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CHEMISTRY
SOLUTIONS
Methods of expressing conc. of solution
 Mole fraction
Ratio between the number of moles of a component in the solution and total number of moles
of different components of solution.
For a solution having 2 components A and B,
nA
Mole fraction of A, xA =
nA  nB
nB
Mole fraction of B, xB =
nA  nB
xA + xB = 1
 Molarity
Number of moles of solute present per litre of solution.
Molarity, M = n n - number of moles of solute
V
Unit = mol V – volume of solution in litres.
L
 Molality
Number of moles of solute present per kg of solvent.
m = n n - number of moles of solution
W
Unit = mol W – mass of solvent in kg
L
If W is in grams. m= n  1000
W
 Solubility of gases in Liquids
Henry’s Law
The solubility of a gas in a liquid is directly proportional to the pressure of the gas.
OR
Partial pressure of the gas in vapour phase (P) is proportional to the mole fraction of the gas in
the solution.
Px P = KHx KH  Henry’s Constant
Unit of KH  Unit of pressure
CHEMISTRY Different gases have different KH values. The higher the value of KH the lower is the
solubility of the gas.
As the temp increases KH value increases and hence solubility decreases.
KH value is independent of pressure.
 Effect of temp
Solubility of a gas in a liquid decreases with rise in temp.
 Application
1) While making soda water CO2 is passed through water under high pressure
2) Scuba divers usually use a mixture of helium, N2 and O2 for respiration. This is because
when air is used under high pressure it will be having high solubility in blood which
will create a problem called “bends”. Helium is having very low solubility.
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3) Aquatic species are more comfortable in cold water rather than in warm water. Azeotropes D.F.P is due to lowering in vapour pressure. Let Tf be depression of freezing point.
Availability of dissolved O2 in water will be less in warm water. Liquid mixtures which get distilled without any change in composition or liquid mixtures To, be the freezing point of pure solvent and T that of solution, then depression in freezing
Raoult’s Law having same composition in the liquid and vapour phases. They are of 2 types minimum point.
For a binary solution of 2 volatile liquids P1 - Partial vapour pressure of first component boiling azeotrope (shown by solutions with positive deviation) and maximum boiling Tf = T0 T
partial vapor pressure of each component x1 and x2 - mole fraction azeotropes (solution with negative deviation) Tf = Kf m
in the solution is proportional to the P1  - vapour pressure of pure component -1 Eg : - Minimum boiling - a solution of 95% of alcohol and 5% water. Kf is a constant called molal depression constant/
mole fraction of the component in the P2 - Partial vapour pressure of second Maximum boiling – a solution of 68% Nitric acid and 32% water. cryoscopic constant. Unit Kg K mol1 and m is
solution. component
Colligative properties molality of solution
For a solution having 2 components P2  - vapour pressure of pure component -2
Properties of dilute solutions containing non-volatile solute which depends on the number of Kf is the depression in freezing point of 1 molal
P1  x1 or P1 = x1 P1  solute particles and not on their nature, they are, Relative lowering on vapour pressure, solution
P 2 = x 2 P2  elevation in boiling point, depression in freezing point and osmotic pressure. n
Tf = Kf 2 1000 Tf = Kf W2  1000
Relative lowering in vapour pressure w1 M 2 W1
Total vapour pressure of solution Vapour pressure of a solution containing non-volatile solute is found to be less than that of K f W2
P total = P1 + P2 pure solvent. This decrease of vapour pressure of a solvent on the addition of non – volatile M2 =  1000
Tf W1
Raoults law can be graphically solute is called lowering in vapour pressure.
The ratio between lowering in vapour pressure and vapour pressure of pure solvent is called Using this equation we can determine molar mass of a solute after measuring Tf
represented as shown below.
relative lowering of vapour pressure.  Common salt is added to roads covered with ice to melt out the ice present. This is possible
Ideal and non-ideal solution
because freezing point of water containing NaCl will be less than 0C.
Solution’s which obey Rault’s law over the entire range of conc. are called ideal solutions. Elevation of B.P.
 Freezing mixtures are usually prepared by using aqueous solutions of salts like CaCl2,
For an ideal solution having 2 volatile component B.P. of a solution containing non volatile solute is found to be greater than that of pure solvent
(A liquid boils when its Vapour pressure = atom pressure) since vapour pressure of a solution
Ca(NO3)2, etc. because freezing point of such mixtures will be less than 0C.
P1 = x1 P1 P2 = x2 P2  Materials called Anti – freeze (Ethylene glycol) is usually added to automobile radiator. This
containing non volatile solute is less than that of pure solvent it can become equal to atom
V mixing = O H mixing = O is to lower freezing point of water.
pressure only at a higher temp)
This increase in B.P. of a solvent on the addition of non-volatile solute is called elevation in Osmosis and Osmotic pressure
Eg:- Solution of, Benzene and Toluene,
B.P. The passage of solvent molecules into a solution through a semi permeable membrane is
Let To be the B.P. of pure solvent and T be the B.P. of called Osmosis
Bromoethane and Chloro ethane
solution. Then The excess pressure that must be applied on the side of solution to prevent osmosis is called
Tb = T T0 Osmotic pressure ()
Solutions which do not obey Rault’s law over the entire range of conc. is called Non Ideal V – volume of solution in litres
Solution. They are of 2 type, solution showing positive deviation and those showing negative Tb is related to molality of solution as V = nRT
n – no. moles of solute
deviation. Tb = Kbm OR  = n/v RT
Positive deviation Kb is a constant called molal elevation constant. It is the  = CRT T – temperature in Kelvin
For this kind of a solution elevation in B.P. of one molal solution  = n RT C is the molar conc.
V
P1 > x1 P1 P2 > x2 P2 m is molality of solution
W2 W2 RT
V mixing > O H mixing > O Unit of Kb = Kg K mol 1  = RT M2 =
VM 2 πV
Eg :- Ethanol + Acetone n2 W2
Tb = Kbm = Kb  1000 = Kb  1000 Using this relation we can determine molar mass of solute after measuring .
Solution showing negative deviation w1 M 2 W1
Molar mass of polymers and proteins are usually measured by Osmotic pressure because other
For this kind of solution K b W2 W1 – mass of solvent
M2 = 1000 colligative properties won’t be having measurable values, number of solute particles will be
P1 < x1 P1 P2 < x2 P2 Tb W1 W2 – mass of solute very less in such cases.
V mixing < O H mixing < O Using this relation we can determine molar mass of a solute after measuring elevation in B.P. Two solutions having same osmotic pressure at a given temperature is called isotonic
This kind of deviation is shown by a solution of  To get hard boiled egg NaCl is added to water. This is to increase the B.P. of water and solutions when such solutions are separated by semi permeable, no osmosis take place.
A and B where A  B interaction is greater than to get the egg cooked at a higher temp. Eg: A solution having 0.9% NaCl is found to be isotonic with blood.
A A and B B interaction.
Depression of freezing point If 2 solutions have different osmotic pressure the one having higher Osmotic pressure is
Eg:- Chloroform + acetone called Hypertonic solution and the one having lower osmotic pressure is called hypotonic
Freezing point of a solution containing non volatile solute is found to be less than that of pure
solvent. This decrease in freezing point of a solvent on the addition of a non volatile solute is solution.
called depression of freezing point.

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If blood cells are placed in a hypertonic solution (more than 0.9%) they will shrink. If placed E.M.F electromotive Force 0.059 [Zn 2 ]
E cell = Ecell  log
in a hypotonic solution (Less than 0.9%) they will swell. The difference in electrode potentials (reduction potential) of 2 electrode constituting an 2 [Cu 2 ]
Reverse Osmosis electro chemical cell is called e. m. f. For the cell,
If a pressure greater than osmotic pressure is applied on the side of solution solvent molecules e.m.f of a cell Ecell = higher reduction potential – lower reduction potential. Cu/Cu2+//Ag+/Ag Cu + 2Ag+  Cu2+ + 2Ag
will flow out of solution. This is called Reverse Osmosis. It is used in the desalination of sea OR
0.059 [Cu 2 ]
water. = E cathode – E anode Ecell = Ecell  log
2 [Ag  ] 2
ELECTROCHEMISTRY Nearnst Equation
Difference between metallic conductors and electrolytic conductors
Nearnst introduced an expression for getting electrode potential of an electrode at any conc.
The branch of chemistry which deals with inter conversion of chemical energy and electrical and temp as, given below. Metallic conductors Electrolyte
energy. Let the reduction reaction taking place at an electrode be:- Current is carried by es. Current is carried by ions.
Electrochemical cell/Galvanic cell Mn+ + neM, then No. chemical change Chemical change take place
It’s device used to generate electricity by conducting a chemical reaction (redox reaction)
E M n  
RT M Resistance increase with rise in Resistance decrease with rise in
eg: Daniel cell
E Mn
M
=
M nF
In n 
M   temperature temperature
Daniel cell E Mn = Electrode potential Conductivity/Specific conductance
It consist of a zinc rod dipped into ZnSO4 solution and Cu rod dipped into CuSO4 solution. M 3
It is the conductance of 1cm of a material (electrolytic solution).
The two metal rods are connected with a wire and two solutions are connected by a salt bridge E M n  = Standard electrode potential
l
containing paste of an inert electrolyte like Na2SO4, KNO3 etc. M
Conductivity,  = G 
R = Gas constant A
Zinc atoms from zinc rod enter into solutions
G = conductance = 1/R R = resistance
as Zn2+ by losing 2e (Oxn). These e flow T = Temp in K
through the external wire and reaches at the n = No. of e involved in electrode reaction l = length
copper rod from where Cu2+ ions accept F = Faradays constant (96500 C) A = Area of cross section.
these es (reduction) and get converted into [M] = Conc – of element Unit of conductance (G) = Ohm-1 (Siemens)
copper. The electrode where [Mn+] = Conc. of metal ion in solution/ conc. of electrolyte Unit of conductivity () = Ohm-1 cm-1
Oxidation take place is called, anode and the If M is a metal [M] = 1 Molar conductivity
one where reduction take place is cathode. RT 1 It is the conductance of an electrolytic solution having one mol of electrolyte.
E M n  
 At anode : Zn Zn2+ + 2e- Then E M n 
M
=
M nF
In n 
M   Molar Conductivity, ΛM =  
1000
– Specific conductance/conductivity
 At cathode : Cu2+ + 2e- Cu M
2.303  RT 1
E M n    log n 
 Net Cell reaction : Zn + Cu2+ Zn2+ + Cu or E Mn
M
=
M nF M   M – Molarity
Salt bridge helps in preventing the accumulation of Zn2+ ions in ZnSO4 solution and SO42- Unit = Ohm cm mol-1
-1 2
at 298K, on substituting the values of R, T and F, relation becomes
ions in CuSO4 solution. Factors affecting conductance of an electrolytic solution
0.059 1
The cell can be symbolically rep. as ZnZn2+//Cu2+/Cu. E M n  
[While writing symbolic representation, anode is shown first and then cathode. While
or E Mn
M
=
M n
log n 
M    Nature of electrolyte
Strong electrolytes have higher conductance compared to weak electrolytes.
representing anode, metal is shown first and then the ion. While rep. cathode ion is shown Nearnst Equation for emf of a cell
 Solvation of ions
first and then the metal ‘/’ is used to show the contact between metal and ion. ‘//’ is used to Let the reaction taking place in an electrochemical cell be.
As the solvation increases conductance decreases.
show the presence of salt bridge. If a gaseous element is involved platinum is also shown]. aA + bB  cC + dD.
 Viscosity of solvent
Daniel cell can provide 1.1 V. RT [C] c [D]d
Ecell = Ecell  ln As the viscosity of solvent increases conductance decreases.
Electrode Potential nF [A]a [B]b
 Inter ionic attraction
 Oxidation potential OR As inter ionic attraction increases conductance decreases.
It is the measure of tendency of an element to get oxidized. 2.303RT [C]c [D]d
 Reduction Potential E cell = Ecell  log  Temperature
nF [A]a [B]b As the temp increases conductance increases.
It is measure of tendency of an element to get reduced.
0.059 [C]c [D]d Measurement of conductivity
Electrode potential under standard condition, 298 K of temp, 1 atm pressure and 1 molar at 298K E cell = Ecell  log
n [A]a [B]b Conductivity of an electrolytic solution can be obtained after measuring resistance of solution
conc. for electrolyte is called standard electrode potential (E).
For daniel cell, the cell reaction is using Wheatstone’s bridge by placing the solution in a conductivity cell.
As per convention, electrode potential is usually expressed as reduction potential.
Zn + Cu2+  Zn2+ +Cu
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1 l Λ°(m) (CH3COOH) = Λ°m(CH3COONa)+ Λ°m(HCl)  Λ°m (NaCl) Fuel cells

