UNIT 4

Entropy
- Entropy is the measure of order or disorder
Increase in entropy (S > 0); thus disorder increases
Decrease in entropy (S < 0); thus disorder decreases
- S system = S products - S reactants
- S surroundings = - H/ T
- S total = S system + S surroundings
or
S system - H/ T
(Standard Unit of Energy is Joules)
Reaction

S system

S surroundings

Feasibility

Example

Exothermic

Always
feasibility

C (g) + O2 (g)
--> CO2 (g)

Endothermic

Not
feasible

CO2 (g) -->

C (g) + O2 (g)

Exothermic

If -H/ T >
S sys;
the
reaction is
feasible
More likely
at low
temp

H2O (g) -->

H20 (l)

Endothermic

If -H/ T
< S sys;
the
reaction is
feasible
More likely
at high
temp

H2O (l) --> H20

(g)

* When looking at the changes in entropy of the system and the surroundings you
have to consider both the enthalpy change in both and the changes in physical
states in the system
Enthalpy of Hydration

- Enthalpy change that takes place when one mole of a gaseous ion dissolves in
sufficient water to give an infinitely dilute solution
M + (g) + aq --> M + (aq)

H hyd

X- (g) + aq --> X + (aq)

H hyd

Rates
- Rate of a chemical reaction is defined as the change in concentration of a reactant or
product per unit time
rate = C / T (mol dm-3 s-1)
Techniques to measure the rate of a reaction (4-8 GF)
-

Measuring the volume of a gas produced

Measuring the change in mass of a reaction mixture
Colorimetry
Titrimetric analysis
Conductrimetric analysis

Measuring the volume of a gas produced accurately

Rate equation & Order of Reaction

aA + bB --> cC + dD
Rate [A] x [B] y
Rate equation = k [A] x [B] y
k
x
y
x

- rate constant
- order wrt A
- order wrt B
+ y - overall order of reaction

* The power to which the concentration of a given reactant is raised in the rate
equation is defined as the order with respect to that reactant
* The sum of the powers of the concentration terms in the rate equation is called the
overall order
* The proportionally constant in the rate equation is called the rate constant

* If a reactant does not appear in the rate equation; the reaction zero order with
respect to that reactant
This is because the reaction has more than one step and that particular reactant
enters the mechanism after the rate determining step
* The rate equation cannot be deduced merely from the stoichiometric equation
because the rate equation depends on the mechanism of the reaction; therefore the
rate equation should be found experimentally and not by simply looking at the
equation
* Even if a reactant affects the rate of a reaction if will not appear in the rate
equation it its in large excess so that its concentration is relatively
unchanged during the reaction (pseudo zero order)
* Overall order of reaction:
The sum of the powers to which the reactant concentrations are raised to in the
experimentally determined rate equation
Deduction of the order of a reaction
1 Initial rate method
- Initial rate is the rate at the instant that the chemicals are mixture
- When concentration of a reactant is changed if the rate does not change the order
with respect to that reactant is zero
Reactant
Concentration

Rate

Order with respect to

that reactant

Doubled

Rate is doubled; increases

by a factor of 2

Tripled

Rate is tripled; increases

by a factor of 3

Doubled

Rate is quadrupled;
increase by a factor of 4
(2^2)

Tripled

Rate is increased by a
factor of 9 (3^2)

Concentration - Time Graphs

- The shape of a concentration - time graph depends on the order of the reaction
- The rate of the reaction is equal to the gradient of a concentration-time graph

- If the concentration-time graph is a curve as shown in the above graphs the order is
either 1 or 2
- The half life is calculate to find the exact order
- Half - life is the time taken to halve the concentration a reactant
- If two consecutive half-lives are the same; the reaction is first order wrt to that
reactant and if it doubles reaction is second order wrt to that reactant
Rate - Concentration Graphs

Activation Energy
- The minimum kinetic energy that should be present in colliding molecules for a
collision to be successful
- A reaction with a smaller activation energy occurs faster than a reaction with a
higher activation energy
- Reaction profile diagrams for typical exothermic and endothermic reactions are given
below:
Exothermic

Endothermic

* The rate constant of a reaction depends on 3 factors:

1) Temperature
2) The activation energy of the reaction
3) Orientation factor (constant for a particular reaction)
(Since activation energy and the orientation factor remains constant (standard) for a
particular reaction; only temperature is seen to affect the rate constant)

Ea - activation energy
R - gas constant
T - absolute temperature
A - Arrhenius constant
- The activation energy can be calculated from the gradient of the graph
Mechanism and the rate determining step
- Rate equation obtained from experimental data can be used to support a proposed
mechanism for a particular reaction
Example: Hydrolysis of tertiary halogenoalkanes

[(CH3)3CI]

[OH]-

Rate/ Mol dm-3 s-1

0.1

0.1

1.11 X 10^-5

0.2

0.1

2.22 X 10^-5

0.3

0.1

3.33 X 10^-5

0.1

0.2

1.11 X 10^-5

0.1

0.3

1.11 X 10^-5

- When the concentration of [(CH3)3CI] is doubled ( #1 to #2) the rate increases by a

factor of two
Therefore the order wrt to [(CH3)3CI] is 1
- When the concentration of [OH]- is doubled; the rate does not increase
Therefore the order wrt to [OH]- is 0
Overall order = 1; Rate = k [(CH3)3CI]
* If the total volume of a mixture is constant; volume concentration

- This means that the hydroxide ions enter the mechanism after the rate determining
step; so there should be at least 2 steps in the mechanism
- The experimentally determined rate equation is consistent with the proposed
method:
SN1
Step 1:

Step 2:

- The reactants that take part in the rate determining step and the steps prior to that
appear in the rate equation
- If the first step is the rate determining step; the rate equation for the overall reaction
is the same as that for the rate determine step
Hydrolysis of Primary Halogenoalkanes

[CH3Br] (moldm-3)

[OH]- (moldm-3)

Rate (moldm-3s-1)

0.1

0.1

1.5 x 10^-5

0.2

0.1

3.0 x 10^-5

0.3

0.1

4.5 x 10^-5

0.1

0.2

3.0 x 10^-5

0.1

0.3

4.5 x 10^-5

- When the concentration of [CH3Br] is doubled; the rate increases by a factor of 2

Therefore the order wrt to [CH3Br] is 1
- When the concentration of [OH]- is doubled; the rate increases by a factor of 2
Therefore the order wrt to [OH]- is 1
Overall order: 2 Rate = [CH3Br] [OH]- The kinetics of this reaction suggests that the rate determining step involves both
halogenoalkanes and the hydroxide ions
- This rate equation is consistent with the proposed mechanism
SN2

- The derivation of the rate equation is more complex when the second or a
subsequent step is rate determining step
- Three molecules cannot collide together & C enters the mechanism after the rate
equation
A + 2B + C --> D + E
Rate = k [A] [B]^2
A + B --> Intermediate 1
Intermediate 1 + B --> Intermediate 2 (rds)
Intermediate 2 + C --> D + E
- According to the rate equation 1 molecule of A and 2 molecules of B should take art
in the rate determining reaction step or before that
- Powers of concentration terms in a single step are the same as the stoichiometry in
that step
Example: A + 2B + 3C --> Products
Rate = [A] [B]2 [C]3
A + C --> Intermediate 1 (AC)
Intermediate 1 + B --> Intermediate 2 (ACB)
Intermediate 2 + C --> Intermediate 3 (AC2B)

Intermediate 3 + B --> Intermediate 4 (AC2B2)

Intermediate 4 + C --> Products (AC3B2)
Reaction of Iodine with Propanone
CH3COCH3 + I2 --> CH3COCH2I + H+ + IExperiments show that the reaction is first order wrt propanone and first order wrt to
H+; but zero order wrt to Iodine
This shows that iodine is not involved in the rate determining step or any step before
that
Step 1:

Step 2:

Step 3:

