CHAPTER - 1 SOLUTIONS

SUMMARY
TYPES OF SOLUTIONS:

CONCENTRATION OF SOLUTIONS
Some basic formulae Mole fraction Molarity (M)
Mass percentage. w/w% For solvent XA=nA/nA+nB no. of moles of
For liquid solutions For solute XB=nB/nA+nB solute/volume of solution (L)
w/w%=massof XA+ XB = 1 Unit=mole/litre [mol/L]
component/total mass of ppm (parts per million)= Molality (m) =
solution mass of solute x106/total no. of moles of solute/mass
mass of solution of solvent(kg)
Unit=mole/Kilogram [mol

Henry’s law: - Statement: - Mole fraction of gas in the solution is directly proportional to
partial pressure of gas in the vapour phase.
PαXB P= KHXB ( KH= Henry’s constant )(greater the KHvalue lower the solubility
APPLICATIONS: 1. Soft drinks are sealed under high pressure to increase solubility of CO2.
2. To avoid Bends, the tanks used by scuba divers are filled with air diluted with helium
(less soluble than N2)
Anoxia,problem at higher altitudes due to low pressure low concentration of O2 in Blood
cells.
 Vapour pressure: -The pressure exerted by the vapours in the equilibrium with liquid at a
given temperature is called vapour pressure
 Raoult’s law: - The partial vapour pressure of each component in the solution is directly
proportional to its mole fraction.
PA α XA PB α XB
PA=PA XAPBoXA
o

PT=PA+PB (Daltons Law)

 Ideal solutions Non-Ideal solutions
Obeys Raoult’s law over the entire range Don’t Obey Raoult’s law
of concentration
e.g. Solution of n-hexane and n-heptane
A-A , B-B = A-B interactions A-A , B-B ≠ A-B interactions
A
0
ΧB PTotal≠ PA+ PB,PTotal≠ P0 ΧA+ PB0ΧB
A
Δmix H= 0 Δmix V = 0 Δmix H≠ 0, ΔmixV ≠ 0
Can be separated by fractional distillation Cannot be separated by fractional

Positive deviation Negative deviation

PTotal> PA+ PB ΔVmix=+ve,ΔHmix=+ve PTotal< PA+ PB ΔVmix=-veΔHmix=-ve
A – B interaction is weaker than A – A and A – B interaction is stronger than
B – B interactions. A – A and B – B interaction
EXAMPLE- Chloroform+acetone,water+HCl
ethanol+water,acetone+ethanol
Minimum boiling Azeotrope Maximum boiling Azeotrope
 Azeotrope(Greek: boiling without change) Mixtures having same composition in liquid
and vapour phase, boil at a constant temperature and cannot be separated by fractional
distillation
 Colligative properties: - The properties of solutions which depend only on the number of
particles of the solute (molecules or ions) dissolved in a definite amount of the solvent and
do not depend on the nature of solute
Relative lowering in Elevation in Depression in Osmotic pressure
vapour pressure boiling point freezing point

PoA-Ps/PoA=X B ΔTb =Tb-𝑻 𝒃𝒐 ΔTf=Tf-𝑻𝒇𝑶 π=CRT

XB=nB/nA+nB ΔTb=Kb m ΔTf= Kf m 𝒏𝑹𝑻

π=
Kb = molal Kf= molal 𝑽
elevation or depression or The excess
[for a very dilute EBULLIOSCOPIC CRYOSCOPIC pressure on
solution constant. It is the constant. It is the solution side
nB<<nA ] elevation in boiling depression in which just
PAo–PS/PAo=nB/nA point of 1 molal freezing point of prevents the flow
solution. 1 molal solution. of solvent
molecules is
called OSMOTIC
PRESSURE.
 OSMOSIS-The net spontaneous flow of the solvent molecules from the solvent to the
solution or from a less concentrated solution to a more concentrated solution through a
semipermeable membrane is called OSMOSIS.
 REVERSE OSMOSIS-The process of movement of solvent through a semipermeable
membrane from the solution to the pure solvent by applying pressure more than osmotic
pressure on the solution side is called reverse osmosis.
 Application-desalination of sea water
 NOTE: The osmotic pressure method advantages over other colligative properties.
 The measurement of osmotic pressure is around the room temperature,
 Gives large measurable value for dilute solution

ISOTONIC SOLUTION HYPOTONIC SOLUTION HYPERTONIC SOLUTION

Two solutions having same solutions having different Solution with higher
osmotic pressure at a given osmotic pressure at a given osmotic pressure is called
temperature are called temperature, the one with hypertonic solution
isotonic solutions. lower osmotic pressure is
π1 = π2 called hypotonic solution
 Abnormal molar mass: ELECTROLYTIC SOLUTIONS: - When the molar mass of a
substance (solute) become higher or lower after its association or dissociation in the
solution it is called abnormal molar mass.
 Van’t Hoff factor: i = Normal molar mass/Abnormal(observed)molar mass
Colligative property after abnormal molar masses: -
 Lowering of vapour pressure: - XB = i PoA-Ps/PoA
 Elevation in boiling point: - ΔTb = i Kb m
 Depression in freezing point: - ΔTf = i Kf m
 Osmotic pressure: - π = iCRT
PROPERTY ASSOCIATION DISSOCIATION
Colligative property Lowers Increases
Molar mass Greater than theoretical lesser
value
i=1 i<1 i>1
α (extent) α=i-1/1/𝑛−1 α=i-1/𝑛−1
=degree of dissociation / [n = no. of particles [n = no. of dissociated
association associated] particles.]

2. ELECTROCHEMISTRY
SUMMARY
Electrochemistry is a branch of chemistry which deals with inter-conversion of chemical
energies and electrical energy
Before going into details of the chapter , you must know……
Redox reaction: In a redox reaction, both oxidation and reduction reaction takes place
simultaneously
Direct redox reaction : Both oxidation and reduction in same vessel.
Indirect redox reaction :oxidation and reduction in different vessels.
Conductors: Materials that allow flow of electrons . these are of two types
Electronic or Metallic Conductors Electrolytic or Solution conductors
1. Movement of electrons in the 1. Movement of ions in molten state or
metallic lattice, e.g., Cu, Ag, etc in aqueous solution of electrolytes, e.g.,
NaCl (aq) or NaCl (fused).
2. Passage of current brings only physical
change. 2. Chemical and physical change both.
3. No transfer of matter 3. Transfer of matter takes place.
4. Generally show increase in resistance with 4. Generally show decrease in
increase in temperature. resistance due to decrease in viscosity
of medium and degree of hydration of
ions.
In this chapter we will focus on Electrolytic conduactance and electrochemical cell
ELECTROLYTES: ELECTRODE :
The substance that in solution or in the molten To pass the current through an
state, conducts electric current and is electrolytic conductor, two rods or
simultaneously decomposed. Their extent of plates are conducted with the battery.
dissociation may vary. These are called electrodes.

Strong electrolytes :
That are 100% decomposed in normal solution. Active Electrodes:
eg.:All salts (except CdBr2, HgCl2), mineral (Basically used in electroplating.)
acids like HCl, H2SO4, HNO3, etc. and Actively participate in the
bases like NaOH, KOH, etc. electrochemical reaction, either by
donating or accepting ions.
Weak electrolytes : which dissociate only to a [Link], Cu,,Pb and Ag electrodes.
small extent in aqueous solution. Inert Electrodes:
eg : All organic acids (except sulphonic (basically used in electrolysis, and
acids), inorganic acids electrolytic cells)
like HCN, H3BO3, etc. and bases like NH3, do not actively participate in the
amines, etc. reaction but facilitate the transfer of
electrons
eg :Pt, Au, graphite, rhodium etc.
Electrical Conductance Specific Conductance or
The property of the conductor (metallic as well Conductivity
as electrolytic) which facilitates the flow of In a conductor if length is 1 cm. And
electricity through it. area is 1 cm2 , the resistance offered is
Conductance =1/ Resistance known as resistivity .R = ρ
Unit : mho-1 The reciprocal of specific resistance or
resistivity is known as specific
conductance or conductivity (κ)kappa.

