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MOLE CONCEPT
1 mole is represented in the form of atoms, molecules and ions as :
LIMITING REAGENT
In the given reaction if number of quantities (either in gm/mole/molecules) are present with exact
co-efficients, chemical reaction goes to completion without any reactant left unused.
However if exact proportion is not present then the one which gets totally consumed is known as
limiting reagent (Limiting reagent decides the product quantity for given information).
e.g., 2H2 + O2 2H2O
In above e.g. 2 moles of H2 reacts exactly with 1 mole of O2 to give 2 moles of H2O. If given moles of H2 are
4 moles and that of O2 are 0.5, then 0.5 moles O2 will act as limiting reagent as it is in minimum amount
and product formation is given w.r.t. O2 i.e., 1 mole of H2O.
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2 Some Basic Concepts of Chemistry Rapid Revision & Formula Bank
EQUIVALENT WEIGHT
Equivalent weight of substance is defined as number of parts by weight of given substance which combines
or displaces 1 part by weight of hydrogen (11.2 L of H2 at STP), 8 parts by weight of oxygen (5.6 L of O2
at STP), 35.5 parts by weight of chlorine (11.2 L of Cl2 at STP).
Atomic weight
1. Equivalent weight of element =
Valency
Molecular weight
5. Equivalent weight of reducing agent =
Number of e lost by one molecule
Molecular weight
6. Equivalent weight of oxidising agent =
Number of e gained by one molecule
LAW OF EQUIVALENCE
According to law of equivalence, for each and every reactant and product,
Equivalents of each reactant reacted = Equivalents of each product formed.
For example :
Suppose, the reaction is taking place as under
A+B C + D.
Then according to law of equivalence,
Equivalents of A reacted = Equivalents of B reacted
= Equivalents of C produced
= Equivalents of D produced
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Rapid Revision & Formula Bank Some Basic Concepts of Chemistry 3
1
Actually SO3 react with H2O to form H2SO4. Here 9 g H2O or mole H2O react with SO3.
2
1
So, moles of SO3 in sample = mole
2
SO3 + H2O H2SO4
1
So, wt. of SO3 = 80 (molecular weight of SO3) = 40 g
2
% free SO3 = 40%
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GASEOUS STATE
F
P N/m2
A
BOYLE’S LAW
1
P at constant n and T.
V
CHARLES' LAW
V T at constant n and P.
t
Vt V0 1
273
AVOGADRO’S LAW
V n (P and T constant); 1 mole of every gas at STP occupies volume = 22.4 lit.
Ideal Gas Equation
On combining the Boyle’s law, Charles' law and Avogadro’s law we get an equation known as ideal gas equation
which correlates P, V, T, of a gas.
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Rapid Revision & Formula Bank States of Matter (Gases, Liquids and Solids) 5
PV = nRT ideal gas equation where R is a constant known as universal gas constant or molar gas
constant.
Numerical value of R
R = 0.0821 litre atm K–1 mol–1
= 8.314 J K–1 mol–1
= 1.987 2 cal K–1 mol–1
Other form of ideal gas equation.
W
Ö PV = RT
M
dRT
Ö P=
M
; (where M is the molecular weight)
RT
PTotal = (n1 + n2 + .......)
V
r1 V1 / t 1 n1 t1 M2 d2
r2 V2 / t 2 n2 t 2 M1 d1
r1 P1 M2
r2 P2 M1 where, V = volume , t = time, M = molar mass, d = density, n = number of moles, P = pressure
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6 States of Matter (Gases, Liquids and Solids) Rapid Revision & Formula Bank
1
PV mNu2
3
m = Mass of one molecule
N = Number of molecules in the container
3 3
KE of n moles = nRT, for n = 1 KE RT
2 2
3 RT 3
Average KE per molecule = 2 N kT , k = Boltzmann’s constant
0 2
3RT
(i) Root mean square velocity (urms) =
M
8RT
(ii) Average velocity(uav) =
M
2RT
(iii) Most probable velocity (ump) =
M
Velocity
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Rapid Revision & Formula Bank States of Matter (Gases, Liquids and Solids) 7
DEVIATION FROM IDEALITY AND van der Waal’s EQUATION
A plot of PV- P at constant temperature for a number of gases shows deviations from ideal behaviour. Therefore
PV = nRT cannot be applied to these gases. Thus another equation must be sought in order to correlate P,V,
T for these gases; which is van der waal’s equation.
n2a
P V nb nRT
V 2
H2
He N2
CO
Z 2
1.0 Ideal
Causes of Deviation
There are two objectionable postulates in kinetic theory of gases.
(1) The volume of a molecule is negligible as compared to total volume of the gas. Actually, gas molecules do
posses some volume which account for the deviation. Hence total volume of gas is not equal to volume of
the vessel.
(2) There is no intermolecular force of attraction between gaseous molecules.
(There exists force of attraction between gaseous molecules otherwise liquefaction of gases would be
impossible).
By correcting these two postulates, we get an equation which can be applied to the gases which deviate
from ideal behaviour. The deviation of a gas from ideal behaviour can also be expressed in terms of
compressiblity factor (Z).
PV
Z [for 1 mole]
RT
for ideal gas Z = 1
for real gas Z > 1 or Z < 1
LIQUID STATE
A liquid is composed of molecules that are constantly moving about at random, each undergoing billions of
collisions per second. However strong attractive forces of the dipole-dipole, H-bonds, prevent them from moving
as freely and as far apart as in a gas.
(a) Vapour pressure : It is the pressure exerted by vapours on surface of liquid at equilibrium. Vapour
pressure does not depend on surface area and volume but it depend on temperature and nature of liquid.
Vapour pressure increases with rise in temperature.
(b) Viscosity : Liquids flows as if they were divided into layers flowing over one another. Resistance offered
to this flow is due to friction between two liquid layers and is called viscosity. Reciprocal of viscosity is
called fluidity. Viscosity of a liquid decreases with rise of temperature.
(c) Coefficient of viscosity : The force in newtons per square metre required to maintain a difference of velocity
of one metre per second between two parallel layers of the liquid at a distance of one metre from each other.
It is expressed in kg m–1 s–1. Liquids having stronger attractive forces are more viscous.
(d) Surface tension : The force that acts at right angles to an imaginary line of unit length at the surface
of the liquid at rest. It is expressed in J m–2 or N m–1. Surface tension generally decreases with the rise
of temperature. Liquids exhibit capillary action and make spherical drops. This can be explained on the
basis of surface tension.
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8 States of Matter (Gases, Liquids and Solids) Rapid Revision & Formula Bank
IMPORTANT POINTS
(1) Critical temperature (Tc) :
It is the temperature above which a real gas cannot be liquefied whatever applied pressure may be
8a
Tc =
2 7R b
a
PC
27b 2
VC 3b
Vc 3 4 Vm 12 Vm (Since b = 4Vm)
RTc
It is ratio of P V which is equal to 2.66 and remains constant for all the gases.
c c
a
TB
Rb
Boyle's temperature of a gas is always higher than its critical temperature (Tc)
(6) Inversion temperature (Ti)
If a compressed gas is allowed to pass through a fine hole, it may show cooling or heating or no change
in temperature depending upon the temperature of the gas. For each gas, there exists a characteristic
temperature known as inversion temperature (Ti)
If T > Ti heating is produced
If T < Ti cooling is produced
If T = Ti neither heating nor cooling
2a
Ti 2TB
Rb
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Rapid Revision & Formula Bank States of Matter (Gases, Liquids and Solids) 9
SOLID STATE
ELEMENTS OF SYMMETRY
The total no. of planes, axes and centre of symmetries possessed by a crystal is termed as its elements of
symmetry. A simple cubical crystal possesses a total of 23 elements of symmetry.
In a Cube
Planes of symmetry = 3 + 6 = 9
Axis of symmetry = 3 + 4 + 6 = 13
Centre of symmetry = 1
Total number of symmetry elements = 23
1 a
1. Simple cube 8 1 0 0 1 r
8 2
2. Body centred 1 3a
8 1 1 0 2 r
cube (BCC) 8 4
3. Face centred 1 1 2a
8 1 0 6 3 4 r
cube (FCC) 8 2 4
r+
Radius ratio -
r
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10 States of Matter (Gases, Liquids and Solids) Rapid Revision & Formula Bank
1 1
i.e., Number of Cl– ions 8 2 6 4
8
1
Number of Na+ ions 12 1 4
4
Examples : Alkali metal halides (except Cs), Halides of Ag (except AgI).
(b) Caesium chloride (CsCl) type structure
Characteristics
(i) It has bcc arrangement
(ii) This structure has 8 : 8 coordination number
(iii) The unit cell of CsCl consists of one Cs+ ion at body centre and eight Cl– ion at each corner i.e. one
CsCl formula unit per unit cell.
Example : CsBr, Csl, CsCN, TlCl, TlBr, TlI, TICN
(c) Zinc blende (ZnS) type structure
Characteristics
(i) It has ccp arrangement in which S2– ions are present at the corners as well as at the centre of each
face of the cube.
(ii) Zn+2 ion are present at alternate tetrahedral void [50% of tetrahedral void.]
(iii) This structure has 4 : 4 coordination number.
Example : CuCl, CuBr, CuI, AgI, and BeS
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Structure of Atom
Postulate
(a) The path of electron is circular. The force of attraction between nucleus and electron is equal to centrifugal
force of the moving electron.
h
(b) Electron can revolve only in those orbits whose angular momentum is an integral multiple of . i.e.,
2
nh
mvr . (m = mass of electron, v = velocity of electron, r = radius of orbit)
2
(c) Electron remains in stationary orbit where it does not lose energy.
(d) Each stationary orbit is with definite amount of energy (E) and E 1 < E 2 < E 3 .......... Similarly
(E2 – E1) > (E3 – E2) > (E4 – E3).
2 2 Z2me 4 2
En ·K
n2h2
where, n = 1, 2, 3 .......
Z = Nuclear charge
e = Charge of electron
m = Mass of electron
h = Planck’s constant
Z2
i.e., E n E1 for H-like atom
n2
H like atoms means atom which consists of one electron.
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12 Structure of Atom Rapid Revision & Formula Bank
19
21.79 10 Z2
i.e., E J/atom
n2
13.6
Z 2 eV per atom
n2
313.6 Z2
= 2 kcal/mol
n
1312 Z2
= kJ/mol
n2
Potential energy = 2 × E
Kinetic energy = – E
Total energy = E
Note : If an atom consists more than one electron, then we take shielding effect into account.
Radii of Orbits
n2
r 0.529 Å
Z
Velocity of Electron
Z
v = 2.188 × 108 × cm/s
n
V Z2
N 6.6 1015
2 r n3
Rydberg Equation
The wavelength ( ), wave number ( ) for the electromagnetic radiation can be calculated by Rydberg equation.
1 1 1
RH Z2 2
n1 n22
Z = Atomic number
RH = Rydberg constant = 109677 cm–1
n2 = Higher orbit
n1 = Lower orbit
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Rapid Revision & Formula Bank Structure of Atom 13
Total number of spectral lines
n(n 1)
(i) when electron jumps from nth level to ground level.
2
(n 2 n1 ) (n 2 n1 1)
(ii) when electron returns from n2 to n1.
2
Note : Remember in this case n1, n2 are energy level or orbit number. If we have given nth excited
state then formula will be different.
n(n 1)
formula is applicable, if hydrogen sample contains several number of H atoms.
2
h
(b) The wavelength of the wave associated with a particle mass 'm' moving with velocity 'v' as .
mv
Note : The waves associated with material particles or objects in motion are called matter waves
or de-Broglie waves.
Velocity v
(c) Number of revolutions per second by an electron in a shell may be given as =
2 r 2 r
1
E mv 2
2
2 Em m2 v 2
2Em mv P
h h
P 2Em
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14 Structure of Atom Rapid Revision & Formula Bank
QUANTUM NUMBERS
The set of four integers required to define the state of electron in an atom are called quantum numbers. The
quantum numbers are
(1) Principal quantum number (n)
(2) Azimuthal quantum number (l)
(3) Magnetic quantum number (m)
(4) Spin quantum number (s)
(1) Principal quantum number, (n), relates to the amplitude (i.e., size) of an electron wave and also the total
energy of the electron. It has integral values of 1, 2, 3, 4 ... etc., also denoted as K, L, M, N .... etc.
(2) Azimuthal quantum number, (l), tells us about the subenergy shell of electron. For each main energy
shell there can be ‘n’ number of subenergy shells. These subenergy shells are designated by different
values of l. For each value of n, l can have values from 0, 1, 2, 3 ... n – 1.
(3) Magnetic quantum number, (m), explains the behaviour of an electron in the external magnetic field or in
other words it tells us about orbitals of the electrons. The values of m gives the number of orbitals associated
with a particular sub shell in shell. For each value of l, m can have values from –l to +l including zero.
e.g., when l = 1, m = –1, 0, +1; l = 2, m = –2, –1, 0, +1, +2
(4) Spin quantum number, (s), gives an idea about the electron spinning on its axis. Each spinning electron
1 1
can have two values of or – .
2 2
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TYPES OF BONDS
1. Ionic Bond
2. Covalent Bond
3. Co-ordinate Bond
4. Hydrogen Bond
Ionic Bond
An ionic bond is formed by complete transfer of one or more electrons from the valency shell of one atom to the
valency shell of another atom. In this way both the atoms acquire the stable electronic configurations of the noble
gases. The atom losing the electrons becomes a positive ion and the atom which gains electron becomes
negative ion.
FAJAN’S RULE
When oppositely charged ions approach each other, there is not only the attraction between the positively
charged cation and the negatively charged anion but also simultaneous repulsion between their nuclei. Thus
there is distortion, or deformation or polarization of anions. The electronic charge of anion does not remain
spherical but gets distorted.
+ – + –
No polarization Polarization of anion
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16 Chemical Bonding and Molecular Structure Rapid Revision & Formula Bank
This polarization of ion results in a electric charge concentration between the two nuclei resulting in a
covalent bond with a large degree of charge separation.
FORMAL CHARGE
DIPOLE MOMENT ( )
Dipole moment is product of the magnitude of charge developed on any one of the two atoms and the distance
between the atoms. ( = q × d), where q = charge developed and d = distance between two atoms. The unit
of dipole moment is debye (D). 1 debye = 1 × 10–18 esu cm = 3.34 × 10–30 coulomb metre (Cm)
(b) Molecule with more than one bond will have more than one bond dipole moments. The resultant of bond
dipole moments of the molecule containing two bonds is given as
2 2
res. 1 2 2 1 2 cos
(e) Dipole moment helps to determine percentage ionic character and can be calculated as
% ionic character = 16|XA – XB| + 3.5 [XA – XB]2, where XA and XB are the electronegativity of A and B
element.
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Rapid Revision & Formula Bank Chemical Bonding and Molecular Structure 17
(c) The arrangement of bond pair electron and lone pair electron is done to minimize the repulsion i.e.,
Lone pair – lone pair > lone pair – bond pair > bond pair – bond pair.
(d) These repulsion - effects result in deviations from idealized shape and alterations in bond angles in
molecules.
+
Bonding
+
S S
1s 1s 1s
– Antibonding
+ –
* 1s
ψ1s
1s
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18 Chemical Bonding and Molecular Structure Rapid Revision & Formula Bank
Bonding
+
2pz 2pz 2 pz
Antibonding
– + – +
* 2 pz
2 pz 2 pz
+
Bonding
+
– –
2py
2py 2py
+ –
Antibonding
– +
*2py
2py 2py
(a) Linear combination of atomic orbitals (LCAO) method is used for the formation of molecular orbitals.
(b) For two atomic orbitals A and B, whose wave function is given as A and B. Then molecular
orbitals (MO) are given as MO = A ± B.
(c) The molecular orbital formed by the addition of atomic orbitals is called bonding molecular orbital. And
molecular orbital * formed by the subtraction of atomic orbitals is called antibonding molecular orbital.
(e) Molecular orbital configuration for diatomic molecules with more than 14 electrons.
(f) Molecular orbitals are arranged with increasing order of energy level.
(g) 2px and 2py similarly *2px and *2py have same energy and follow Hund’s rule.
1
(h) Bond order = [Bonding electrons – Antibonding electrons].
2
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Rapid Revision & Formula Bank Chemical Bonding and Molecular Structure 19
1
(i) Bond order Bond strength Bond length .
e.g., N2 = 14 electrons
Molecular orbital configuration
1
B.O = [10 – 4] = 3
2
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Chapter 5
Chemical Thermodynamics
(a) Extensive property of a system are those whose magnitude depends on the amount of matter present
in the system. These are additive in nature. For example, volume, internal energy, enthalpy, entropy, mass
etc. Sum, subtraction and multiplication of two extensive property is extensive.