Altering the order by the method of excess reagents

A + 2B --> C + D
Rate = k [A]^p [B]^q
* If the concentration of B is made 10 times that of A;the change in concentration of B
during the reaction is negligible
Therefore when excess of B is used that concentration becomes virtually constant; so:
Rate = k [A]^p

Catalysts
A catalysts is a substance which speeds up a chemical reaction by providing an
alternate pathway with a lower activation energy and remains chemically unchanged

- Catalysts can be divided into two groups:

* Homogenous catalysts
* Heterogenous catalysts
Homogenous Catalysts
- Catalysts & the reactants are in the same phase:
Example: Chlorine free radicals act as homogenous catalysts in the gas phase
Cl + O3 --> ClO. + O2
ClO. + O3 --> Cl. + 2O2
H2SO4 (aq)
CH3COOH (aq) + C2H5OH (aq) --> CH3COOC2H5 (aq) + H20 (l)
Esterification is given in the above equation and sulfuric acid is used as the catalyst
Heterogenous Catalysts
- A heterogenous catalyst is in a different phase than the reactants
N2 + 3H2 --> 2NH3
(Refer Unit 5 Catalysts)

Chemical Equilibria
In a dynamic equilibrium; the rate of the forward reaction and the rate of the reverse
reaction are the same
Therefore there is no further change in concentrations of reactants or products
Equation Law
aA + bB cC + dD
Kc = [C]c [D]
[A]a [B] b

Kc - equilibrium constant
- The equilibrium constants depends only on temperature
- The units of equilibrium constant changes depending on the equation
- The equilibrium constant of the reverse reaction is the reciprocal of the equilibrium
constant of the forward reaction
Kc = 1/ Kc
Worked Example:
0.256g of HI was heated at 764K in a sealed flask of volume 100cm3 (0.01 dm3) ;
when equilibrium was reached the flask was cooled quickly
It was found that the mixture contained 0.00028 mol of I2
Calculate the value of Kc
2HI (g) I2 (g) + H2 (g)
HI
Start (Moles)
0.002
(0.256/127.9)
Change (Moles) 0.00144
(0.002 - 0.0056)
Equilibrium
Concentration
(Moles / Volume)

0.0144

I2
0

H2
0

0.00028
0.0028

Kc = 0.0028 X 0.0028
0.01442
= 0.038

Concentration of Water in Equilibrium Expressions

0.00028
0.0028

- When water is a reactant or product; but not a solvent; it is included in the Kc

expression
- When water is the solvent; even if it is a reactant or product; the concentration of
water is not included in the Kc expression
- When used as a solvent; the concentration of water does not change because it is in
large excess so the concentration term remains constant and its value is not
incorporated into Kc
Worked Example:
1 mole of ethanol and 2 moles of ethanoic acid were mixed in a sealed flask and left
to reach equilibrium
The equilibrium mixture contains 1.15 moles of acid. Calculate Kc
CH3COOH (l) + C2H5OH (l) CH3COOC2H5 (l) + H2O (l)
Start (Moles)

Change (Moles) 1.15

Equilibrium
Concentration
(Moles / Volume)

0.15

0.85

0.85

1.15/ V

0.15 / V

0.85 / V

0.85 / V

Kc = 0
.7225/ V2
0.1725/ V2
= 4. 19
The equilibrium constant in terms of Partial Pressure (Kp)
- The pressure of a gas is due to the collisions of its molecules with the wall of the
container its molecules with the wall of the container
* The partial pressure of a gas in a mixture of gases is the pressure that that gas
would exert if only that gas occupied the whole volume of the contained at a particular
temperature
- The partial pressure of a gas A; P(A) is equal to the product of the mole fractions of A
and the total pressure
P(A) =

n (A)
x total pressure
total number of moles

- However every gas molecule in the mixture contributes to the total pressure
So the total pressure; P is equal to the sum of all the partial pressures of the gases in a
mixture
- Since only gases have partial pressures; solids and liquids are not included in the Kp
equation
Example: aA (s) + bB (g) cC (g) + dD (g)

Kp = P(C)c x P(D)d
P(B)b
Worked Example
Ammonium hydrogen sulfide decomposes when heated according to the following
equation:
NH4HS (s) NH3 (g) + H2S (g)

Kp = 0.142 atm2 at 50C

a) State the expression for Kp

Kp = P(NH3) P(H2S)
b) Calculate the Partial Pressure of both gases at 50C and hence the Total Pressure
Since the molar ratios of both gases are the same; the Partial Pressures of both gases
are the same; hence:
Kp = P(NH3) P(H2S)
Kp = X2
0.142 = X2
X = 0.377 atm (Partial Pressure of each gas)
Therefore Total Pressure; P = 0.377 atm x 2 = 0.754 atm
Equilibrium Constant & Entropy Change
- As we already have learnt; the more positive the value of Stotal; the more and more
the reaction goes to the right hand side
- Stotal decides the magnitude of the equilibrium constant (K)
It is related by the following equation
Stotal = RlnK
R - gas constant

Worked Example:
Use the data below to calculate the value of the equilibrium constant at a temperature
of 25C
AgCl (s) Ag+ (aq) + Cl- (aq)
Hsol = + 66 KJmol-1
Stotal = Ssystem + Ssurroundings
Ssurroundings = -H/ T = -(66 x 1000)/ 298 = -221.48 Jmol-1K-1
Ssystem = Sproducts - Sreactants

= (73 + 57) - 96
= 34 Jmol-1K-1
Stotal = 34 Jmol-1K-1 + (-221.48 Jmol-1K-1)
= - 187.48 Jmol-1K-1
Stotal = RlnK
- 187.48 = 8.31lnK
e

(- 187.48/ 8.31)

=K

K = 1.6 X 102 mol2dm-6

Distribution of a substance between two immiscible layers

I2(water) I2 (hexane)
K = [I2] hexane
[I2] water

- K is known as Partition Constant or Distribution Constant

- Equilibrium constant for different reaction are calculated based on data from
experiments
ICT can be used to present and analyze data; in order to calculate K

Reaction Quotient (Q)

xA + yB --> mC + nD
Kc = [C]m [D]n
[A]x [B]y
- The right hand side of the above equation is called the concentration term or the
reaction quotient; Q
- Q = K; the system is in equilibrium
No further change in concentrations of reactants or products
- Q < K; system is not in equilibrium

The concentration of reactants is greater than that of products

Reactants reach to produce move products in order to increase the numerator of Q
Equilibrium shifts to the right
- Q > K; system is not in equilibrium
The concentration of products is greater than that of reactants
Products will react to give more reactants; increasing the denominator of Q and
reducing the value of Q
Equilibrium shifts to the left
Applications of Rates & Equilibrium
Many important industrial reactions are reversible
Chemists and chemical engineers are devising new methods by applying the
theoretical ideas and models that explain how fast reactions go (rates) and in which
direction and how far (equilibrium)
Factors affecting a system at equilibrium
1 Temperature:
For an exothermic reaction; the equilibrium constant decreases with increasing
temperature
If the reaction is endothermic; the equilibrium constant increases with increasing
temperature
Therefore temperature changes also affects equilibrium position
- For exothermic reactions:
An increase in temperature causes Kc to become smaller; Q will be larger than the
new value of Kc and the system is not at equilibrium
The system reacts to restore the equilibrium; it is done by making more reactant
molecules until Q = K; therefore the position of equilibrium shifts to the left
- For endothermic reactions:
An increase in temperature causes Kc to become bigger; therefore Q is small than the
new value of Kc and the system is not at equilibrium
The system reacts to restore the equilibrium
It is done by making more product molecules until Q = K; therefore the position of
equilibrium shifts to the right
Example:
[Cu(H2O)6]2+ + 4Cl- CuCl42- + 6H2O
(blue)
(yellow)
At room temperature - the solution contains a mixture of both ions
Cooling - produces move blue colour