, (Kappa) = 
R A 2) Calculation of degree of dissociation of a weak electrolyte. Devices used to convert energy released during the combustion of fuels like H2, CH4 etc
For a conductivity cell l is a constant called cell constant (cm-1) After calculating Λ°m of a weak electrolyte with the help of Kohlraush’s law we can get directly into electrical energy are called fuel cell.
A
degree of dissociation () as, Eg :- Hydrogen – Oxygen fuel cell
1
 =  Cell constant. ΛM H2  O2 fuel cell
R  =
1000 Λ M It consists of a metallic chamber separated into 3
Molar conductivity Λ m =   compartments using porous graphite partitions (these
M Batteries
graphite walls act as electrodes)
Only alternating current (AC) is used for conductivity measurement. This is to prevent Electrochemical cells used for commercial purpose are called batteries. They are of 2 types 1
H2 gas is fed to one outer compartments and O2 gas
electrolysis. (If DC is used anions and cations will get deposited at electrode. When AC is batteries and 2 batteries.
is fed to the other compartments.
used charge of electrode changes continuously). - 1 batteries
A dilute solution of base is taken in the central compartment
Variation of conductivity and molar conductivity with concentration These are non-rechargeable cells. The cell reactions in such cells are irreversible in
The reactions taking place in the cell are;
Conductivity or specific conductance decreases with increase in dilution or decrease in nature.
concentration because the no. of ions presents per cm3 of the solution decreases. Eg :- Dry cell, Hg cell etc. At Anode
2H2 + 4OH  4H2O + 4e
In the case of a strong electrolyte as the dilution increases or conc. decreases there is a slight Dry cell
increase in molar conductivity. This increase is because of the decrease in inter ionic A Zn container is acting as anode. A graphite rod surrounded by powdered MnO2 is At Cathode
attraction. acting as cathode. O2 + 2H2O +4e  4OH
In the case of a weak electrolyte as the dilution increase A paste of NH4Cl and ZnCl2 is acting as electrolyte. Net reaction 2H2 + O2  2H2O
there is a steep rise in molar conductivity. This is The reaction taking place in the cell are; Advantages of fuel cell
because of increase in degree of dissociation, which will At Anode 1) Fuel cell will not cause pollution 2) Very high efficiency (around 70%)
provide more ions.
Zn  Zn2+ + 2e Corrosion
Molar conductivity gets its maximum value at zero conc. or infinite dilution. This is called The phenomenon of destruction of metals in which they get converted into their compounds
At Cathode
limiting molar conductivity (Λ°m). In the case of strong electrolyte. Λm is related to Λ°(m) by like oxide, sulphides, carbonates etc is called corrosion.
the expression. MnO2 + NH4+ + 1e MnO(OH) + NH3
Eg :- Rusting of Iron, Tranishing of Ag (Silver gets converted into its sulphide). Formation
(Manganese oxyhydroxide)
Λm = Λm  A C of a green coating on the surface of Cu (Copper gets converted into basic Copper carbonate
NH3 combines with Zn2+ to produce a complex [Zn(NH3)2]2+
C = Conc. CuCO3.Cu(OH)2)
The cell can supply a potential of 1.5V.
A = Constant Mechanism of rusting of Fe
On keeping for a long time acidic ammonium chloride may corrode Zinc container.
If we plot Λ(m) against C . We get a straight line with its slope = A and intercept = Λ°m. It is an electrochemical phenomenon in which tiny electrochemical cells are setup on the
- 2 Batteries surface of iron. A spot on the surface acts as Anode where oxidation of Fe into Fe2+ takes
In the case of a strong electrolyte Λ°(m) can be determined graphically. But it is not possible in Rechargeable cells are called 2 batteries cell reaction in such cells are reversible in place.
the case of a weak electrolyte because the graph is not a straight line. nature. Eg : Lead storage cell, Nickel – Cadmium cell, Lithium ion battery Fe  Fe2+ + 2e
Kohlraush’s law Lead Storage cell es released will flow through the metal and reach at another spot which will work as cathode.
At zero conc. limiting molar conductivity of an electrolyte can be taken as equal to sum of Anode – Spongy lead From here these es are accepted by Oxygen present in the atmosphere along with the help of
limiting molar conductivity of cations and anions. Cathode – A grid of lead packed with PbO2 H+ ion (H+ ion are supplied by carbonic acid produced on surface of Fe due to dissolution of
Λ°m (HCl) = °m(H+) + °m(Cl-) 38% solution of H2SO4 acts as electrolyte. Reactions taking place in cell are CO2 in moisture on the iron surface)
Λ°m (CH3COOH) = °(CH3COO) + °H+ At Anode O2 + 4H+ + 4 e 2H2O
Λ°m (CaCl2) = ° (Ca2+) +2 °(Cl) Pb + SO42  PbSO4 + 2e Fe2+ ions are further oxidised by atom O2 into Ferric Oxide which will come out as rust in the
Λ°m (Al2(SO4)3) = 2° (Al3+) + 3°(SO42-) At Cathode form of hydrated Ferric Oxide. (Fe2O3. xH2O)
Application of Kohraush’s law PbO2 + SO42+ 4H+ +2e  PbSO4 + 2H2O Prevention of Corrosion
1) To determine limiting molar conductivity of a weak electrolyte. Net reaction Pb+ PbO2 + 2H2SO4  2PbSO4 + 2H2O Barrier protection – A coating of paint, grease or oil is given in the surface of Fe which will
Limiting molar conductivity of electrolyte can be calculated from limiting conductivity On recharging the reaction takes place in the opposite direction. avoid the contact with air and moisture.
values of strong electrolytes on the basis of Kohlraush’s law. 2Pb SO4 + 2H2O  Pb + PbO2 + 2H2SO4 Sacrificial protection
For, Eg: Λ°m(CH3COOH) can be calculated from Regenerating Pb, PbO2 and H2SO4 A coating of more reactive metal like Zn is given on the surface of iron. Then Zn will act as
Λ°m values of strong electrolytes. anode and it will be undergoing Oxidation instead of Iron. (The process of giving a coating of
Zn over Fe is called galvanizing)
CH3COONa, HCl and NaCl as
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Cathodic protection Zero Order Reaction Bimolecular reaction

Equipment made of Iron are connected to blocks of more reactive metal like Mg or Zn. The Decomposition of NH3 on the surface of platinum H2 + I2  2HI
more reactive metal will work as anodes, Iron will work as cathode and it will get protected Pt Difference between order and molecularity
2 NH3  N2 + 3H2 rate = k [NH3]
from corrosion. Order Molecularity
Photochemical combination of H2 and Cl2
CHEMICAL KINETICS hv Sum of powers of conc. terms in rate law Number of reactants molecules
H2 + Cl2  2 HCl rate = k [H2] [Cl2]
equation undergoing simultaneous collision
Rate of Reaction  First order reaction
Determined experimentally It’s a theoretical concept
The change in conc. of a reactant or product per unit time is called rate of reaction. Decomposition of N2O5
For reaction R  P , rate of reaction can be expressed as 2N2O5  2N2O4 + O2 rate = k [N2O5] order = 1 Order can be a whole no, fractional It is always a whole number
 [ R ] [ P ]  Second order reaction number or even zero
Rate = OR =
t t H2 + I2  2HI rate = k [H2] [I2] order = 1+1= 2
 [R] = change in conc. of reactant in the time t  Third order reaction Half life of a reaction
 [P] = change in conc. of product 2NO + O2  2NO2 rate = k [NO]2 [O2] order = 3 Time required for half of the reactants to get converted into products in a reaction is
Unit – mol L1 S1  Fractional order
called half life (t½ )
For a zero order reaction
For the reaction CHCl3 + Cl2  CCl4 + HCl rate = k [CHCl3] [Cl2]1/2
aA + bB  cC + dD Order = 1 + 1 = 1 1 = 3
R 0  R 
2
k =
2 2 t
 1 Δ[A]  1 Δ[B] 1 Δ[C] 1 Δ[D]
rate =
a t
=
b t
=
c t
=
d t
Pseudo order reaction R 0
When t = t½ [R] =
Reactions which appear to follow higher order but actually follows lower order. 2
For the reaction
Eg : Hydrolysis of ethyl acelate. Sub in above equation,
N2 + 3H2  2 NH3 rate expressions are,
CH3 COOC2 H5 + H2O  CH3 COOH + C2H5 OH R 0  R 0
= R 0
- Δ[N 2 ] - 1 Δ[H2 ] 1 Δ[NH3 ]
Rate = = = Rate = k [CH3 COOC2 H5 ] k = 2
t 3 t 2 t t1 2 t 1
Here water is present in excess.  Its conc. can’t affect the rate of reaction . 2 2
Factors influencing rate of a chemical reaction
 Unit of rate constant k =
R 0 t1 = R 0
Conc. of Reactants: Rate of reaction increases with conc. of reactants. 2t 1 2 2k
Consider the reaction
According to law of mass action rate of a chemical reaction is directly proportional to the 2