Where l /A is called cell constant

Unit of (κ) is Siemen Cm-1
Molar Conductance
the conductance of all the ions produced by variation With temp With conc.
ionization of 1 g-mole of an electrolyte when increase decrease
present in V ml of solution. It is denoted by Ʌm. conductivity Increaseas decreases
Molar increases increases
conductivity
Unit : Siemen Cm2mol-1 conductance increases decreases

Kohlrausch’ law of independent migration of Applications of Kohlrausch’s Law :

ions: 1. Determining Λ0 m of a weak
Molar conductivity of an electrolyte, at infinite electrolyte:
dilution, can be expressed as the sum of 2. Degree of dissocition,
individual contributions from its individual ions. α=Λm/Λ0m
If the limiting molar conductivity of the cations is 3. Determination of solubility of
denoted by and that of the anions by , sparingly soluble salt:
then the limiting molar conductivity of electrolyte
is: where, C is molarity of
Molar conductivity, sol’n and hence solubility
Where v+ and v- are the number of cations and
anions per formula of electrolyte 4. Determination of ionic product of
water
Λ0m (H2O) = λ0H+ + λ0OH-
(complete dissocition of water)

Then. KW=C2
Ionic mobility :For aqueous solution, greater the charge or smaller the size of gaseous
ion, greater will be the size of aqueous ion. When such a big ion moves in solution, it
experiences greater resistance by the size of solvent particles. This results in a decrease
in its conductance as well as ionic mobility. Following are the increasing order of ionic
mobilities of some ions:
Li+< Na+< K+< Rb+< Cs+ ; < F-< Cl-< Br- <I- ;<Al+3 <Mg+2< Na +
Weak electrolytes : These are not completely ionized in polar solvents like water and
hence an equilibrium between ions and unionised salt exists
AB+ ⇌ A+ + B-.
We can calculate degree of dissociation( α) and equilibrium constant (K),using expression
K =cα2 /(1-α), if α<<1 then use K =cα2
Electrode Potential: A metal placed in a solution of its ions obtains either a positive or
negative charge with respect to the solution. On account of this, a definite potential is
developed between the metal and the solution. This potential difference is called electrode
potential.
Standard Electrode Potential:The potential difference developed between metal
electrode and the solution of its ions of unit molarity (1 M) at 25ºC (298 K).
EMF of a cell: It is the difference in the potential across left and right electrodes due to
which electrons flow from anode to cathode.
Standard EMF: The EMF values of an electrode under standard conditions (1 atm, 298
K) and the unit concentrations of its ions

ELECTROCHEMICAL CELLS
ELECTROLYTIC CELLS DANIEL CELLS GALVANIC CELLS
Devices in which electrolysis A specific type of voltaic cell A broader term
(chemical reaction involving with a copper cathode and zinc encompassing any
oxidation and reduction) is carried anode, using copper sulfate and electrochemical cell
out by using electricity or in which zinc sulfate solutions, that converts chemical
conversion of electrical energy into respectively. It is known for its energy to electrical
chemical energy is done. reliable and consistent voltage energy through a
(non spaontaneous redox reaction output. spontaneous redox
is carried out) reaction.

Cell reaction : Cell representation : Cell representation :

Zn/Zn+2 (aq.) II Cu+2(aq.)/Cu Cu/Cu+2
(aq.)IIAg+/Ag
QUICK COMPARISION
1. Redox reaction Redox reaction Redox reaction
Non spontaneous Spontaneous Spontaneous
[Link] is negative EOcell ispositive EOcell is positive
[Link] is +ve Anode is -ve Anode is -ve
[Link] is -ve Cathode is +ve Cathode is +ve
[Link] of electron anode to Anode to cathode Anode to cathode
cathode
[Link], electroplating
 Cell Batteries

Faraday’s law of electrolysis Reference Electrode To determine the cell potential of

First law:the amount of individual half cell , reference electrode is required.
substance deposited at The electrode cell potential of reference electrodes are
electrode is proportional to known.a and on coupling with other electrode, a
quantity of charge passed voltaic cell is constituted.
through the electrolyte. Standard Hydrogen Electrode, SHE or NHE
W=zit Electrode : Platinized
z is electrochemical equivalent Platinum
Electrolyte: 1M HCl
(freshly prepared)
Temperature : 298 K
Hydrogen gas
Pressure : 1 atm or 1 bar

Nernst Equation :
Suppose, we reduced the conc. of Zn +2 in the Zn/Cu
Second law :the masses of cell from its unit activity value of around 0.5 M to a
different substances deposited much smaller value:
at the respective electrodes will Zn/Zn+2 (0.001M) II Cu+2 /Cu
be in the ratio of their equivalent This will reduce the value of Q for the cell reaction
masses,when same quantity of
current is passed. ∆G more negative than ∆G0 , so than
W =Z x Q, E would be more positive than Eº
When Q = 96500 coulomb 0 o
∆G = –nFE ; ∆G = –nFE
W becomes gm equivalent mass 0
Using ∆G = ∆G + RT lnQ;
E,
For a general reaction;

Faraday’s first law and second Salt bridge completes the

Page 14 of 110 up of a cell

law can be combined circuit, maintains
electroneutrality and
also minimises liquid junction potential.

Preferential Discharge Theory: Electrolysis of solutions containing more than two ions,
the ion that requires the least energy (or has the highest reduction potential) to be
discharged will be preferentially discharged at the respective electrode.
Cont.
electrolyte elect Cathodic reaction Anodic reaction Remarks if any
rode
1. Molten NaCl Pt One cation and on
anion
[Link] PbBr2 Pt --do---
[Link] aq. AT pH 7
(two competing At cathode : Na+ and water both can be reduced
reactions are Pt
possible both at
cathode and
anode)
The products At anode : both water and chloride ion can be oxidised.
vary with
concentration.

A.) Very dilute aq. NaCl solution

water with high reduction potential is reduced at cathode

In small [Link] electrolysis of water becomes more predominant yielding oxygen at

anode.
B. )High Concentration of Sodium Chloride : Hydogen at cathode
At anode oxidation of water being more positive is more feasible, so the evolution of
oxygen gas should happen at the anode. But, the evolution of oxygen from water has an
overvoltage of -0.6V, making the voltage for the oxidation of water as -[Link], chloride
is, oxidised to chlorine at the anode.

BATTERIES :Consist of two or more galvanic [Link] are of two types.

PRIMARY BATTERY
When the reactants have been converted to products, no more electricity is
[Link] cell reaction can not be reversed and cell becomes dead.
A. ) DRY CELL
 B. ) MERCURY CELL

SECONDARY BATTERY :The cell reaction can be reversed by passing electricity

through the battery(charging).It can be used again and again.
LEAD STORAGE BATTERY :

FUEL CELLS :Electrical cells that are discharged to convert the energy from the
combustion of fuels (hydrogen, carbon monoxide, methane, etc.) directly into the
electrical energy are called fuel cells.

Corrosion of Iron (Rusting)

Rusting of iron which is the most commonly seen example happens when iron comes
in contact with air or water. The reaction could be seen as a typical electrochemical cell
reaction..

PREVENTION OF RUSTING :
BARRIER COATINGS :Paint acts as a coating to protect the metal surface from the
electrochemical charge that comes from corrosive compounds.
HOT-DIP GALVANIZATION :The iron in the steel reacts with the zinc to create a
tightly bonded alloy coating which serves as protection.
CATHODIC PROTECTION :To prevent corrosion, the active sites on the metal surface
are converted to passive sites by providing electrons from another source, typically
with galvanic anodes attached on or near the surface. Metals used for anodes include
aluminum, magnesium, or zinc.

Chapter- 3 Chemical Kinetics

Summary
 Rate of a Chemical Reaction: It is the change in concentration of a reactant or
product per unit time.
Expression for rate of reaction: Units of rate of a
Consider a reaction, reaction: mol L-1s–1
R→P

Average Rate
Instantaneous Rate
It is the change in concentration of reactants in Rate of a chemical reaction at a
a given interval of time. particular moment of time, is known as
instantaneous rate of reaction.

 Factors Influencing Rate of a reaction:

(i) Effect of concentration of reactants (pressure in case of gases).
(ii) Effect of temperature

The molecules in this reaction Moving very Increasing the temperature causes the K.E.
slowly, which makes it hard for collisions to of the molecules to increase thus causing
occur. This iscausing the reaction to proceed at the molecules tomove faster which causing
a very slow rate collisions tooccur more frequently. More
collision meansthe rate increases
(iii) Effect of catalyst

 Rate Law Expression: It is a mathematical expression in which rate of reaction is

expressed in terms of molar concentration of reactants with each term raised to power,
which may or may not be equal to the stoichiometric coefficient of the reacting species in
a balanced chemical equation.

 Order of a Reaction: The sum of powers of the concentration of the reactants in

the rate law expression is called the order of that chemical reaction.
Order of a reaction can be 0, 1, 2, 3 and even a fraction. A zero-order reaction means that
the rate of reaction is independent of the concentration of reactants.
 The integrated rate equations

Zero order reaction First order reaction

𝟐.𝟑𝟎𝟑 [𝐑]𝐨
k= log
𝒕 [𝐑]

Where
[R]0 = initial concentration of reactant,
[R] = the final concentration at time ‘t’ ,
t = time taken
 Important Graph plots for zero order and first order reaction-
Graph -1 Graph -2 Graph -3
(zero order reaction) (First order reaction) (First order reaction)
Line [R] = -kt + [R]0
equation

Figure

Plot [R] vs time ln[R] vs time Log [𝑅]0 vs time

[𝑅]
Slope –k -k k/2.303
Intercept [R]0 ln [R]0 0
  Half life period: The half-life of a reaction is the time in which the concentration of
a reactant is reduced to one half of its initial concentration. It is represented as t1/2.
 The half life period for a zero order reaction is directly proportional to the initial
concentration of the reactants and inversely proportional to the rate constant.
 For a first order reaction, half-life period isconstant, i.e., it is independent of initial
concentration of the reactingspecies.
 Graph plots for half life period of reaction-
Graph -1 for zero order Graph-2 for First order of
reaction reaction
Line equation [R]0
t1/2 =
2𝑘
Figure

Plot between t1/2 vs [R]0 t1/2 vs [R]0

Slope 1 No slope (independent to
2𝑘 initial concentration of
reactant)
Intercept 0
 pseudo first order [Link] concentration of water does not get altered
much during the course of the reaction. So, the reaction behaves as first order
[Link] reactions are called pseudo first order reactions.
Inversion of cane sugar is pseudo first order reaction.