Heating - produces more yellow colour

The forward reaction is endothermic
When the temperature is increases the endothermic reaction is favoured (more yellow)
* However the rate of a reaction increases with increasing temperature
This is true for both exothermic and endothermic reactions
2 Pressure:
- Pressure has a marked effect on gaseous equilibria
- However the pressure of a gaseous system or the volume of the container
has no effect on the value of the equilibrium constant; K
- The effect of pressure on the equilibrium position depends on the number of moles of
gaseous molecules on each side of the equation
Increase in pressure:
This is usually done by decreasing the volume of the container in which the reactants
are mixed
Example: N2 (g) + 3H2 (g) 2NH3 (g)
Kp = P (NH3)2
P(N2) x P(H2)3
- When the pressure is increases; the partial pressure of reactants increases by a
greater factor
- Therefore Q becomes smaller than Kp and the system is not in equilibrium anymore
- To restore equilibrium; the position of equilibrium shifts to the right so increase the
partial pressure of the products
Decrease in pressure:
This is usually done by increasing the volume of the container in which the reactants
are mixed
- When the pressure decreases; the partial pressure of the reactants decrease by a
greater factor
- Kp remains constant and Q becomes greater than Kp; so the system is not at
equilibrium
- The system reacts to restore the equilibrium by moving the position of equilibrium to
the left to reduce the partial pressure of the products
* When an increase pressure causes the numerator and denominator of the reaction
quotient term rise by the same factor. The value of Q does not change and Kp = Q
Thus the system is still in equilibrium and the position of equilibrium does not change
3 Concentration:
2SO2 (g) + O2 (g) 2SO3 (g)

Kc = [SO3]2
[SO2]2 [O2]2
- If the concentration of reactants is increased; the denominator of Q increases;
causing Q to decrease
Kc remains the same so Kc > Q; so the system is not in equilibrium
- To resort the equilibrium; the position of equilibrium shifts to the right
4 Catalysts:
- A catalyst has no effect on the equilibrium constant or the reaction quotient
Therefore the position of equilibrium does not change
- A catalyst speeds up both the forward and reverse reactions equally; therefore
equilibrium is reached faster
* The application of rates and equilibria is important in industrial and pharmaceutical
processes; because it enables us to:
1) Maximise the percentage conversion of reactant to product (increases the
equilibrium yield)
2) Make this amount of product as quickly as possible (increases the rate of
reaction)
3) Lower costs
4) Have a high atom economy
- Industrial processes are not in equilibrium since the products are removed from the
reaction mixture (eg: Haber Process)
- Chemical industries usually use a continuous flow method

Acid - Base Equilibria

- Acids were first defined as substances with a sour taste
- Bases were first defined as soapy substances
- However taste and field tests are not recommended; because many acid and bases
can be harmful
- Later on Arrhenius proposed a theory

The Arrhenius Theory

- Acids are substances that produce H+ ions when dissolved in water
- Bases are substances that product OH- ions when dissolved in water
- The Arrhenius Theory was limited to aqueous solutions; therefore Bronsted & Lowrie
extended the Theory to include non-aqueous solvents
The Bronsted - Lowrie Theory
- An Acid is a substance that gives a proton (H+ ion) to a base
- A base is a substance that accepts a proton (H+ ion) from an acid
Acid - Base Conjugate Pairs
- An Acid is a proton donor
- A Base is a proton acceptor
- Acid - Base equilibria involves a transfer of protons
HA (aq) + H2O (l) H3O+ (aq) + A- (aq)
Forward Reaction - acid: HA
base: H2O
Reverse Reaction - acid: H30+
base: A- A- is the base derive from the acid HA by the loss of a proton; therefore A- is known
as the conjugate base of HA
- H3O- is the acid derived from H20 after accepting a proton; therefore H3O+ is known
as the conjugate base of H2O
Base (1)
Conjugate Acid (1)
HA (aq) + H2O (l) H3O+ (aq) + A- (aq)
Acid (2)
Conjugate Base (2)
Examples:
1) Give the formulae of the conjugate bases of:
Remember: a conjugate base is formed by the loss of a proton
Acid

Conjugate Base

HCl
H2O
HSO4-

ClH3OSO4 2-

2) Give the formulae of the conjugate acids of:

Remember: a conjugate acid is formed by the gain of a proton

Base
H2O
OHSO42HSO4-

Conjugate Acid
H2O
H2O
HSO4H2SO4-

- Some substances can act as acids and bases; these are known as amphoteric
substances (example: water)
H2O + HCl --> H3O+ + Cl-

water acts as a base

H2O + NH3 --> NH4+ + OH-

water acts as an acid

Strong & Weak Acids

- A strong acid is an acid which is completely ionised in an aqueous solution; forming
hydrated hydrogen ions (H3O+)
HCl + H2O --> H3O+ + Cl- A weak acid is an acid that is only slightly (DO NOT SAY PARTIALLY) ionised in
aqueous solutions and forms a small proportion of H3O + ions
CH3COOH + H2O CH3COO- + H3O+
Strong & Weak Bases
- A strong base is a base which is completely ionised in a aqueous solution; forming
OH- ions
NaOH + H2O --> H3O+ + Cl- A weak base is a base that is only slight (DO NOT SAY PARTIALLY) ionised in
aqueous solutions and forms a small proportion of OH- ions
NH3 + H2O OH- + NH4+
Acid & Base Dissociation Constants
- A weak acid is in equilibrium with its conjugate base
HA + H2O H3O+ + AKc = [A-] [H3O+]
[HA] [H2O]
- Since water is the solvent; the concentration of water remains constant
So Kc x [H2O] = [A-] [H3O+]
[HA]
Ka = [A-] [H3O+]
(acid dissociation constant)
[HA]

- A weak base is in equilibrium with its conjugate acid

NH3 + H2O NH4+ + OHKc = [NH4+] [OH-]
[NH3] [H2O]
- Since water is the solvent; the concentration of water remains constant
So Kc x [H2O] = [NH4+] [OH-]
[NH3]

Remember H3O+ can be written as H+

Kb = [NH4+] [OH-]
dissociation constant)
[NH3]

(base

- Ka and Kb depend on the temperature and the nature of the reaction (Stotal = RlnK)
The pH Scale
- The pH scale is used to show the degree of acidity of a substance
It runs from -1 to +14
pH = - log [H3O+]
- The lower the pH (the higher the H + / H3O+ concentration) so the higher the acidity
Example:
[H3O+] moldm-3

pH

0.001
0.01
0.1
1

3y
2
1
0

- pH has no units
- The H+ / H3O+ concentration can be found using the pH value
Since; log [H3O+] = pH
[H3O+] = 10 - pH
Auto ionization of Water
- Water can act as an amphoteric substance; therefore one water molecule can
protonate another
Base (2) Conjugate Acid (2)
H2O + H2O --> H3O+ + OHAcid (1)
Conjugate Base (1)
Kc = [H3O+] [OH-]
[H2O]2

- Only a small amount of water is ionised at any time, so its concentration remains
virtually unchanged (constant)
So the ionic product of water (Kw):
Kw = [H3O+] [OH-]
- The value of Kw at 25C is 1.0 x 10-14 mol2dm-6
- Pure water has the same concentration of H3O + and OH-

Worked Example (pH of pure water at 25C):

(at 25C) [H3O+] [OH-] = 1.0 x 10-14
(for pure water) [H3O+] = [OH-]
[H3O+] 2 = 1.0 x 10-14
[H3O+] = 1.0 x 10-7
pH = - log 1.0 x 10-7 = 7
- Since Kw = [H3O+] [OH-]
logKw = {-log[H3O+]} + {-log[OH-]}

pKw = pH + pOH
pKw = pH + pOH

Worked Example (pKw of pure water at 25C):