product of molar conc. of reactants. RP Rate = k [R]n 1

For a zero order reaction. t /2 is directly proportional to initial conc. of reactant.
-1 -1
For the reaction, rate mol L S For a first order reaction
k = =
aA +bB  cC +dD rate  [A ]x [B] y [R]n (mol L-1 ) n 2.303 [R] 0
k = log
OR rate = k [A ]x [B] y Unit of rate constant (k) mol 1 n L n 1 S 1 t [R]
x and y may or may not be equal to a and b. For zero order reaction R 0
When t = t1 [R] =
k is a constant called rate constant of the reaction Unit of k = mol 10 L 0 1 S 1 = mol 1 L 1 S 1 2 2
For a zero order reaction rate and rate constant have the same unit Substituting in above equation,
(The above equation is called Rate law equation. It can’t be written by looking at the balanced
2.303 [R]0 2.303
equation for the reaction. It can be written only on the basis of experiment).  For first order k = log = log2
t [R] t
Order of the reaction Unit of k = mol 11 L 1 1 S 1 = S 1 1
2
0 1
2
2
The sum of powers of conc. terms in the rate law equation is called order of reaction. For the  2nd order reaction 2.303
reaction, Unit of k = mol 12 L 2 1 S 1 = mol 1 LS 1 k =  .3010
t1
aA +bB  cC +dD  Molecularity 2

Rate  [A ]x [B] y .693 0 .693

The number of reactant molecules undergoing simultaneous collision in a reaction is k = t1 =
Rate = k [A ]x [B] y called molecularity. It can be taken as equal to sum of co-efficient in balanced equation t1 2 k
2
Order = x+y x - order with respect to the reactant A. (possible only in eleminatory reaction) For a first order reaction half life period is independent of initial conc. of reactant.
y - order with respect to reactant B. Unimolecular reaction Effect of temperature
Examples for reactions of different order. NH4 NO2  N2 + 2H2O As the temperature increases, rates of most of chemical reaction increases. This behaviour can
be explained with help of activated complex theory or collision theory.

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Activation Complex Theory hence melting point increases up to the middle of the series and there after decreases. Lanthanides contraction
In a reaction, reactant molecules Ist give an unstable intermediate compound called activated This is because of the increase in the number of half filled d-orbitals orbitals which can In lanthanides electron filling takes place in 4f orbital. In Lanthanide elements as the atomic
complex. This activated complex then get converted into products. The formation take part in bonding up to the middle of the series. number increases these is a steady decrease in the atomic and ionic radii. This steady decrease
of activation complex requires some amount  Transition metals exhibit variable oxidation states eg: Mn exhibits +2, +4, +6 and +7 Fe in the atomic or ionic radius is called lanthanoide contraction. This is because in these
of energy called activation energy, thus there exhibits +2 and +3. This is because in transition metals there is not much difference in elements electron filling take place is highly diffused 4f orbitals. Electrons in these orbitals
exist an energy barrier between reactants and the energies of ns and (n-1)d orbitals. Therefore along with electrons of ns orbitals have poor screening effect. Hence attractive force between nucleus and electrons in the
products. electrons in (n-1)d orbitals can also take part in chemical combination. Sc exhibits only valence shell increases and hence size decreases.
As the temp increase more and more reactant +3 oxidation state. This is because after loosing 3 electrons it can get stable noble gas Consequences of lanthanoide contraction
molecules can get the activation energy can configuration. Zn, Cd and Hg exhibits +2 because after loosing 2 electrons they get the 1) Elements in 2nd transition series (4d series) and 3rd transition series (5d series) have
cross the energy barrier and can convert in to stable configuration (n-1)d10 ns0 in which all d orbitals are completely filled. similar atomic radii and hence show similar properties. Zr and Hf have quite similar
product.  Most of the transition metal atoms and ions are paramagnetic in nature. This is because properties and hence it is difficult to separate them.
Arrhenius Equation Progress of reaction of the presence of unpaired electrons in d-orbitals. Paramagnetism depends on the 2) Due to lanthanoide contraction basic character of hydroxides of these elements decrease
Arrhenius introduced an expression connecting rate constant of a reaction (k) and temp (T) as, number of unpaired electrons according to the equation M  n(n  2) . M represents from La(OH)3 to Lu (OH)3
k = Ae Ea/RT A = Arrhenius factor. magnetic moment in the unit Bohr magneton (BM) and n represents the number of COORDINATION COMPOUND
Ea = Activation energy unpaired electrons. Sc3+ is diamagnetic due to the absence of unpaired electrons. Mn2+
is paramagnetic with 5 unpaired electrons. Zn2+ is diamagnetic due to the absence of These are compounds formed on mixing 2 or more stable compounds and in these compounds
R = Gas constant
unpaired electrons. If in a transition metal ion the electronic configuration is d1 to d9 it co-ordinate bonds are formed between a central metal atom or ion and neutral
T = Temperature in Kelvin
will be paramagnetic. If the configuration is d0 (Sc3+) or d10 (Zn2+) the ion will be molecules/negatively charged ions.
The above equation can be written in the logarithmic form as. diamagnetic .
Ea Eg: [Cu(NH3)4]SO4 K4[Fe(CN)6]
log k = log A   Transition metals usually form coloured compounds. This is due to the d-d electronic
Central metal atom/ion
2.303 RT transition in transition metal ions by absorbing energy in the form of radiation having
This is an equation for a straight line in the form y = mx + definite wavelength. Only those transition metal ions with partially filled d-orbitals are Every co-ordination compound will be having a central metal atom or ion. In the complex
c. A straight line will be obtained on plotting log K and coloured. Transition metal ions with d0 (Sc3+) or d10 (Zn2+) are colorless. [Cu(NH3)4]SO4 the central metal is Cu2+. In K4[Fe(CN)6] central metal is Fe2+.
 Ea Potassium Dichromate K2Cr2O7
In Ni(CO)4 central metal is Ni.
1/T with its slope = and intercept = log A.
2.303 R Ligands
 Preparation
Let k1 be the rate constant of a reaction at temp T1 and k2 be rate constant of reaction at temp Potassium dichromate is prepared from chromite ore (Fe Cr2O4). First chromite ore is The neutral molecules or negatively charged ions bonded to the central metal atom / ion
T2 . fused with sodium carbonate in presence of air to get sodium chromate. The fused mass is through co-ordinate bonds are called ligands. In the complex [Cu(NH3)4]SO4 ligands are 4
molecules of NH3. In [Co(NH3)3Cl3] ligands are 3 molecules of NH3 and 3 Cl ions.
k2 Ea  T2  T1  extracted with water and the solution containing sodium chromate on treating with an acid
  
2.303R  T1T2 
log gives sodium dichromate. The solution having sodium dichromate on treating with potassium Based on the no. of donor atoms through which ligands can get bonded to the central metal,
k1
chloride gives potassium dichromate. they are classified into unidentate, bidentate and polydentate ligands.
Using this relation we can determine rate constant of a reaction at a temp if we know rate A ligand which can get bonded only through one donor atom is called unidentate ligand
4FeCr2O4 + 8Na2CO3 + 7O2  8Na2CrO4 + 2Fe2O3 + 8CO2
constant at another temperature. Also we can calculate Ea of a reaction if we know rate
2Na2CrO4 + 2H+  Na2Cr2O7 + 2Na+ + H2O Eg: NH3, Cl, CN, etc.
constants at 2 different temperatures.
Na2Cr2O7 + 2KCl  K2Cr2O7 + 2NaCl A ligand having 2 donor atom is called bidentate.
Effect of catalyst
Potassium Permanganate KMnO4 Eg:- H2N  CH2  CH2  NH2
Presence of a catalyst can increase the rate of a
 Preparation 1,2 – Ethane diamine
chemical reaction. This is because catalyst
provides a new path of lower activation energy It is prepared from MnO2 (Pyrolusite) First Manganese dioxide is fused with potassium Oxalate ion COO
for the reaction. hydroxide in presence of air to give potassium manganate. The fused mass is extracted with 
more and more molecules can easily cross water and the solution having potassium manganate on electrolytic oxidation gives potassium COO
the energy barrier. permanganate. A ligand having more than two donor atom is called polydentate.
2MnO2 + 4KOH + O2 2K2MnO4 + 2H2O Eg:- EDTA (hexadentate)
THE d AND f BLOCK ELEMENTS
K2MnO4 Electrolyt
 ic oxidation
  KMnO4 When a bidentate or polydentate ligand is
General Properties of transition elements bonded to a central metal atom/ion to form a
Inner Transition Elements (F-Block)
ring like structure, the ligand is called
 Transition metals are usually hard metals with high melting points (with the exception
f-Block consists of two series, lanthanoids (the fourteen elements following lanthanum) and chelating ligands and the complex thus
of Zn, Cd and Hg). This is due to the strong metallic bonding existing among transition
actinoids (the fourteen elements following actinium). They have the general outer shell produced is called chelate.
metal atoms. From left to right in a transition series the strength of metallic bonding and
configuration (n2) f114 (n1)d01 ns2 Eg: [Cu(en)2]2+
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Co-ordination entity 4. 1 valency is equal to oxidation state of the metal and 2 valency is equal to co-  The no. of a particular kind of ligand is indicated by prefixes di, tri, tetra, penta, hexa
A complex species obtained by the combination of central metal atom/ions and ligands is ordination no. etc. or by using bis, tris, tetrakis.
called co-ordination entity. 5. Every metal has a fixed no. of 2 valency.  If different types of ligands are present their names are given in the alphabetical
Eg: [Cu(NH3)4]2+ [Ni(CO)4] [Fe (CN)6]4 6. The ions/ molecules satisfying secondary valencies are directed towards fixed order.
Co-ordination sphere positions in space. giving a definite geometry to the complex.  If the co-ordination entity is negatively charged its name should end in “-ate”
The portion of a complex enclosed in square bracket where co-ordinate bonds are formed is CoCl3 reacts with NH3 to reduce 4 different complexes with different colours and different  Oxidation number of central metal is indicated by Roman numeral in parenthesis.
called Co-ordination sphere. And the portion of the complex coming outside the co-ordination properties. Compound Name
sphere is called ionization sphere. Yellow CoCl3.6NH3 [Co(NH3)6]Cl3 (Werner’s formula) [Co(H2O)6]Cl3 Hexaaquacobalt (III) chloride
Co-ordination Number Purple CoCl3.5NH3 [Co(NH3)5Cl]Cl2 [Co(NH3)5Cl]Cl2 Pentaaminechloridocobalt (III) chloride
The number of ligand donor atoms to which the central metal is bonded (or number of Co- Green CoCl3.4NH3 [Co(NH3)4Cl2] Cl [Cr(NH3)6]Cl3 Hexaaminechromium (III) chloride
ordinate bond formed) is called Co-ordination number. In the case of a complex having only Violet CoCl3.3NH3 [Co(NH3)3Cl3] [Pt(NH3)2Cl2]Cl2 Diaminedichlorido platinum (IV) chloride
monodentate ligands Co-ordination no. can be taken as no. of ligands. st
I complex has 3 ionisable chloride ions and hence one mole of the complex gives 3 moles of K3[Fe(CN)6] Potassiumhexacyanoferrate (III)
Complex Co-ordination No. AgCl Precipitate on mixing with AgNO3 solution 2nd complex gives 2 moles of AgCl 3rd K4[Fe(CN)6] Potassiumhexacyanoferrate (II)
th
[Cu(NH3)4]SO4 4 complex gives 1 mole of AgCl and 4 one willn’t react with AgNO3. Na3[Au(CN)4] Sodium tetracyanoaurate (I)
List of ligands, Charge and names. [Cr(NH3)6SO4]Cl Pentaaminesulphatochromium(III) chloride
[CO(NH3)3Cl3] 6
Ligand Name K[Ag(CN)2] Potassiumdicyanoargentate (I)
[CO(en)3]Cl3 6  monodentate [Ni(en)3]Cl3 Tris1,2-ethanediamine nickel (III) Chloride
[CO(en)2Cl2]Cl 6 Cl - Chloro or chlorido Na[Al(OH)4] Sodium tetrahydroxo aluminate (III)
Oxidation no. of central metal atom/ion Br - Bromo [Pt(NH3)4Cl NO2]Cl2 Tetramine chloridonitro platinum (IV) chloride
Oxidation no. of central metal in a complex can be calculated as shown below. I - Iodo [Co(NH3)5CO3]Cl Pentaamine carbonatocabalt (III) Chloride.
1) [Cu(NH3)4]SO4 SO42 -
Sulphato [Ni(CO)4] Tetracarbonyl nickel (O)
2
x + 4  0 + 1 2 = 0 CO3 - Carbonato
Isomerism in Co-ordination Compounds
x2 = 0 NO2 - Nitro or nitrito – N I Structural Isomerism
x = +2 ONO (When Oxiygen act as donor)- nitrito – O a) Ionization isomerism