C12H22O11 + H2O H+ C6H12O6 + C6H12O6

Cane sugar Glucose Fructose

Rate = k [C12H22O11]
 Activation Energy: The energy required to form this intermediate, called activated
complex(C), is known as activation energy (Ea).
 According to Kinetic theory of Molecular gases, the average kinetic energy of
reacting gaseous molecules is directly proportional to absolute temperature.
K.E T
As temperature increases, speed of reacting molecules increases. Thereby, the
frequency of collisions also increases and hence rate of reaction increases.
 Experimental evidence shows that for every 10 degree rise in temperature, the rate
of a reaction will be doubled.
 If ‘E’ is the energy barrier, then the number of molecules that crosses over the
energy barrier is more at higher temperature than at low temperature.
 Activated complex (Transition State theory):It is the reaction intermediate possessing
energy that correspond to top of energy barrier.
 Threshold energy(ET):The minimum amount of energy whichthe reactant must
possess in order to convert into products is known asthreshold energy.

 Important formula to relate activation energy , temperature and rate constant-

Where: k1 and k2 are the values of rate constants attemperatures T1 and T2

respectively
Ea= Activation energy, R= Gas constant
 Graph:-

Plot between ln k vs 1/T ,

Straight line equation

𝐸𝑎
slope = - and intercept = lnA
𝑅

 Effect of Catalyst: A catalyst is a substance which alters the rate of a reaction

without itself undergoing any permanent chemical change.
 Catalyst help to increase the rate of chemical reaction. It carries the reaction
through the path of lower activation energy.
 Collision frequency: The number of collisions persecond per unit volume of the
reaction mixture is known ascollision frequency (Z).
 Effective collisions:To facilitate breaking of bonds between reacting species and
formation of new bonds to form products are called as effective collisions.
*******************

CHAPTER-8 d & f-BLOCK ELEMENTS

SUMMARY
General introduction-
 The TRANSITION ELEMENTS are those elements which have partially filled d-sub
shell in their elementary form or in their commonly occurring oxidation states.
 Zn, Cd and Hg not regarded as transition elements because they do not have
partially filled d- subshell
ELECTRONIC CONFIGURATION - (n-1) d1-10 ns1-2
There are four transition series in d-Block of elements –

GENERAL CHARACTERISTICS OF d- BLOCK ELEMENTS

 Metals with high tensile strength, ductility, malleability, thermal and electrical
conductivity.
 Solids except Mercury with high Melting and Boiling Points.
1. Atomic Radii
 The atomic radii decrease with increase in atomic number.
 In the middle of the series atomic radii become almost constant.
 At the end of the series the atomic radii show a small increase.
 On moving down the atomic radii increase due to increase in number of shells.
  However the atomic radii of second and third transition series are almost same.
due to ‘LANTHANOID CONTRACTION’.

2. Metallic Character and Enthalpy of Atomisation

 Metallic character is due to low ionisation energies.
 These are hard metals with high enthalpies of atomisation. This is due to strong
bonding due to overlap of unpaired electrons of different atoms.
 Values of enthalpies of atomisation increase with increase in number of unpaired
electrons.
3. Densities
 All transition metals have high density due to small size and high atomic mass.
 Densities increase in a series due to increase in atomic mass and decrease in
atomic size.
4. Melting and Boiling Points
 In general transition metals have high melting and boiling points. This is due to
strong metallic bonds.
 The melting points in a series rise to a maximum value in middle and then
decrease. This can be explained on basis of number of unpaired electrons.
5. Ionisation Enthalpies and Electrode Potentials
 IE1 of d-block elements is higher than s-block elements but lower than p-block
elements.
 In a series ionisation enthalpies generally increase from left to right due to increase
in nuclear charge.
 The stability of a particular oxidation of an element depends on total value of all of
its ionisation enthalpies. Lower is the total of ionisation enthalpies for a particular
oxidation state, more is the stability of that oxidation state.
 The stability of a particular oxidation in aqueous solution depends on values of
electrode potentials. Higher is the value of oxidation potential of a metal more is
stability of its particular oxidation state in aqueous solution.
 The oxidation potential of a metal involves the following process –
M(s) → M+(aq) + e-
6. Oxidation States
 Most of the transition elements show variable oxidation states.
 The variable oxidation is due to the participation of (n-1)d electrons beside ns
electrons. This is due to the fact that ns and (n-1)d electron differ very less in
energy and (n-1)d electron can also participate in bond formation beside ns
electrons.
 The highest oxidation states are found in their fluorides and oxides.
  Except Sc, the most common oxidation state for first transition state is +2.

 The elements with highest oxidation state lies in or near middle of the series.
 For all elements the lowest oxidation state is equal to number of ns electrons while
the highest oxidation state is equal to sum of ns and (n-1)d electrons only for first
five elements.
 In +2 and +3 oxidation states the bonds are mostly ionic while in higher oxidation
states these are essentially covalent.
 Within the group highest oxidation state increase down the group.

7. Formation of coloured ions

 Most of the compounds of transition elements are coloured in solid/solution form.
 This can be explained on basis of presence of incomplete (n-1)d sub-
shell/presence of unpaired electrons/d-d transition.
8. Magnetic Properties
 Most of the compounds of transition elements are paramagnetic in nature.
 This can be explained on basis of presence of unpaired electrons in (n-1)d sub-
shell.
 Higher is the number of unpaired electrons in a substance, the greater is its
paramagnetic character.

 , where n is the number of unpaired electrons and μ is the

magnetic
moment in units of Bohr magneton (BM).
9. Formation of Complexes
 Transition elements form a large number of coordination complexes. This tendency
of transition elements is due to-
1. Small size of atoms and ions of transition metals.
2. High nuclear charge.
3. Availability of vacant d-orbitals of suitable energy to accept lone pair of
electrons from
other groups.
`For example- [Ni(NH3)6]2+, [Co(NH3)6]3+, [Fe(CN)6]4-, [Zn(OH)4]2-
10. Formation of Interstitial Compounds
 Transition elements form large number of interstitial compounds with H, B, C, and N.
 This is because the small atoms of these elements get trapped in vacant spaces of
the lattice of the metal.
 Interstitial compounds are generally non-stoichiometric e.g. TiH1.7, VH0.56, etc.
11. Catalytic Properties
Many transition elements and their compounds act as catalysts in various chemical
[Link] transition elements have ability to form reaction intermediates due to
variable oxidation states. The formation of reaction intermediates leads the reaction to
a path of lower activation energy increasing the [Link] some cases transition metals
provide adsorption surface to reactants and increase their concentrations.
12. Alloy Formation
 Transition metals form a large number of alloys e.g. steel, bronze, brass, etc.
 This is because the transition elements are quite similar in size and their atoms can
easily accommodate themselves in each other’s lattice.
13. Preparation of Potassium dichromate ( ): It is prepared by fusion of
chromate ore (FeCr2O4) with sodium carbonate in excess of air.

2Na2CrO4 + 2H+ → Na2Cr2O7 + 2 Na+ + H2O

 Effect of pH on chromate and dichromate ions: The chromates and

dichromates are inter-convertible in aqueous solution depending upon pH of
the solution. The oxidation state of chromium in chromate and dichromate is
the same.

 Potassium dichromate acts as a strong oxidizing agent in acidic medium:

Thus, acidified potassium dichromate will oxidise iodides to iodine, sulphides to

sulphur, tin(II) to tin(IV) and iron(II) salts to iron(III). The half-reactions are noted
below:

14. Preparation of Potassium permanganate (KMnO4):

a) Potassium permanganate is prepared by fusion of MnO4 with alkali metal hydroxide
(KOH) in presence of O2 or oxidising agent like KNO3. It produces dark green K2MnO4
which undergoes oxidation as well as reduction in neutral or acidic solution to give
permanganate.

b) Commercially, it is prepared by the alkaline oxidative fusion of MnO2 followed by the

electrolytic oxidation of manganate (Vl).

c) In laboratory, Mn²+ salt can be oxidized by peroxodisulphate ion to permanganate ion.