(b) The property whose magnitude does not depend upon quantity of matter present in a system is known
as intensive property of the system. It is not an additive property. Examples are : temperature, pressure,
density etc. Sum, subtraction, multiplication division of two intensive properties is intensive.
It is the energy associated with a system by virtue of its molecular constitution and motion of its molecule.
Such motion may be translational, rotational, vibrational etc.
Processes :
When a change is observed in the properties of system, a process is said to be taking place. This may be
a chemical reaction or a physical process, like crystallization. Processes are of two types.
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Rapid Revision & Formula Bank Chemical Thermodynamics 21
q and W for some simple processes
Reversible Process q W
Vf Vf
Isothermal expansion nRTln nRTln
Vi Vi
Vi = Initial volume
Vf = Final volume
If a reaction is the sum of two or more constituent reactions, then H for the overall process must be sum of
the H of the constituent reactions.
H
A D
H1 H3
B H2 C
For A D, H = H1 + H2 + H3.
qrev
S
T
where qrev = Heat absorbed when the process is carried out reversibly and isothermally.
Vf
Example : For reversible isothermal expansion of an ideal gas S nRln .
Vi
G = H – TS
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22 Chemical Thermodynamics Rapid Revision & Formula Bank
Use :
(i) At a given pressure and temperature if for an anticipated change dG for system is negative, process is
spontaneous and if positive, process is spontaneous in reverse direction. Also if dG = 0, system is in
equilibrium with respect to the given reaction or process.
(ii) –dG = maximum work done by system on non-expansion surrounding e.g., cell doing electrical work on
circuit.
IMPORTANT POINTS
At equilibrium, G = 0 and Q = K
Gº = –RT logeK
= –2.303 RT log10K
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Chapter 6
Solutions
SOLUTIONS
A homogeneous mixture of two or more non-reacting substances is known as solution. Homogeneity or
heterogeneity depends upon particle size and states of matter present in the solution. Every solution is made
up of a solvent (present in larger quantity) and one or more solute (present in smaller quantity).
UNITS OF CONCENTRATION
(i) Molarity (M)
It is the number of moles of solute present per litre of solution.
n w W 1000
M
V Mw Vin litre Mw Vin cc
W
M × Vin cc = M 1000
w
M × V (ml) = millimoles
Molarity changes with temperature of the solution. Increase in temperature generally decreases the molarity.
It is the most convenient method to express concentration of the solution. On dilution, molarity decreases.
(ii) Molality (m) :
Number of moles (n) of solute present per kg of solvent
n w w
m 1000
W in kg M Win kg M Win g solvent
XA XB 1
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24 Solutions Rapid Revision & Formula Bank
(iv) In terms of %
Wt.of solute
% by weight = 100
Wt.of solution
Wt.of solute
% weight by volume 100 (In case of solid dissolved in a liquid)
Vol.of solution
Volume of solute
% by volume 100 (In case of liquid dissolved in another liquid)
Volume of solution
HENRY’S LAW
Solubility of a gas at a given temperature in a solvent is directly proportional to its partial pressure. If P is the
partial pressure of a gas and Xg is its mole fraction in solution. Then P = KHXg where KH is Henry's law constant
for that gas
i.e., relative lowering of vapour pressure is equal to the mole fraction of solute.
(b) Raoult’s Law of miscible liquid-liquid solution
For ideal solution the partial vapour pressure is directly proportional to their mole fraction at constant
temperature. For two components A and B in liquid solution.
PA XA
PB
PA PA X A PA + P°A
P°B P=
PB XB V.P
X
PB PB XB
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Rapid Revision & Formula Bank Solutions 25
Non-Ideal Solution
Ideal Solution
Positive Deviation Negative Deviation
3. Hmix = 0 Gmix = –ve 3. Hmix = +ve Gmix = –ve 3. Hmix = –ve Gmix = –ve
Vmix = 0 Smix = +ve Vmix = +ve Smix = +ve Vmix = –ve Smix = +ve
=1 A =0 =0
=1 =0
A
A =1 A
A A
B = 0 B =1 =1
B =0 B
B = 0 B = 1
COLLIGATIVE PROPERTIES
A colligative property of a solution is one that depends on the number of particles of solute in solution.
p ps
(a) Relative lowering of vapour pressure, solute .
p
poA pA n2 n2 w2 M1
= = for dilute solutions.
poA B n1 n 2 n1 M2 w1
po p A w M
poA m W
w = Wt. of solute
m = Mol. wt. of solute
W = Wt. of solvent
M = Mol. wt. of solvent
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26 Solutions Rapid Revision & Formula Bank
(b) Osmotic pressure : The excess pressure which must be applied on a solution to prevent the passage
of solvent into it through a semipermeable membrane.
Determination is done using Barkley-Hartley method:
Semipermeable membrane egg membrane;
Chemical Semipermeable membrane cupric ferrocyanide.
= CRT = n/V. RT; V = nRT : Van’t Hoff equation for dilution solutions
w2 w 2 .RT
n M
M2 ; 2 V
Molal elevation constant or ebullioscopic constant, Kb. It is the increase in boiling point when
the molality of the solution is unity.
Tb = Kbm, when, m = 1, Tb = Kb
WB 1000
MB = Kb
Tb WA
MRTb2
Kb
1000 H vap
Molal depression constant. or cryoscopic constant (Kf). It is the decrease in freezing point when the
molality of solution is unity
Tf = Kf.m
when, m = 1, Tf = Kf
WB
MB = 1000 Kf
Tf WA
MRTf2
Kf
1000 H fusion
Kb and Kf are intensive properties of solvent and do not depend upon the quantity and nature of solute.
Mcal
Mobs
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Rapid Revision & Formula Bank Solutions 27
Since,
1
Colligative property
Molecular mass of solute
∆Tb iK b m
∆Tf iK f m
i CRT
Relation between degree of association or dissociation ( ) & Van’t Hoff’s factor (i)
1 n(i 1)
For association i = 1 + n 1 or 1 n
where n = Number of particles that associate.
i 1
For dissociation i = 1 + (n – 1) or =
n 1
where n = Number of particles obtained on dissociation.
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Chapter 7
Equilibrium
where, ng = np – nr
Unit of Kp and Kc
ng
Unit of Kp = (atm )
ng
Unit of Kc = (mol L 1 )
If ng 0, no unit of Kp and Kc
For a reaction A nB
or P aA bB cC ...
where a + b + c .... = n
D d
(n 1) d
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Rapid Revision & Formula Bank Equilibrium 29
For (i) & (ii)
n=2
D
1
d
D = Vapour density of the gas before dissociation = Molecular weight/2
d = Vapour density of equilibrium mixture
n = Total number of moles obtained after dissociation from 1 mole of dissociating molecule.
Relation between Equilibrium Constant (K) and Standard free energy Change ( G°)
G 2.303RT log K c
G 2.303 RT log K p
LE-CHATELIER’S PRINCIPLE
It states that, if a system in equilibrium is disturbed by any external agency such as pressure, temperature,
concentration etc. then equilibrium will get shifted to counter balance the effect of that disturbance.
For exothermic reaction, ( H ve ) increase in temperature favours backward reaction, while decrease in
temperature favours forward reaction.
(3) Pressure
Effect of pressure is mainly applicable to gaseous reactions, since liquids & solids are incompressible in
nature.
If ng 0 pressure has no effect on equilibrium constant.
ng 0 then on increasing pressure, equilibrium will get shifted in the backward direction.
If ng 0
ng 0 no effect on equilibrium on addition of inert gas
ng 0
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30 Equilibrium Rapid Revision & Formula Bank
If ng 0 no effect on equilibrium
Equilibrium will get shifted in that direction where no. of moles are more.
IONIC EQUILIBRIUM
C C 2
Ka C [If << 1]
C(1 )
Ka Ka
or Ka V and H C C. K aC
C C
Kb Kb
or Kbx V and [OH ] C C. K b .C
C C
BUFFER SOLUTIONS
HCOOH HCOONa
[Salt]
pH pK a log
[Acid]
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Rapid Revision & Formula Bank Equilibrium 31
[Salt ]
pOH pK b log
[Base]
[Salt]
pH= 14 – pOH = 14 – pK b log
[Base]
[Salt]
pH = pKw – pK b log
[Base]
SALT HYDROLYSIS
Consider the salt BA, which on hydrolysis will give acid and base inside the aqueous solution.
BA + H2O BOH + HA
(a) Salt made up of strong acid, strong base will not hydrolyse it will simply ionise. And pH of aqueous
solution will be neutral. The pH of aqueous solution is independent with dilution i.e., pH = 7. e.g., NaCl,
Na2SO4.
(b) Salt made up strong acid and weak base will hydrolyse, e.g., NH4Cl.
Kw 1
Kh pH = [pKw – pKb – logC]
Kb 2
(c) Salt made up of weak acid and strong base, e.g., CH3COONa.
Kw 1
Kh pH = [pKw + pKa + logC]
Ka 2
(d) Salt made up of weak acid and weak base. The pH and h of these salt solutions depend on Ka and Kb
but independent with concentration, e.g., CH3COONH4.
Kw 1
Kh pH = [pKw – pKb + pKa]
K a .K b 2
Kh
Note : Kh = Ch2, h , where h = degree of hydrolysis.
C
SOLUBILITY PRODUCT
When a sparingly soluble salt is dissolved in water, it forms saturated solution but concentration of salt is very
low. Therefore in saturated solution of such electrolytes, solid electrolyte is in equilibrium with the ions as
represented below:
AgCl Ag+ + Cl–
Applying Law of chemical equilibrium
[ Ag ] [Cl ]
K
[ AgCl]
K sp [ Ag ] [Cl ]
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where Ksp is a constant known as solubility product. It remains constant at constant temperature for a given
salt and defined as the product of ionic concentration of a sparingly soluble electrolyte in a saturated solution.
if Ksp = I.P. (Ionic product) then solution is said to be saturated
if Ksp > I.P. then solution is said to be unsaturated
if Ksp < I.P. then solution is said to be supersaturated (Condition for precipitation)
AgNO3 Ag NO3
x x
AgCl(s)
Ag (aq) Cl (aq)
(S x) (S)
[Ag+]Total = (x + S)
Ksp = (x + S) S
In general due to common ion effect solubility of salt decreases.
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Chapter 8
Redox Reactions
and Electrochemistry
REDOX REACTIONS
CONCEPT OF OXIDATION & REDUCTION
Oxidation Reduction
OXIDATION NUMBER
Oxidation number change is defined as the change (real or imaginary) which an atom appears to have undergone
when it is present in redox reaction. There are certain rules laid down in order to determine the oxidation number.
(a) Oxidation number of an atom in free elements is zero.
(b) Oxidation number of oxygen is –2, while in peroxides it is –1, in OF2 it is +2.
(c) Oxidation number of hydrogen is +1, while in metal hydrides it is –1.
(d) Oxidation number of an ion is equal to the electrical charge present on it.
(e) Oxidation number of group IA elements is +1 and that of group IIA elements is +2.
(f) For complex ions, the algebraic sum of oxidation numbers of all the atoms is equal to the net charge
on the ion.
(g) In case of neutral molecules the algebraic sum of the oxidation number of all the atoms present in the
molecules is zero.
(h) Oxidation number of an atom never be greater than its valence electron. e.g., valence electron for Cr is 6.
Increase in oxidation number of an element in a reaction is known as oxidation while decrease in oxidation
number of an element in a reaction is known as reduction.
Besides +ve and -ve values, fractional values of oxidation number (as average) are also possible.
Balancing of H2O can also be done as per the medium given
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34 Redox Reactions and Electrochemistry Rapid Revision & Formula Bank
(1) Acidic Medium : Add H2O on that side of reaction where oxygen are deficient and double number of H+
on opposite side of reaction.
(2) Basic Medium : Add H2O on that side of reaction where oxygen are excess and double number of OH–
on opposite side of reaction.
ELECTROCHEMISTRY
STANDARD ELECTRODE POTENTIAL
Standard Electrode Potential : The potential difference developed between metal electrode and the solution
of its ions of unit molarity (1 M) at 298 K is called standard electrode potential.
ELECTROCHEMICAL SERIES
Table in which the standard reduction potentials of various electrodes have been arranged in the increasing order
is called electrochemical series or activity series or electromotive series.
Electrode Electrode reaction E°(volts)
Li+/Li Li+ + e– = Li – 3.045 (Lowest)
Zn+2/Zn Zn+2 + 2e– = Zn – 0.763
H+/H2, Pt 2H+ + 2e– = H2 0.0 (Standard)
Cu+2/Cu Cu+2 + 2e– = Cu + 0.34
F2/F–, Pt F2 + 2e– = 2F– + 2.887 (Highest)
Ecell
º
E(anode)
º
E(cathode)
º
(If standard oxidation potential are given)
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Rapid Revision & Formula Bank Redox Reactions and Electrochemistry 35
(c) Predicting feasibility of a redox reaction : In general, a redox reaction is feasible only if the species
which has higher reduction potential is reduced i.e., accepts the electrons and the species which has lower
reduction potential is oxidised i.e. loses the electrons. Otherwise, a redox reaction is not feasible. In other
words, the species to release electrons must have lesser reduction potential as compared to the species
which has to accept electrons.
(d) To predict whether a metal can liberate hydrogen from acid or not, only the metals which have negative
reduction potentials, can liberate hydrogen from the acids.
Cathode Anode
(i) Sign Positive Negative
(ii) Half reaction Reduction Oxidation
(iii) Direction of electron Into the cell Out of the cell
movement
2.303RT +n
Intercept = E°ox and Slope log [M ]
nF
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36 Redox Reactions and Electrochemistry Rapid Revision & Formula Bank
2. Reduction Potential : When electrode is positively charged w.r.t. solution then it acts as cathode, and
reduction takes place.
M+n + ne– M
2.303RT 1
Ered E red . log
nF [M n ] Ered
2.303RT
Ered E red . log [M n ]
nF
Intercept = E°red
+n
log [M ]
2.303RT
Slope = .
nF
H2(g)
(at 1 atm)
+ Pt black
H3O (aq)
electrode
(1 M)
Hydrogen electrode
Pt, H2(gas)|H (aq). 1M
1 bar
0.059 0.059
E logH E pH
1 1
2. Metal-Metal ion Half Cell :
Ag | Ag+(aq)
Ag(s) Ag+(aq) + e–
E = E° – 0.0591 log [Ag+]
3. Metal-Metal-Insoluble Salt anion Half Cell :
Ag | AgCl | Cl–(aq)
Ag + Cl–(aq) AgCl(s) + e–
1
E = E° – 0.0591 log
[Cl ]
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Rapid Revision & Formula Bank Redox Reactions and Electrochemistry 37
4. Calomel Electrode :
Hg, Hg2Cl2 | Cl–(aq)
2Hg(l) + 2Cl–(aq) Hg2Cl2(s) + 2e–
0.0591 1
E E . log
2 [Cl – ] 2
0.0591 1
E E . log
2 [OH – ] 2
0.0591 [Fe 3 ]
E E . log .
1 [Fe 2 ]
OH O
+ –
+2H + 2e
OH O
Hydroquinone Quinone
0.0591
E E . log [H ] 2
2
0.0591
E E . log [H ].
1
ELECTROLYSIS
(a) The decomposition of the electrolyte due to the passage of electricity is known as electrolysis.
(b) During electrolysis, electrical energy changes into chemical energy.
(c) To have electrolysis we must use direct current.
(d) Electrolysis is a redox phenomenon.
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38 Redox Reactions and Electrochemistry Rapid Revision & Formula Bank
t = Time in second
E(equivalent mass)
Z
96500
(b) Second law : If the same quantity of current is passed through different electrolytic solutions then
the weights of different substances deposited at the respective electrodes is directly proportional to
their chemical equivalents.
ELECTROLYTIC CONDUCTION
Molten true electrolyte and the aqueous solution of electrolytes contain free ions and conduct electricity due
to the movement of ions.
According to Ohm's law,
l l
R or R
a a
a
R
l
1 1 l
R a
then R
1
Conductance (G) =
R
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Rapid Revision & Formula Bank Redox Reactions and Electrochemistry 39
1 1 l Cell constant l
Specific conductance (K) = ( is called cell constant)
R a Resistance a
MOLAR CONDUCTIVITY ( m )
The conducting power of all the ions furnished by one mole of an electrolyte in any solution is termed as its
molar conductivity
–1
Conductivity (K) [ cm–1 ]
m . Unit of = ohm–1 cm2 mol–1
Concentration of solution in moles per unit volume (cm3 ) m
Molar conductivity of weak electrolyte increases with increase in dilution or decrease in concentration due
to increase in ionisation but specific conductivity decreases with increase in dilution because number of ions
per cm3 of solution decreases.