2) K3 [Fe(CN)6] CN - Cyano Isomers capable of producing different ions in solution are called ionization isomers.
x + 6  (1) + 3  (+1) = 0 SCN - thiocyanato Eg:- [Co(NH3)5SO4]Br  [Co(NH3)5SO4]+ + Br
x6+3 = 0 OH - hydroxo and
x3 = 0 NH3 - amine [Co(NH3)5 Br]SO4  [Co(NH3)5 Br ]2++SO42
x = +3 H2O - Aqua (The first complex on treating with Ag NO3 solution gives AgBr, a pale yellow
3) Ni (CO)4 CO - Carbonyl precipitate. But the 2nd complex will not react with AgNO3.
x+40 = 0 NO - Nitrosyl The 2nd complex with ract with BaCl2 to produce a white precipitate of BaSO4. But Ist
x = 0  Bidentate one will not react with BaCl2)
4) K3 [Co(Ox)3] Oxoxalate CH2  NH2 - 1,2 – Ethane diamine b) Linkage Isomerism
x + 3  2 + 3  +1 = 0  (Ethylene diamine (en)) This type of Isomerism arises bcz of the difference in the nature of linkage of an
x 6 +3 = 0 CH2  NH2 ambident ligand (a monodentat ligand which can get co-ordinate to the central metal through
x = +3 COO 2 different donor atom) to the central metal.
Werner’s theory of Co-ordination Compound  Eg: [Co(NH3)5NO2]Cl2 and [Co(NH3)5ONO] Cl2
1. Every metal possess 2 types of valancies – primary valancy (1) and secondary COO (C2O42) - Oxalato (Ox) c) Co-ordination Isomerism
valency (2). Nomenclature of co-ordination compound This kind of isomerism is found in complexes where the cation as well as anion are
2. Primary valency is called ionisable valaency and it is usually satisfied by (ve) ion. A co-ordination compound can be named on the basis of following rule. complex species. Here isomers are produced as a result of exchange of ligand b/w central
3. 2 valency is called non ionisable valency and it is satisfied by neutral molecules or  Positive part of the compound is named first and then negative part. metal ions.
(-ve) ions.  While naming the co-ordination entity ligands are named first and then the central Eg: [Co(NH3)6] [Cr(CN)6] and [Cr(NH3)6] [Co(CN)6]
metal.

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d) Solvate/Hydrate isomerism (Compound having asymmetric, molecules or Nomenclature

These are isomers in which water molecule act either as ligands or as water of molecules with non super imposable mirror In the common system name of an alkyl halide is derived by writing the name of the
hydration. images can exhibit optical isomerism). alkyl group followed by the name of halogen as ‘halide’.
Eg: [Cr(H2O)6]Cl3 and [Cr(H2O)5Cl] Cl2 . H2O Optical isomers of [Co(en)3]3+ are shown CH3Cl – Methyl chloride
II Stereo Isomerism below. CH3CH2Cl – Ethyl chloride
It arises bcz of the difference in the spatial arrangement of ligands around the central The complex [CO(en)2 Cl2]+ can exhibit CH3CH2CH2Br – n – Propyl bromide
metal. It is classified into geometrical isomerism and optical isomerism. geometrical isomerism the Cis form of this CH3 – CH – CH3 – Iso- Propyl bromide
Geometrical Isomerism
complex can also exhibit optical isomerism. 
Br
These are isomers in which identical ligands occupy adjacent positions or opposite position
CH3CH2CH2CH2Cl – n – Butyl chloride
around the central metal. These isomers are named as cis and trans. Importance & Application of Co-ordination Complex CH3 – CH – CH2Cl
(Square planar complexes of the type ML2X2 or ML2XY and octahedral complexes of the 1) Chlorophyll, a complex of Mg helps in Photosynthesis. 
type ML4X2 and ML2Z2 can exhibit geometric isomerism here L, X and Y are monodentate 2) Hemoglobin, a complex of Fe helps in carrying O2 into cells. CH3 – Iso – butyl chloride
ligand and Z, bidentate ligand). Cis and trans isomers of [Pt(NH3)2Cl2] are shown below. 3) Vitamin B12 is a complex of cobalt CH3 – CH2 – CH – CH3 – Sec – butyl chloride
4) Cis platin, Cis isomer of [Pt(NH3)2Cl2] is used in treatment of cancer. 
5) EDTA – is used in the treatment of lead poisoning. Cl
CH3
6) Complex [Ag(CN)2] and [Au(CN)2]  in solution are used as electrolytes in the
Trans form Cis form 
electroplating of metal articles with Ag and gold respectively.
CH3 – C – Cl – Tert – butyl chloride
7) In photography the unreacted AgBr on the film is washed out as a complex
(Co(NH3)4Cl2] + 
[Ag(S2O3)2]3- by using hypo (Na2S2O3).
CH3
HALOALKANES & HALOARENES  In the IUPAC system alkyl halides are named as haloalkanes.
 Compounds obtained by the replacement of one or more hydrogen atoms of aliphatic CH3Cl CH3 CH2 Cl
Chloromethane Chloroethane
hydrocarbons with halogen atoms are called halo alkanes or alkyl halides and compounds
obtained by replacing one or more hydrogen atoms of aromatic hydrocarbons are called aryl CH3 CH2 CH2 Cl CH3 – CH – CH3
halides or haloarenes.
1 – Chloropropane

Co(en)2Cl2]+  These compounds can be represented by the general formula R – X. Cl
2 – Chloropropane
R – alkyl group (–CH3, – C2H5 etc) or aryl group (–C6 H5) X – Cl – Br or – I CH3CH2CH2CH2Cl CH3 – CH – CH2 – CH3
 Alkyl halides can be classified into 1, 2 or 3. 1 – Chlorobutane

Cl
2 – Chlorobutane

CH3 – CH – CH2Cl
Octahedral complexes of the type. ML3X3 can exhibit a special kind of geometrical isomerism 
called facial (fac) and Meriodional (mer) isomerism. CH3
 Compounds in which halogen atom is bounded to an sp3 hybridized carbon atom next to a 1 – Chloro – 2 – methylpropane
Eg: [Co(NH3)3(NO2)3]
carbon – carbon double bond are called allyl halides. CH3
CH2  CH – CH2Cl 
Allylchloride 2 – Chloro – 2 – Methyl propane
CH3 – C – CH3
 Compounds in which halogen atom is bonded to an sp3 hybridized 
carbon next to an aromatic ring is called benzylic halide. Cl
 Compounds in which halogen atom is bonded to an sp2 hybridised carbon atom of carbon –  Aryl halides are named as haloarenes
Mer Fac carbon double bond is called vinyl halide.
Optical Isomerism CH2 = CH – Cl
These are isomers which can rotate the plane of plane polarized light in opposite direction. Vinyl chloride
The isomer which is rotating the plane of plane polarized light towards right is called dextro
 In aryl halides halogen atom is attached to sp2 hybridized carbon.
isomer (d) and that which rotating the plane of plane polarized light towards left is called
laevo (l)  In alkyl halides halogen atom is attached to sp3 hybridized carbon.