Potassium permanganate acts as a strong oxidizing agent in acidic medium, neutral
or faintly basic medium:
In acidic medium:
Acidified permanganate solution oxidises oxalates to carbon dioxide, iron(II) to iron(III),
nitrites to nitrates and iodides to free iodine. The half-reactions of reductants are:
In neutral or faintly basic medium:

15. Properties of the lanthanoids:

 General electronic configuration is [Xe] 4f1-14 5d0-1 6s2.
 The metals are silvery-white in colour, malleable, ductile, having low tensile
strength and are good conductors of heat and electricity.
 They have relatively high density and possess high melting points.
 The lanthanides exhibit a principal oxidation state of + 3. However, some
elements also exhibit + 2 (Eu2+) and + 4 (Ce4+) oxidation states.
 Many of the lanthanide ions are coloured due to the electronic transition
between different 4 f-levels.
 The majority of the lanthanide ions exhibit paramagnetism due to the presence
of unpaired electrons. The lanthanoid ions that do not exhibit paramagnetism
are those with either no 4f-electrons, e. g., La3+ and Ce4+ or with a completed
4f-level, e.g., Yb2+ and La3+..
 The lanthanoid compounds are generally predominantly ionic.
lanthanoid contraction
 Steady decrease in the atomic and ionic (Ln3+ ) radii with the increase in atomic
number of the lanthanoid elements is called lanthanoid contraction.
Cause of lanthanoid contraction
 This is because the additional electron goes to 4f-subshell which have poor
shielding effect.
Consequences of Lanthanoid Contraction
 There is decrease in basic strength of hydroxides from La to Lu.
 Lanthanoid contraction causes the radii of the members of the third transition
series to be very similar to those of the corresponding members of the second
series.
 a consequence of the lanthanoid contraction, account for their occurrence
together in nature and for the difficulty faced in their separation.
Properties of actinoids:
 General electronic configuration is [Rn] 5f1-14 6d0-1 7s2.
 The elements are all silvery-white metals.
 The melting points of the actinoids are moderately high.
 The ionic size of the actinoids decreases gradually along the series.
 The actinoids have the ability to exhibit several oxidation states. However,
+4 oxidation state is preferred in actinides.
  ome actinoid elements can exist in + 6 oxidation state, e.g., uranium,
neptunium and plutonium.
 Many actinoid elements are radioactive. The elements beyond uranium are
man-made.
 The actinides have a much greater tendency to form complexes than
lanthanides.
 Actinoid contraction is greater from element to element than lanthanoid
contraction resulting from poor shielding by 5f electrons.
Mischmetall :It is a well-known alloy which consists of a lanthanoid metal
and iron
and traces of S, C, Ca and Al.

Chapter 5: CO-ORDINATION COMPOUNDS

Summary –
 Coordination Compounds
Compounds in which a central metal atom or ion is linked to a number of non metal ions
or neutral molecules by coordinate bonds
 Type of addition compounds-
1. Double Salt [Link] compound
Dissociate into simple ions completely Do not dissociate into simple ions in
when dissolved in water. water
e.g. Mohr’s salt, FeSO4.(NH4)2SO4.6H2O e.g. K4[Fe(CN)6].Complex ion
Potash Alum K2SO4Al2SO4.24H2O [Fe(CN)6]4- does not dissociate
into Fe2+ and CN− ions.

IMPORTANT TERMINOLOGY OF COMPLEX COMPOUND.
(i) Coordination entity: It constitutes the central metal ion or atom bonded to a fixed
number of ions or molecules represented within a square bracket.
(ii) Central atom/ion: The atom/ion to which a fixed number of ions/groups are bound in a
definite geometrical arrangement around it, is called the central atom or ion.
iii) Ligands: Ligands are the neutral or negative ions donate lone pairs to the central
metal ion via coordinate bonds, acting as Lewis bases. Its may be classified as-
Monodentate/ Ligands which Contain only one donar atom Ex-Cl- ;H2O;
-
Unidentate: NH3 ; NO2 .
Didentate Ligands which Contain two donor atoms. Ex-C2O42-(ox);
NH2CH2CH2NH2(en)
Polydentate which Contain two or more donor atoms present in a single
ligand. Ex-(EDTA)4-
Chelating ligands Di-or polydentate ligands that uses two or more donor atoms to
bind to a single metal ion to form ring-like complexes.(Ox); (edta)
 Ambidentate A ligand that can ligate through two different atoms, one at a
- - -
ligand time. Ex-NO2 ; SCN ,CN
Coordination number: The [Link] ligand donor atoms to which the metal is directly
bonded through coordinate bond. It determine the geometry of coordination complex.
Counter ions: The ionisable groups written outside the square bracket. Ex- K+ in
K4[Fe(CN)6] OR 3 Cl- in [Co(NH3)6]Cl3
Coordination Polyhedron: The spatial arrangement of the ligand atoms which are
directly attached to the central metal atom/ion. They are commonly Octahedral, Square-
planar or Tetrahedral.
Oxidation number: The charge that the central atom would carry if all the ligands are
removed along with their pairs of electrons shared with the central atom.
Homoleptic complexes: Complexes in which only one kind of Ligand . Ex-[Co(NH3)6]3+
Heteroleptic complexes: Complexes in which more than one kind of Ligand Ex-
[Co(NH3)4 Cl2]+
 Key Points of Werner’s theory of coordination theory-
Developed by Alfred Werner in [Link] coordination compounds metals show two types of
valencies-Primary and Secondary.
IUPAC NOMENCLATURE- The following rules are used when naming complex.
 (i) The cation is named first in both positively and negatively charged Complex.
(ii) The ligands are named in an alphabetical order before the name of the central metal.
(iii) Names of the anionic ligands end in –o.
(iv) Prefixes mono, di, tri, etc., are used to indicate the number of the individual ligands in
the coordination entity. When the names of the ligands include a numerical prefix, then the
terms, bis, tris, tetrakis are used.
(v) Oxidation state of the metal in cation, anion or neutral coordination entity is indicated
by Roman numeral in parenthesis.
(vi) If the complex ion is a cation, the metal is named same as the element. For example,
Co in a complex cation is called cobalt and Pt is called platinum. If the complex ion is an
anion, the name of the metal ends with the suffix – ate. For example, Co in a complex
anion, {Co(SCN)4}- 2 is called cobaltate.
IUPAC names of some coordination compounds
1 K2[Zn(OH)4] Potassium tetrahydroxozincate(II)
2 K3[Al(C2O4)3] Potassium trioxalatoaluminate(III)
–
3 [Pt(NH 3)BrCl(NO 2)] Amminebromidochloridonitrito-N-platinate(II) ion
4 [CoCl2(en)2]Cl Dichloridobis(ethane-1,2-diamine)cobalt(III) chloride
5 [Ni(CO) 4] Tetracarbonylnickel(0)
 ISOMERISM IN COORDINATION COMPOUNDS
 Two or more substances having the same molecular formula but different spatial
arrangements are called isomers and the phenomenon is called isomerism.
 Coordination compounds show two main types of isomerism-
A) Structural Isomerism B) Stereoisomerism
A) Summary of Structural Isomerism:
[Link]. Type Description
1 Ionisation Isomerism Exchange of counter-ions between the coordination
sphere and ionizing sphere.
[Co(NH3)5SO4]Br and [Co(NH3)5Br]SO4.
2 Linkage Isomerism Ligand binds through different atoms (e.g., NO₂ binds
through nitrogen or oxygen).
[Co(NH3)5(NO2)]Cl2 and [Co(NH3)5(ONO)]Cl2
3 Coordination Distribution of ligands between two metal centers
Isomerism differs.
[Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6]
4 Solvation Isomerism Arises due to the presence of solvent molecules as a
ligand or as free solvent molecules in the crystal
lattice.
[Cr(H2O)6]Cl3 and [Cr(H2O)5Cl]Cl2.H2O
B) Summary of Stereo Isomerism: Stereoisomers have the same chemical formula and
chemical bonds but theyhave different spatial [Link] are of two kinds
A. Geometrical isomerism [Link] isomerism

Geometrical Isomerism -This type of isomerism arises in heteroleptic

complexes due to different possible geometric arrangements of the ligands
COORDINATION [Ma2b2][Pt(NH3)2Cl2]
NO-4
(Square planar
complexes)
Tetrahedral complexes do not show geometrical isomerism.
Reason: The relative positions of the unidentate ligands attached to the central metal
atom are the same with respect to each other
COORDINATION [Ma2b4]=[Co(NH3)4Cl2 ]+
NO 6
(Octahedral
Complexes

[Ma3b3]
[Co(NH3)3(NO2)3]

Optical Isomerism: Optical isomers are mirror images that cannot be

superimposed on one another and are called as enantiomers.
Optical isomers of [Co(en)3]+3

Bonding in Coordination Compounds (Valence Bond Theory) : Key Points of VBT

1. The central metal atom/ion provides empty hybrid orbitals (equilivalent energy orbitals)
to accept lone pairs from ligands, forming coordinate bonds.
2. Hybridization and Geometry of the complex-
Coordination number Type of hybridisation Acquired geometry
4 sp³ Tetrahedral
4 dsp² Square planar
6 sp³d² Octahedral
6 d²sp³ Octahedral

3. Magnetic Behavior: VBT to explain paramagnetic (unpaired electrons) or diamagnetic

(all paired electrons) nature.
4. Spectro chemical series: The arrangement of common ligands in the increasing order
of their crystal-field splitting energy (CFSE) values.
I−< Br−< S2−< SCN−< Cl-−< N3-< F−< OH−< C2O42−∼ H2O < NCS−∼ H−< CN−< NH3< en ∼
SO32−< NO2<phen< CO
Examples: 1. [Cr(NH₃)₆]³⁺
Atomic no. of Cr = 24 → Cr³⁺ = 21 electrons → 3d³
 NH₃ is a neutral ligand (weak field).

