparing the peaks because the peak depends on the
amount of UV absorbed by each component.