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Methods of Preparation chlorine or bromine in the presence of Lewis 

 
From alcohols acid like Fe or FeCl3 CH3 – CH2 – CH – CH3   CH3 – CH = CH – CH3
alco. KOH

(i) By treating an alcohol with hydrogen halide in presence of a dehydrating agent like  HBr 2 – Butene
anhydrous zinc chloride.
Br
CH3 OH + HCl ZnCl 2  CH3Cl + H2O
Methanol Chloromethane 2. Reaction with metals
(ii) By treating an alcohol with phosphorous halides (PCl3 or PCl5) a. Reaction with magnesium
When an alkyl halide is heated with magnesium in ether medium alkyl magnesium halide
CH3CH2OH PCl
3  CH3CH2Cl CH3OH 
5  CH3Cl
PCl

Ethanol Chloro ethane Methanol Chloromethane (Grignard reagent) is obtained. R – X + Mg ether

 R –Mg – X
Reaction with iodine is reversible in nature, require the presence of oxidising agent like HNO3
CH3 CH2 Br + Mg ether

 CH3 CH2 Mg Br
(iii) By treating an alcohol with sulphonyl chloride. or HIO3, which will oxidise HI produced into iodine. Fluoro compounds are not prepared by Bromoethane Ethyl magnesium bromide
CH3CH2OH SOCl 2  CH3CH2Cl this method because of the high reactivity of fluorine.
Ethanol Chloroethane
Sandmeyer’s reaction Grignard reagents are highly reactive. They can be easily converted into a number of other
organic compounds. A Grignard reagent can react with water, alcohol or amine to produce a
(This is the most suitable method for getting an alkyl chloride because the biproducts SO2 and When a freshly prepared diazonium salt solution is treated with cuprous chloride and HCl or
hydro carbon.
HCl are gases and they will escape) Cuprous bromide and HBr chlorobenzene or brombenzene will be obtained as product.
R – Mg – X + H2O → R – H + MgX(OH)
From Alkenes Diazonium salt can be prepared by treating an aromatic primary amine like aniline with an ice
cold solution of sodium nitrite and HCl CH3 Mg Br + H2O → CH4 + MgBr(OH)
By the addition of hydrogen halides into alkenes. Methyl Magnesium Methane
CH2 = CH2 + HCl → CH3CH2Cl bromide
Ethane chloroethane
b. Reaction with sodium metal – Wurtz reaction
(During addition of hydrogen halide into an ansymmetrical alkene, addition takes place
according to Markownikoff’s rule, positive part, H goes to the carbon having more number Alkyl halides react with sodium metal in either medium to give hydrocarbons. (The
of hydrogen atoms.) hydrocarbon obtained will be having double the number of carbon atoms than in the starting
alkyl halide)
CH3 – CH = CH2 + HBr → CH3 – CH – CH3 Physical properties
2 R – X + 2Na ether

 R – R + 2 NaX
Propene
  Boiling points higher than those of hydrocarbons.
2 CH3Cl + 2 Na ether
 CH3 – CH3 + 2NaCl
Br  Boiling points follow the order Chloromethane ethane
2 – Bromopropane
RI > RBr > RCl > RF
(But when HBr is added to an alkene in the presence of a peroxide addition takesplace  Among isomeric halo alkanes as the branching increases boiling point decreases. 2CH3CH2Cl + 2Na ether
  CH3CH2CH2CH3 + 2 NaCl
Chloroethane Butane
contrary to Markownikoff’s rule)  Boiling points of isomeric dihalobenzenes are nearly the same. But the melting point of
CH3 – CH = CH2 + HBr Peroxide
  CH3 – CH2 – CH2 – Br para isomer is higher than that of ortho and meta isomeres. This is because of the Reactions of Haloarenes
Propene 1 – Bromopropane symmetry and hence higher packing efficiency of para isomer. Replacement by hydroxyl group
Halogen Exchange  Alkyl halides and aryl halides are not soluble in water. They are soluble in orgainic Presence of electron withdrawing groups at ortho and
solvents. para positions increase the reactivity of haloarenes
a) Finkelstein reaction: Alkyl iodides can be prepared by treating alkyl chlorides or
bromides with sodium iodide in dry acetone. Reactions of Haloalkanes Fittig reaction
R – X + NaI → R – I + NaX –C – X bond in alkyl halides is polar in nature with the halogen atom carrying slight negative Aryl halide will react with sodium metal to produce higher aromatic hydrocarbon.
C2H5Br + NaI → C2H5I +NaBr charge and carbon carrying slight positive charge.
Bromo ethane Iodo ethane
The polar nature of bond makes C – X bond weak and hence chemical reactivity will increase.
b) Swartz reaction : Alkyl fluoride can be prepared by treating alkyl chloride or bromide 1. Elimination reaction
with silver fluoride. When a haloalkane is heated with alcoholic solution of potassium hydroxide elimination of a Wurtz –Fittig reaction
CH3Br + AgF → CH3F + AgBr hydrogen halide molecule take place leading to the formation of an alkene. Here elimination When a mixture of alkyl
Bromomethane Fluoromethane
of hydrogen takeplace from  – carbon and hence this is called  – elimination. The reaction halide and aryl halide is treated with
Preparation of Aryl Halides is also called dehydrohalogenation.
  sodium in ether, alkyl arene will be
o From aromatic hydrocarbons by electrophilic substitution CH3 – CH2Cl alco.
  CH2 = CH2
KOH
obtained.
Aryl chlorides and bromides are prepared by Chloroethane HCl ethene

electrophilic substitution of arenes with Saytzeff rule : - Dehydro halogenation take place in such a way that a more substituted
alkene is obtained as the major product.
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Polyhalogen Compounds CH3–CH2 – CH – CH3 Sec – Butyl alcohol 2 – Butanol (ii) By using Grinard reagents
1. Trichloromethane (Chloroform) – CHCl3  Addition of Grignard reagent into formaldehyde gives 1 alcohol
It is used as a solvent for fats, alkaloids iodine etc. It is also used as an anesthetic. OH O O MgBr
Chloroform used as anesthetic may undergo slow oxidation in the presence of air and sunlight CH3 – CH – CH2 – OH || 
to produce poisonous gas called carbonyl chloride or phosgene. Therefore it is usually stored  Iso butyl alcohol 2 – Methyl – 1– Propanol H–C–H + CH3 MgBr  H– C – H   CH3 – CH2OH
H 2O

in dark coloured bottles completely filled up to the mouth. CH3 Methanal Methyl magnesium  Ethanol
(Formaldehyde)
2CHCl3 + O2 light 
 2COCl2 + 2HCl CH3
bromide
CH3
Chloroform Carbonyl Chloride
 Addition of Grignard reagent into an aldehyde other than formaldehyde gives 2 alcohol.
CH3 – C – OH Tert – butyl alcohol 2 – Methyl – 2 – Propanol O O MgBr OH
ALCOHOLS, PHENOLS & ETHERS
 ||  
CH3 CH3 – C – H + CH3 – MgBr  CH3 – C – H   CH3 – CH – CH3
H 2O

Alcohols and Phenols Ethanal 

Names of certain phenols are given below. 2- Propanol
 Alcohols and Phenols are compounds having the functional group – OH and the general (Acetaldehyde) CH3 Isopropyl alcohol
formula R – OH (R – alkyl group or aryl group)
Addition of grignard reagent into a Ketone gives 3 alcohol.
 Alcohols can be classified on the basis of number of hydroxyl group present as mono,
O O MgBr OH
di, tri or poly hydric alcohols.
CH3OH CH2OH CH2OH ||  
  CH3 – C – CH3 + CH3 – MgBr  CH3 – C – CH3   CH3 – C – CH3
H 2O
Methanol Preparation of Alcohols
(Monohydric) CH2OH CHOH 1. From alkenes
Propanone  
(Acetone)
Ethylene glycol  An alkene on hydration in presence of H2SO4 gives alcohol CH3 CH3
(dihydric)
CH2OH  3. From Alkyl halides 2- methyl – 2- propanol
Eg: CH2 = CH2 + H2O 
H
 CH3 – CH2OH
Glycerol (trihydric) Ethene Ethanol When an alkyl halide is treated with aqueous solution of NaOH or KOH alcohol will be
 On the basis of the nature of carbon atom on which hydroxy group is present alcohols  obtained.
CH3 – CH = CH2 + H2O 
H
 CH3 – CH – CH3
can be classified into 1, 2 and 3 alcohols R – X + NaOH  R – OH + NaX

CH3 Propene CH3CH2Cl + NaOH CH3CH2OH + NaCl
OH
 2 – propanol Chloroethane Ethanol
CH3CH2OH CH3 – CH – CH3 CH3 – C – CH3 (Markownikoff’s addition) Preparation of Phenols
Ethanol   1. From Chlorobenzene
1 – Propanol can be prepared from propene by hydroboration oxidation reaction as
1 OH OH
shown below.
2- Propanol 2- methyl – 2 - Propanol CH3 – CH = CH2   CH3 – CH2 – CH2 – OH
(i ) B2 H 6

2 3 (ii) H2O2/OH–, H2O 1 – Propanol

Nomenclature
2. From aldehydes and ketones 2. From diazonium salt
In the common system alcohols are named as alkyl alcohols
(i) By reduction
In the IUPAC system name of an alcohol is obtained on replacing the ending – ‘e’ of
An aldehyde on reduction with H2/Ni or LiAlH4 gives 1 alcohol. A ketone on reduction
corresponding alkane with -‘ol’
gives 2 alcohol.
Compounds Common name IUPAC name
CH3CHO   CH3 CH2OH
H 2 / Ni

CH3OH Methyl alcohol Methanol Ethanal Ethanol

CH3CH2OH Ethyl alcohol Ethanol (Acetaldehyde) (Ethyl alcohol)
Properties
CH3CH2CH2OH n – Propyl alcohol 1- Propanol  Alcohols and phenols have higher boiling points compared to hydrocarbons,
O haloalkanes, haloarenes, ether etc. This is because of the ability of alcohols and phenols
CH3 – CH – CH3 Isopropyl alcohol 2 – Propanol || to take part in intermolecular hydrogen bonding.
 CH3 – C – CH3   CH3 – CH – CH3
H 2 / Ni

OH  As the number of carbon atoms increases boiling point increases.