Hybridization: d²sp³ ; Geometry: Octahedral; Magnetic: Paramagnetic (due to 3

unpaired electrons)
Some more example:-
[Link]. Complex Oxidati Type of Hybrid Geometry Magnetic
on State Ligand ization Nature

1 [Cr(NH₃)₆]³⁺ +3 Weak d²sp³ Octahedral Paramagnetic

2 [Ni(CN)₄]²⁻ +2 Strong dsp² Square planar Diamagnetic
3 [Fe(CN)₆]4⁻ +2 Strong d²sp³ Octahedral Diamagnetic
4 [FeF₆]³⁻ +3 Weak sp³d² Octahedral Paramagnetic
Crystal Field Theory - Key Points of CFT
1. Electrostatic Model: CFT treats ligands as point charges (or dipoles in the case of neutral
ligands like NH₃ or H₂O). The interaction between these ligands and the metal's d-orbitals causes
splitting of energy levels.
2. Degeneracy of d-orbitals is Lifted: In a free metal ion, the five d-orbitals are degenerate (have
the same energy). In a complex, due to the ligand field, these orbitals split into groups with
different energies.
3. Geometry-Dependent Splitting:
4. Octahedral field (common for 6 ligands): The d-orbitals split into two sets:
Lower energy: t2g → (dxy,dxz,dyz), Higher energy: eg→ (dz2, dx2−y2),
Energy difference = Δ₀ (octahedral splitting energy)

The splitting of degenerate levels due to the presence of ligands in a definite geometry is
termed as crystal field splitting
Weak field ligands Strong field ligands
Δo < P Δo > P
Form high spin complexes Form low spin complexes
5. Tetrahedral field (4 ligands): Lower energy: eg→ (dz2,dx2−y2), Higher energy: t2g →
(dxy,dxz,dyz), Energy difference = Δt (Tetrahedral splitting energy)
 Why Coordination Compounds are Colored-
1. d–d Transitions: In transition metal complexes, the d-orbitals split in the presence of
ligands (crystal field splitting). Electrons can be excited from a lower-energy d orbital to a
higher one using visible light.
2. Charge Transfer Transitions:Electrons are transferred between the metal and ligands.
These transitions also absorb light in the visible region, producing color.
3. Ligand Field Effect: Different ligands cause varying d-orbital splitting (Δ). Strong-field
ligands like CN⁻ cause more splitting than weak ones like H₂O, affecting the colour of
complexes. For example, [Ti(H₂O)₆]³⁺ is violet because Ti³⁺ (3d¹) absorbs blue-green light,
promoting the electron from t₂g to eg level(t2g1eg0 → t2g0 eg1). Without ligands, no crystal
field splitting occurs, so the substance remains colourless.
Note: (i) For example, removal of water from [Ti(H2O)6]Cl3 on heating renders it
colourless. Similarly, anhydrous CuSO4 is white, but CuSO4.5H2O is blue in colour.
(ii) Zn²⁺, Cd²⁺, Sc³⁺, etc.: These are colorless in solution because they have no d–d
transitions (either d⁰ or d¹⁰ configuration).
BONDING IN METAL CARBONYLS: In metal carbonyls, the M–C bond has both σ and
π character. The σ bond forms by donation of a lone pair from CO to the metal vacant d
orbital, and the π bond forms by back-donation from the metal’s d-orbital to the CO π*
antibonding orbital. This two-way interaction creates a synergic effect, strengthening the
M–CO bond.

HALOALKANES AND HALOARENES

SUMMARY
 When one or more hydrogen atoms in a hydrocarbon—either aliphatic or aromatic—are
replaced by halogen atoms, the resulting compounds are known as alkyl halides
(haloalkanes) and aryl halides (haloarenes), respectively.
 CLASSIFICATION OF HALOALKANE AND HALOARENE
 Based on the number of Halogen Atoms

 Based on the type of carbon atom to which the halogen is attached

 Halogen
attached to
sp3 carbon

Halogen
attached to
sp2 carbon

 Nature of C-X bond: Carbon-halogen bond of alkyl halide is polar in nature because
chlorine is more electronegative in nature. The carbon atom has a partial positive charge
and halogen atom has a partial negative charge.
 Nomenclature:

 Methods of Preparation for Haloalkane:

1. From Important Point:
Alcohol (i) Thionyl chloride(SOCl2) is
preferred because the other
two side products are
escapable gases. Hence the
reaction gives pure alkyl
halides.
(ii) The order of reactivity of
alcohols with a given
haloacid(HCl) is 3°>2°>1°.
2. From (i) Reaction follows free radical
Hydroca substitution reaction.
rbons (ii) if a molecule has different
types of carbon atoms
(primary, secondary,
tertiary), different products will
be formed.
(i) Alkene reacts with
hydrogen halide
(ii) Major and minor product is
given by Markovnikov’s rule.
In this reaction, brown color of
bromine water disappears,
indicating the presence of
unsaturation (C=C or C≡C).

3. (i) Name reaction: Finkelstein

Halogen Reaction
Exchan
(ii) NaCl or NaBr formed as
ge
side product is precipitated in
dry acetone and facilitates the
forward reaction.
(i) Name reaction: Swarts
Reaction
 Physical Properties
 Haloalkanes have higher boiling points than alkanes due to stronger intermolecular forces
of attraction, including dipole-dipole and dispersion forces.
 For the same alkyl group, boiling points of alkyl halides decrease as RI > RBr > RCl > RF
due to stronger van der Waals forces with heavier halogens.
 The boiling points of isomeric haloalkanes decrease with increase in branching. Example
is given below:

 Melting and boiling point order for dihalobenzene is given below:

Note: Para-isomers have higher melting points than ortho- and meta-isomers due to their
symmetrical structure, allowing better crystal lattice packing.
 Solubility: Despite of polar nature of alkyl halides, they are insoluble in water due to the
inability to form hydrogen bonds. Still, they are soluble in non-polar solvents.
 Density: The density increases with an increase in the number of carbon atoms, halogen
atoms, and atomic mass of the halogen atoms.
 CHEMICAL PROPERTIES
1. Reaction with Metal:
(a) Haloalkanes react with magnesium in dry (b) Wurtz reaction: This reaction
ether to form RMgX, a compound known as a produces symmetrical alkanes with
Grignard reagent. The reaction is given below: twice the number of carbon atoms as
in the original alkyl halide. The
reaction is given below:
Note: Traces of moisture must be avoided as
Grignard reagents are highly reactive due to their
nucleophilic nature and react with proton sources like
water, alcohols, or amines to form hydrocarbons.
Hence, the reaction is carried out in dry ether.

2. Nucleophilic substitution reaction:

 General definition: The reaction in which a strong nucleophile replaces the already
existing weak nucleophile in a molecule is called nucleophilic substitution reaction.
 Groups like cyanides and nitrites possess two nucleophilic centres and are called
ambident nucleophiles. The example is given below:
R-X + AgCN  R-NC ; R-X + KCN  R-CN
 Substitution nucleophilic unimolecular (SN1) and Substitution nucleophilic
bimolecular (SN2)

 Mechanism:

= SN1

= SN2
Note: (i) Tertiary halides are the least reactive because bulky groups hinder the
approaching nucleophiles.

(ii) In SN1 rate of reaction depends on the stability of carbocation. Allylic and benzylic
halides are highly reactive in SN1 reactions due to resonance-stabilized carbocations.

(ii) For a given alkyl group, the reactivity of the alkyl halide R-X, follows the same
order in both the mechanisms R–I> R–Br>R–Cl>>R–F
  STEREOCHEMICAL ASPECTS OF NUCLEOPHILIC SUBSTITUTION REACTIONS
 Some important Terms
(i) A tetrahedral carbon bonded to four different substituents is called a chiral carbon/chiral
center/ asymmetric carbon/stereocentre.
The objects or molecule which are non- The objects or molecule which
superimposable on their mirror image superimposable on their mirror images
are said to be chiral and property is are called achiral.
known as chirality. Optically inactive
Optically active
(ii) Nonsuperimposable mirror-image molecules are called enantiomers.