Strong electrolyte
Weak electrolyte
KOHLRAUSCH’S LAW
It states that at infinite dilution the molar conductivity of an electrolyte [known as limiting molar conductivity]
can be expressed as the sum of the contribution from its individual ions.
o o o
m V V (where V+ and V– are the number of cations and anions per formula unit of electrolyte
o o
respectively and and are limiting molar conductivities of the cation and anion respectively).
Application
Some typical applications of Kohlrausch's law are
o
(i) Determination of m for weak electrolyte
1000.K salt
Concentration of sparingly soluble salt (Cm ) o o
(V V )
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40 Redox Reactions and Electrochemistry Rapid Revision & Formula Bank
IMPORTANT POINTS
F = Faraday
(3) Concentration cells are made up of same electrode but dipped in different concentration of its own ion.
(5) Primary Cells : The reaction occurs in one direction only and the cell cannot be recharged.
e.g., Mercury cell.
(6) Secondary Cells : The cells that can be recharged by passing current through it. e.g., Lead storage cell.
Fuel Cell : Energy is obtained by combustion of fuels.
(7) Rusting of iron is the example of corrosion which is a electrochemical process.
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Chapter 9
Chemical Kinetics
K t 10
Temp. coefficient between 2 or 3.
Kt
The rate constant (K) and temperature are related by Arrhenius equation given by
Ea /RT
K e
–Ea
logK slope =
2.303R
1/T
Ea
Ea
Arrhenius equation, K = Ae RT
i.e., ln k ln A .
RT
Ea
log10 K log10 A
2.303 RT
1
By plotting graph log K vs activation energy can be determined.
T
(vi) Presence of catalyst : The positive catalyst lowers down the activation energy. The greater the decrease
in activation energy higher will be the reaction rate.
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42 Chemical Kinetics Rapid Revision & Formula Bank
Exothermic Endothermic
Energy Energy
H H
HR
HR HP
HP
ORDER OF REACTION
A. Zero order reaction : A reaction is said to be of zero order if the rate of reaction is independent of
concentration of the reactant.
Rate Expression :
Let A Product
[K is a constant called Rate Constant]
x
K
t
Characteristics :
(a) Unit of K = mol L–1 time–1
(b) Half life period : Time required for the completion of half of the reaction.
Half life for zero order reaction is directly proportional to initial concentration of the reactant
t 1/ 2 a
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Rapid Revision & Formula Bank Chemical Kinetics 43
Rate Expression
Let A Product
initially a 0
after time t (a – x) x
2.303 a
K log
t (a x )
Characteristics
(a) Unit of K = time–1
(b) Half-life period : The half life period is independent of initial concentration of the reactant.
0.693
t1/ 2
K
log C
t
K
The slope of this line gives the value of from which K can be calculated.
2.303
General expression of unit of rate constant K = mole1–n litren–1 time–1, where n is the order of reaction
Reaction Order Rate law eqn. Rate constant Half life period
1 [A 0 ]
A product 0 Rate = k k [A 0 ] [A] t1/ 2
t 2k
2.303 [A ] 0.693
A product 1 Rate = k[A] k log 0 t1/ 2
t [A] k
1 1 1 1
2A product 2 Rate = k[A]2 k t1/ 2
t [A] [A 0 ] [A 0 ] k
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Chapter 10
Surface Chemistry
ADSORPTION
The phenomenon of attracting and retaining the molecules of a substance on the surface of a liquid or a solid
resulting into higher concentration of the molecules on the surface is called adsorption.
ADSORPTION ISOTHERM
A relation or graph between x/m (x are number of moles of adsorbate and m is the mass of adsorbent) and
the pressure (P) of the gas at a constant temperature is called adsorption isotherm.
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Rapid Revision & Formula Bank Surface Chemistry 45
A. Freundlich Adsorption Isotherm
Freundlich gave an equation x/m KP1/n (n > 1) to explain the effect of pressure on amount of gas adsorbed
where K and n are parameters of the equations depending upon the nature of the gas and solid.
x
increases with increase in pressure. Since n > 1, so x/m does not increase, as rapidly as 'P'
m
x 1
log = logK + log P (Taking log on both sides)
m n
1
n
pe=
Slo
log x/m
Intercept = log K
log P
x aP
where a and b are two Langmuir parameters.
m 1 bP
x a
(At very high pressure 1 + bP ~ bP)
m b
x
and = aP (At very low pressure 1 + bP ~ 1)
m
x
So at high pressure of the gas remains constant and nature of graph is linear at very high pressure
m
x/m
Pressure
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m 1 bP b 1
x aP a aP
m 1 1 b
A plot of against gives a straight line with slope and intercept equal to and respectively
x P a a
1
Slope = a
m
x
b
Intercept = a
1
P
COLLOIDS
Colloidal state of matter is a state in which the size of particles is such (10Å – 10000Å) that they can pass
through filter paper but not through animal or vegetable membrane.
CLASSIFICATION OF COLLOIDS
(i) Based on physical state of dispersed phase and dispersion medium–The physical state of dispersed
phase and dispersion medium may be solids, liquids or gases, eight types of colloidal system are possible.
Note : A gas mixed with another gas form a homogeneous mixture and not a colloidal system.
(ii) Based on nature of interaction between dispersed phase and dispersion medium–
Divided into two types namely Lyophilic and Lyophobic Colloids
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Rapid Revision & Formula Bank Surface Chemistry 47
3. Stability Quite stable and not easily precipitated Precipitated by adding small amount
or coagulated of suitable electrolyte
KEY POINTS
1. Colloid is not a substance, it is a state of a substance, which depends upon particle size.
2. Emulsifier : Long-chain hydrocarbons terminating in polar end groups are added to stabilise emulsion.
3. In true solutions, particle size is less than 1 nm and in suspensions, the particle size is more than
1000 nm.
4. The coagulating power of an electrolyte is inversely related to its coagulating value.
5. A phenomenon in which the molecules of dispersion medium are allowed to move under influence of
electric current, whereas colloidal particles are not allowed to move, is called electro-osmosis.
6. The presence of electrical charge (either positive or negative) on colloidal particle is responsible for stability
of colloidal solutions.
7. Gold number of a protective colloid is minimum weight of it in milligrams which must be added to
10 ml of a standard red gold sol so that no coagulation of gold sol (i.e., change of colour from red to
blue) take place when 1 ml of 10% NaCl solution is rapidly added to it. Obviously, smaller the gold number
of a protective colloid, greater is the protective action e.g., gelatin has very small value of gold number.
8. Gold number is assigend to lyophilic colloids only.
9. Multimolecular colloids consist of aggregated atoms or molecule e.g., gold, sulphur sol.
10. Macromolecular colloids have dispersed phase particles as macromolecule or polymers e.g. protein sol.
11. Substances which possess surface activity i.e., property to lower surface tensions of liquids or the
tendency to increase surface area, are called surfactants.
12. The substances which at low concentration in a medium behave as normal strong electrolyte but at higher
concentration exhibit colloidal properties due to formation of aggregated particles are called associated
colloids or micelles. Their formation take place above a particular temperature called kraft temperature (Tk)
and above a particular concentration (CMC – Critical Micelle Concentration), e.g., soaps and detergents.
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48 Surface Chemistry Rapid Revision & Formula Bank
ADDITIONAL POINTS
1. SnO2 forms a positively charged colloidal sol in acidic medium and negatively charged sol in basic
medium.
2. Delta is generally formed as result of coagulation when river meets the ocean.
3. A solid metal in a finely divided state is a better catalyst.
4. H2O is absorbed by anhydrous CaCl2 whereas, it is adsorbed on silica gel.
5. Gases are adsorbed on solid surface (Ni, Co, Pt, Pd etc.) but absorbed in solvent phase.
6. During adsorption, H = –ve, S = –ve hence adsorption is spontaneous at low temperature, when
G = – ve.
At adsorption equilibrium G = 0 and rate of adsorption becomes equal to rate of desorption.
7. Easily liquefiable gases (e.g., HCl, NH3, CO2) are adsorbed to greater extent than others (H2, N2, O2 etc.)
8. The adsorption of gases on finely divided metal surface is also called occlusion.
9. As temperature increases, rate of chemisorption first increases and then decreases.
Temperature Temperature
10. Freundlich adsorption isotherm is only a special case of Langmuir adsorption isotherm for intermediate
pressures (Freundlich isotherm fails at high pressure of the gas).
11. Catalytic promoters increase the activity of catalyst e.g. Mo acts as promoter for Fe. (catalyst) in Haber
process of formation of NH3.
12. The potential difference set up across the surface of separation of two oppositely charged layers just in
contact with each other on the surface of colloid is known as electrokinetic or zeta potential.
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Chapter 11
Some Basic Principles of Organic Chemistry
and Purification and Characterisation of
Organic Compounds
HOMOLOGOUS SERIES
It is a series of similarly constituted organic compounds in which members possess the same functional
group, have a similar or almost similar characteristics, can be represented by the same general formula, and
the two consecutive members differ by – CH2 – group in their molecular formula.
e.g., General formula for saturated alcohol is CnH2n+1 – OH
( CH2 ) ( CH2 )
CH3 OH CH3 CH 2 OH CH3 CH2 CH2 OH
Methanol Ethanol Propanol
ISOMERISM
Compounds having same molecular formula but different in their physical and chemical properties are called
isomers. This phenomenon is called isomerism.
They are classified into two types
1. Structural isomerism or constitutional isomerism
2. Stereo isomerism
1. Structural isomerism : When same molecular formula represents two or more compounds which differ in
the arrangement of atoms within the molecule, then such compounds are called structural isomers and the
phenomenon is called structural isomerism. It is of the following types :
(i) Chain isomerism : When the same molecular formula represents two or more compounds which differ
in the nature of carbon chain (straight or branched), the isomers are called chain isomers and the
phenomenon is known as chain isomerism.
(ii) Position isomerism : Compounds having same structural formulae but differ only in the position of the
substituent atoms or groups on the carbon chain are called position isomers.
Example : C3 H7 OH has two position isomers
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50 Some Basic Principles of Organic Chemistry and Purification and Characterisation of Organic Compounds Rapid Revision & Formula Bank
(iii) Functional isomerism : When any two compounds have same molecular formula but possess different
functional groups, they are called functional isomers and the phenomenon is called functional isomerism.
Examples of functional isomerism are
(a) Alcohol and ether (CH3–CH2–CH2–CH2–OH and CH3–CH2–O–CH2–CH3)
O O
|| ||
(b) Carboxylic acid and ester, etc. CH3–CH2–C–OH and CH3–C–OCH3
(iv) Metamerism : It arises due to different alkyl chains on either side of the functional group in the molecule.
For example ethers, esters, amines, ketones etc. can exhibit metamerism.
Example :
(a) Metamers of C2H5 – O – C2 H5 are
CH3
CH3CH2CH2–O CH3 CH3–O–CH
Methyl propyl ether CH3
Methyl isopropyl ether
O
||
(b) Metamers of CH 3CH 2–C–O–CH 3 are
O O
|| ||
CH3–C–O–CH2–CH3 H–C–O–CH2–CH2–CH3
Ethyl ethanoate Propyl methanoate
O
||
It is to be noted that CH 3CH 2CH 2–C–O–H is not the metamer of above compounds. Because this
compound is an acid while the above compounds are isomeric esters.
(v) Tautomerism : The phenomenon due to which two or more structurally distinct compounds are in dynamic
equilibrium due to shift in the position of an atom or group in a molecule is known as tautomerism and the
structural isomers are known as tautomers. Tautomerism may be catalysed by an acid, a base or traces
of transition metal ions etc.
Structural Requirement for Tautomerism
O
|| O
When unsaturated functional group (e.g., –C– , N , –N = O) have -hydrogen, the compound may
O
exhibit tautomerism.
A– B=C A= B– C
H H
Tautomers
In simple keto-enol tautomerism generally keto form is more stable, the stability of enol form may increase
due to extended conjugation, aromaticity or intramolecular hydrogen bonding.
H H
e.g., CH2 – C = O CH2 = C – O
H H
More stable > 99% Less stable < 1%
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Rapid Revision & Formula Bank Some Basic Principles of Organic Chemistry and Purification and Characterisation of Organic Compounds 51
2. Stereo isomerism : The compounds that have the same constitution and sequence of covalent bonds but
differ in relative positions of their atoms or groups in space are called stereoisomers and this type of
isomerism is known as stereoisomerism. This isomerism can be further classified as geometrical
isomerism and optical isomerism.
COOH COOH
Ph Ph Ph H C C
HO H and H OH
C=C and C=C
H H H Ph
CH3 CH3
Stereoisomers
Stereoisomers
Geometrical isomerism : When stereoisomerism arises due to restricted rotation (because of the
presence of double bond or ring), then it is known as geometrical isomerism.
H3C CH3 H3C H
C=C and C=C
H H H CH3
cis trans
These are geometrical isomers because they have different spatial arrangement due to the presence of
restricted rotation (due to double bond).
Note : (i) Geometrical isomers may be named as cis-trans isomers, E-Z isomers or syn-anti
isomers.
(ii) Geometrical isomers are also known as diastereomers (stereoisomers which are not
the mirror images of each other). Therefore geometrical isomers have different physical
properties and similar chemical properties.
(iii) Geometrical isomers do not rotate plane polarised light (unless they also happen to be
chiral).
Enantiomers : Nonsuperimposable mirror images are known as enantiomers. They have similar physical
and chemical properties in symmetric environment. But they may behave differently in asymmetric
environment. They also rotate plane polarised light in opposite directions but the magnitude of rotation
is identical. Specific rotation of S-alanine is +8.5 while that of R-alanine is –8.5, while melting point of
both the enantiomers are 297°C.
Dextrorotatory substances : Those substances which rotate the plane polarised light in clock-wise
direction are known as dextrorotatory substances. The rotation is labelled as (+).
If the rotation is counterclockwise, the compound is called Laevorotatory. No relationship exists
between D and L (represents relative configuration) and dextrorotatory and laevorotatory substances. A
compound with D configuration may be (+) or (–). This information can be obtained only by putting the
molecule in Polarimeter (instrument used to obtain direction and extent of rotation of plane polarised light).
Specific rotation : Specific rotation of a chiral compound is a constant at a particular temperature and
wavelength (589 nm).
observed rotation (in degree)
Specific rotation c concentration (g/ml)
l
c l
l length of sample tube (dm)
Racemic mixture : A mixture containing equal amount of two enantiomers is called racemic mixture or
racemate. A racemic mixture is optically inactive due to external compensation. Racemic mixture can be
resolved into optically pure form by several methods.
Percentage enantiomeric excess : It tells us how much one enantiomer is present in excess of the
racemic mixture.
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52 Some Basic Principles of Organic Chemistry and Purification and Characterisation of Organic Compounds Rapid Revision & Formula Bank
n 1
Number of meso forms = 2 2
BOND FISSION
In any reaction, bond between the reactant molecule is broken, Bond fission in organic molecules can take
place in one of the two ways.
1. Homolytic Bond Fission
R1 R1
R2 C X R2 C + X
R3 R3
Result of homolytic fission is free radical. (Alkyl free radical may be sp2 or sp3 hybridised)
2. Heterolytic Bond Fission
(a) In the heterolytic bond fission bonding electron pair may move away from carbon, which results into
the formation of carbocation.
R1 R2
Heterolysis
R2 C X R1 C + X [X is more electronegative than carbon]
R3 R3
R1
1. Charged electrophiles X , R
NUCLEOPHILE
Nucleophiles are nucleus loving, they are electron rich having at least one non-bonding pair of electrons in
valence shell.
It can be of three types.
2. Neutral Nucleophiles - N H
H , R O
3
ELECTRONIC EFFECTS
Electronic Effects
δδδ δδ δ δ–
CH3 CH2 CH2 CH2 Cl
As shown above the charge decreases from to to position. Hence inductive effect decreases as
number of bonds increases.
Order of –I effect : (CH3)3 N > –NO2 > –CN> –F > –COOH > –Cl > –Br > –I > –OR > –OH > –NH2 > C6H5– > –H
Order of +I effect : (CH3)3C– > (CH3)2CH– > CH3–CH2– > –CH3 > –H
Uses of Inductive Effect :
(i) Stability of ions: Stability of ions can be explained by using the concept of inductive effect and
hyperconjugation.
(a) Stability of Carbocation
e.g., (CH3)3C (CH3)2 CH CH3CH2 CH3
(b) Stability of Carbanions
O O
(CH3 )3 C O (CH3 )2 CHO CH3 CH2 CH3 (groups with +I effect decrease the stability of anion)
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54 Some Basic Principles of Organic Chemistry and Purification and Characterisation of Organic Compounds Rapid Revision & Formula Bank
(ii) Acidic Properties : It is possible to compare the acidic strength of various organic compounds using
the inductive effect concept, e.g., in carboxylic acid
The strength of an acid depends upon the ease with which it can ionize to give proton or on the stability of the
conjugate bases formed, i.e. if the conjugate base formed is more stable, then the acid is more acidic.