[H3O+]/ [OH-] = 1.0 x 10-7

pH/ pOH = - log 1.0 x 10-7 = 7
pKw = 7 + 7 = 14
- A neutral solution is one in which the concentration of H3O + and OH- ions are equal
- In all aqueous solutions at 25C (not necessarily neutral solutions):
[H3O+] [OH-] = 1.0 x 10-14
- Acidic Solutions:
[H3O+] > [OH-]
[H3O+] > 1.0 x 10-7
pH < 7
- Alkaline Solutions:
[H3O+] < [OH-]

[H3O+] < 1.0 x 10-7

pH > 7
Worked Example:
At a higher temperature; Kw was found to be 1 X 10 -12 mol2dm-6
a) Is this ionization of water exothermic or endothermic
Endothermic; Kw increases with increasing temperature (as the ionization of water is
endothermic, so an increase in temperature shifts equilibrium to the right).
b) At this temperature; calculate the pH of a neutral solution
(in a neutral solution the concentration of H3O + and OH- ions are equal) So:
[H3O+] [OH-] = 1 x 10-12
[H3O+] = 1 X 10 -12
[H3O+] = 1 X 10 -6
pH = - log [1 X 10 -6] = 6
pH of a Weak Acid
- A weak acid is in equilibrium with its conjugate base as given below
HA + H2O H3O+ + AKa = [H3O+] [A-]
[HA]
- [HA] in the above equation is the equilibrium concentration of HA
However; since the ionization of a weak acid is negligible; the initial concentration of
HA can be used in these calculations
Therefore we assume:
[HA]initial = [HA]equilibrium
Worked Example:
Calculate the pH of a 0.135 moldm-3 solution of ethanoic acid
Ka = 1.8 X 10 -5 moldm-3 at 25C
CH3COOH + H2O H3O+ + CH3COOKa = [ H3O+ ] [ CH3COO-]
[CH3COOH]
CH3COOH

H3O+

CH3COO-

Initial
Concentration

0.135

Equilibrium
Concentration

0.135 - X

1.8 X 10 -5 =

X2
0.135

(since we assume [CH3COOH] initial =

[CH3COOH]

equilibrium)
X = 1.56 X 10-3
pH = -log 1.56 X 10-3
pH = 2.81
* Assumptions made in this calculation:
1) Ethanoic acid (weak acid) is only slightly ionised; therefore the initial concentration
and the equilibrium concentration are the same
2) The auto ionization of water is negligible (which
concentration)

could affect the H3O +

pKa Calculations
- pKa = -logKa
- Ka = 10 -pKa
Worked Example:
The pKa of methanoic acid is 3.75
Find Ka
Ka = 10 -pKa
Ka = 10 -3.75 = 1.78 X 10 -4
- Strong Acids
Ka > 1
pKa < 0
- Weak Acids
Ka < 1
pKa > 0
Diprotic Acids
- A diprotic acid produce two H + ions per
molecule; example: H2SO4
- The first dissociation of the acid is
complete
H2SO4 --> H+ + HSO40.1M

0.11M 0.1M

- HSO4- is a weak acid; so the second

dissociation is a slight ionization

Proving that Ka x Kb = Kw
HA + H2O--------> H3O+ + AKa= [H3O+] [A-] / [HA] ----------------(1)
A- + H2O---------> HA + OHKb= [HA] [OH-] / [A-] ----------------(2)
(1) * (2)
Ka x Kb = [[H3O+] [OH-]
So:

HSO4- --> H + +SO4-2

Ka = [ H+ ] [ SO4 -2]
[HSO4-]
Ka = [ H+ ] [ SO4 -2]
[0.1]

(H+ concentration = HSO4- concentration)

Given that Ka = 1 X 10-2

[ H+ ] = 0.0316 moldm-3
* The calculated value obtained for the concentration of H + in the equilibrium mixture
is higher than the actual value of H + ions at equilibrium resulting from the ionization of
HSO4This is because in reality; the H+ ions produced by the first (complete) ionization
suppresses the formation of H+ from the second ionization (as the higher concentration
of H+ ions would cause equilibrium to shift to the left)
Therefore the overall calculated H+ i ion concentration is less than the calculated value
Salts of Weak Bases
Example: NH4Cl
- Ammonium chloride solution is completely ionised as given below
NH4Cl (aq) --> NH4+ (aq) + Cl- (aq)
- Ammonium ions can act as acid (conjugate acid os NH4Cl)
NH4+ (aq) +H2O (aq) NH3 (aq) + H3O- (aq)
Ka = [NH3] [H3O+]
[NH4+]
- When calculated; the pH of NH4Cl is less than 7; so a solution of NH4Cl is acidic
The weaker the base; the stronger its conjugate acid and the more acidic a solution of
its salt becomes
Salt of a Weak Acid
Example: CH3COO-Na+
- CH3COO-Na+ dissociates completely in water
CH3COONa --> CH3COO- + Na+
- CH3COO- ions can act as a base (conjugate base)
CH3COO- + H2O CH3COOH + OHKb = [CH3COOH] [OH-]
[CHCOO-]
Worked Example:
Calculate the pH of 0.1 M of Sodium Ethanoate solution (at 25C)
Ka of CH3COOH = 1.75 x 10-5

Since Ka x Kb =Kw
(1.75 x 10-5) x Kb =Kw
(1.75 x 10-5) x Kb = 1 x 10-14
Kb = 5.7 x 10-10
Kb = [CH3COOH] [OH-]
[CHCOO-]
5.7 x 10-10 = [CH3COOH] [OH-]
0.1
[OH-] = 7.56 x 10-6
[OH-] x [ H3O+ ] = 1 x 10-14
[H3O+ ] = 1 x 10-14
7.56 x 10-6
+
[H3O ] = 1.32 x 10-9
pH = -log 1.32 x 10-9
pH = 8.88

(We assume that [CH3COOH] = [OH-])

- When calculated; the pH of CH3COO-Na + is more than 7; so a solution of CH3COONa+ is alkaline

The weaker the acid; the stronger its conjugate base and the more alkaline a solution
of its salt
(Refer George Facer page 103)
- Salts of strong acids and bases dissolved in water without any reaction taking place
Therefore these salts are neutral
Example: NaCl --> Na+ + ClNa+ and Cl- do not react with water as their electronic configurations make them
relatively stable and are therefore inert
Buffer Solution
- A solution which resists pH changes due to the addition of small amounts of an acid
or a base is known as a Buffer Solution
There are two main types of buffer solutions:
1) A mixture of a weak acid with its salt
Example: CH3COOH & CH3COONa
2) A mixture of a weak base with its salt
Example: NH3 and NH4Cl
Ethanoic Acid & Sodium Ethanoate Mixture
- Sodium ethanoate is fully ionised in water
CH3COONa (aq) --> CH3COO- (aq) + Na+ (aq)

- Ethanoic acid is slightly ionised in water and this ionization is suppressed due to the
presence of a high concentration of ethanoate ions
CH3COOH + H2O --> CH3COO- + H3O+
- Therefore the mixture acts as a large reservoir of CH3COOH and CH3COO- ions
-When a small of acid is added;
CH3COO- + H3O+ --> CH3COOH + H2O
- When a small amount of base is added;
CH3COOH + OH- --> CH3COO- + H2O
- The ratio of acid concentration to salt concentration does not change
[CH3COOH] : [CH3COO-]
- Therefore the pH of the solution remains virtually constant
* For the buffer to perform well; the ethanoic acid and ethanoate ions must be present
in equal concentrations
Such a mixture can easily be prepared by half neutralizing ethanoic acid using a strong
base (NaOH)
- The half neutralization point is when an acid or base is
Worked Example:
50CM3 of 1M CH3COOH is neutralised by 25CM3 of 1M NaOH
CH3COOH + NaOH --> CH3COO-Na+ + H2O
Initial
Concentrations
Final
Concentrations