(a) Enantiomers rotate (b) Enantiomers (c) They only differ with respect to the
the plane polarized possess identical rotation of plane polarised light.
light in opposite physical properties (i) If rotates plane-polarized light to
direction hence it is namely, melting point, the right (clockwise) is called
known as optical boiling point, refractive dextrorotatory (d-form) and marked
isomers. index, etc. with a (+) sign.
(ii) If it rotates light to the left
(anticlockwise), it is laevorotatory (l-
form) and marked with a (–) sign.

(iii)

INVERSION, RETENTION AND RACEMISATION

 Inversion: (a) A process in which the relative configuration of an atom in a molecule
changed. (b) Inversion takes place in SN2.
 Retention: It is the process in which configuration of substrate and product remains the
same.
 Racemisation: (a) The process in which optically active compounds are converted into
optically inactive compounds with zero optical activity.
(a) Racemisation takes place in SN1.

3. Elimination reaction/Dehydrohalogenation/ β-elimination

 Elimination of hydrogen atom from β -carbon and a halogen atom from the α-carbon atom
simultaneously takes place.
 The strong base like alcoholic KOH is used in this reaction.
 Mechanism:

Note: If more than one α-hydrogen is available, multiple alkenes may form. The major
product is predicted by Saytzeff’s rule. The example is given below:

 PREPARATION OF HALOARENE:
(i) The given reaction is an example of an electrophilic
aromatic substitution reaction, where X₂ can be Cl₂ or Br₂.
(ii) The ortho and para isomers can be easily separated
due to large difference in their melting points.
Electrophilic substitution reaction
(i) Name Reaction: Sandmeyer’s reaction

For Chloro or bromobenzene For iodobenzene

 CHEMICAL PROPERTIES OF HALOARENE:
1. When chlorobenzene reacts with aqueous NaOH at high temperature and pressure, a
substitution reaction occurs, forming phenol.
Introducing NO2 groups at the ortho and para positions makes the reaction condition
milder and increases the reactivity towards substitution reactions. The reactions are given
below:
Note: The effect is not observed when the NO₂ group is attached at the meta position
because in meta-nitrobenzene, none of the resonance structures place a negative charge
on the carbon with the –NO₂ group.
So, the nitro group at the meta position doesn't help stabilize the negative charge, and it
doesn't increase the reactivity of the ring. The reaction in given below:

2. Electrophilic substitution reactions:

(a) Haloarenes undergo electrophilic substitution. The halogen is slightly deactivating due
to –I effect but directs new groups to the ortho and para positions due to resonance, which
increases electron density at these sites.

(b) The major product is the para-substituted compound, as it is favored over the ortho
product.
(a) Halogenation

(b) Nitration

(c) Sulphonation

(d) Friedel-Crafts
reaction
 3. Reactions with Metals
(a) Wurtz-Fittig reaction

(b) Fitting reaction

 Polyhalogen Compounds
(a) Dichloromethane Used as a solvent(in drug industry), paint remover, propellant in
(Methylene chloride) aerosols
Harms the central nervous system, Skin contact causes intense
burning and mild redness. Eye contact can burn the cornea.
(b) Trichloromethane The main use of chloroform today is to produce the refrigerant
(Chloroform) Freon R-22.
Chloroform slowly oxidizes in air and light to form poisonous
phosgene gas(carbonyl chloride). It is stored in dark, tightly
sealed bottles to keep air out.

(c)Triiodomethane Iodoform was once used as an antiseptic, but its effects come
(Iodoform) from releasing free iodine, not iodoform itself, and its unpleasant
smell has led to its replacement by other iodine-based
formulations.
(d) Tetrachloromethane Use in the manufacture of refrigerants and propellants for aerosol
(Carbon tetrachloride) cans, feedstock in the synthesis of chlorofluorocarbons.
used as a cleaning fluid, both in industry, as a degreasing agent,
and in the home, as a spot remover and as fire extinguisher.
It cause dizziness, light headedness, nausea and vomiting, which
can cause permanent damage to nerve cells.
(e) Freons Chlorofluorocarbon compounds of methane and ethane. Eg:
Freon 12 (CCl2F2 )
Extremely stable, unreactive, non-toxic, noncorrosive and easily
liquefiable gases.
It is manufactured from tetrachloromethane by Swarts reaction.
In stratosphere, freon is able to initiate radical chain reactions
that can upset the natural ozone balance.
(f) DDT is chemically stable and fat soluble. It is not metabolized
p,p’Dichlorodiphenyltrichl very rapidly by animals; it is deposited and is stored in the fatty
oroethane tissues.
(DDT) Being non-biodegradable its residues accumulate in environment
and are toxic to mammals etc.

Structure of DDT is given below:

[Link], PHENOLS AND ETHERS

SUMMARY
 VI) FROM GRIGNARD
REAGENTS

v)FROM CARBONYL
I) FROM
ALKENE (BY ACID COMPOUNDS( FROM
CATALYSED HYDRATION) CARBOXYLIC ACIDS
AND ESTERS:

PREPARATION
OF ALCOHOLS
II) FROM ALKENE (BY
HYDROBORATION–
OXIDATION:)
IV)FROM CARBONYL
COMPOUNDS( FROM
KETONES)

III) FROM CARBONYL COMPOUNDS(

FROM ALDEHYDES)
 ii) From benzenesulphonic iv) Fromcumene
acid PREPARATION

OF PHENOLS

iii) Fromdiazonium salts

i) By dehydration of
ii) Williamson synthesis
alcohols PREPARATION

OF ETHERS

PHYSICAL PROPERTIES OF ALCOHOL ,PHENOL AND ETHERS-(KINDLY GO

THROUGH THE DIKSHA LINK GIVEN )-
[Link]
(a) Acidity of alcohols and phenols:

 2R – OH + 2Na →2R – ONa +H2

 2C6H5 – OH + 2Na →2 C6H5 – ONa + H2
 Alcohols are weaker acids than water due to (+I effect) group
present in alcohols, which decreases the polarity of -O-H bond
 Acid strength of alcohols: 1° > 2° > 3°
 Phenol is more acidic than alcohols due to stabilization of
phenoxide ion through resonance

 Presence of electron withdrawing groups increases the acidity of

phenol by stabilizing phenoxide ion
 presence of electron releasing groups decreases the acidity of
phenol by destabilizing phenoxide ion.

(b)Esterification

Acetylation of salicylic acid produces aspirin.

 (a) Reaction with hydrogen halides:
Alcohols react with hydrogen halides to form alkyl halides.
ROH + HX →R–X + 𝐻2𝑂
Reactivity of Alcohols: Tertiary > Secondary > Primary
Lucas Test: - Used to distinguish primary, secondary and tertiary alcohols
Lucas reagent (conc. HCl and 𝑍𝑛𝐶𝑙2)
Alcohols are soluble in Lucas reagent while Alkyl halides (RX) are
immiscible and produce turbidity in solution. tertiary alcohols- Immediate
turbidity ,Secondary alcohols- Turbidity appears After 5 minutes, Primary
alcohols- No turbidity at room temperature.

(b) Reaction with phosphorus trihalides:

(C)Dehydration:

a The relative ease of dehydration of alcohol is Tertiary > Secondary >

(d)Oxidation- it involves loss of dihydrogen from an alcohol

molecule
Primary alcohol → Aldehyde → Carboxylic acid

Primary alcohol → Carboxylic acid (strong oxidizing agent, acidified

𝐾𝑀𝑛𝑂4 )

When the vapours of a primary or a secondary alcohol are passed

over heated copper at 573 K, dehydrogenation takes place .
 CHEMICAL REACTIONS OF PHENOL

CHEMICAL REACTIONS i) Nitration

OF PHENOLS  The ortho and

para isomers can
be separated by
(a)Electrophilic aromatic steam distillation.
substitution on aromatic ring  o-Nitrophenol is
of Phenol steam volatile
due to
intramolecular
hydrogen
bonding while p-
nitrophenol is

ii)Halogenation (Bromination).

-When the reaction is carried

out in solvents of low polarity
such as CHCl3 or CS2 and at
low temperature, mono-
bromophenols are formed.

-When phenol is treated with

bromine water, 2,4,6-

(b)Kolbe’s reaction -Phenoxide ion generated by

treating phenol with sodium
hydroxide is even more reactive
than phenol towards
electrophilic aromatic
substitution. Hence, it
undergoes electrophilic
substitution with carbon dioxide,
(C) Reimer-Tiemann reaction

(d)Reaction of phenol with

zinc dust
(e) Oxidation

Oxidation of phenol with chromicacid /Na2Cr2O7 produces a

conjugated diketoneknown as benzoquinone.

CHEMICAL REACTIONS OF ETHERS

(a) Reactions involving  Reactions involving Cleavage of C–O bond in ethers
Cleavage of C–O bond in
ethers

 When primary or secondary alkyl groups are present, it is

the lower alkyl group
that forms alkyl iodide (SN2 reaction).