Fluoroacetic acid (most acidic) FCH2 COOH 217 × 10–5 FCH2COO– (most stable)
Chloroacetic acid ClCH2 COOH 155 × 10–5 ClCH2–COO–
Bromoacetic acid BrCH2COOH 138 × 10–5 BrCH2COO–
Iodoacetic acid ICH2 COOH 75 × 10–5 ICH2COO–
Acetic acid (least acidic) CH3COOH 1.8 × 10–5 CH3 COO (least stable)
sp3
H CH3
H C C
CH3
H
H H H H
H C CH = CH2 H C = CH – CH2 H C = CH – CH2 H C = CH – CH2
H H H H
°
H H H H
° °
H C CH2 H C = CH2 H C = CH2 H C = CH2
H H H H
°
H H H H
H C CH2 H C =CH2 H C = CH2 H C = CH2
H H H H
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3. Electromeric Effect : The temporary electron density charge in substrate in presence of attacking reagent
facilitate the attack of attaching reagent is called electromeric effect.
+E effect: When electron density pilled on centre to which attacking reagent attacks then electromeric
effect is +E effect, observed in presence of electrophile.
+
e.g., E
C—C C—C
+
Electron density
E migration
–E effect: When electron density is removed from the centre to which attacking reagent attacks then
electronic effect is –E effect, observed in presence of nucleophile.
e.g., Nu
C—O C—O
Electron density
Nu migration
4. Mesomeric or Resonance Effect : The effect involves permanent delocalization of conjugated electrons
in a conjugated system. Intermediate structures formed are called resonating structures. The structure
that collectively represents all resonating structures is called the resonance hybrid.
Resonating structures are imaginary having no physical significance. The average structure i.e. resonance
hybrid represents the actual molecule. Resonance is also known as -electron delocalisation, which is
a permanent effect, it is distance independent effect. Normally this effect is more powerful than
hyperconjugative effect.
Resonating structures must be valid Lewis structures, they must have same position of atomic nuclei,
same number of paired and unpaired electrons and the part of molecule taking part in resonance must
be planar.
O O H
O O
CH3– C C –CH3
CH CH3– C C –CH3
CH
H
Position of H atom is changing Invalid resonating structure
H H H H
C=C H C–C H
H C=C H C–C
H H H H
Invalid resonating structure
Number of unpaired
electrons is changing
R–C=O R–C O
Less contributing More contributing
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(b) Non charge separated resonating structures are more contributing than charge separated resonating
structures.
X H X H
C=C C–C
H H H H
More contributing Less contributing
(c) Resonating structure which places negative charge on more electronegative atom is more contributing
as compared to resonating structure which places negative charge on less electronegative atom.
O O
C=C C–C
The difference between energies of most stable resonating structure and the resonance hybrid is
called the resonance energy of the molecule.
Electron Donating Mesomeric Effect (+M Effect) : Groups with +M effect releases -electron towards
unsaturated system. This effect makes certain positions in the molecule of high electron densities. This
effect in chlorobenzene is shown as
Cl + Cl + Cl + Cl Cl
+M Effect
Electron Withdrawing Mesomeric Effect (–M Effect) : This effect is observed when the displacement
of -electrons from unsaturated system is towards the atom or group. This effect in benzaldehyde is
shown as
–M Effect H O H O H O H O H O
C C C C C
REACTION INTERMEDIATES
Carbocations :
Structure :
R1
R2 R3
2
sp hybridised
Trigonal planar
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Stability: Carbocations are stabilised by electron donating groups and are destabilised by electron withdrawing
groups.
CH3
|
H2C = CH CH3 CH3 – CH2 CH3 – CH CH3 – C
| |
CH3 CH3
Increasing order of stability with increasing number of electron donating groups
Carbanions :
Structure :
C
R1 R3
R2
Pyramidal
Carbon bearing the negative charge is sp3 hybridised, when lone pair on carbon not involve in resonance.
Stability: Carbanions are stabilised by electron withdrawing groups and they are destabilised by electron
donating groups
CH3 CH3
CH3 CH2 – CH3 CH C CH3
CH3 CH3
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Structure : The exact type of hybridisation of the carbon atom bearing an unpaired electron depends on the
nature of the substituent. Generally alkyl radicals are planner and as electronegativity of bonded group increase
it adopts pyramidal shape e.g., CF3 is pyramidal. In presence of resonance it surely adopts planner shape.
R2
Unpaired electron is
R1 C present in unhybridised Unpaired electron is
px orbital C present in sp3
R3 F F hybridised orbital
Trigonal planar F
Stability : Free radicals are stabilised by resonance, hyperconjugation and steric effect. Both electron donating
and electron withdrawing groups stabilize free radicals.
CH3
CH3 CH3
Increasing stability
R R R—R
2CH 3 C H2 CH 2 CH 2 CH 3 CH 3
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62 wt. of Mg 2 P2 O7 formed
Phosphorus Carius method %P= × × 100
222 wt. of organic comp.
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Chapter 12
Hydrocarbons and
Environmental Chemistry
HYDROCARBONS
ALKANES
Methods of Preparation :
I. Reactions where number of carbon atoms are increased
1. Wurtz Reaction
dry ether
2R X 2Na R R 2NaX
Here other metals in the finely divided state may also be used such as Cu, Ag etc.
(i) Methane cannot be prepared by this method.
(ii) Only symmetrical alkane with even number C-atoms can be prepared by this method in good
yield.
(iii) The reaction fails with 3°-alkyl halides.
(iv) Alkenes are produced as by products.
2. Corey-House Synthesis:
electrolysis
2RCOONa (aq) R-R 2NaOH 2CO H
2 2
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Mechanism:
RCOONa RCOO– + Na+
2H2O 2H+ + 2OH–
Anodic Reaction
2RCOO– 2RCOO• + 2e–
2RCOO• R - R + 2CO2
Cathodic Reaction
2H+ + 2e– H2
(i) Methane cannot be prepared by this method
(ii) Unsymmetrical hydrocarbon (alkane) cannot be prepared
II. Reactions where number of carbon atoms are retained
1. Sabatier-Senderen’s Reduction
H H
Raney Raney | |
C=C + H2 Ni C–C ; –C C – + 2H2 Ni
—C—C—
200 - 300°C
| | 200 - 300°C | |
H H H H
HCl
(a) R X Zn R H HX
R
Red P
C = O + 4HI R–CH3 + H2O + 2I2
(b) 150°C
H
R1
2H 2H
Re d P
C = O + 4HI R1 – CH2 R2 H2O 2I2
150 C
R2
2H
O
2H
(c) R—C 6HI Re d P
R CH3 2H2O 3I2
H 150 C
OH
H
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(d) Clemmensen’s Reduction
R R H
Zn Hg/HCl
C=O 4H C + H2O
R H
R
Zn Hg / HCl
R1 C R2 4H H2O R1 CH2 R2
||
O
When acid sensitive group is present in a compound, Clemmensen's reduction is not used.
(e) Wolff-Kishner’s Reduction:
R R R H
KOH Glycol
C = O + NH2 – NH2 C=N + H2O C + N2
453K 473K
R R NH2 R H
When base sensitive groups are present in the compound, Wolff-Kishner's reduction is not used.
4. (a) Using Grignard’s Reagent
ether
R - X + Mg RMgX
RMgX + H – OH R – H + MgX(OH)
+ H – NH2 R – H + MgX(NH2)
+ H – OR R – H + MgX(OR )
+
H–O–C–R R–H + MgX (O–C–R )
|| ||
O O
(b) Using Alkyl lithium compound
R NH2 + R–Li (R NH) Li + R – H.
III. Reaction where number of carbon atoms are decreased
Decarboxylation by sodalime
CaO
RCOONa + NaOH 630 k R – H + Na2CO3
R R
CaO
CH – CH2 – COOH + NaOH CH – CH3 + Na2CO3
630 K
R R
Ni C
CO + 3H2 250 C
CH4 + H2O
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Physical Properties
Boiling Point (B.P.)
B.P. increases with the increase of molecular mass. Among the isomers, straight chain alkanes have higher
b.p. than branched chain alkanes.
Melting Point (M.P.)
The melting points do not show regular variation with increase in molecular size. The even number members
have higher m.p. as compared to next alkanes with odd number of carbon atoms (ALTERATION EFFECT).
Solubility
They are soluble in non-polar solvents. Hence, insoluble in polar solvents such as water.
Chemical Properties
Alkanes are generally inert towards acids, bases, oxidising and reducing agents but they give following reactions:
(1) Halogenation. Alkanes undergoes substitution reaction with halogen. Cl2 and Br2 only in presence of
ultra violet light or high temperature (573 – 773K).
Decreasing order of reactivity of halogens towards alkanes.
F2 > Cl2 > Br2 > I2
Fluorination and chlorination are less selective as these reagents are more reactive, while bromination
of alkane is more selective (less reactive).
(3) Oxidation :
Cu
(a) 2CH4 O2 2CH3 OH
573 K /100 atm
(b) Mo2 O3
CH4 O2 HCHO H2O
O
Manganese acetate
(c) 2R – CH3 + 3O2 2R – C – OH + 2H2O
373-430 K
or
Ag2O
(4) Isomerization :
CH3
AlCl3 + HCl
CH3 – CH2 – CH2 – CH3 200°C, 35 atm
CH3 – CH – CH3
AlCl3 + HCl
CH3(CH2)4 – CH3 CH3 – CH – CH2 – CH2 – CH3 + CH3 – CH2 – CH – CH2 – CH3
CH3 CH3
2-methyl pentane 3-methyl pentane
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(5) Aromatization :
Cr2O3
CH3 ( CH2)4 CH3 + 4H2
773K, 10-20 atm
Benzene
CH3
Cr2O3
n-heptane + 4H2
773K, 10-20 atm
Toluene
Ni
CH4 H2 O CO 3H2
Conformations of Alkanes
When different three dimensional arrangements are possible for a compound due to rotation along a single
bond, then these different arrangements are known as conformers and the phenomenon is known as
conformation. In fact C–C rotation is hindered by an energy barrier of 1 to 20 kJ mol–1. There are infinite
number of conformers possible. Out of infinite number of conformers, extremes can be discussed as
Conformers of ethane :
H H H H
H
H H
H H
H H H
H H
H H
H H H H H
H H H
Eclipsed Staggered Eclipsed Staggered
(i) It may be noted that one extreme conformation of ethane can be converted into other extreme conformer
by rotation of 60° about C–C bond.
(ii) Skew conformers have energy in between staggered and eclipsed.
P.E. eclipsed
12.55 kJ/mol
Staggered
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Conformers of propane :
CH3 CH3
H
H H
H
H H
H H H H
Eclipsed Staggered
Conformers of Butane :
H H
H H H CH H H H H H H
CH3 3 H
(I) (II) (III) (IV)
Staggered Partially eclipsed Gauche Fully eclipsed
CH3 CH3
H
H CH3
60º 60º
CH3
H H H H H
H
(V) (VI)
Gauche Partially eclipsed
OH H
H H OH
OH
H OH H OH
H H HO H
H
H H H
(a) (b) (c)
[Gauche] [Eclipsed] [Anti]
(Intramolecular (Have also intramolecular hydrogen
hydrogen bonding) bonding but also have torsional strain)
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ALKENES
Preparations of Alkenes
From Alcohols: When alcohol is treated with conc. acids (H2SO4, H3PO4) at higher temperature alkene is obtained.
CH3 CH3
H
+H
H3C C O H2C = C + H2O
CH3 CH3
Acid catalyzed dehydration of alcohol is a reversible reaction. Alcohols can be converted to alkene in the
presence of conc. H+, while alkenes can be converted to alcohol in the presence of dilute H+.
The ease of dehydration of alcohols depends on the stability of carbocations formed. Hence, the order of
reactivity of alcohols is ter–> sec–> pri– because the incipient carbocation stability is
ter–> sec–> pri–
Note : Since the carbocation stability is the primary criteria, so, the initially formed carbocation
undergoes molecular rearrangement to give more stable carbocation.
Hydride shift
Example (Hydride shift)
H2SO4
CH3 – CH – CH – CH3 CH3 – C = CH2 – CH3 + CH 2 = C – CH 2 – CH 3
170°C
CH3 OH CH3 CH3
(Major) (Minor)
Al2O3
(CH3)3 C – OH CH3 – C = CH2
250°C
alc KOH
CH3 – CH2 – CH2 – CH2 – Br CH3 – CH2 – CH = CH2
(i) The base used may be strongly basic anions like OH–, RO–, C2H5O–.... (CH3)3CO– etc.)
(ii) Alkyl substrates with good leaving group (X–, etc) give good yield of elimination product.
(iii) One may also use sulphonates.
II. Dehalogenation reactions of vicinal dihalide :
Br
Zn/AcOH
or
C C C=C
NaI in Acetone
Br
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Br
2R — CH + Zn R — CH = CH — R
Br
IV. By heating Quaternary ammonium hydroxide again Hofmann elimination occurs and less
substituted alkene is formed as the major product :
– H3C
–
(A) (B) OH (A)
HO
CH3 H2C = CH2 + N — CH2 — CH2 — CH3
Major
H H
H3C
H2C — CH2 — N — CH2 — CH — CH3
H3C
CH3
H2C = CH — CH3 + N — CH2 — CH3
Minor
H3C
H H
Pd/BaSO4 + H2
R—C C—R Quinoline
C=C
R R
cis alkene
VI. Under the presence of alkali metals in liquid ammonia, substituted alkynes are converted into
trans-alkene. It is important to remember that terminal alkynes do not give this reaction.
H R
Na/ liq.NH3
R—C C—R C=C
R H
trans-alkene
CH2COONa electrolysis
| + 2H2O CH2 = CH2 + 2CO2 + 2NaOH + H2
CH2COONa
Sodium succinate
Mechanism follows free radical pathway.
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VIII. Pyrolysis
Physical Properties
Solubility
They are insoluble in water but soluble in organic solvents.
Boiling point
The boiling point of cis–alkenes is usually higher than corresponding trans–alkenes (More polarity).
Melting point
The melting point of trans-alkenes is usually greater than cis-alkene. (trans form is more symmetrical).
Chemical Properties
Electrophilic addition reaction is the most important reaction of alkenes and alkynes. Beside electrophilic
addition reaction, it also gives Free radical addition, hydrogenation and oxidation reactions.
X Y
R R R X
–
X
C = CH2 C — CH3 C — CH3
R H—X R R
Planar Racemic mixture
H3C H3C
+
H /H2O
C = CH2 C — CH3
H3C H3C
OH
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H2 O Br2 HOBr
HBr
CH3 – CH = CH2 CH3 – CH2 – CH2 – Br
Peroxide
Note : Only HBr adds to unsymmetrical double bond according to anti-Markownikoff's rule. Other
HX (HF, HCl and HI) do not give peroxide effect.
5. Oxy-Mercuration-Demercuration
O Hg(OAc)
R R R
1. Hg (O — C — CH3) 2 , Oxymercuration NaBH4
C = CH2 C — CH2 C — CH3
H2O Demercuration
R R R
OH OH
6. Addition of Oxygen:
Ag CH2 CH2
CH2 = CH2 + ½ O2
570 K
O
7. Ozonolysis:
O
CCl4 Zn/H2O
C=C + O3 C C 2 C=O
– H2O2
O O
8. Hydroboration Oxidation
0°C H2 O2
R CH CH2 B 2H6 ether
(R CH2 CH2 )3 B OH–
R CH2 CH2 OH H3BO3
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(b) With hot KMnO4 or acidic KMnO4
[O]
CH2 CH2 2HCOOH 2CO 2 2H2 O
Hot KMnO 4
KMnO 4
CH3 CH CH2 CH3 COOH CO 2 H2 O
H
Hot CH3
(CH3 )2 C C(CH3 )2 2 C=O
KMnO4 CH3
This type of reaction takes place at a carbon atom attached to double bond carbon. This is called allylic
substitution.
11. Wohl Ziegler Reaction
H
CH3 – CH = CH2 + C h CH 3 – CH – C H2
2
CH2
13. Isomerization :
700 - 970 atm
CH2 – CH2 – CH2 – CH = CH2 or Al (SO ) ; 470 K CH3 – CH2 – CH = CH – CH3
2 4 3
14. Polymerization :
Pressure
CH2 = CH2 ( CH2 – CH2)n
O2
ALKYNES
Preparation of Alkynes
1. From Dehydrohalogenation of vicinal or geminal dihalides
Br Br
(i) NaNH2 (2equ.)
(a) CH3 — C — CH3 CH3 — C C—H
(ii) H+
Br
(i) NaNH2 (2equ.)