0.05

0.025

0.025

0.025

0.025

* The half neutralisation technique is very useful in determining the dissociation

constant
CH3COOH + H2O H3O+ + CH3COOKa = [H3O+] [CH3COO-]
[CH3COOH]
At the half neutralisation point:
[CH3COO-] = [CH3COOH]
So:
Ka = [H3O+] (as the concentrations of CH3COO- and CH3COOH cancel out)

pKa = pH
- When a weak acid is half neutralised by a strong base pH = pKa
- Ionisation of the weak acid is suppressed by the CH3COO- formed by the complete
ionisation of the salt
Therefore CH3COO- ion concentration is equal to the salt concentration (this is an
assumption)
- Since the ionisation of the weak acid is suppressed
[CH3COOH] initial = [CH3COOH] at equilibrium
- Since Ka = [Salt] [H3O+]
[Acid]
pKa = pH - log [Salt]
[Acid]
pH = pKa + log [Salt]
[Acid]
- The above equation can be used
for buffer solutions
Worked Example:
- 1/3 of the number of mole of a weak acid HA was neutralised by adding aqueous
NaOH
The pH of the buffer was 4.2
Calculate Ka
HA + NaOH --> NaA + H2O
(Since the initial moles are unknown we take it as X)
Initial
Moles
Final Moles

X
(X - 1/3X)

1/3 x
-

1/3X 1/3X

(concentration in terms of X) [HA] = 2 [A-]

HA + H2O A- + H3O+
Ka = [A-] [H3O+]
[HA]
Ka = [A-] [H3O+]
2[A-]
Ka = [H3O+]
2
4.2 = -log [H3O+]

10-4.2 = [H3O+]
[H3O+] = 6.3 X 10-5
Ka = 6.3 X 10-5/ 2
= 3.15 X 10-5
Ammonia - Ammonium Chloride Buffer
- NH4Cl is fully ionised as given below
NH4Cl (aq) --> NH4+ (aq) + Cl- (aq)
- The weak base ammonia is only partially ionised and this ionisation is suppressed
due to the high concentration of NH4 + in the medium
NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)
- Therefore the buffer solution acts as a large reservoir of NH4 + ions and NH3
- When a small amount of acid is added:
H3O+ + H2O --> NH4+ + H2O
- When a small amount of base is added:
OH- + NH4+ --> NH3 + H2O
- As a result the concentration ratio of NH3: NH4 + stays the same
So the pH becomes virtually constant
The Rule of Two
- The rule of two gives a approximate pH of weak acids; weak bases and their salts
- pH of a 0.1M Strong Acid is 1 and 0.1M Strong Base is 13
out
Solution (example)

pH

Strong AcId (HCl)

Strong Base (NaOH)

13

Salt of a strong base and

strong acid (NaCl)

Weak Acid (CH3COOH)

1+2=3

Weak Base (NH3 (aq))

13 - 2 = 11

Salt of a weak acid and a

strong base (CH3COONa)

7+2=9

Salt of a strong acid and

weak base (NH4Cl)

7-2= 5

Solution (example)
Salt of weak acid and a
weak base

pH
7

Tip: you add or subtract 2 from the standard pH values depending on the strength of
various substances; for example if there is a strong acid and a weak base your final pH
value must be less than 7 as the acid is stronger so you subtract 2 from the standard
pH value of 7
(The standard values are the first three values listed in the table)
pH changes during Acid - Base Titrations
- The end point of a titration is when the appropriate colour change takes place
- The equivalence point is when the two reactants are mixed in the exact proportions
as indicated by the chemical equation
This is also called the neutral point
Strong Acid - Strong Base Titrations
- 25cm3 of 0.1M HCl is placed in a conical flask and 0.1M NaOH is filled into a burette
- The equivalence point is reached when 25cm3 of NaOH is added
- The salt present at the equivalence point is NaCl
It is not hydrolyzed
therefore the solution is neutral at the equivalence point so the pH is 7

Weak Acid - Strong Base Titrations

Strong Acid - Weak Base Titrations

Weak Acid - Weak Base Titrations

- No vertical section as the pH does not change rapidly at the equivalence point
Therefore the end point cannot be detected
Summary
Conical
Flask

Burette

Initial
pH

Vertical
Range

pH value at
equivalenc
e point

Final pH

Strong Acid

Strong Base

3 - 11

Just below 13

Weak Acid

Strong Base

7 - 11

Just below 13

Strong Acid

Weak Base

3-7

Just below 11

Conical
Flask
Weak Acid

Burette

Weak Base

Initial
pH
3

Vertical
Range
-

pH value at
equivalenc
e point
7

Final pH

Just below 11

Remember: we measure the pH of the conical flask so the initial pH depends only on
the strength of the acid and the final pH depends mostly on the strength of the base
For the vertical range the values range from +/- 4 (2x2) from 7 towards a more acidic
pH for strong acid (for the lower value) and a more alkaline pH for a strong base (for
the higher value) A weak acids or weak base does not have an effect on the range so
that particular value (either the lower value or higher value) will stay at 7 (the neutral
value)
If both a weak acid and a weak base is mixed there will be no vertical range
The pH value at the equivalence point is usually the mean of the lowest value and the
highest value of the range (other than for Weak Acids and Weak Bases where the pH is
7)
Acid - Base Indicators
- Indicators are use to detect the end point of titrations
me
* Acid-base indicators are either weak acids or weak bases
- Therefore they are partially ionised in water
HIn + H2O H3O+ +In^ Colour 1
^ Colour two
In - weak acid indicator
- If an acid is added to a solution which contains the indicator; the position of
equilibrium moves to the left producing more HIn
Therefore colour 1 produced
- If an alkali is added to the mixture; added OH- reacts with H3O +. As a result the
position of equilibrium shifts to the right producing more of colour 2
* Therefore the colour of the indicator changes depending on the pH
Ka =Kind = [H3O+] [In-]
[HIn]
pH = pKind + log [In-]
[HIn]

* For the eye to detect one colour; the concentrations of the substances should be as
given below:

For Colour 1: [HIn] = 10 [In-]

pH = pKind + log [In-]
10[In-]
pH = pKind + log 10-1
pH = pKind - 1
For Colour 2: [In-] = 10[HIn]
pH = pKind + log 10[Hln]
[Hln]
pH = pKind + log 10
pH = pKind + 1
- Therefore for an indicator to give a sharp colour change at the end point; the range
of pKind +/- 1 must lie within the vertical section of the pH curve
- Since weak acids- weak base titrations do not have a vertical section on its pH curve;
an indicator cannot be used to detect the end point
- Due to the sensitivity of the human eye; the pH range of an indicator is usually +/- 2
pH units
* The ideal indicator of a given acid-base titration:
1) Has a pKaindicator value exactly equal to the pH of the half equivalence point
2) Kind = [H3O+] [In-] = Ka
[HIn]
In the middle point of the colour change of the indicator
[HIn] = [In-]
Therefore pH = pKa
* The best indicator has a pKa value equal to the pH value of the equivalence point
pKa = pHequivalence
3) A good indicator must show a rapid colour change at the end point

Worked Example:

For each of the titrations listed below; state which of the indicators (A; B or C) could be
used to find the equivalence point

Indicator

pKind

3.7

7.1

9.6

a) H2SO4 & KOH: Indicator B

b) H2SO4 & NH3: Indicator A
c) HCl & NaOH: Indicator B

Isomerism
- Isomers are different compounds that have the same molecular formula
Structural Isomers
- Compounds with the same molecular formula but different structural formulae
There are three types of Structural Isomers:
1) C-Chain Isomers:
Example:

2) Positional Isomers:
Example:

3) Functional Group Isomers:

Example:

Stereo Isomers
- Compounds with the same structural formula but different spacial arrangements
There are two types of Stereo Isomers:
1) Geometric Isomers (Cis-trans & E-Z)
2) Optical Isomers
Geometric Isomerism
Geometric isomerism arises due to:
1) Restricted free rotation around a double bond
2) Each double bond carbon is attached to two different groups

Optical Isomerism
- If two objects are mirror images of each other and they are not super imposable; they
are said to be chiral
- Chiral molecules are asymmetrical