• when one of the alkyl group is a tertiary group, the halide

formed is a tertiary
halide (SN1reaction)

(b) Electrophilic substitution-

alkoxy group (-OR) is ortho,
para directing
 MECHANISM OF REACTIONS-

II) Dehydration of Alcohols

I)Preparation of Alcohols (From alkenes)- By
acid catalysed hydration
Protonation of alkene to form carbocation by
electrophilic attack of H3O+

CHAPTER-8
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS
SUMMARY:
 Nature of Carbonyl Group
 The carbon and oxygen of the carbonyl group are sp2 hybridised and the carbonyl
double bond contains one sigma-bond and one π-bond with the bond angle 1200.
 The electronegativity of oxygen is much higher than that of the carbon,
so their electron cloud is shifted towards the oxygen. Therefore, C—O bond is polar in
nature .
In carboxylate ion –ve charge is delocalized on two electronegative O-atoms hence
 shows resonance which indicate that CO group is not a true carbonyl group in carboxylic
acids.
 Nomenclature
(i) Nomenclature of Aldehydes IUPAC system, the suffix ‘e’ of alkane is replaced by the
suffix ‘al’. e.g.
Compound Common name IUPAC name
HCHO Formaldehyde Methanal
CH3CHO Acetaldehyde Ethanal
(ii) Nomenclature of ketones IUPAC system, the suffix “e” of alkane is replaced by ‘one’.
e.g.
Compound Common name IUPAC name
H3CCOCH3 Dimethyl ketone (acetone) Propanone
H3CCOC2H5 Ethyl methyl ketone Butanone
(iii) Nomenclature of carboxylic acids IUPAC system, the suffix “e” of alkane is replaced
by ‘oic’acid. e.g.
Compound Common name IUPAC name
HCOOH Formic acid Methanoic acid
H3CCOOH Acetic acid Ethanoic acid
CH3(CH2)2COOH Butyric acid Butanoic acid
 Reactivity of aldehyde and Ketones :
HCHO > RCHO > RCOR > RCOOR > RCONH2.
 Physical Properties of Aldehydes and Ketones
1. Methanal (HCHO) is a gas at room temperature, and its 40% aqueous solution is
known as formalin, which is used to preserve biological specimens .
It is used in silvering of mirrors and decolourising vat dyes.
2. Ethanal (CH3CHO)
It is a volatile liquid. Other aldehydes and ketones are liquid or solid at room temperature.
 The boiling points of aldehydes and ketones are higher than hydrocarbons and ethers of
comparable molecular mass due to high magnitude of dipole-dipole interactions.
 Aldehydes and ketones have lower boiling point than those of alcohols of similar
molecular masses due to absence of intermolecular hydrogen bonding.
 The lower members of aldehydes and ketones are miscible with water due to the
formation of hydrogen bond with water. However, the solubility decreases with increase in
length of alkyl chain.
 Acetophenone is a hypnotic (sleep producing drug) so used as a medicine under the
name hypnone.
 Lower members are soluble in water because they can form H-bond with water. Higher
members are insoluble in water due to large size of their hydrophobic group.
 Preparation of Aldehydes :
a. Dehydrogenation of primary alcohols
b. Controlled oxidation of primary alcohols.
c. Controlled and selective reduction of acyl halides Aromatic aldehydes can be prepared
by-
(i) Oxidation of toluene with chromyl chloride or CrO3 in the presence of acetic
anhydride
(ii) Formylation of arenes with carbon monoxide and Hydrochloric acid in the presence
of anhydrous aluminium chloride / Cuprous chloride
(iii) Hydrolysis of benzal chloride
 Preparation of Ketones :
a. oxidation of secondary alcohols b. Hydration of alkenes
c. Reaction acyl chlorides with dialkylcadmium d. By friedel crafts reaction
 Preparation of Carboxylic acids :
a. oxidation of primary alcohols, aldehydes and alkenes b. hydrolysis of nitriles
c. Treatment of grignard reagent with carbon dioxide.
 IMPORTANT NAMED REACTIONS
.1. ROSENMUND REDUCTION:

2. STEPHEN REACTION
𝐇𝟑𝐎+
RCN + SnCl2 + HCl  RCH=NH →−−→ RCHO

3. ETARD REACTION:

4. CLEMMENSEN REDUCTION
>C=O Zn-Hg/HCl >CH2 + H2O

5. WOLFF-KISHNER REDUCTION
NH2NH2
>C=O >C=NNH2 KOH/ethylene glycol /H2O >CH2 + N2
 6. ALDOL CONDENSATION
Aldehydes and ketones having at least one α-hydrogen condense in the presence of
dilute alkali as catalyst to form β-hydroxyaldehydes (aldol) or β-hydroxy ketones (ketol).
The reaction is given below:

7. CROSS- ALDOL CONDENSATION

When aldol condensation is carried out between two different aldehydes and / or ketones,
a mixture of self and cross-aldol products are obtained.

8. CANNIZZARO REACTION
Aldehydes which do not have an α-hydrogen atom, undergo self oxidation and reduction
(dispropotionation) reaction on treatment with concentrated alkali,to yield carboxylioc acid
salt and an alcohol respectively.

ADDITION OF AMMONIA AND ITS DERIVATIVES:

 REACTIONS OF CARBOXYLIC ACID:
1. HELL-VOLHARD-ZELINSKY REACTION (HVZ)

2. ESTERIFICATION
H+
RCOOH + R‘OH →→ RCOOR + H2O
Carboxylic acid alcohol
3. DECARBOXYLATION

sodalime = NaOH and CaO in the ratio of 3 : 1

REACTIONS OF BENZOIC ACID
 DISTINCTION OF ORGANIC PAIRS
Distinguish between :-
Alcohol Phenol
It does not give FeCl3 test It gives neutral FeCl3 (violet) test
Benzaldehyde Acetophenone
It give Fehling’s solution test It doesn’t give Fehling’s solution test
and Tollens reagent test and Tollens reagent test
Acetic acid Formic acid
It doesn't gives tollen's reagent It gives tollen's test
and fehling's solution test and fehling's solution test
Ethanal Propanal
It gives iodoform test It doesn't give iodoform test
Propanol Ethanol
It doesn't give iodoform test It gives iodoform test
Pentan-2-one Pentan-3-one
It gives iodoform test It doesn't gives iodoform
Benzoic acid benzene
On adding NaHCO3 effervescence of No effervescence obtained
CO2 produced
Note: Learn properly since one question on distinguish between organic pairs is ask

CHAPTER : 9 AMINES
SUMMARY
1. Amines are alkyl / aryl derivatives of ammonia. In amines nitrogen atom is sp3 hybridized and
contains one lone pair.
2. Amines can be classified as 10, 20 and 30 based on the number of hydrogen atom present on
nitrogen.

10 Amine 20 Amine 30 Amine

CH3-NH2 = Methanamine CH3-NH- CH3 (CH3)3N

N-methylmethanamine N,N-
dimethylmethanamine
Propan-2-amine

 PREPRATION OF AMINES
 . Reduction of Nitro
compound gives aliphatic
and aromatic amines
(reducing agent
Sn/HCI,Fe/HCI)
Reduction with Fe/HCI is
preferred as FeCI2 is
formed during reduction
get hydrolyzed to release
HCI

Ammonolysis of alkyl
halides: -
Reagent: Ethanolic solution
of ammonia.
Disadvantage: Mixture of amines formed

Reduction of nitriles
(H2/Ni or Na(Hg)/C2H5OH
Reducing agents: - R – CN →−−−−−−−−−−−−−−−−−−→ R−CH2NH2
LiAlH4, H2/Ni, Na/C2H5OH

By the reduction of
amides CH3CONH2 +(LiAlH4 +H2O) → CH3CH2NH2

5. Hoffmann bromamide
Reaction: An amide is R − CONH2 + Br2 + 4NaOH → R − NH2 + Na2CO3 + 2NaBr +
heated with Bromine in aq. 2H2O
solution of NaOH/KOH
gives primary amine.
6. Gabriel phthalimide
synthesis: Only primary
aliphatic amines are
prepared by this method,
primary aromatic amine
cannot be prepared
because aryl halides do
not undergo substitution
reaction.
PHYSICAL PROPERTIES: (i) Primary amines are water soluble as H-bonding follows 10 > 20 >30.
(i) The order of boiling points of isomeric amines is as follows:
Primary > Secondary > Tertiary (Directly depends on the extent of hydrogen bonding)
CHEMICAL PROPERTIES:
1. Basic Nature- Amines are basic in nature, it accepts proton from an acid.
 3 >20>10>NH3( Basic nature in gaseous phase)
0

 20>30>10>NH3( Basic nature of ethyl substituted amines in aqueous phase)

 20>10>30>NH3(Basic nature of Methyl substituted amines in aqueous phase)
 Aniline is weaker base than ammonia ( Its pKb value is large, lone pair of electrons are
involved in resonance)
Acetylation: Replacement of H-atom from –NH2 or >NH by Acid chloride, anhydride and esters
(C2H5)2NH + CH3COCl CH3CON(C2H5)2 + HCl
3. Reaction with Nitrous acid: Forms aliphatic diazonium salts which being unstable,
liberate nitrogen gas quantitatively and alcohols after reacting with water
4. Reaction with Hinesberg reagent(C6H5SO2CI): (Test for 10,20, and 30 amines)
a. 10 amine forms a salt which is soluble in alkali
b. 20 amine forms a salt which is insoluble in alkali
c. 30amine do not react with Hinsberg reagent
5. Carbylamine reaction: (i) Primary aliphatic and aromatic amine reacts with chloroform and
KOH to form alkyl/aryl isocyanides(foul smell compound distinguish test for primary amine
from secondary and tertiary amine
R-NH2 + CHCI3+3KOH  R-NC + 3KCI + 3H2O
6. REACTIONS OF ANILINE
–NH2 group is ortho and para directing and a powerful activating group. Direct
nitration of aniline yields tarry oxidation products in addition to the nitro derivatives.
 Aniline is converted into acetanilide by acetylation with acetic anhydride and then the desired
substitution is carried out followed by hydrolysis the lone pair on nitrogen is less available for
donation to benzene ring by resonance. Therefore, activating effect of -NHCOCH3 group is
less than that of amino group.