Propanone   As the branching increases boiling point decreases.
CH3 CH2CH2CH2OH n – Butyl alcohol 1 – Butanol (Acetone) OH  Alcohols are soluble in water because of their ability to form hydrogen bonds with
2- Propanol water molecules. Solubility decreases with increase in molecular mass.
(Isopropyl alcohol)
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 Phenols are only partially soluble in water this is because the large sized non polar 2 alcohol on oxidation gives a ketone which will not undergo further oxidation easily. (ii) Halogenation
benzene ring prevents the formation of hydrogen bonds with water molecules CH3 – CH – CH3 [O ]
CH3 – C – CH3 When phenol is treated with a solution of
Reactions involving cleavage of – O – H bond. | || bromine in carbon disulphide a mixture of ortho
1. Reaction with sodium metal OH O bromophenol and para bromo phenol is obtained.
Alcohols and phenols react with sodium metal liberating hydrogen gas and they get 2- Propanol Propanone When phenol is treated with bromine water a
converted into sodium salts. This reaction shows the acidic behaviour of alohols and white precipitate of 2, 4, 6 – tribromo phenol is
3 alcohol will not undergo oxidation under normal conditions.
phenols. But alcohols are less acidic than water and phenols are more acidic. (alcohol < obtained.
Action of Copper catalyst
water < phenol)
When the vapours of a 1 alcohol is passed over heated Cu catalyst an aldehyde will be
2R – OH +2Na  2 R – ONa + H2 (iii) Kolbe’s reaction 2, 4, 6 - tribromophenol
obtained.
2CH3 CH2OH + 2Na  2 CH3 CH2 ONa + H2 When sodium salt of phenol is treated with CO2 followed by acidification salicylic acid ( 2-
Ethanol Sodium salt of ethanol CH3CH2OH  Cu
CH3CHO + H2
Ethanol 573K Ethanal
hydroxy benzoic acid) will be obtained.
(Sodium ethoxide)
(Acetaldehyde)

When the vapours of a 2 alcohol is passed over Cu catalyst a ketone will be obtained.
CH3 – CH – CH3  Cu
CH3 – C – CH3 + H2
573K
| || (iv) Reimer – Tiemann reaction
OH O When phenol is treated with a mixture of chloroform and
Reactions involving cleavage of C – O bond Isopropyl alcohol Acetone
NaOH followed by acidification salicylaldehyde (2 –
1. Reaction with hydrogen halides (2 – Propanol) (Propanone) Hydroxy benzaldehyde) is obtained.
Alcohols can react with hydrogen halides in presence of dehydrating agent like ZnCl2 to
When the vapours of a 3 alcohol is passed over Cu catalyst an alkene is obtained. 2. Reaction with zinc dust
produce alkyl halides
CH3 CH3 When phenol is distilled with zinc dust benzene is obtained.
R – OH + HX ZnCl 2  R – X + H2O
| |
CH3OH + HCl ZnCl 2  CH3Cl + H2O
CH3 – C – CH3 Cu
CH3 – C = CH2 + H2O
Order of reactivity 3 > 2 > 1 573K
Lucas test to distinguish 1, 2 and 3 alcohol 
2 – methyl propene Some commercially important alcohols
OH
When an alcohol is treated with Lucas reagent, a mixture of conc. HCl and anhydrous ZnCl2 a 2 – methyl – 2 – propanol (Isobutylene) 1. Methanol (Wood spirit)
turbidity will get produced in the reaction mixture due to the formation of alkyl chloride.
(Tert – butyl alcohol) Methanol is manufactured by treating carbon monoxide with hydrogen under high
3 alcohol readily reacts with Lucas reagent to produce turbidity. 2 alcohol reacts with Lucas pressure and temperature in presence of a catalyst.
reagent to produce turbidity only within 5 to 10 minutes. 1 alcohol will not react with Lucas Note: ZnO  Cr2O3
CO + 2H2    CH3OH
reagent at room temperature. During the action of Cu catalyst on 1 and 2 alcohols dehydrogenation take place. But when 200 atm
2. Reaction with phosphorous halides 3 alcohol is used dehydration take place. 573K
Reactions of Phenols Methanol is poisonous in nature. It’s consumption may cause blindness and even death.
Alcohols react with phosphorous halides to produce alkyl halides.
It is used as a solvent in paints, varnishes etc. and for making formaldehyde.
CH3OH   CH3Cl
PCl 5
CH3CH2OH   CH3CH2Br
PBr 3 1. Electrophilic substitution
2. Ethanol
3. Dehydration –OH group is an ortho – para directing group and it is also an activating group.
It is manufactured by the fermentation of molasses (the liquor left behind after the
When an alcohol is heated with conc. H2SO4, dehydration of alcohol take place leading to the (i) Nitration
crytallisation of sugar from sugar cane juice) or starch.
formation of an alkene When phenol is treated with dilute nitric acid a
(i) From molasses
CH3CH2OH    CH2 = CH2 + H2O
ConcH 2 SO 4 mixture of ortho nitro phenol and para nitro phenol
Ethanol Ethene is obtained. To a dilute solution of molasses yeast is added. The enzyme invertase supplied by yeast
converts cane sugar into glucose and fructose. Another enzyme zymase converts glucose and
Order of reactivity 3 > 2 > 1 When phenol is treated with a mixture of fructose into ethanol.
Oxidation conc. HNO3 and conc. H2SO4 C12H22O11 + H2O    C6H12O6 + C6H12O6
Invertase

Alcohols can be subjected to oxidation with alkaline or acidified KMnO4. A 1 alcohol on C6H12O6   2C2H5OH + 2CO2
Zymase

oxidation first gives an aldehyde which on further oxidation gives a carboxylic acid. 2, 4, 6 – trinitrophenol (picric acid) is
Ethers
CH3CH2OH [O ]
CH3CHO [O ]
CH3COOH obtained.
Compounds having the general formula R – O – R1. Ethers can be classified into simple or
Ethanol Ethanal Ethanoic acid.
symmetrical ethers and mixed or unsymmetrical ethers.

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In simple ethers R and R1 are same alkyl or aryl groups R – O – R1 + HX  R – X + R1OH  Acetophenone
Eg: CH3OCH3, C2 H5 – OC2H5 etc. When excess of HX is used the alcohol produced will also get converted into alkyl halide.
In mixed ethers R and R1 are different R1OH + HX  R1X + H2O  Benzophenone
Eg: CH3 O C2 H 5 The order of reactivity of hydrogen halides is HI > HBr> HCl
Nomenclature CH3O CH3 + HI  CH3I + CH3OH Preparation of aldehydes and Ketones
In the common system name of an ether is obtained by writing the names of alkyl groups Note:- 1. By the oxidation of alcohols
followed by the word ether.  When an unsymmetrical ether is treated with HI alkyl iodide is produced from the A 1 alcohol on oxidation gives an aldehyde and 2 alcohol on oxidation gives Ketone.
In the IUPAC system ethers are named as alkoxy alkanes. The smaller alkyl group along with smaller alkyl group.
CH3 CH2 OH [O 
]
CH3CHO
oxygen is named as alkoxy and the other as alkane. CH3O C2H5 + HI  CH3I + C2H5OH Ethanol Ethanal
Compound Common Name IUPAC name  When anisole is treated with HI a
mixture of phenol and methyl iodide will CH3 – CH – CH3 [O
 ]
CH3 – C – CH3
CH3OCH3 Dimethyl ether Methoxy methane
be obtained. | ||
CH3OC2H5 Ethyl methyl ether Methoxy ethane
OH O
C2H5OC2H5 Diethyl ether Ethoxy ethane 2- Propanol Propanone
CH3O – CH – CH3 Methyl iso – propyl ether 2 – Methoxy propane ALDEHYDES, KETONES & CARBOXYLIC ACIDS (Isopropyl alcohol) (Acetone)
| Aldehydes and Ketones
Aldehydes are compounds having the general formula R – CHO with functional group 2. By the action of copper catalyst (Dehydrogenation)
CH3
O When the vapours of a 1 alcohol is passed over hot Cu catalyst an aldehyde will be obtained.
Methyl phenyl ether Methoxy benzene.
|| When the vapours of a 2 alcohol is passed over Cu catalyst Ketone is obtained.
(Anisole)
 CHO ( C  H ) CH3 CH2 OH  Cu
CH3CHO + H2
Ethanol 573K Ethanal
O
Methods of preparation
|| CH3CH CH3 
Cu
CH3 CCH3
1. By the dehydration of alcohols | 573K ||
Ketones are compounds having the general formula R C  R1 with functional group
When excess an alcohol is heated with concentrated sulphuric acid at a temperature of >C=O. OH O
2 – Propanol Propanone
413 K an ether will be obtained. Both aldehydes and ketones have >C=O group and they are togetherly called carbonyl
2CH3CH2OH   CH3CH2OCH2CH3
H 2 SO 4
compounds. 3. From alkenes by ozonolysis
Ethanol 413K Diethyl ether
Nomenclature
Note:- In the common system the name of an aldehyde is derived from the name of corresponding
Only symmetrical ether can be prepared by this method. Ethers cannot be prepared by acid by replacing the ending – ic acid with aldehyde.
the dehydration of 2 and 3 alcohols because in these cases alkenes are obtained instead of In the IUPAC system name of an aldehyde is derived by replacing the ending – e of
ethers. corresponding alkane with – al. Name of a ketone is obtained by replacing the ending – e with
2. Williamson’s synthesis – one.
When an alkyl halide is treated with sodium salt of an alcohol ether will be obtained. Compound Common Name IUPAC Name
R – X + R1 ONa  R – O – R1 + NaX HCHO Formaldehyde Methanal
CH3Cl + C2H5ONa  CH3OC2H5 CH3CHO Acetaldehyde Ethanal
Chloro methane Sodium salt Ethyl methyl ether
CH3CH2CHO Propionaldehyde Propanal
of ethanol (Methoxy ethane)
CH3 – CH2 – CH2 – CHO  Butanal
Physical properties of ethers 4. By the hydration of alkynes
 Benzaldehyde
When an alkyne is passed through a dilute solution of sulphuric acid in presence of mercuric
 Boiling points of ethers are much lower than those of isomeric alcohols. This is due to
the absence of hydrogen bonding in ethers. sulphate hydration of alkyne take place leading to the formation of an aldehyde or
ketone.Acetylene (ethyne) gives aldehyde but all other alkynes give ketones.
 Lower ethers are soluble in water. This is because of their ability to form hydrogen CH3COCH3 Acetone Propanone
bonds with water molecules. CH3COCH2CH3  Butanone HC  CH + H2O H  CH3CHO
2 SO 4

Ethyne HgSO4 Ethanal

Chemical Properties CH3COCH2CH2CH3  2 - Pentanone
1. Reactions involving cleavage of C – O bond CH3CH2COCH2CH3  3 – Pentanone CH3 – C  CH + H2O H  CH3–C– CH3
2 SO 4