(b) R — C — CH3 R—C C—H
(ii) H
Br
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2. Dehalogenation Reaction
X X
| |
Zn dust
(a) –C–C– –C C– + 2ZnX2
| |
X X
X
Zn dust
(b) 2R – C X R–C C – R + 3ZnX2
X
3. Kolbe’s Electrolytic Decarboxylation
R COOK
C Electrolysis
|| + 2H2O R–C C – R + 2KOH + 2CO2 + H2
C
R COOK
cis or trans
4. Formation of Higher alkyne
NaNH2
(i) CH CH CH C Na
H3 C Br Br Br
Br2/CCl4 Br2/CCl4
CH3 – C CH C=C CH3 – C – C – H
Br H Br Br
Trans-1, 2-dibromopropene 1, 1, 2, 2-tetra bromo
propane
+ 2+
OH O
H , Hg tautomerise
R–C C – H + H2O R – C = CH2 R – C – CH3
Ketone
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2. Reaction of Acidic H Atom
(i) Alkynes having acidic H atom react with metals like Na, K to evolve H2 gas.
CH C – Na
+ Na + 1/2 H2
CH (1 mol) C–H
Monosodium
acetylide
CNa C – Na
+ Na + 1/2 H2
C–H C – Na
Disodium acetylide
NaNH2
HC C H NaNH2 HC CNa NH3 NaC CNa NH3
(ii) Reaction with Tollens reagent : When terminal alkyne reacts with Tollen's reagent (Ammoniacal
AgNO3 solution) white precipitate of silver acetylide is obtained,
C–H +
C – Ag
+ 2 [Ag(NH3)2] + 2NH4Cl + 2H2O
C–H C – Ag
(White precipitate)
These acetylides are not decomposed by H2O like acetylide of Na but by mineral acids like dil HNO3.
C – Ag CH
+ 2HNO3 2AgNO3 +
C – Ag CH
HC CCu
+ Cu2Cl2 + 2NH4OH + 2NH4Cl + 2H2O
HC CCu
(red ppt)
dicopper acetylide
These reactions are used to distinguish terminal alkynes from other alkynes.
3. Polymerization Reaction
(i) When acetylene is passed through red hot Cu tube, benzene is obtained.
CH 773K
3 C6H6
CH
CH3
red hot Cu or Fe tube
Similarly, CH3 – C CH
H3C CH3 (Major)
(Mesitylene)
Cl
CH CuCl/NH4Cl HCl
(ii) 2 or CH2 = CH – C CH CH2 = CH – C = CH2
CH Cu2Cl2/NH4Cl Vinyl acetylene Chloroprene
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AROMATIC HYDROCARBONS
Huckel's rule of Aromaticity : Cyclic, conjugated, planar and having (4n + 2) electrons.
where, n = 0, 1, 2, 3 ... (Any positive integer including zero)
Few Examples of Aromatic Species :
, , , ,
–
Aromatic ions are more stable than corresponding acyclic non-aromatic ions.
Antiaromatic Compounds :
Antiaromatic compounds are cyclic, conjugated, planar and contain 4n electrons (where n is a positive
integer) Anti-aromatic compounds are less stable than acyclic counter part.
Examples :
–
, ,
Red hot
1. 3HC CH Cu Tube
OH
Zn-dust
C
OH (NaOH + CaO)
+ Na2CO3
NH2 N NCl H
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5. Through Grignard reagent.
Br H
–
Mg H3O Br
MgBr + Mg
Ether OH
H
+ E
E –H
Slow E Fast
-complex
(Resonance stabilized)
(i) Halogenation
Cl
FeCl3
+ Cl2 dark + HCl
Benzene
I
HIO3
+ I2 + HI
Hence, it is carried out in the presence of conc. nitric acid or HIO3 to oxidise the Hydrogen Iodide
formed.
(ii) Nitration
NO2 NO2
H2SO4 conc. H2SO 4 conc.
+ HNO3 330K
H2O HNO3 363 373K
NO2
SO3H SO3H
+ H2SO4 + SO3 Heat H2O or + ClSO3H Heat HCl
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76 Hydrocarbons and Environmental Chemistry Rapid Revision & Formula Bank
CH 3
+ CH3Cl Anhydrous AlCl3 + HCl
H3C CH3
CH
+ CH3CH2CH2Cl Anhydrous AlCl 3
O
Acylation : Reactive intermediate is acylium ion R–C+ which cannot undergo rearrangement.
COCH3
+ CH3 – COCl Anhydrous AlCl3 + HCl
.. .. ..
Ortho and para substitution : Electron releasing groups like - R (alkyl) – O .. H, – O
.. R, – NHR,
..
– NHCOR are activating groups i.e., they increase electron density at ortho and para position,
therefore, are ortho and para directing towards electrophilic substitution reactions.
Meta substitution : Electron withdrawing groups such as – NO2, – CHO, – COOH, – COCH3, – CN,
– SO3H, – COOR are called deactivating groups. They decrease electron density at ortho and para-
position, therefore, electrophilic substitution takes place at meta-position.
2. Halogenation of side chain :
CCl3
+ HCl
Benzotrichloride
or trichlorophenyl methane
3. Oxidation :
O O
H C–OH H C
V2O 5 Heat
+ 5O2 P2O5 O + H2O
770 K
Benzene H C–OH H C
O O
Maleic acid Maleic anhydride
2-Butene-1,4-dioic acid
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Rapid Revision & Formula Bank Hydrocarbons and Environmental Chemistry 77
ENVIRONMENTAL CHEMISTRY
ENVIRONMENTAL POLLUTANTS
Any substance which causes pollution in the environment is known as environmental pollutant. It can be
atmospheric, water and soil pollution.
WATER POLLUTION
The quality of drinking water is very important for human welfare. The pollution of water by sewage has been
linked with the spreading of diseases such as cholera and typhoid fever.
In addition, water is also contaminated by industrial wastes, like :
(i) Heavy Metals : Such as Cd, Pb and Hg may be present.
(ii) Detergent and Fertilizers : They may contain PO 4–3 as additives which encourages the growth of algae
that reduces the dissolved oxygen concentration of water. This process is known as Eutrophication.
(iii) Acid Polluted Water (pH < 3) : This is deadly to most forms of aquatic life.
(iv) Polychlorinated Biphenyls (PCBs) : PCBs are resistant to oxidation and their release into the environment
causes skin disorders in humans. They are reported to be carcinogenic.
Chemical oxygen demand (COD) : BOD measurement takes few days, so another parameter called COD
measurement is required. In COD measurement sample of fixed volume is treated with oxidising agent
(usually K2Cr2O7 in acidic medium). The reagent oxidises most of the polluting substances including those
which are resistant to microbial oxidation.
AIR POLLUTION
Air is very essential for life, particularly oxygen which is needed for breathing. But at the same time air is
polluted due to various human activities. Man made, pollutants such as gases like CO, NO, NO2 , SO2 ,
H2SO4, hydrocarbons and aerosols etc are being constantly released in the atmosphere leading to air pollution.
Atmospheric Pollution
Tropospheric pollution : Troposphere extends upto height of 10 km from sea level. It contains 80% of total
mass of air and water vapour. Pollution is also caused by SO2, SO3, NO2 etc.
Stratospheric pollution : Extends (10–50) km above sea level. It contains N2, O2 and ozone.
1. Combustion processes Dust, fumes, smoke SO2, NO2, CO, Organic vapours
2. Chemical processes Dust, fume, mist Process dependent
(cement and fertilizers) (CO2, SO2, CO, NH3, NO2
organic vapours)
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78 Hydrocarbons and Environmental Chemistry Rapid Revision & Formula Bank
Smog
It is a combination of smoke and fog. This is the best known example of air pollution. Smog is of two types:
(1) Classical smog : Occurs in cool humid climate and is chemically reducing smog and has high
concentration of SO2.
(2) Photochemical smog : Occurs in warm, dry and sunny climate. It is an oxidising smog. Major component
of photochemical smog is NO.
Acid Rain
Rain water normally has pH of 5.6 due to the formation of H+ ions from the reaction of rain water with CO2
present in atmosphere.
When pH of rain water drops below 5.6 it becomes acidic. Acid rain caused by the presence of oxides of
sulphur and nitrogen in the atmosphere. Oxides of sulphur are released into the environment largely because
of fossil fuel combustion, ore smelting etc. Nitrogen oxides emitted into the atmosphere mainly from automobile
exhausts and fossil fuel combustion. SO2 and NO2 after oxidation and reaction with water are major contributors
to acid rain.
Acid rain is toxic to vegetation and aquatic life. It damages building and statues and dissolves heavy metals
from soils, rocks etc. The heavy metals such as Cu, Pb, Hg, Al etc leached from soil enters well water and
produce a variety of toxic effects.
SOIL POLLUTION
It is caused by pesticides and other chemicals which are added to the soil to grow better crops. Solid wastes
are another cause of land pollution.
Pesticides are used to kill unwanted organisms. Synthetic pesticides are of great concern for us. Pesticides
affect human being through eating, drinking and so on.
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Rapid Revision & Formula Bank Hydrocarbons and Environmental Chemistry 79
Insecticides : Control of insects by insecticides help to curb disease for example (malaria and yellow fever)
and protects crops. e.g., organochlorine like DDT.
Bhopal gas tragedy occurred on 2nd Dec. 1984 in Bhopal (Union Carbide Ltd.).
Methyl iso-cyanate (MIC) was used to manufacture the insecticide called Carbyl or Sevin (commercial name).
There were three tanks in the plant that stored MIC. Due to increase of pressure in one of the tanks valve
was released, hence MIC escaped into atmosphere. This MIC was
(a) Hydrolysed due to presence of water in surrounding ponds.
CH3 — N = C = O + H2O CH3NH2 + CO2 + Heat
MIC
O
CH3 CH3
N N
3 CH3–NCO Catalyst + Heat
O N O
CH3
Both reactions are exothermic in nature. So escaping tendency of MIC increased and caused immense loss
of life and injury to people and livestock.
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Chapter 13
Organic Compounds
Containing Halogen
ALKYL HALIDES
(c) By the action of thionyl chloride (SOCl2)- Alkyl chlorides can be prepared by heating alcohol (1° or 2°)
and thionyl chloride in the presence of pyridine (base). (Darzen's Reaction)
Pyridine
ROH SOCl 2 RCl SO 2 HCl
Alcohol Thionyl Alkyl Gaseous by
(1 or 2 ) chloride chloride product
2. From Alkenes
3. From Alkanes
CH 4 Cl2 Light or
CH Cl 3 HCl
Methane 250–400 C Methyl chloride
(Chloromethane)
The mechanism is a free radical mechanism. The reactivity of halogen depends upon the nature of halogen
used to abstract hydrogen hence F2 > Cl2 > Br2 >I2
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Rapid Revision & Formula Bank Organic Compounds Containing Halogen 81
4. From silver salts of fatty acids (Borodine - Hunsdiecker Reaction)
CCl 4
C 6H5 COOAg Br2 C 6H5Br AgBr CO 2
Silver benzoate Reflux Phenyl
bromide
5. By halogen exchange
The reaction is possible because sodium iodide is soluble in methanol and acetone whereas sodium
chloride and sodium bromide are insoluble
(b) Reaction of Grignard's reagent with I2.
RMgX I 2 R I MgXI
(where, X Cl or Br)
PHYSICAL PROPERTIES
1. Lower members such as CH3Cl, CH3Br, CH3F, C2H5Cl etc are colourless gases at room temperature. Other
alkyl halides upto C18 are colourless sweet smelling liquids and higher members are solids.
2. B.P. of haloalkanes decrease in order RI > RBr > RCl (for same size of alkyl group)
3. B.P. of haloalkanes with same halogen atom increase with increasing size of alkyl groups.
4. For isomeric haloalkanes, b.p. decrease with increasing branching i.e. 1° > 2° > 3°
Example : n-butyl chloride > isobutyl chloride > tert butyl chloride
5. Chloroalkanes are lighter than water whereas bromides and iodides are heavier. Their densities decrease
in order of RI > RBr > RCl
CHEMICAL PROPERTIES
Halogen derivatives of alkanes are highly reactive as the halogen atoms are easily replaced. These derivatives
especially the alkyl halides are widely used in the synthesis of many organic compounds.
The Chemical reactions of alkyl halides may be classified into three types :
(A) Nucleophilic substitution reactions.
(B) Elimination reactions.
(C) Miscellaneous reactions.
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82 Organic Compounds Containing Halogen Rapid Revision & Formula Bank
Overall order of the reaction is two and it is one with respect to CH3Br and one with respect to OH .
Note : (i) This reaction takes place in one step without involving any reactive intermediate.
(ii) INVERSION of CONFIGURATION takes place if leaving group X– and Nu are of same
priority.
(iii) Rate of reaction of alkyl halides towards SN2 reaction is governed by steric hindrance in alkyl
halide.
SN1 Reaction
This reaction involves more than one steps.
This SN1 reaction is independent of nature and concentration of nucleophiles.
Alkyl halides which give more stable carbocations are more reactive towards SN1 reactions.
SN1 reactions involve racemization with partial inversion.
Br
Lesser the steric hindrance, greater the reactivity of alkyl halide towards SN2 reactions.
CH3 Br > CH3 — CH2 — Br > CH3 — CH — Br > (CH3)3 C — CH2 — Br > (CH3)3 C — Br
CH3
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Rapid Revision & Formula Bank Organic Compounds Containing Halogen 83
2. Strength and concentration of nucleophile :
for SN1 : As nucleophile does not participate in rate determining step, therefore there is no effect of concen-
tration and strength of nucleophile on rate of reaction.
for SN2 : Increasing the concentration of nucleophile increases the rate for SN2, a better nucleophile will yield
better products.
3. Solvent Effect : Polar protic solvent favours SN1 whereas polar aprotic solvent favours SN2 mechanism.
4. Nature of leaving group : Good leaving group always increases rate of nucleophilic substitution reactions
for the same reason the order of reactivity for SN reactions of halides follow the given trend :
RI > RBr > RCl > RF
Miscellaneous reactions
1. Reaction with magnesium (formation of Grignard's reagent).
Dry ether
R – X + Mg RMgX
For a given alkyl group, the ease of formation of Grignard’s reagent is of the order :
iodide > bromide > chloride
2. Reduction (formation of alkanes)
Alkyl halides are reduced to alkanes by any of the following reducing agents :
(a) H2 in the presence of Ni, Pt or Pd (catalytic hydrogenation).
(b) Lithium-aluminium hydride (LiAlH4).
(c) Nascent hydrogen obtained from Zn-Cu couple and alcohol or Zn and HCl or Sn and HCl or Na and
alcohol.
Friedel Craft’s reaction
Formation of Alkyl benzene
Anhydrous AlCl3
C 6H 6 CH3 CH2 Cl C 6H5 CH2CH3 HCl
Ethyl benzene
Vinylic halides and aryl halides do not give a silver halide precipitate, when treated with alc. AgNO3 because
vinylic and phenyl cations are very unstable and therefore, do not form readily.
ARYL HALIDES
General methods of Preparation
1. From arenes by direct halogenation
FeCl3 , 298K
(i) C6H6 Cl2 C6H5 Cl HCl
Benzene Chlorobenzene
FeBr3 ,
C6H6 Br2 C6H5Br HBr
Benzene Bromobenzene
Cl
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84 Organic Compounds Containing Halogen Rapid Revision & Formula Bank
3. With NBS
When toluene is treated with NBS (N-bromosuccinimide) in the presence of peroxides, benzyl bromide is formed.
CH2CO CH2CO
C 6H5 – CH3 + NBr Peroxides C 6H5 – CH2Br + NH
Toluene CH2CO Benzyl bromide CH2CO
NBS Succinamide
4. From Diazonium salts
(a) Sandmeyer’s reaction
(i) Preparation of chlorobenzene
+
N2 Cl Cl
CuCl / HCl + N2
Benzenediazonium Chlorobenzene
chloride
–
C6H5 N2 Cl KI CHI6 5 HCl N2
Benzenediazonium Iodobenzene
chloride
HBF4
CHF
6 5 N2 BF3
HCl Fluorobenzene
Benzenediazonium Benzenediazonium
chloride fluroborate
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Rapid Revision & Formula Bank Organic Compounds Containing Halogen 85
5. By Hunsdiecker Reaction :
COOAg Br
Distillation
+ Br2 + AgBr + CO2
CCl4, 350 K
Physical Properties
(i) They are colourless stable liquids.
(ii) Insoluble in water but soluble in inorganic solvent.
(iii) Boiling and melting points : Their boiling and melting point is higher than alkyl halides. Boiling point increases
with increasing size of halogen.
F Cl Br I
Boiling points of isomeric dihalo benzenes are very nearly the same but the melting point of para isomers is
higher than ortho and meta isomer.