 Aniline do not undergo Friedel craft reaction as it forms salt with the catalyst AlCl3

Sulphonation: Aniline reacts with concentrated sulphuric acid to form anilinium

hydrogensulphate, which on heating at 453–473 K yields p-aminobenzene sulphonic
acid (sulphanilic acid) as the major product.

Bromination: Aniline reacts with bromine water at room temperature to give a white
precipitate of 2,4,6-tribromoaniline.

7. .REACTIONS OF BENZENE DIAZONIUM CHLORIDE

 Note: Primary aromatic amines form arenediazonium salts which are stable for a short time in
solution at low temperatures (273-278 K). The stability of arenediazonium ion is explained on
the basis of resonance.

SECTION – A (1 Mark)

10 BIOMOLECULES
 Monosaccharides : Cannot be hydrolysed further to simpler molecules. Example:
Glucose, fructose, Ribose etc.
 Reactions of glucose (Open Chain structure):

 Reactions of glucose could not be explained by open chain structure.

1. Glucose does not give Schiff’s test and it does not form the hydrogensulphite.
2. The pentaacetate of glucose does not react with hydroxylamine (due to absence of free —
CHO group.)
3. Glucose is found to exist in two different crystalline forms which are named as α and β.
Reducing sugars Non reducing sugars
Aldehydic/ ketonic groups free so Aldehydic/ ketonic groups are bonded so cannot
reduce Fehling’s/ Tollens solution and. reduce Fehling’s solution and Tollens’ reagent.
Eg- maltose and lactose. Eg- Sucrose Anomers
Anomer: The two cyclic hemiacetal forms of glucose differ only in the configuration of the
hydroxyl group at C1, called anomeric carbon. Such isomers, i.e., α –form and β -form, are
called anomers.
Invert sugar:
 Sucrose is dextrorotatory but after hydrolysis gives dextrorotatory glucose and laevorotatory
fructose. Since the laevorotation of fructose (–92.4°) is more than dextrorotation of glucose (+
52.5°), the mixture is laevorotatory.
 Thus, hydrolysis of sucrose brings about a change in the sign of rotation, from dextro (+) to
laevo (–) and the product is named as invert sugar
Disaccharides: Hydrolysis, they generally give two monosaccharides unit. The linkage
between two monosaccharide units through oxygen atom is called glycosidic linkage.
Example:
Disaccharides Monomers
(i) Sucrose α-D-glucose and of β-D-fructose
(ii) Lactose β-D-galactose and β-D-glucose.
(iii) Maltose Two α-D-glucose
Polysaccharides: Polysaccharides contain a large number of monosaccharide units joined
together by glycosidic linkages.
Starch (i) Main storage of plants
(i) polymer of α-glucose and consists of two components— Amylose and Amylopectin.

Amylose Amylopectin
It is water soluble which constitutes It is insoluble in water and constitutes about
about 15-20% of starch. 80-85% of starch.
It is a long unbranched. It is a branched chain polymer
α-D-(+)-glucose units held together by branching occurs by C1–C6 glycosidic linkage
C1– C4 glycosidic linkage.
Cellulose: it is the most abundant organic substance in plant kingdom and main constituents
of cell [Link] is a straight chain polysaccharide composed only of β-D-glucose units
which are joined by glycosidic linkage between C1 of one glucose unit and C4 of the next
glucose unit.
Glycogen: The carbohydrates are stored in animal body as glycogen. It is also known as
animal starch. It is present in liver, muscles and brain. It is polysaccharides of α-D glucose.
Proteins: All proteins are polymers of α-amino acids.
Amino Acids:
Essential amino acids Non- essential amino acids
 which cannot be synthesised in the body  which can be synthesised in
and must be obtained through diet, the body
 eg- Valine, Leucine.  eg - Glycine, Alanine

.Zwitter ion: In aqueous solution, amino acids

exist as a dipolar ion known as Zwitter ion

Peptide linkage: peptide linkage is an amide

formed between –COOH group and NH2 group
of two successive amino acids in peptide chain.

Primary (10) Secondary (20) structure of Tertiary (30) structure of proteins

structure of proteins
proteins
sequence of amino (i) Secondary structure of : (i) Further folding of the secondary
acids that is said to protein refers to the shape in structure. It gives rise to two major
be the primary which a long polypeptide molecular shapes viz. fibrous and
structure of protein. chain can exist. (ii) Exist in globular. (ii) The main forces which
two types of structures viz. α stabilise the 3° structures of proteins
-helix and β -pleated sheet are hydrogen bonds, disulphide
structure and the binding linkages, van der Waals and
force is hydrogen bond electrostatic forces of attraction

Fibrous proteins Globular proteins

Polypeptide chains run parallel and Globular proteins chains of polypeptides coil
water insoluble. around to give a spherical shape. water soluble.
Eg- are keratin(in hair, wool, silk) and Eg-Insulin and albumins Stab.
myosin (present in muscles).

Denaturation of Proteins: (i) When a protein is subjected to physical change like change in
temperature or chemical change like change in pH, the hydrogen bonds are disturbed. Due to
this, globules unfold and helix get uncoiled and protein loses its biological activity. This is
called denaturation of [Link]- The coagulation of egg white on boiling, curdling of milk
(ii) During denaturation 2° and 3° structures are destroyed but 1º structure remains intact.
Enzymes: Enzymes are essential biological catalysts which are required to catalyse biological
reactions, e.g., maltase, lactase, invertase, etc. Almost all the enzymes are globular proteins
Vitamins: Organic compounds required in the diet in small amounts to perform specific
biological functions for normal maintenance of optimum growth and health of the organism.
 Vitamin Deficiency diseases Vitamin Deficiency diseases
Vitamin A Xerophthalmia (hardening of Vitamin B6 Convulsions
cornea of eye) Night blindness
Vitamin B1 Beriberi Vitamin Scurvy (bleeding
(Thiamine) C(Ascorbic acid) gums)
Vitamin B 2 Cheilosis Vitamin D Rickets, osteomalacia
Vitamin Pernicious anaemia Vitamin E fragility of RBCs and
B12 muscular weakness
Vitamin K Increased blood clotting time
Nucleic acid
 Particles in nucleus of the cell, responsible for
heredity, are called chromosomes which are made
up of proteins and another type of biomolecules
called nucleic acids.
 Two types of nucleic acid that is deoxyribonucleic
acid (DNA) and ribonucleic acid (RNA).nucleic acids
are long chain polymers of nucleotides, so they are
also called polynucleotides.
 Complete hydrolysis of DNA (or RNA) produces a
pentose sugar, phosphoric acid, and nitrogen-
containing heterocyclic compounds known as bases.
 A unit formed by the attachment of a base to 1’
position of sugar is known as [Link]
nucleoside is linked to phosphoric acid at 5’-position
of sugar moiety, we get a nucleotide.

DNA RNA
β-D-2-deoxyribose sugar is present. β- b-D-ribose sugar is present
DNA contains four bases viz. adenine (A), RNA also contains four bases adenine (A),
guanine (G), cytosine (C) and thymine (T) guanine (G), cytosine (C) and uracil (U).
DNA has a double strand helix structure. RNA has a single stranded α-helix
The two strands are complementary to [Link] molecules are of three types
each other. The two strands held together and they perform different functions. They are
by hydrogen bonds between pairs of bases (i) messenger RNA(m-RNA), (ii) ribosomal RNA
(r-RNA) and (iii) transfer RNA (t-RNA).
DNA has a unique property of replication RNA usually does not replicate.
DNA controls the transmission of hereditary RNA controls the synthesis of proteins.
effects
Nucleotides are joined together by phosphodiester linkage between 5’ and 3’
carbon atoms of the pentose sugar.
A simplified version of nucleic acid chain is as shown below