HgSO4
When an ether is treated with hydrogen halide a mixture of alcohol and alkyl halide will be Propyne || Propanone
obtained. O
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5. From acid chloride (Rosenmund reduction) electron releasing alkyl groups. Electron releasing groups will decrease the positive charge on 4. Aldol condensation
When an acid chloride is subjected to reduction with hydrogen in presence of palladium and carbonyl carbon and hence chance for nucleophilic addition decreases. Following are some of Aldehydes and Ketones having  – hydrogen atom react with dilute alkali to give β – hydroxy
barium sulphate an aldehyde will be obtained. the examples for nucleophilic addition reactions. aldehyde (aldol) or β – hydroxy Ketone (Ketol) which readily lose water on heating to give
O (i) Addition of HCN unsaturated aldehyde or ketone

|| Addition of HCN into an aldehyde or ketone produce cyanohydrins which on hydrolysis give 2CH3 CHO   CH3 – CH – CH2 – CHO 
dilNaOH
CH3 – CH = CH – CHO
R – C – Cl H2

  R – CHO  - hydroxy acids. Ethanal  -H2O But-2-enal
Pd/BaSO4 O OH OH OH
O O || | | CH3 CH3
|| || HO  
CH3 – C – H + HCN → CH3 – CH – CN 2 CH3 – CH – COOH
H
CH3 – C – Cl  2  CH3– C – H Acetaldehyde Cyanohydrin Lactic acid
2CH3 COCH3   CH3 – C –CH2 – CO – CH3 
dilNaOH 
CH3 – C = CH – CO – CH3
Acetyl Chloride Pd/BaSO4 Acetaldehyde (Ethanal)
-H2O
2. Reduction Propanone 
4 – Methylpent – 3 – ene – 2 - one
(i) Reduction to alcohols OH
An aldehyde on reduction with H2/Ni or H2/Pd or LiAlH4 gives a 1 alcohol. A ketone on 5. Cannizzaro reaction
reduction gives 2 alcohol. When an aldehyde not having  - hydrogen is treated with concentrated alkali undergo self
CH3C = O H  CH3CH2OH
2 / pd oxidation and reduction to give a mixture of alcohol and salt of carboxylic acid.
| Ethanol 1 2 HCHO ConcNaOH
  CH3OH + HCOONa
6. From nitriles (Stephen reduction) Methanal Methanol sodium salt of formic acid
H
Nitriles on reduction with SnCl2 and HCl give imines which on hydrolysis give aldehydes. Ethanal (acetaldehyde)
2  HCl H 2O / H 
R – CN SnCl
  R – CH = NH    R – CHO O OH
SnCl 2  HCl H 2O / H 
CH3CN   CH3CH = NH    CH3CHO || |
Nitriles can also be reduced into imines with DIBAL – H CH3C  CH3 H  CH3CH CH3
2 / pd

Acetone 2- propanol 2
(Di – isobytyl aluminium hydride)
6. Electrophilic Substitution
7. From aromatic hydrocarbons ii) Reduction to hydrocarbons Carbonyl group in aromatic aldehydes and
Aldehydes and ketones can be reduced into hydrocarbons with zinc amalgum and ketones act as deactivating and meta directing
hydrochloric acid (Clemmensen reduction) or with hydrazine and potassium hydroxide in group towards electrophilic substitution.
ethylene glycol (wolf kischner reduction). Carboxylic Acids
CH3COCH3   CH3 CH2 CH3
Zn / Hg
These are compounds containing –COOH group.
Propanone (Acetone) HCl Propane
Friedel Craft’s acylation Nomenclature
Aromatic ketones can be prepared by treating an aromatic hydrocarbon with an acid chloride In the IUPAC system name of a carboxylic acid is obtained by replacing the ending – e of
in presence of anhydrous aluminium chloride corresponding alkane with – oic acid.
Compound Common Name IUPAC Name
HCOOH Formic acid Methanoic acid
Acetophenone Ethyl benzene
CH3COOH Acetic acid Ethanoic acid
3. Haloform reaction Benzoic acid Benzoic acid
Properties of aldehydes and ketones
When an aldehyde or Ketone having CH3CO group is treated with sodium hydroxide and
1. Nucleophilic addition halogens, haloform will get produced
Carbon atom of carbonyl group (>C = O) Carries positive charge. Therefore nucleophiles like Structure of Carboxyl group
O
OH, NH2, CN etc can attack the carbon – oxygen double bond to produce addition O
||
products. ||
CH3  C H   CHCl3
NaOH / Cl 2
–C–O–H
When acetaldehyde and methyl ketones having CH3CO group is treated with sodium
Methods of Preparation
hydroxide and iodine yellow precipitate of iodoform will be obtained. This reaction is called
iodoform test. 1. From 1 alcohols and aldehydes
Aldehyes are more reactive towards nucleophilic addition than ketones. This is because an 1 alcohols and aldehydes on oxidation with acidified KMnO4 or K2Cr2O7 give carboxylic
CH3 COCH3   CHI3
NaOH / I 2

aldehyde will be having only one electron releasing alkyl group where as Ketones have two acids
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O  O 
CH3CH2OH  CH3CHO  CH3COOH Properties of carboxylic acids CH3CH2NH2 Ethyl amine Ethanamine
Ethanol Ethanoic acid CH3CH2CH2NH2 n – propylamine Propan – 1 – amine
Physical properties
2. From nitriles and amides Carboxylic acids have higher boiling points than CH3 – CH – CH3 Isopropyl amine Propan – 2 – amine
Nitriles (cyanides) and amides on hydrolysis in presence of an acid or base produce aldehydes, Ketones and even alcohols this is because of 
carboxylic acids. the dimerisation of carboxylic acid molecules through NH2
O hydrogen bonding. (CH3)2NH Dimethyl amine N – Methyl methanamine
|| Lower acids are soluble in water due to their ability to form hydrogen bonds with water CH3NHCH2CH3 Ethyl methyl amine N – Methyl ethanamine
R – CN 

 R – C – NH2 
H O/H 2
 RCOOH
H O/H 2

molecules. Higher acids are not soluble in water because large sized non polar alkyl group (C2H5)2NH Diethyl amine N – Ethyl ethanamine
O prevents the formation of hydrogen bonds with water molecules. (CH3)3N Trimethyl amine N, N – Dimethyl methanamine
|| Chemical properties Aniline Benzenamine
 
CH3 CN   CH3 – C – NH2 
H O/H 2
 CH3COOH
H O/H 2
1. Acidity
Methyl cyanide Ethanamide Ethanoic acid
(Ethane nitrile) (acetic acid) Carboxylic show acidic character. They turn blue litmus into red, react with metals to liberate N – Methyl aniline N – Methyl benzenamine
H2 and react with alkalis to produce salt and water.
(On partial hydrolysis cyanides give amides)
3. From Grignard reagent 2RCOOH + 2Na  2RCOONa + H2
A Grignard reagent on addition with CO2 followed by hydrolysis gives carboxylic acids. RCOOH + NaOH  RCOONa + H2O N, N – Dimethyl aniline N, N – Dimethyl benzenamine.
O 2RCOOH + Na2CO3  2RCOONa + H2O + CO2
|| RCOOH + NaHCO3  RCOONa + H2O + CO2

R – Mg – X + O = C = O ether  R – C – OMgX   RCOOH
H O/H 2 Reaction of a carboxylic with sodium bicarbonate produce brisk effervescence due to the Preparation of amines
O liberation of CO2 gas. This reaction is used as a test for carboxylic acids. 1. From nitro compounds
|| Carboxylic acids exhibit acidic character because of the presence of polar – O – H bond
 Nitro compounds on reduction with H2/Pd or with Sn/HCl give 1amines.
CH3MgBr + O = C = O   CH3 – C – OMgX   CH3COOH
ether H O/H 2
which ionise to supply H+ ions and because the carboxylate ion produced after ionisation is
Methyl magnesium bromide Ethanoic acid C2H5 – NO2   C2H5 – NH2
H / Pd 2

stabilized through resonance.

The above method is suitable for converting an alkyl halide into carboxylic acid having
one carbon atom more than that present in the alkyl halide
O
||
 2. Halogenation (HVZ reaction) 2. From alkyl halides (Ammonolysis)
CH3Br  Mg
CH3MgBr CO 
 CH3 – C – OMgX 2
 CH3COOH
H O/H 2

When a carboxylic acid having  - hydrogen atom is treated with Cl2 or Br2 in presence of red When an alkyl halide is treated with ammonia a mixture of 1, 2 and, 3 amines and
4. From acid halides and acid anhydrides
phosphorous  - halo acid will be obtained. This reaction is called Hell – Volhard zelinsky quaternary ammonium salt will be obtained.
Acid chlorides and acid anhydrides on hydrolysis produce carboxylic acids. reaction. R X R X R X
R – X + NH3  R – NH2   R2NH   R3N   R4NX
RCOCl   RCOOH + HCl
H O 2
R – CH2 – COOH   R – CH – COOH
Cl / P 2 Quaternary ammonium salt
3
(RCO)2O   2RCOOH
H O 2
 When excess of ammonia is used the major product formed will be 1 amine. When excess of
5. From esters Cl alkyl halide is used quaternary ammonium salt will be the major product.
Esters on hydrolysis in acid or alkaline medium give carboxylic acids. In alkaline medium salt CH3 COOH  CH2 – COOH
Cl / P 2

3. From nitriles (Cyanides)

of carboxylic acid is obtained
Ethanoic acid

2 – Chloro ethanoic acid Nitriles on reduction with H2/Pd or with LiAlH4 produce 1 amines.
RCOOR1 + H2O   RCOOH + R1OH
H O 2 Cl
AMINES CH3 CN   CH3CH2NH2
H / Pd2

RCOOR1 + NaOH  RCOONa + R1OH Methyl cyanide Ethyl amine

(Alkaline hydrolysis of esters is called saponification because fats and oils which are esters of Compounds having the functional group – NH2 are called amines. They are classified into 1,
2 and 3 amines. 1 amines are compounds with the general formula R – NH2, 2 amines 4. From amides
fatty acids on alkaline hydrolysis produce sodium or pottassium salts of carboxylic acid called
soap). have the formula R2NH and 3 amines are compounds with the formula R3N. a) Reduction
6. From alkyl benzenes In amines the type of hybridization of nitrogen is SP3. Amides on reduction with LiAlH4 give 1 amines having the same number of carbon
Nomenclature atoms as that in the amide.
Alkyl benzenes on oxidation with alkaline KMnO4 produce aromatic carboxylic acids
In the common system amines are named as alkyl amines.In the IUPAC system they are CH3CONH2   CH3CH2NH2
LiAlH 4

Acetamide Ethanamine
named as alkanamines.
(Ethanamide) (Ethyl amine)
Compound Common Name IUPAC Name
CH3NH2 Methyl amine Methanamine
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b) Hoffmann bromamide reaction Chemical Properties Polysaccharides