Chemical Properties
Haloarene gives SN reaction rarely only under drastic conditions because of partial double bond character between
C–X bond. i.e., at high temp. & pressure and in presence of certain catalyst.
(i) Replacement by hydroxyl group (Formation of phenols) (Dow’s process)
Cl ONa OH
623 K HCl
+ NaOH + NaCl
aqueous 300 atm
Chlorobenzene Sod. Phenoxide Phenol
Cl NH2
473 K
2 + 3NH3 + Cu2O 60 atm
2 + Cu2Cl2 + H2O
Chlorobenzene Aniline
C6H5 Cl
KNH
Liquid NH3
C6H5NH2 KBr
2
Bromobenzene 240 K Aniline
Pyridine
2C 6H5Br Cu 2 (CN)2 2C 6H5 CN 2CuBr
Bromobenzene 470 K Cyanobenzene
(Benzonitrile)
473
C 6H5 Cl CH3 ONa C 6H5 OCH3 NaCl
Sod. methoxide Cu salts Anisole
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86 Organic Compounds Containing Halogen Rapid Revision & Formula Bank
Cl Cl Cl
Cl
FeCl3
+ Cl2 HCl
+
Cl
o- p-
Dichloro benzene
(b) Nitration
Cl Cl Cl
NO2
H2SO 4 ,∆
+ HNO3 +
H2O
NO2
o- p-
Nitrochlorobenzene
Cl Cl
Cl
CH3
AlCl3
+ CH3Cl +
HCl
CH3
o- p-
O
Cl Cl
Cl
C – CH3
AlCl3
+ CH3 COCl +
HCl
Acetyl chloride
COCH3
o- p-
Chloro acetophenone
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Rapid Revision & Formula Bank Organic Compounds Containing Halogen 87
Some Important Halogen Compounds
DDT : On heating with chloral in the presence of concentrated sulphuric acid, chlorobenzene forms
(p, p' - dichlorodiphenyl trichloroethane (commonly known as DDT-a powerful insecticide.)
But it is not biodegradable because it contains halogen atoms attached to the benzene rings.
Cl H H Cl Cl H Cl
Cl – C – C = O + Conc. H2SO4
Cl – C – C
H2O
Cl H Cl Cl Cl
Chloral Chlorobenzene DDT
(2 molecules)
2, 2-bis-(p-chlorophenyl)
1, 1, 1-trichloroethane
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Chapter 14
Organic Compounds
Containing Oxygen
ALCOHOLS
Molecules containing –OH group are termed as alcohols. Classification of alcohols they are classified
as primary, secondary or tertiary alcohol according to the carbon that is bonded with –OH.
Again when any molecule contain 1, 2 or 3 –OH groups then it is called mono, di or tri hydric alcohols
OH OH OH OH OH
respectively. (as in case of alkyl halides) CH3 – CH2OH CH2 – CH2 CH2 – CH – CH2
Ethyl alcohol Ethylene glycol Glycerol
(monohydric) (dihydric) (trihydric)
OH
H2SO4
CH3 – CH = CH2 + H2O CH3 – CH – CH3
(ii) Oxymercuration followed by demercuration :
OH OH
Hg (OAc)2 NaBH4
CH3 – CH = CH2 + H2O THF
CH2 – CH – CH2 OH–
CH3 – CH – CH3
Hg(OAc)
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Rapid Revision & Formula Bank Organic Compounds Containing Oxygen 89
2. From Alkyl Halides :
When alkyl halides are treated with aq. KOH or aq. NaOH or moist Ag2O, alcohols are formed.
R X OH R OH X –
O
LiAlH4 or NaBH4
R–C–H R – CH2OH
O OH
LiAlH4 or NaBH4
R–C–R
O
(i) LiAlH4
R – C – OR (ii) H3O
+ R – CH2OH + R – OH
O
(i) LiAlH4
R–C–X (ii) H3O
+ R – CH2OH
O O
(i) LiAlH4
R–C–O–C–R (ii) H3O+ 2R – CH2OH
O
– CH2 – OH Yes Yes Yes Yes
–C–H
C=O CH – OH Yes Yes Yes Yes
– COOH – CH2OH Yes No Yes Yes
O
– C – Cl – CH2OH Yes Yes No Yes
O
(R – C – O)2O R – CH2OH Yes No Yes Yes
O
– CH2OH + Yes No Yes Yes
– C – OR R – OH
C=C CH – CH No No Yes Yes
(LiAIH4 reduces)
C = C only
when it is
conjugated with
Phenylic system
OH
R [(CH3)2CHO]3Al R
C = O + CH3 – CH – CH3 CH – OH + (CH3)2C = O
R
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90 Organic Compounds Containing Oxygen Rapid Revision & Formula Bank
O OMgX OH
H2O/H+ OH
– C – + R – MgX –C–R – C – R + Mg
X
In this reaction
Formaldehyde gives 1°-alcohol
Other aldehydes give 2°-alcohol
Ketones give 3°-alcohol
(ii) From carboxylic acid and their derivatives :
O O
Z
R – C – Z + R – MgX R – C – R + Mg
X
O OMgX OH
H3O+
R – C – R + R – MgX R–C–R R–C–R
R R
(iii) From epoxides :
O OMgX OH
H2O/H+ OH
CH3 – CH — CH2 + R – MgX CH3 – CH – CH2 CH3 – CH – CH2 + Mg
X
R R
5. Hydrolysis of Ether :
Ethers undergo acid hydrolysis with dilute H2SO4 under pressure to give corresponding alcohols.
dil. H2SO 4
R O R H2 O R OH R OH
Physical Properties
(i) Physical state : At ordinary temperature, lower members are colourless liquids with burning taste and
pleasant smell.
(ii) Boiling Point : The boiling point of alcohols rise regularly with the rise in the molecular weight. Amongst
isomeric alcohols, the boiling point decrease in the order.
1° > 2° > 3°
Alcohols have high boiling point then hydrocarbons and haloalkanes of similar molecular mass due to
intermolecular hydrogen bonding.
(iii) Solubility : The extent of solubility of any alcohol in water depends upon the capability of its molecules
to form hydrogen bonds with water molecule.
(iv) Alcohols are lighter than water, however, the density increases with the increase in molecular mass.
Chemical Properties
1. Reactions involving cleavage of O – H Bond
Alcohols are acidic in nature but they are less acidic than water hence they do not give H+ in aqueous
solution. They do not change the colour of litmus paper.
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Rapid Revision & Formula Bank Organic Compounds Containing Oxygen 91
Their acidic strength increases by increasing–I strength of the groups attached and decreases by increasing
+I strength of the groups.
(i) Alcohols do not react with aqueous alkali, as they do not give H+ in aqueous solution.
(ii) Action of active metal : When alcohols are treated with active metal they form alkoxides with the
liberation of H2 gas.
2ROH 2Na 2R O N a H2
(iii) Esterification : When carboxylic acid is treated with alcohols in the presence of acid as catalyst,
esters are formed.
Alcohol reactivity order 1° > 2° > 3°.
O O
H+
R – C – OH + H – O – R R – C – OR + HOH
Note : (a) OH is removed from carboxylic acid and H is removed from alcohol.
(b) Overall reaction is SN2 in which alcohol acts as nucleophile.
(iv) Reaction with Grignard Reagent : When Grignard reagents are treated with alcohol (or any proton
donor) they form alkanes.
R – MgX + H – OR R – H + R – OMgX
Other proton donors can be carboxylic acids, phenols, alkynes, H2O, Amines, NH3 etc.
2. Reactions Involving Cleavage of C– O Bond
(i) Reaction with HX : Most alcohols undergo SN1.
Anhyd. ZnCl2
(a) R OH HCl(g) R Cl H2 O
Note : HCl + anhyd. ZnCl2 is called Lucas reagent. Lucas test is used to distinguish primary,
secondary and tertiary alcohols.
H / H2SO 4
(b) R OH HBr conc .
R Br H2O
H / H2SO 4
(c) R OH HI conc .
R I H2 O
Reactivity order of HX is
HI > HBr > HCl
(ii) Alkyl chlorides can also be prepared by following methods :
R – OH + PCl5 R – Cl + POCl3 + HCl
3R – OH + PCl3 3R – Cl + H3PO3
R – OH + SOCl2 R – Cl + SO2 + HCl (Darzen's process)
Darzen’s process is the best method as the other by-products are gases.
3. Reduction :
Alcohols are reduced to alkanes when they are treated with red P + HI.
HI red P
R OH R H ZnO
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92 Organic Compounds Containing Oxygen Rapid Revision & Formula Bank
4. Oxidation :
O O
[O] [O] [O]
CH 3OH H–C–H H – C – OH CO2
O
Cu
(i) CH3 – CH2 – OH CH3 – C – H + H2 (Dehydrogenation)
573K
OH O
Cu
(ii) CH3 – CH – CH 3 573K CH 3 – C – CH 3 + H 2 (Dehydrogenation)
(iii) Tertiary alcohols undergo dehydration to give alkene under similar condition.
CH3 CH2
Cu
CH3 – C – OH 573 K
CH3 – C + H2O
CH3 CH3
PHENOLS
OH
and their derivatives are called phenols. In phenol R– of alcohol is replaced by aryl ring.
..
.. H
H–C H O
.. H–C C
108.5° 111.7° H
H H H
Bond angle increases with the increase in hindrance.
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Rapid Revision & Formula Bank Organic Compounds Containing Oxygen 93
Method of Preparation
1. From Aryl Sulphonic Acids (Industrial Method):
When aryl sulphonic acids are fused with NaOH at 570 – 620 K followed by hydrolysis phenols are formed.
623 K H+
+ NaOH (aq.) 320 atm
Note : Condition of reaction become less vigorous when –M groups are present at ortho or para or
both position to the chlorine atom.
+
NH2 N2 Cl OH
NaNO2 + HCl H2O
+ N2 + H–Cl
0 – 5°C H2SO4
+ + HCl
N=N
4. Cumene Process :
CH3 CH3
CH3 C H CH3 C–O–O–H OH
H O
+
H3PO4 light H /H2O
+CH3 – C = CH2 O2 + CH3—C—CH3
Propene
Benzene Cumene Cumene hydroperoxide
5. Grignard's Synthesis :
1 H2O / H
OH
C6H5MgBr + O2 C6H5OMgBr C6H5OH + Mg
2
Br
6. From Salicylic Acid :
OH OH OH
COOH COONa NaOH(CaO)/
+ NaOH –Na2CO3
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94 Organic Compounds Containing Oxygen Rapid Revision & Formula Bank
Chemical Properties
NaOH / C2H5I
C6H5OC2H5
C6H5SO2Cl
C6H5SO2OC6H5
(Hinsberg reagent)
OH
Br2, water
2, 4, 6 tribromophenol
dil. HNO3
or o & p nitrophenol
(ArOH)
HNO3 / H2SO4
2, 4, 6 trinitrophenol (minor) + [Major is oxidative cleavage]
HNO2 / H2SO4
p-nitroso phenol
COCH3
(1) CH3COCl
OH + Para product
(2) D
SO3H
H2SO4
HO3S OH
–
(i) OH (ii) CH2O CH2O
HO CO2OH excess Bakelite
–
COOH
(i) OH HCl
OH
(ii) CO2
+
HCN / HCl H
OH CHO
AlCl3
CHCl3 / KOH
Salicylaldehyde
Pthalic anhydride
Phenophthaline
H2SO4 /
OH OH
CH3COCl AlCl3 COCH3
+
COCH3
CHCl3 / NaOH / D H2O
Salicylaldehyde
–
(i) OH (ii) C6H5N2Cl
N N OH
Ni / 3H2
OH
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Rapid Revision & Formula Bank Organic Compounds Containing Oxygen 95
ETHERS
Ethers are those organic compounds which contain two alkyl groups attached to an oxygen atom, i.e.,
R–O–R. They are regarded as dialkyl derivatives of water or anhydrides of alcohols.
–2H
H–O–H R–O–R H2O
R – OH HO – R
Water 2R Ether Alcohol ( 2 moles )
Ethers may be of two types : (i) Symmetrical or simple ethers are those in which both the alkyl groups
are identical and (ii) unsymmetrical or mixed ethers are those in which the two alkyl groups are different.
CH3–O–CH3; C6H5–O–C6H5 CH3–O–C2H5; CH3–O–C6H5
Symmetrical (simple) ethers Unsymmetrical (mixed)ethers
Like water, ether has two unshared pair of electrons on oxygen atom, yet its angle is greater than normal
tetrahedral (109°28´) and different from that in water (105°). This is because of the fact that in ethers the
repulsion between lone pairs of electrons is overcome by the repulsion between the bulky alkyl groups.
Preparation of Ethers :
1. By dehydrating excess of alcohols : Simple ethers can be prepared by heating an excess of primary
alcohols with conc. H2SO4 at 413K. Alcohol should be taken in excess so as to avoid its dehydration to
alkenes.
Conc . H2SO 4
C 2H5 – OH HO – C 2H5 C 2H5 – O – C 2H5 H2 O
Ethanol ( 2 molecules ) 413 K Diethyl ether
Dehydration may also be done by passing alcohol vapours over heated catalyst like alumina under high
pressure and temperature of 200 – 250°C.
2. By heating alkyl halide with dry silver oxide (only for simple ethers) :
Remember that reaction of alkyl halides with moist silver oxide (Ag2O + 2H2O = 2AgOH) give alcohols
C2H5I + Ag2O (moist) C2H5OH + AgI
3. By heating alkyl halide with sod. or pot. alkoxides (Williamson synthesis):
C2H5ONa + ICH3 C2H5OCH3 + NaI
CH3 CH3
| |
+
However CH3–Cl + NaO–C–CH3 CH3–O–C–CH3 + NaCl
| |
CH3 CH3
If alkyl halide is other than methyl halide and it is treated with tertiary alkoxide ion, Hofmann elimination
takes place instead of Williamson's ether synthesis.
Cl CH3
| |
+
CH3–CH2–CH–CH3 + NaO–C–CH3 CH3–CH2–CH=CH2 + HCl
|
CH3 (Major)
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96 Organic Compounds Containing Oxygen Rapid Revision & Formula Bank
Limitations :
1. In this reaction alkoxide ion may be 1°, 2°, 3°.
2. Alkyl halide must be 1°.
3. In the case of 3° alkyl halide elimination occurs to produce alkene as major product.
4. In the case of 2° alkyl halide both elimination and substitution products are obtained.
Chemical Properties :
A. Properties due to carbon-oxygen bond :
1. Hydrolysis :
H2SO 4
C 2H5 – O – C 2H5 H2 O 2C 2H5 OH
Ethyl alcohol
The hydrolysis may also be effected by boiling the ether with water or by treating it with steam.
CH3
| CH3
O–C–CH3 |
OH
| + HI + I–C–CH3
CH3 |
CH3
B. Properties Due to Benzene Nucleus :
Alkoxy group, being o-, p- directing, anisole undergoes substitution in o- and p- positions. However,
–OR group is less activating than the phenolic group.
(i) Nitration :
OCH3 OCH3 OCH3
NO2
conc. HNO3
+
conc. H2SO4
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Rapid Revision & Formula Bank Organic Compounds Containing Oxygen 97
(ii) Bromination :
OCH3 OCH3
Br Br
Br2/Fe
Anisole
Br
2, 4, 6, Tribromoanisole
CS2 Br
+ Br2 +
Anisole 2-Bromoanisole
Br
4-Bromoanisole
(iii) Sulphonation :
Anisole
SO3H o-Methoxybenzene
sulphonic acid
p-Methoxybenzene
sulphonic acid
CrO3 acetone
CH3 .CH2 OH CH3 .CHO H2O
Ethyl alcohol Acetaldehyde
(Primary Alcohol)
CH2OH CHO
MnO2
[O],
Benzyl alcohol Benzaldehyde
Controlled oxidation of 1°- alcohol and 2° - alcohol with PCC + CH2Cl2 or CrO3 forms aldehyde and
ketone respectively.
Ketones in good yield can be prepared by Oppenauer oxidation of secondary alcohols.