- Most chiral compounds have a carbon atom attached to 4 different atoms or groups
- A chiral centre in a molecule leads to two optical isomers known as enantiomers
- An enantiomer is an isomer than it non-superimposable on its mirror image

- The two forms of lactic acid have similar chemical and physical properties; except for
their effect on plane polarised light
However the biochemical reactions of optical isomers can be different
Plane - Polarised Light

- Unpolarised light has oscillations or vibrations in all directions/ in all planes

- When unpolarised light is passed through a polaroid/ polarizer the waves will have
oscillations in one place
This is known as Plane Polarised Light

- When plan polarised light is passed through a single enantiomer; it will rotate the
plane of plane polarised light because it is optically active

- One enantiomer rotates the plane of the plane polarised light clockwise and it is the
(+)-isomer and the other one will rotate it anti-clockwise so it known as the (-)-isomer
- The two enantiomers are name D & L as well
- A solution obtaining equimolar amounts of the enantiomers is called a racemic
mixture
- It does not rotate the plane of the plane polarised light
- The extent of the rotations (angle of rotation) can be measured using a polarimeter
(refer page 126 George Facer)
- The angle of rotation depend on:
1) The nature of the enantiomer
2) The concentration of the enantiomer
- If a molecule has 2 different chiral centers there are four optical isomers:

The four optically active isomers are:

A+ B+
A+ BA- B+
A- B-

Optical isomerism and reaction mechanism

- The optical activity of reactivity of product and reactant of organic reactions can help
chemists to determine the mechanisms of reactions
Example: Nucleophilic substitution of halogenoalkanes can take place either through
SN1 or SN2 reactions

SN2

- Optically active alcohol with an inverted stereo structure is obtained

SN1

- In this mechanism a carbo-cation is formed as the intermediate and it is a planar

structure
If the nucleophile attacks from the top; a enantiomer is formed and if its attacks from
the bottom the other enantiomer is formed
- The two enantiomers are formed in equal amounts so it will be a racemic mixture
with no optical rotations
- Optical activist of the halogenoalkanes and the products of the reaction can be used
as evidence for the mechanism
Carbonyl Compounds

- This group is known as the carbonyl group

- There are two important groups of carbonyl compounds

1) Aldehydes

2) Ketones

Examples of Aldehydes:

Examples of Ketones:

Physical Properties of Carbonyl Compounds

- Methanol is a gas and other carbonyl compounds are liquids at room temperature
- Carbonyl compounds are polar; therefore dipole-dipole and london forces are formed
between molecules
Therefore carbonyl compounds have boiling and melting temperatures than alkanes
and alkenes with the same number of electrons
- Intermolecular hydrogen bonds are not formed in carbonyl compounds as +
hydrogen is not present
Therefore boiling and melting temperatures lower than the alcohols with the same
number of electrons
Solubility of Carbonyl Compounds
- Lower members of carbonyl compounds are soluble in water; however the solubility
decreases with the increasing carbon chain length (the bulkiness of the R-group
negates the hydrogen bonds between the - O and + H)

- These compounds dissolve in water by making hydrogen bounds

- Propanone is an excellent solvent for organic substances as well
- Lower members of aldehydes have pungent smells
- Ketones have much sweeter smells
- Complex aldehydes and ketones are used in perfumes
Reactions of Carbonyl Compounds
- The polar nature of C=O makes the carbon atom susceptible for nucleophilic attack

- A nucleophile is a species with a lone pair of electons that can make a convalent
bond with + atoms
Reaction 1: Addition reaction with HCN
- Aldehydes and ketones undergo
hydroxynitriles (cyanohydrines)

addition

reactions

with

HCN

to

produce

- In this reaction HCN molecule is added across the C=O groups

- HCN is a weak acid and provides very few CN- ions
HCN H+ + CN- Therefore a base is added to produce more nucleophile ions
HCN + OH- CN- + H2O

- This happens in the presence of KCN in cold alkaline solution

- If the pH is very low; there wont be enough CN- ions for the first step
- If the pH is very high; there wont be enough HCN for the second step
- The mechanism for a ketone is the sam; but the reaction takes place at a slower rate
Example: Reaction with propanone

Stereochemistry of the Reaction

- Aldehydes and ketones are planar around the carbonyl there CN- can attack from the
top or bottom

- The product of the above addition reaction is chiral

Therefore we get a racemic mixture of the two optical isomers
Reduction of Aldehydes and Ketones (gives an alcohol)
- Aldehydes and ketones can be reduced using lithium tetrahydride aluminate (lithium
aluminum hydride; LiAlH4) dissolved in ether (sodium tetrahydride borate; NaBH4)
Aldehydes: reduced to primary alcohols
Ketones: reduces to secondary alcohols
- This reduction takes place in two steps:
1) H- is added to + carbon atom
(dry conditions are needed for this step; therefore LiAlH4 is dissolved in ether)
2) Addition of an aqueous solution of an acid to protonate the O- formed in the first
step

- LiAlH4 reacts specifically with polar - bonds therefore it reduced the C=O group in
aldehydes; ketones; acids; acid derivatives and CN groups (cyanides) but it doesn't
reduce the -bond in the C = C double bond
- However the H2/ Pt can reduce both C =O and C = C

Bradys Reagent
- Bradys reagent is 2, 4 - dinitrophenylhydrazine ( 2, 4 - DNP)

- Aldehydes and Ketones react with Bradys reagent to form yellow or orange
crystalline solids
These derivatives are known as 2, 4 - dinitrophenylhydrazones

- The above reaction is a condensation reaction

It can be used as a test for carbonyl compounds
- When Bradys reagent is added a yellow precipitate is given by simple aldehydes and
ketones and an orange precipitate is given by aromatic aldehydes and ketones
- The melting temperature of the solid can be determined after the purification and
recrystalisation

- The carbonyl compound can be identified by comparing the experimental melting

point with the melting point in the data booklet
Procedure with Brady's Reagent
Step 1: React the carbonyl compound with a solution of 2, 4 - dinitrophenylhydrazine
Step 2: Filter off the solid
Step 3: Re-crystallize the solid using a minimum volume of hot ethanol
Step 4: Dry the purified produce and determine the melting point
Step 5: Refer to the data booklet and identify the solid
Oxidation
- Only aldehydes are oxidised
- Oxidation of aldehydes can be carried out using different methods
Procedure for the Oxidation of Aldehydes
Method 1: Warm the solution with acidified potassium dichromate solution (K2Cr2O7)
(Acidified K2Cr2O7 turns from orange to green)

Method 2: Add potassium manganate (VII)

For an acidic solution of KMnO4:
MnO4- (purple) is reduced to Mn2+ (colourless)
For an alkaline or neutral solution of KMnO4:
Brown precipitate of MnO2 formed
* In an alkaline solution the final colour can be green as well
Method 3: Warm with Fehlings solution (Test for aldehydes)
The deep blue solution gives a red-brown precipitate
Fehlings solution is a mixture of copper sulfate and sodium potassium tartarate in
alkali

Method 4: Warm with Tollens Solution

- Tollens solution is made by adding a few drops of NaOH to silver nitrate and
dissolving the precipitate in dilute ammonia
- Ag(NH3)2+ is present in the solution
- When the aldehyde is warmed with the above solution; a silver mirror is formed
inside the test tuber

- Ketones do not undergo oxidation so the above methods can be used to distinguish
between aldehydes and ketones
Iodoform Reactions
- Ethanal and methylketones undergo this iodoform reactions
- A mixture of I2 and NaOH is warmed with the compound
- Compounds with
(iodoform)

give a yellow precipitate of tri-iodomethane

- The following functional groups give positive results with iodoform tests:
1) Aldehydes: ethanal only

2) Ketones: methyl ketones

3) Alcohols: ethanol and methyl secondary alcohols

* Iodoform reactions can be used to reduce the carbon number of an organic

compounds by one
Carboxylic Acid and Carboxylic Acid Derivatives
- Carboxylic acids are compounds with a - COOH group
General Formula: CnH2n+1CO2H
Number
of
Carbon
Atoms