When an amide is treated with bromine and alkali (NaOH or KOH) a 1 amine having one Diazonium group is a very good leaving group. It is easily substituted by groups such as Cl–, Carbohydrates which yield a large number of monosaccharide units on hydrolysis are called
carbon less than that in the amide will be obtained. This reaction is called Hoffmann Br–, I–, CN– and OH–. N2 escapes as a gas. polysaccharides eg: starch, cellulose etc.
bromamide reaction. 1. Sandmeyer’s reaction Reducing and non-reducing sugars
O When a freshly prepared diazonium salt solution is treated with All those carbohydrates which reduce Fehling’s solution and Tollen’s reagent are called
|| CuCl and HCl or CuBr and HBr chloro benzene or reducing sugars. (All monosaccharide are reducing sugars.)
CH3 – C – NH2    CH3 – NH2
NaOH / Br 2
bromobenzene will be obtained. Examples for reducing sugars are : glucose, fructose, maltose, lactose etc.
Ethanamide Methanamine
2. Gatterman reaction Carbohydrates which cannot reduce Fehling’s solution and Tollen’s reagent are called non
(Acetamide) (Methyl amine)
When a diazonium salt is treated with Cu/HCl or Cu/HBr reducing sugars. Eg: Sucrose, Starch, cellulose etc.
C6H5 – CONH2    C6H5 – NH2
NaOH / Br 2
chlorobenzene or bromo benzene will be obtained. Classification of Mono Saccharides into aldoses and ketoses
Benzamide Aniline
If a monosaccharide contains an aldehydic group it is called aldose. Eg: glucose
Physical Properties
3. Preparation of iodo benzene (Replacement by iodine) If a monosaccharide contains a keto group it is called ketose. Eg: Fructose
 Lower aliphatic amines are gases
When a diazonium salt solution is treated with potassium iodide Monosaccharides can also be classified into triose, tetrose, pentose etc on the basis of number
 Amines with 3 or more carbon atoms are liquids and higher ones are solids.
solution iodobenzene will be obtained. of carbon atoms. Glucose and Fructose are hexoses.
 Boiling points are lower than those of corresponding alcohols
4. Preparation of fluorobenzene (Replacement by fluorine) Glucose (C6H12O6)
 Lower aliphatic amines are soluble in water. higher amines and aryl amines are not
When benzene diazonium chaloride is treated with Preparation
soluble. Solubility is lower than that of alcohols. Out of butan – 1- ol and butan – 1 –
fluoroboric acid benzene fluoroborate will be Glucose can be prepared by the hydrolysis of cane sugar (C12H22O11) with dil HCl or H2SO4
amine, butan – 1 – amine is less soluble.
obtained which on heating decomposes to yield H
 Among isomeric amines order of solubility is 1 > 2 > 3 C12H22O11 + H2O   C6H12O6 + C6H12O6
fluorobenzene. Cane sugar Glucose Fructose
Chemical Properties 5. Preparation of benzene (Replacement by hydrogen) (Sucrose)
1. Carbyl amine reaction When benzene diazonium chloride is treated with
When a 1 amine is heated with chloroform and alcoholic KOH foul smelling iso cyanide Disaccharides
hypophosphorous acid benzene will be obtained.
(carbyl amine) will be obtained. This reaction is used as a test for 1 amines. A disaccharide on hydrolysis yields two monosacharide molecules. The linkage between two
6. Preparation of phenol (Replacement by – OH group)
R – NH2 CHCl / alco
. KOH
 R – NC
3 monosaccharide units through oxygen atom is called glycosidic linkage. eg: Sucrose, maltose
An aqueous solution of benzene diazonium
and lactose
2. Hinsberg Test chloride on warming gives phenol.
Sucrose on hydrolysis gives a mixture of glucose and fructose.
Hinsberg reagent is benzene sulphonyl chloride. It is used to distinguish 1, 2 and 3 amines. 7. Preparation of Nitrobenzene (Replacement by – NO2 group)
C12H22O1 + H2O → C6H12O6 + C6H12O6
When a 1 amine is treated with benzene sulphonyl chloride N – alkyl benzene sulphonamide When benzene diazonium chloride is treated with Sucrose glucose fructose
soluble in alkali will be obtained. hydro fluoro boric acid diazoniun fluoro borate
C2H5 NH2 + C6H5SO2Cl  C6H5SO2NHC2H5 will be obtained which on heating with sodium The two monosaccharides units are hold together by glycosidic linkage between C1 of glucose
Ethyl amine Benzene N – Ethyl benzene nitrite solution in the presence of copper gives and C2 of fructose. Since the reducing groups of glucose and fructose are involved in
Sulphonyl chloride Sulphonamide nitro benzene . glycosidic formation, sucrose is a non reducing sugar.
Sucrose is dextrorotatory but after hydrolysis it gives dextro rotatory glucose and
2 amine react with Hinsberg reagent to produce N, N – dialkyl benzene Sulphonamide which BIOMOLECULES
laevorotatory fructose. Since the laveo rotation of fructose (92.4) is more than dextro
is insoluble in alkali.
Carbohydrates rotation of glucose (+52.5), the mixture is lavevo rotatory. Thus hydrolysis of sucrose brings
(C2H5)2 NH + C6H5 SO2Cl  C6H5SO2N (C2H5)2
Diethyl amine N, N – diethyl benzene sulphonamide
Carbohydrates are poly hydroxy aldehydes or ketones or the compounds which produce such about a change in sign of rotation, from dextro to laevo. Therefore hydrolysis of sucrose
units on hydrolysis. (Cane sugar) is called inversion and the product obtained is called invert sugar.
3 amine will not react with Hinsberg reagent. Classification of Carbohydrates Maltose is composed of two units of glucose in which C1 of one glucose is linked to C4 of
Diazonium Salts Carbohydrates can be classified into monosaccharides, oligosaccharides and polysaccharides. another glucose unit. The aldehydic group on the second glucose unit is free. Therefore
Compounds of the general formula R N+2X – are called diazonium salts R – aryl group X – Monosaccharides maltose is a reducing sugar.
Cl–, Br–, HSO4–, BF4– etc Lactose (milk sugar) is composed of one unit of galactose and one unit of glucose. The
A carbphydrate that cannot be hydrolysed into more simple carbohydrate molecules are called
Method of preparation of benzene diazonium chloride monosaccharides eg: glucose, fractose, ribose etc. linkage is between C1 of galactose and C4 of glucose. The aldehydic group on the glucose unit
When aniline is treated with an ice cold solution of sodium nitrite and hydrochloric acid is free therefore lactose is a reducing sugar.
Oligosaccharides
benzene diazonium chloride will be obtained. This reaction is called diazotisation. Polysaccharides
Carbohydrates that yield two to ten monosaccharide units on hydrolysis are called
C6H5  NH2 + NaNO2 + 2HCl   C6H5 N2Cl + NaCl + 2H2O
273 K
oligosaccharides. They are further classified into disaccharide, trisaccharide etc. Examples Poly saccharides contain a large number of monosaccharide units joined together by
for disaccharides are sucrose, lactose, maltose etc. glycosidic linkages. Eg: starch, cellulose etc.

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Starch proteins. The coagulation egg white on boiling, curdling of milk are examples for
Starch is a polymer of  - glucose and consists of two components – amylose and denaturation.
amylopectin. Amylose is water soluble and consists of unbranched chain of  - glucose. Enzymes
Amylopectin is insoluble in water. It is a branched chain polymer of  - glucose. Enzymes are biological catalysts. Chemically they are proteins.
Cellulose Vitamins
Cellulose is a straight chain polymer of  – glucose. They are organic compounds required in the diet in small amounts to perform specific
Proteins biological functions for normal maintenance of optimum growth and health of the organism.
Proteins are polymers of  - amino acids Vitamins are classified into fat soluble vitamins and water soluble vitamins. Fat soluble
Amino acids vitamins are A, D, E and K water soluble vitamins are B group vitamins and vitamin C
Amino acids contain amino (–NH2) and carboxyl (–COOH) groups.  - amino acids have the (ascorbic acid).
following general formula R – CH – COOH Diseases caused by the deficiency of vitamins are given below.
 Vitamin A – Xerophthalmia
NH2 Vitamin B1 – Beri Beri
R – can be hydrogen or some other groups. Glycine is the simplest amino acid. Vitamin B2 – Cheilosis
CH2 – COOH. Vitamin C – Scurvy
 Nucleic Acids
NH2 Nucleic acids are polymers of nucleotides. They are of two types, deoxy ribo nucleic acid
Except glycine all other amino acids are optically active. Because of the presence of acidic – (DNA) and ribonucleic acid (RNA). A nucleotide is made of a sugar unit, phosphate group
COOH and basic – NH2 group in the same molecule amino acids can exist – as zwitter ions and a nitrogenous base.
(internal salt) Structural differences between DNA and RNA
R – CH – COO– DNA is double stranded and RNA is single Stranded. The two Strands in DNA are held
together by hydrogen bonds. The sugar unit in DNA is 2 – deoxyribose and that in RNA. It is

ribose. The bases in DNA are adenine, guanine, cytosine and thymine. The bases in RNA are
N+H3
adenine, guanine, cytosine and urasil.
Structure of Proteins
Biological functions of Nucleic acids
Proteins are polymers of amino acids and they are connected to each other by peptide bond (–
DNA carries genetic informations. It is the chemical basis of heredity. DNA also stores the
NH–CO–)
informations for protein synthesis. The main function of RNA is protein synthesis. (Three
Primary structure of Proteins types of RNA are involved in protein synthesis. They are messenger RNA, ribosomal RNA
The sequence of amino acids in the polypeptide chain of a protein is called 1 structure. Any and transfer RNA.)
change in this 1 structure creates a different protein. ***
Secondary structure of proteins
The 2 structure of a protein refers to the shape in which a long polypeptide chain can exist.
Two types of 2 structures are possible,  - helix and  – pleated sheet structure.
Tertiary structure of protein
The 3 structure of proteins represents overall folding of the polypeptide chain. The resultant
protein may be having either fibrous shape or globular shape. Examples for fibrous proteins
are keratin (present in hair, wool, silk) myosin (present in muscles). They are not water
soluble. Eg: albumin is globular protein. It is water soluble.
Quaternary structure of proteins
Some of the proteins are composed of two or more polypeptide chains referred to as sub
units. The spatial arrangement of these subunits with respect to each other is known as
quaternary structure.
Denaturation of proteins
When a protein is subjected to changes in temperature or pH 2 and 3 structures of proteins
may get destroyed. Then the protein loses its biological activity. This is called denaturation of

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