R CH3 R CH3
[(CH3)3CO]3Al
CHOH + C=O (Aluminium C=O + CHOH
R´ CH3 t-butoxide) R´ CH3
Sec. alcohol Acetone Ketone Isopropanol
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98 Organic Compounds Containing Oxygen Rapid Revision & Formula Bank
Cu
CH3 OH HCHO H2
573 K
Methanol Formaldehyde
CH3 Cu
CH3
CHOH C = O + H2
573 K
CH3 CH3
Isopropanol Acetone
2. From Alkynes :
dil. H2SO 4
CH CH H2 O [CH2 CHOH] CH3 CHO
Acetylene HgSO 4 Vinyl alcohol Acetaldehy de
(Unstable )
OH O
H2SO4 Tautomerisation
CH3C CH + H2O CH3.C CH2 CH3 C CH3
HgSO4
Unstable Acetone
CH3 CH3
H2O
CH3 – C N + CH3 MgI CH3 – C = NMgI CH3 – C = O + NH2MgI
Acetone
O
H2/Pd + BaSO4, S
R C Cl R CHO + HCl
Boiling xylene
Acid chloride
O
Pd/BaSO4,S
CH3 C Cl CH3 CHO + HCl
Boiling xylene Acetaldehyde
Acetyl chloride
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Rapid Revision & Formula Bank Organic Compounds Containing Oxygen 99
(b) Aromatic Ketones : (Friedel-Craft's acylation)
anhy.
(i) C 6H6 CH3 COCl C 6H5 COCH3 HCl
Benzene AlCl3 Acetophenone
anhy.
(ii) C 6H 6 C 6H 5COCl C 6H5 COC 6H 5 HCl
AlCl3 Benzophenone
Chemical Properties
Both aldehydes and ketones contain a carbonyl group in the structure and hence show marked similarity in
their chemical behaviour.
(a) Nucleophilic addition reactions
Reactivity of carbonyl compounds towards nucleophilic addition reaction is governed by ELECTRONIC
FACTOR and STERIC FACTOR. Aldehydes are more reactive than ketones.
O
HCHO > CH3CHO > CHO > CH 3 — C — CH 3
Decreasing reactivity
(1) Addition of hydrogen cyanide : Aldheydes and ketones react with hydrogen cyanide to form cyanohydrins.
CH3 CH3 OH
C = O + HCN C
H H CN
Acetaldehyde Acetaldehyde cyanohydrin
CH3 CH3 OH
C = O + HCN C
CH3 CH3 CN
Acetone Acetone cyanohydrin
C6H5 C6H5 OH
C = O + HCN C
CH3 CH3 CN
Acetophenone Acetophenone cyanohydrine
Benzophenone does not react with hydrogen cyanide because of steric hindrance. On the other hand,
aromatic aldehydes (e.g., C6H5CHO) when refluxed with alcoholic potassium cyanide solution undergo
dimerization to form benzoin.
OH O
–
CN
2C6H5CHO C6H5 – CH – C – C6H5
ethanol
Benzaldehyde Benzoin
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100 Organic Compounds Containing Oxygen Rapid Revision & Formula Bank
(2) Addition of sodium bisulphite : Aldehydes and methyl ketones react with a saturated aqueous
solution of bisulphite to form crystalline sodium bisulphite derivatives.
CH3 CH3 OH
C = O + NaHSO3 C
H H SO3Na
Acetaldehyde Sod. bisulphite Acetaldehyde sod. bisulphite
C6H5 C6H5 OH
C = O + NaHSO3 C
H H SO3Na
Benzaldehyde Benzaldehyde sod. bisulphite
Aromatic ketones and aliphatic ketones having higher alkyl groups do not react with sodium bisulphite.
This is due to the fact that the large SO23 ion cannot attack the carbonyl carbon atom when it is
surrounded by larger substituents (steric hindrance).
Thus C2H5COC2H5, C6H5COCH3, C6H5COC6H5 do not react with sodium bisulphite. Methyl ketones give
this reaction.
(3) Addition of Grignard reagents :
H H CH3 H CH3
H2O
C = O + CH3MgI C C
H H OMgI H OH
Formaldehyde Ethyl alcohol (primary alcohol)
CH3
H3C H3C CH 3 H2O
|
C = O + CH3MgI C CH3 C OH
H3C H3C OMgI |
Acetone CH3
ter. butyl alcohol (ter. alcohol )
(4) Addition of alcohols (Acetal formation) : Aldehydes (not Ketones) react with alcohols in presence
of dry HCl gas to form hemi-acetals (hemi means half) which being unstable immediately react with
another molecule of alcohol to form stable acetals. For example,
CH3 dry HCl gas CH3 OC2H5 CH3 OC2H5
C2H5OH
C=O + C2H5OH C C
H H OH dry HCl H OC2H5
(–H2O)
Acetaldehyde hemiacetal Acetaldehyde acetal
(1-Ethoxyethanol) (1, 1-diethoxyethane,
Gem diether)
3
R R O — CH2
HO — CH2 2
C = O + C
—
—
1 (cyclic compound)
R HO— CH2 R O — CH2
Ethanol Ethylene glycol Ethylene glycol acetal
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Rapid Revision & Formula Bank Organic Compounds Containing Oxygen 101
(5) Reduction by metal hydrides such as lithium aluminium hydride
CH3 CH3 H
LiAlH4
C=O C or CH3CH2OH
H H OH
H –O H
Perkin reaction : Condensation of an aromatic aldehyde with acid anhydride in presence of base
(sodium salt of the acid from which the anhydride is derived) to form , -unsaturated acid is known
as Perkin reaction. For example,
CH3COONa
C6H5 CHO (CH3 CO)2 O C6H5 CH CHCOOH CH3 COOH
Benzaldehyde Acetic anhydride Cinnamic acid
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102 Organic Compounds Containing Oxygen Rapid Revision & Formula Bank
Fehling solution : [Alkaline solution of copper sulphate containing sodium potassium tartarate
(Rochelle salt)]
Benedict Solution : Its a solution of CuSO4, sodium citrate and sodium carbonate. When heated
with aldehyde it gives a reddish brown ppt. of Cu2O.
Note : Benzaldehyde although reduces Tollen’s reagent, it does not reduce Fehling and
Benedict solutions
(c) Cannizzaro reaction : This reaction is preferentially given by those aldehydes which do not contain -
hydrogen. In Cannizzaro reaction, one molecule of the aldehyde is oxidised to acid at the expense of the
other which is reduced to alcohol i.e., disproportionation reaction takes place. The reaction occurs in the
presence of concentrated solution of any base.
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Rapid Revision & Formula Bank Organic Compounds Containing Oxygen 103
Ketones can be reduced to secondary alcohols with aluminum isopropoxide in 2-propanol solution
[Me2CHO]3 Al
R 2C O R 2 CHOH (Meerwein Ponndorf's verley reduction)
Me2CHOH
[Me2CHO]3 Al
R 2C O R 2 CHOH
Me2CHOH
CH3 CH3 OH
NaOH
C = O + CHCl3 C
CH3 CH3 CCl3
1, 1, 1-Trichloro-2-methylpropanol-2
(Chloretone) used as hypnotic drug
Haloform reaction : Methyl ketones or alcohols which can be oxidized to methyl ketone gives this
test.
O
e.g., R heat
C CH3 + 3Br2 + 4NaOH RCOONa + CHBr3 + 3H2O + 3NaBr
Bromoform
(reddish brown ppt.)
CHO CHO
conc. HNO3
conc. H2SO4
NO2
Benzaldehyde m-Nitrobenzaldehyde
CHO CHO
conc. H2S2O7
SO3H
Benzaldehyde 3-Benzaldehyde
sulphonic acid
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104 Organic Compounds Containing Oxygen Rapid Revision & Formula Bank
CARBOXYLIC ACIDS
Preparation :
1. By the oxidation of primary alcohols and aldehydes
[O] [O]
RCH2OH RCHO RCOOH
Primary alcohol Aldehyde Carboxylic acid
–
(+H2O) H2O/OH
R–C N RCONH2 RCOO + NH3
+
H
+ R–COOH
H2O/H
R–COOH + NH4 +
heat
CH3 COOC 2H5 KOH(aq.) CH3 COOK C 2H5 OH
Ethyl acetate Potassium acetate
Cl OH O
3KOH(aq.)
H – C – Cl (–3 KCl)
H – C – OH –H2O
H–C
Cl OH OH
Chloroform Formic acid
Unstable
COOH
CH2
heat CH3COOH + CO2
COOH
Malonic acid
O
Dry OH
CH3—C—OMgBr H2O
CH3MgBr + CO2 CH3COOH + Mg
ether
Methyl mag.
bromide Br
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Rapid Revision & Formula Bank Organic Compounds Containing Oxygen 105
O
OH
H2O
C 6H5MgBr CO 2 C 6H 5 – C – OMgBr C 6H5 COOH + Mg
Phenyl magnesium
bromide
Benzoic acid
Br
Product in above reactions have one more carbon than that in Grignard reagent taken.
7. By oxidation of alkyl benzenes
R COOH
KMnO4 /OH–
K 2Cr2O7 or conc. HNO3
Benzoic acid
Physical properties
1. The first three members (C1 to C3) are colourless, pungent smelling liquids, the next three (C4 to C6) have
unpleasant odours. Acids with 7 or more carbon atoms have no distinct smell because of low volatility.
Two molecules of carboxylic acids are held together not by one but by two strong hydrogen bonds.
O -- H – O
C6H5 or R – C C – R or C6H5
O -- H – O
Dimers of carboxylic acids
The behaviour of formic acid is exceptional. It exists as a dimer in vapour state and a polymer in liquid
and solid states.
2. In normal carboxylic acids, the even members have markedly higher melting points than the odd members
preceding or following it.
e.g., the acidic strength of the corresponding halogen acids also follows the same order i.e.
Ortho effect : Among derivative of aromatic carboxylic acid, ortho derivative is the most acidic. This
effect is known as ortho effect.
OH
e.g., > > >
OH
(–I)
OH (–I < + R)
CH3
> > >
CH3
(+I) CH3 (+I, + H)
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106 Organic Compounds Containing Oxygen Rapid Revision & Formula Bank
Chemical Properties
Na Metal 1
R – CH2 – COONa + H
(1) 2 2
NaOH
R – CH2 – COONa + H2O
(2)
NaHCO3
R – CH2 – COONa + CO2 + H2O
(3)
CH3MgBr
R – CH2 – COOMgBr + CH4
(4)
NaOH (CaO)
R – CH3 – Na2CO3
(5)
SOCl2
R – CH2 – COOH RCH2COCl + SO2
(6)
PCl5
R – CH2 – COCl
(7)
Na3,
R – CH2 – C – NH2
(8)
O
P2O5,
R – CH2 – C – O – C – CH2 – R
(9)
O O
R OH/H2SO4
R – CH2 – C – OR
(10)
O
(i) P + X2, (ii) H2O
R – CH – COOH
(11)
X
Derivatives of carboxylic acids : These are formed by the replacement of –OH group of acid by some other
suitable group e.g. RCOCl, RCONH2, RCOOR and (RCO)2O.
Order of Reactivity Towards Nucleophilic Substitution Reaction :
Carboxylic acid derivatives reacts with a nucleophile through addition/elimination mechanism via tetrahedral
intermediate over all substitution product is obtained.
Properties :
H2O
CH3COOH + HCl Fumes in air
C2H5OH
CH3COOC2H5 + HCl
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Rapid Revision & Formula Bank Organic Compounds Containing Oxygen 107
Acid Anhydrides : (RCO)2O, prepared by dehydration of carboxylic acid.
H2O
2CH3COOH
C2H5OH
CH3COOC2H5 + CH3COOH
NH3 CH3CONH2 + CH3COOH
(CH3CO)2O
C2H5NH2 CH3CONHC2H5 + CH3COOH
Esters : RCOOR prepared by reaction of acid with alcohol or acid chloride or anhydrides with alcohol.
H2O/H+
CH3COOH + C2H5OH
NaOH (aq)
CH3COONa + C2H5OH
NH3 CH3CONH2+ C2H5OH
CH3COOC2H5
CH3OH; HCl (aq) CH3COOCH3 + C2H5OH
LiAlH4 CH3CH2OH
OH
(1) 2C2H5 MgBr
CH3—C—C2H5
(2) H2O / H+
C2H5
Acid amides : RCONH2 – It is prepared by reaction of carboxylic acid or its derivatives with NH3. It is
amphoteric in nature.
Acid amides act as weak acids as well as weak bases. Lone pair of N is delocalised with electrons of C = O group.
O O
H H
C—N C N
R H R H
HCl
CH3CONH2.HCl
Na
CH3CONH Na
H2SO4, H2O
CH3COOH + (NH4)2SO4
NaOH
CH3CONH2 CH3COONa +NH3
P2O5,
CH3CN + H2O
(NaNO2 + HCl)
CH3COOH + N2 + H2O
Br2 + KOH
CH3NH2 + K2CO3 + KBr + H2O (Hofmann bromamide reaction)
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Chapter 15
Organic Compounds
Containing Nitrogen
Ni/H2
C6H11NH2
Na2Cr2O7
Aniline black
H2SO4
Na2Cr2O7
O O
H2SO4
NH2 NH2
Br2/CS2 Br
+
Br
NH2
Br2/H2O Br Br
Br
HNO2/H2SO4
m-Nitro Aniline
(i) CH3COCl
+ o & p-Nitro Aniline
(ii) HNO3/H2SO4 (iii) H3O
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Rapid Revision & Formula Bank Organic Compounds Containing Nitrogen 109
DIAZONIUM SALT
1. Preparation of benzene diazonium chloride
NH2 N N
–
NaNO2 + HCl Cl
0° – 5°C
C2H5OH
+ N2+ HCl + CH3CHO
H3PO2 + H2O
+
+ N2 + HCl + H3PO3
Cu
Cl
HCl/CuCl
+ N2 + HCl
Cu
Br
HBr/CuBr
+ N2 + HCl
Cu
N2Cl CN
NaCN
+ N2 + NaCl
+ CuCN
OR OH
+
N NCl
H2O
H2SO4
I
KI
+ N2 + KCl
HBF4
+ N2 + BF3 + HCl
C6H6
biphenyl
NaOH
B. Coupling Reaction :
Coupling of benzene diazonium chloride with phenol takes place in slightly basic medium while that of
aniline take place in slightly acidic medium. These compounds produce Azo dyes with benzene diazonium
chloride.
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110 Organic Compounds Containing Nitrogen Rapid Revision & Formula Bank
OH
N=N OH
(pH 8)
p-Hydroxy azobenzene
(orange dye)
N(CH3)2
OH
N=N
OH
Phenylazo- -naphthol
(Red dye)
NaNO2/HCl –
HO3S NH2 HO3S N NCl
0°C
p-sulfanilic acid
Me
N
Me
Me
HO3S N=N N
Me
Methyl orange
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Chapter 16
Polymers, Biomolecules,
Chemistry in Everyday Life
POLYMERS
Polystyrene or Styrene C6 H5 – CH = CH2 Plastic toys, house hold wares radio and
Styron television bodies
Buna-S Styrene CH = CH2, Butadiene Manufacture of tyres, rubber sole, water proof
CH2=CH–CH=CH2 shoes
Polyacrylates Methyl methacrylate Lenses, light covers, light shades, air craft
windows... etc.
CH3
Polyethyl CH2 = C – COOCH3 Latex paints adhesives
acrylate CH2 = CH – COOC2H5
Polytetrafluoro Tetrafluoro ethylene CF2 = CF2 For nonstick utensils coating etc.
ethylene (PTFE)
(Teflon)
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112 Polymers, Biomolecules, Chemistry in Everyday Life Rapid Revision & Formula Bank
Condensation Polymers
Terylene (i) Ethylene glycol– For wash and wear fabric tyre cords, seat
or dacron HO – CH2 – CH2 – OH belts and sails
(ii) Terephthalic acid –
HOOC COOH
H
O
N
Nylon 6 Caprolactam – Mountaineering ropes, tyre cords fabrics
OH
Bakelite Phenol Formaldehyde, HCHO As binding glue for wood varnishes, lacquers
Urea (i) Urea NH2 — C — NH2 Buttons, bottle caps, surgical items
formaldehyde
resin (ii) Formaldehyde HCHO
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Rapid Revision & Formula Bank Polymers, Biomolecules, Chemistry in Everyday Life 113
Biodegradable Polymer
OH
Poly- -hydroxy (a) CH3 – CH – CH2COOH As packaging
butyrate-Co- 3- hydroxybutanoic acid orthopaedic devices
hydroxy valerate and in controlled
[PHBV]. drug release.
OH
(b) CH3 – CH2 – CH – CH2COOH
3-hydroxypentanoic acid
BIOMOLECULES
Carbohydrates
1. Carbohydrates are mainly compounds of carbon, hydrogen and oxygen.
2. General molecular formula initially considered was Cx(H2O)y
e.g., glucose – C6H12O6, sucrose C12H22O11 etc.
But many of the compounds which behave as carbohydrates, do not follow the general molecular formula
Cx(H2O)y formula.
3. Thus carbohydrates are the class of compounds that include polyhydroxy aldehydes or polyhydroxy
ketones.
4. Carbohydrates are also known as saccharides.
Classification
The carbohydrates are classified into three major classes
(i) Monosaccharides
(ii) Oligosaccharides
(iii) Polysaccharides
Monosaccharides
(i) Monosaccharides are simple sugars with single unit of polyhydroxy aldehyde or polyhydroxy ketones.