Name

Methanoic
Acid

Ethanoic
Acid

Propanoic
Acid

Structure

Formula

*
- The physical and chemical properties of carboxylic acids are largely governed by two
factors:
1) Polarity of the carboxyl group
2) Length of the carbon chain
Physical Properties
- Members in this homologous series are liquids up to the 9th member
Thereafter they are solids
- Carboxylic acids have strong smells example: Vinegar (ethanoic acid)
Rancid Butter (butanoic acid)
- Carboxylic acids with a few carbons are soluble in water due to the formation of
hydrogen bonds with water molecules

- The solubility of carboxylic acid decreases as the hydrocarbon length increases

Carboxylic Group: Hydrophilic
Hydrocarbon Group: Hydrophobic

(Refer page 146 Table 7.2 GF)

- Benzoic acid is a solid at room temperature; sparingly soluble inc old water and
soluble in hot water
- The unusual pattern in melting point is due to the dimerisation of the acid
Methanoic acid and ethanoic acid are found as dimers due to the hydrogen bonding
This does not happen in acids with more carbon atoms

- The boiling point changes as we expect; because the hydrogen bonds break when
the acid melts
Therefore the boiling temperature increases with increasing carbon atoms

Worked Example:
Explain why Methylpropanoic acid has a lower melting point than butanoic acid

- Methylpropanoic acid has fewer point of contact (for the formation of hydrogen
bonds) than butanoic acid
Further; there are stronger dispersion forces in butanoic acid
Therefore butanoic acid has a higher melting point
Preparation of Carboxylic Acids
Method 1: Oxidation of Primary Alcohols or Aldehydes

Method 2: Hydrolysis of nitriles

- Nitriles are compounds with - CN group
- When a nitrile is heated under reflux with a dilute acid a carboxylic acid is formed
CH3CN + H+ + 2H2O -------------> CH3COOH + NH4+
- If the nitrile is heated under reflux with an aqueous alkali; a salt of the carboxylic
acid is formed
Then the carboxylic acid can be obtained by adding a strong dilute acid
CH3CN + OH- + H2O ------------> CH3COO- + NH3
CH3COO- + H+ ------------> CH3COOH
Method 3: Iodoform

Reactions of Carboxylic Acids

1) Reaction with water:
CH3COOH + H2O ------------> CH3COO- + H3O+
pH 3
2) Reduction
- Lithium tetrahydriodoaluminate dissolved in dry ether is used as the reducing agent

- H- is a powerful nucleophile
It attacks the carbonyl group to produce a primary alcohol after a series of reactions
- An aqueous solution of an acid must be added to get the final product?
3) Neutralisation
- Carboxylic acids react with bases to form salt and water
CH3COOH + NaOH ------------> CH3COO-Na+ + H2O
(Basic Salt)
4) Reaction with metal carbonates:
2CH3COOH + Na2CO3 ------------> 2CH3COO-Na+ + H2O + CO2
5) Reaction with metals:
Carboxylic acids form hydrogen gas:
2CH3COOH + Zn ------------> (CH3COO)2Zn + H2
6) Esterification:
- Carboxylic acids react with alcohols in the presence of concentrated H2SO4 catalysts
in a reversible reaction to form an ester
Carboxylic acid + alcohol

Conc H2SO4

ester + water
Heat

- Esters are substances with pleasant fruity smells

- When an acid chloride is used instead of carboxylic acid; the reaction is irreversible

- Advantages of this reaction:

1. The reaction is not reversible
2. HCl gas is formed and leaves the reaction mixture

7) Halogenoalkanes
- Carboxylic Acids react with anhydrous PCl5 to form acyl chlorides

- Steam fumes of HCl form

Carboxylic Acid Derivatives
1) Hydrolysis of Esters:
- Esters can be hydrolyzed under acidic or alkaline conditions
- When the ester is refluxed with dilute HCl or dilute H2SO4 it give a carboxylic acid
and an alcohol

- The yield of this reaction is low; because it is reversible

- When an ester is boiled under reflux with aqueous NaOH; a salt of the carboxylic
acid and the alcohol forms

- The organic acid can be obtained by adding a dilute strong acid like HCl or H2SO4
to the salt of the carboxylic acid
- This reaction gives a higher yield as it is not reversible
Natural Esters
- Fats and oils are collectively called lipids; they are esters of glycerol and long
chained carboxylic acids called fatty acids
Therefore natural esters are referred to as triglycerides

- When fats and oils are boiled with concentrated NaOH solution; the ester link is
hydrolyzed producing sodium salts of fatty acid and glycerol

- Sodium salts of long chained carboxylic acids can be precipitated from the aqueous
solution by treating it with saturated NaCl
This is known as Salting Out
- The sodium or potassium salts of long chained carboxylic acid are the main chemical
substances in salts
The alkaline hydrolysis of esters is referred to as trans-esterification
Trans-esterification (refer GF pg 153 - 155)
- When an ester reacts with another carboxylic acid
This acid part of the ester is replaced by the new acid
CH3COOC2H5 + HCOOH HCOOC2H5 + CH3COOH
- This type of reactions are used in the manufacture of low fat margarine
- In this reaction the incoming acid is saturated (no double bonds present)
- The advantage of this method is that it doesntt form trans-fats
- Just like the above reaction the alcohol part can be replaced by an alcohol part
CH3COOC2H5 + CH3OH CH3COOCH3 + C2H5OH
- This type of reaction is used in the manufacture of biodiesel where the incoming
alcohol is methanol or ethanol and the product alcohol is glycerol
- The natural oil ester is mixed with methanol and a catalyst
Trans-esterification takes place forming the methyl ester

Polyesters
- Polyesters are condensation polymers
- A polyester can be produced by reaction a dicarboxylic acid with a diol

- The most common polyester is terylene

Acyl Chlorides (Acid Chlorides)

Functional group:

- Most acid chlorides are volatile liquids at room temperature

- They dissolve in several organic solvents
- They react with water; therefore soluble in water as well
- Methanoyl chlorides cannot be isolated as it decomposes at room temperature into
CO & HCl

- Acid chlorides can be prepared using the reaction of carboxylic acid with PCl5 (in dry
conditions)
CH3COOH + PCl5 --------> CH3COCl + POCl3 + HCl
- The carbon atom in the - COCl group is +; therefore it is susceptible to nucleophilic
attack
- C-Cl bon is weaker than C-O- bond as Cl is a larger atom than oxygen atom
- Therefore C-Cl bond breaks more easily; furthermore Cl- is a good leaving group
- Therefore the molecule is very susceptible to nucleophilic attack in substitution
reactions and it takes place via addition and elimination

Reactions of Acyl Chlorides

1) Reaction with water:
CH3COCl + H2O --> CH3COOH + HCl
- This reaction occurs at RTP
- Steamy fumes of HCl are formed
* Acyl chlorides must be kept away from water as they react with water

2) Esterification
CH3COCl + CH3OH --> CH3COOCH3 + HCl
(methyl ethanoate)
- Acyl chlorides react with alcohol to form esters and misty fumes of HCl
- The reaction takes place at room temperature without any catalysts
- It gives a higher yield; because the reaction is non-reversible
- Good evidence for the higher reactivity of acyl chlorides than carboxylic acids
3) Reaction with ammonia:
- When an acid chloride reacts with concentrated ammonia at RTP; an amide and
hydrogen chloride are formed
- HCl reacts with ammonia to produce a white smoke of ammonium chloride

4) Reaction with Lithium Aluminum Hydride:

CH3COCl + 4[H] ------------> CH3CH2OH + HCl
Spectroscopy
- Different regions of the electromagnetic spectrum is used in spectroscopy
- Electromagnetic radiation consists of an oscillating electric and magnetic field of a
wide range of frequencies
- When electromagnetic radiation is passed through a substance; some of the radiation
is absorbed (Refer GF 160 - 168 Pg)

Mass Spectroscopy
Worked Example:
a) Explain how a sample is ionised in mass spectroscopy
The gaseous sample is bombarded with high energy electrons
An electron gets knocked out from the outermost shell by the high energy electron
X (g) + e- -------> X+ (g) + 2eb) How are positive ions accelerated and deflected
Through the electric field and magnetic field respectively

Microwaves

Microwaves are important in heating as it can cause the rotation

of polar molecules such as water

Microwaves cannot cause the rotation of non-polar molecules

such as CCl4 and O2

The rotation of polar molecules increases as they become aligned

with the oscillating electric fi led produced by microwave. As a
result the molecules collide and rotation energy is converted into
kinetic energy and the way heats up

If water is frozen, molecules do not absorb microwaves, because

the molecules cannot rotate at fi xed positions

Defrosting in a microwave oven works because the surface of

frozen food is covered with a thin layer of liquid water. When this
thin layer heats up nearby ice melts and this happens until the
whole food is defrosted

Microwaves are used in pharmaceutical industries to heat up

various chemicals

The advantage of microwave heating is that theres less heat loss

and less chance of damaging fragile molecules

The following diagram explain we can use microwaves in a

chemistry lab

The microwaves can selectively heat up the aqueous layer, but

not the organic layer. Therefore the solubility of a substance in
the aqueous layer increases. So microwaves are useful in
analytical sciences
Nuclear Magnetic Resonance (NMR) Spectroscopy

NMR Spectroscopy uses the radio frequency region in the

electromagnetic spectrum

Proton is another name given to a hydrogen nucleus as there are

no neutrons

The hydrogen nucleus can spin clockwise and anticlockwise and

this spinning nucleus can produce a magnetic fi eld

Both the spin states are degenerate (have the same energy)

When an external magnetic fi eld is applied the degeneracy is

lost. That is the 2 spin states will have two diff erent energies
(split in energy)

The spin aligned state (the spin state which is aligned with the
magnetic fi eld) has a lower energy level than the spin opposed
state

E matches with the size of the energy in the radio frequency

region. When the exact frequency is applied a resonance takes
place. This means that nuclei (protons) will jump from a lower
spin state to a higher spin state.

The magnitude of E depends on the magnitude of the applied

magnetic fi eld. The stronger the magnetic fi eld, the greater the
split

E also depends on the extent of shielding of the nucleus by the

electron cloud around it. If the nucleus is more shielded it will
experience the eff ect of the magnetic fi eld to a lesser extent

As an example consider a proportional molecule:

There are three diff erent hydrogen nuclei, they are in three
diff erent chemical environments.

Type 3 is most shielded or least deshielded

Type 1 is least shielded or most deshielded

In an NMR Spectrometer a fi nal radio frequency is maintained and

the strength of the magnetic fi eld is increased from a lower value
to a higher one. The 3 types of protons will resonate at 3
diff erent strengths of the magnetic fi eld. It will produce 3 peaks
in the NMR Spectrum in the 1:2:3 intensity ratio.

Under a given magnetic fi eld:

Shielded protons split low
Deshielded protons split high

We use a standard known as TMS (Tetra methyl silane). Protons in

TMS produce one peak in the NMR Spectrum. It is used to be the
origin on the O value in the scale that shows the chemical shift of
the NMR Spectrum. Chemical shift () is measured in ppm.

The extent to which a certain peak diff ers from the TMS peak is
called a chemical shift

TMS is chosen because:

- only a trace amount is needed
- It is a volatile liquid that can be evaporated off easily
- Molecules of TMS do not interact with molecules of the sample

Protons in most organic compounds show nuclear resonance at

chemical shift value that are positive with respect to TMS protons

The sample being investigated is dissolved in a solvents such as

D2O or CCl4 as these solvents do not show resonance due to the
absence of hydrogen atoms

Low Resolution NMR Spectrum of CH3CH2CHO

-

A low resolution NMR give the number of diff erent types of

hydrogen atoms in the molecules (number of peaks) and the ratio
of the diff erent types of the hydrogen atoms (ratio of the peak
heights).
Worked Example:
Give the number of peaks and the approximate ratio of their
heights in the low resolution NMR Spectrum of the following
molecules
1) Propanal: 3 peaks in the ration 1:2:3

2) Propane: 2 peaks in the ration 1:3

Worked Example:
Draw the low resolution NMR of:

High Resolution NMR Spectroscopy

-

In a high resolution NMR Spectrum, a peak produced by the

hydrogen atoms in a given chemical environment is split into a
set of sub-peaks by the neighboring hydrogen atoms.

If the number of neighboring hydrogen atoms in n. the peak is

split into (n + 1) sub-peaks, this is known as the (n + 1) rule.

High resolution NMR Spectroscopy is more informative in

structure determination.

The ratio of the heights of the sub-peaks are given below

n

After Splitting

Ratio

Singlet

n/a

Doublet

1:1

Triplet

1:2:1

Quartet

1:3:3:1

Quintuplet

1:4:6:4:1

(multiplet)

Hydrogen atom in OH, CHO and COOH are not split and they do
not cause any splitting

Splitting due to neighboring hydrogen atoms is called coupling

Magnetic Resonance Imaging (MRI)

-

The same principle used in NMR is used

Useful to detect the condition of soft tissues such as brain and

heart tissue without causing any damage. Therefore known as a
non-invasive technique

Therefore the patient does not suff er any ill eff ect.

The chemical shift of the hydrogen atoms in soft tissues are

diff erent to those in hard tissues. This is used in MRI scanners.

Chromatography
-

It is a separation technique.

Chromatography of all types have the same basic principle. In every

chromatography technique the sample is dissolved in a suitable solvent
and washed through stationary phase by a mobile phase known as the
eluent.

There are different types of chromatography methods:

Paper Chromatography
Thing layer chromatography

High performance (pressure) liquid chromatography (HPLC)

Gas- Liquid Chromatography ( GLC or GC)

Stationary phase is a solid or a liquid, whereas the mobile phase is a

liquid or a gas

High Performance (Pressure) Liquid Chromatography (HPLC)

-

A column packed with a solid of uniform particle size is used as the

stationary phase.

The sample dissolved in a suitable solvent is added to the top of the

column

Then the liquid used as the mobile phase is forced through the column
under high pressure.

The time taken for a particular component in the sample to pass through
the column is known as the retention time.

The components in the same have different retention times depending on

the different strengths of interactions of the component with the
stationary phase and the mobile phase.

Example: A component which is more soluble in the mobile phase and

less absorbed onto the stationary phase can pass through the column
faster and will have a lower retention time .

A high pressure is used in order to increase the speed at which the eluent
passes through the column. This will reduce the diffusion of component
molecules spreading out of the bands.

If the column is connected to an IR Spectrometer the components can be

identified.

Usually a polar stationary phase and non-polar eluent was used in early
chromatography was used in early chromatography techniques.
If the two phases are reversed it is known as Reserve Phase High
Performance Liquid Chromatography (RPHPLC)
RPHPLC is used in pharmaceutical industry to separate and identify the
purity of drugs.
Retention time is a characteristic for a particular component. It can be
used to separate different components.
-

Gas Liquid Chromatography

The sample has to evaporate and then it is injected into the top of
chromatography column.
The injected sample is forced through the column by the movement of an
inert gas (gaseous mobile phase).
The column is an inert solid and the liquid stationary phase is adsorbed
onto the surface of the column.
The mobile phase is an inert gas such as hydrogen, argon, oxygen,
nitrogen or air.
This is known as a carrier gas. Depending on the strength of the
interaction between the sample and the liquid stationary phase, different
substances pass through the column at different rates.
The detector of the instrument can identify the thermal conductivity
changes of the carrier gas after it is mixed with the sample.
GLC is also coupled with IR Spectroscopy in order to identify the
components in the sample mixture.
This method can be used to separate mixtures of volatile liquids.