(ii) General molecular formula CnH2nOn (with some exceptions).
Oligosaccharides
(i) Oligosaccharides are made up of 2-9 units of monosaccharides or simple sugars.
(ii) Oligosaccharides with two, three and four monosaccharides respectively known as disaccharides, and
trisaccharides and tetrasaccharides.
(iii) Sucrose is the example of this class.
H
C12H22O11 H2 O C 6H12O 6 C 6H12O 6
(sucrose) (glucose) (fructose)
Polysaccharides
(i) Polysaccharides are made up of 'n' number of monosaccharide units (above 10 carbon atoms).
(ii) Starch, cellulose and glycogen are the examples of this class.
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114 Polymers, Biomolecules, Chemistry in Everyday Life Rapid Revision & Formula Bank
nH2O
(iii) (C 6H10 O 5 )n nC 6H12 O 6
starch H glucose
Note : Monosaccharides and oligosaccharides are collectively known as Sugars as they are soluble
in water and sweet in taste. Whereas polysaccharides on other hand are known as
Non-sugars.
Monosaccharide-Glucose
Glucose is known as dextrose and also known as grape sugar.
Preparation
Hydrolysis of cane sugar in presence of alcohol gives glucose (along with fructose)
Glucose and Fructose have same molecular formula but different structural formula.
Chemical Properties
(i) Reaction with PCl5 :
CHO CHO
CH2OH CH2Cl
Glucose Penta-chloroglucose
CHO CHO
(CHOH)4 + (CH3CO)2O (CHOCOCH3)4
CH2OH CH2OOCCH3
Penta-acetate glucose
(iii) Reduction :
CHO CH2OH
Na-Hg
(CHOH)4 + 2H (CHOH)4
H2O
CH2OH CH2OH
Sorbitol
CHO COOH
CHO COOH
(CHOH)4 + Ag2O (CHOH)4 + 2Ag (mirror)
CH2OH CH2OH
Gluconic acid
CHO COOH
HNO3
(CHOH)4 + 3[O] (CHOH)4
CH2OH COOH
Saccharic acid
(Glucaric acid)
H2NNHC6H5
CH NNHC6H5 CH NNHC6H5
C NNHC6H5 C O
H2NNHC6H5
(CHOH)3
CH2OH
Note : Due to this isomerisation, fructose even it does not contain – CHO group reduces Fehling's
solution and Tollen's reagent in alkaline medium.
Structure of D-Glucose
(i) Open chain structure :
The reaction of glucose with
(a) HI to give hexane
(b) Hydroxylamine to form monoxime
(c) HCN to form cyanohydrin, gives the existence of the open chain structure of glucose
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116 Polymers, Biomolecules, Chemistry in Everyday Life Rapid Revision & Formula Bank
Disaccharides
(i) Disaccharides are composed of two molecules of monosaccharides linked by glycosidic linkage.
(ii) The disaccharides may be reducing or non reducing in nature depending upon linkage.
+
H2O/H
Sucrose (C12H22O11) -D Glucose + -D Fructose
(C1) (C2 )
+
H2O/H -D Glucose + -D Galactose
Lactose (C12H22O11)
(C4 ) (C1)
+
H2O/H -D Glucose + -D Glucose
Maltose (C12H22O11) (C1) (C4 )
6 CH2OH
-linkage
5 O O
H H O CH2OH
H 2
4 OH H 1 OH H
HO -linkage
H , -glycosidic linkage
3 2 HOH2C
H OH H OH
Glucose unit Fructose unit
(ii) Lactose
-linkage
CH2OH H OH
3 2
O O
HO H
H OH H
1
OH H 1
-glycosidic linkage
4 H
H H H O OH
5
H OH CH2OH
6
(iii) Maltose
CH2OH CH2OH
O H H O
H H
H H
1 4
OH H OH H
HO O OH -glycosidic linkage
H OH -linkage H OH
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Rapid Revision & Formula Bank Polymers, Biomolecules, Chemistry in Everyday Life 117
Polysaccharides :
In polysaccharides, thousands of monosaccharide units are joined together by glycosidic linkage.
Starch : (C6H10O5)n
+
H /H2O
(C6H10O5)n C12H22O11 C6H12O6
Starch Maltose D-glucose
(i) Starch does not reduce Fehling’s solution or Tollen’s reagent.
(ii) Starch does not form an Osazone.
(iii) Starch is a mixture of two polysaccharides i.e., amylose (15-20%) and amylopectin (80-85%).
Amylose is water soluble and amylopectin is water insoluble component of starch.
Cellulose : (C6H10O5)n
(i) Cellulose is a straight chain polysaccharide composed of only D-glucose units with 1-4 glucosidic
linkage.
(ii) Cellulose does not reduce Tollen’s reagent or Fehling’s solution.
AMINO ACIDS
Proteins are made up of amino acids. All naturally occurring amino acids are -amino acids, where amine group
is connected with -carbon of carboxylic acid. Amino acids have amphoteric character. A free amino group
is basic, a free carboxyl group is acidic. Lysine and Arginine are Basic Amino Acids because they carry
two amino groups and one carboxyl group is acidic. Glutamic acid (glutamate) and Aspartic acid (aspartate)
contain one amino and two carboxyl groups each and are classified as Acidic Amino Acids. Alanine, glycine,
valine and phenylalanine are Neutral Amino Acids as these contain one amino and one carboxyl group.
R CH COOH R CH COO
–
NH2 NH3
+
Amino acid (R = side chain)
COOH -C COOH
H2N — C — H H2N — C — H
CH2 CH2
CH2 COOH
CH2
Aspartic acid
H2C — NH2
COOH
Glutamic acid
(polar)
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Amino Acids which occur in Proteins: Glycine, alanine, serine, cysteine, aspartic acid, glutamic acid,
asparagine, glutamine, methionine, threonine, valine, leucine, isoleucine, lysine, histidine, arginine, phenylalanine,
tyrosine, tryptophan and proline.
PROTEINS
Proteins are polyamides formed from amino acids. The -carbon atom of the amino acids is asymmetric
and show optical isomerism (stereo). Proteins consist mainly of L isomers of amino acids. There are 20
commonly occurring amino acids in proteins. Amino acids form zwitter ion. Lack of essential amino acids
in diet can cause diseases such as Kwashiorkor.
Peptide Bond and Structure of Proteins: Amino acids are joined together by an amide linkage called
peptide bond.
Proteins are long polymers of amino acids linked by peptide bonds (polypeptides). The sequence in which
the amino acids are arranged in a protein is called the primary structure.
The secondary structure arises due to the regular folding of the backbone of the polypeptide chain due
to intramolecular hydrogen bonding in -helix and intermolecular hydrogen bonding in -plated sheet
between the carboxyl and amino groups. Lead to the formation of -helix and -pleated sheet.
Tertiary Structure of Proteins: The tertiary structure of proteins represents overall folding of the
polypeptide chain i.e., fruther folding of the secondary structure. It gives rise to two major molecular
shapes viz fibrous and globular. The main forces which stabilises the 2° and 3° structures of proteins
are hydrogen bonds, disulphide linkages, van der Waals and electrostatic forces of attraction.
Quarternary 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 sub-units with respect to each other
is known as quaternary structure.
ENZYMES
Enzymes are biological catalysts which increase the rate of biochemical reactions even under mild
conditions of temperature and pH without taking part in reaction.
Properties of Enzymes :
(i) They speed up reactions up to ten million times compared to the uncatalyzed reactions.
(ii) They are very specific in their action on substrates and each enzyme catalyzes only specific type of reaction.
(iii) They are active at moderate temperature and pH.
(iv) The action of enzymes are inhibited by various organic and inorganic molecules.
Enzymes and Diseases : Certain diseases are caused by enzyme deficiencies. The congenital disease
phenylketonuria, is due to a deficiency of the enzyme phenylalanine hydroxylase. Albinism is another
disease caused due to deficiency of an enzyme tyrosinase. Many heart attacks are caused by blood clot
formation in a coronary artery. The enzyme streptokinase is used to dissolve the clot.
NUCLEIC ACIDS
1. Nucleic acids play an essential role in transmission of the hereditary characteristics and the
biosynthesis of proteins.
2. There are two classes of nucleic acids : DNA (deoxyribonucleic acid) and RNA (ribonucleic acid).
Nucleic acids are the long polymers in which the monomeric units are nucleotides. The structural
units of nucleotides are made up of three essential components; a nitrogenous base, a pentose sugar
(a 5-carbon sugar), and a phosphate group.
3. In nucleic acids, the individual nucleotides are linked through phosphate groups to give rise to long
polynucleotide structures.
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Rapid Revision & Formula Bank Polymers, Biomolecules, Chemistry in Everyday Life 119
Structure of DNA
DNA consists of two strands of polynucleotides coiled around each other in the form of a double helix.
Diameter
20Å
5' 3'
P
P
S C G S Nitrogeneous
P base pair
P T=A
S
3.4 Å S
P
P
S S
Sugar-phosphate backbone
P
P
S S
G C
P
One complete turn 34 Å
P
S A=T S
P
P
G C S
S
P
P
S
A=T S
Major groove
P
SS
P
Minor groove
P
P
C G S
S
P
P
S
T=A S
3' 5'
VITAMINS
Vitamins are organic compounds necessary for normal health but cannot be synthesised in human body.
Deficiency of vitamins causes many disorders and diseases. Vitamins B and C are water soluble while
vitamins A, D, K and E are fat soluble.
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Antipyretics
Antipyretics are substances used to bring down body temperature in high fever. e.g. Aspirin, Phenacetin and
Paracetamol.
Aspirin is a common antipyretic. It should not be taken empty-stomach as it generates salicylic acid which may
ulcerate stomach wall and can cause bleeding. Calcium and sodium salts of aspirin are more soluble and less
harmful.
OCOCH3 OH C2H5
COOH
NH — C — CH3 NHCOCH3
O
Aspirin 4–acetamidophenol Phenacetin
(Paracetamol)
Analgesics
These are drugs used for relieving pain. Aspirin and some other antipyretics act as analgesics also. Certain
narcotics (which produce sleep and unconsciousness) are also used as analgesics. Examples of narcotics
are morphine, marijuana, codeine, pethidine and heroin. They are known to be habit-forming.
RO
C6H5 COOC2H5
–
O Cl
N — CH3 N
R = H, Morphine CH3 H
R = CH3, Codeine
Pethidine hydrochloride
Antibiotics
Antibiotics are chemical substances produced by micro-organisms (bacteria, fungi and moulds) that can inhibit
the growth or even destroy other micro-organisms. Penicillin is used against large number of infections caused
by various bacteria. It is an effective drug for pneumonia, bronchitis, sore throat and abscesses. Other
antibiotics like streptomycin and tetracycline are used against diseases caused by bacteria.
Some antibiotics are specific for certain diseases, for example, streptomycin for tuberculosis and
chloramphenicol for typhoid.
Broad spectrum antibiotics are medicines effective against several different types of harmful micro-organisms,
e.g., tetracycline, chloramphenicol. Penicillin has a narrow spectrum. Ampicillin and amoxicillin are derivatives of
penicillin.
Chloramphenicol is a broad spectrum antibiotic. It is rapidly absorbed from the gastro-intestinal tract and hence
can be given orally in case of typhoid, dysentry, acute fever, certain form of urinary infections, meningitis and
pneumonia.
Sulpha drugs like sulphanilamide, sulphadiazine and sulphaguanidine act against micro-organisms like
antibiotics and have been used in place of them.
Tranquilizers
The chemical substances which act on the central nervous system and has a calming effect to reduce anxiety
are specified as tranquilizers. They are used for the treatment of mental diseases they are also used for making
sleeping pills. They are habit forming and should not be taken without proper prescription. They do not add
any energy into the person but help to remove the emotional distress or depression and the person is able to
work to his full capacity. The most commonly used tranquilizers are barbituric acid and its substituted derivatives
such as luminal and seconal.
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Rapid Revision & Formula Bank Polymers, Biomolecules, Chemistry in Everyday Life 121
CHEMICAL IN FOOD
During processing of food, a number of chemicals are added to it to increase its life and also to make it more
attractive. Some of these chemicals which are present in food are discussed below.
1. Chemical preservatives : Growth of micro organisms in a food material can be inhibited by adding certain
chemical substances. Such chemical substances which are added to food materials to prevents their
spoilage are known as chemical preservatives. The most commonly used preservatives includes table salt,
sugar, vegetable oils and sodium benzoate. Sodium benzoate is used in limited quantity salts of sorbic
acid and propanoic acid are also used as preservatives.
2. Artificial sweetening agent : Sugar is the natural sweeting agent. However, excess of sugar leads to
many diseases such as obesity, diabetes. Many artificial sweetening agents have been isolated which are
more sweeter than sugar. Ortho-sulphobenzimide also called saccharin is the first popular sweetening agent.
Some other artificial sweetener are aspartame, sucralose, alitame etc.
CLEANSING AGENT
Two types of detergents are used as cleansing agent. These are soaps and synthesis detergents. These help
in removal of fats which bind other materials to the fabric or skin.
These days detergents are much in vogue and get preference over soaps because they work even in hard water.
Synthetic detergents are classified into three main categories namely anionic, cationic and non-ionic and each
category has its specific use. Detergents with straight chain of hydrocarbons are preferred over branched chain
as the latter are non-biodegradable and consequently cause environmental pollution.
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Chapter 17
Classification of Elements and
Periodicity in Properties
Note : Size of Iso-electronic ions : These are such cations or anions which carry the same number
of electrons. The size of such ions depends upon the effective nuclear charge. Greater the
nuclear charge of an ion, greater will be the force of attraction for same number of electrons.
As a result, the size of the ion decreases. For example :
N3–, O2–, F–, Na+, Mg2+ and Al3+ are isoelectronic ions, among these N3– is largest (1.71 A) and
Al3+ is smallest (0.50 A).
B. Ionization Enthalpy
It is the amount of energy required to remove most loosely held electron from the ground state of an Avogadro
number of the isolated atoms, ions or molecules in the gaseous state. The ion formed by loss of first electron
may lose further electrons and thus we may have successive ionization energies for removal of 2nd, 3rd and
4th electrons in the gaseous state.
Ionization is always an endothermic process and ionization energies are therefore always assigned positive
values.
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Rapid Revision & Formula Bank Classification of Elements and Periodicity in Properties 123
Factors influencing Ionization energy
(1) Successive Ionization - Generally ionization energy increases for successive ionizations.
(2) Atomic size - Ionization energy decreases as the size of atom increases.
(3) Value of Z (atomic number) - Higher the value of Z, higher is the I.E.
(4) Distance of electron from the nucleus - Smaller the distance of the electron from the nucleus, larger
is the ionization energy
(5) Shielding effect - Higher is the shielding of the electron to be removed, lower is the I.E. Shielding effect
of the electrons of different orbitals follows the order s > p > d > f.
(6) Penetration effect - Higher the penetration power of the electron to be removed higher is the I.E. The
penetration power of electrons of various orbitals follow the order s > p > d > f.
(7) Nature of shell - Ionization energy increases if the electron to be ionized from the species belongs to a
half filled shell or a completely filled shell. The relative stability of these configurations follows the order
d 5 < p 3 < d 10 < p 6.
(8) Changes in the quantum shell - During the successive ionization, the electron to be ionized belongs
to the lower quantum shell the I.E. therefore increases many folds. It is the combined effect of (a) effective
nuclear charge (b) stability of completely filled shells (c) closer proximity of the lower shell to the positively
charged nucleus.
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D. Electronegativity
It may be defined as : “The tendency of an atom to attract shared electron pair towards itself in a molecule”.
The small atoms attract electrons more strongly than larger ones, hence they are more electronegative.
The numerical value of electronegativity depends upon the ionisation potential and electron affinity. Higher
ionisation potential and higher electron affinity both imply higher electronegativity. To measure electronegativity,
an arbitrary scale was developed by Linus Pauling which is known as electronegativity scale. On this scale
fluorine has maximum electronegativity of 4.0 and Li has a value of 1.0 while inert gas have no value
of electronegativity.
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Chapter 18
General Principles and Processes
of Isolation of Metals
Copper
(i) Cuprite : Cu2O
(ii) Copper pyrites : CuFeS2
(iii) Copper glance : Cu2S
(iv) Bornite : Cu2FeS3
(v) Malachite : CuCO3.Cu(OH)2
(vi) Azurite : [2CuCO3].Cu(OH)2
Zinc
(i) Zincite : ZnO
(ii) Calamine : ZnCO3
(iii) Zinc blende : ZnS
(iv) Willemite : Zn2SiO4
Aluminium
(i) Corundum : Al2O3
(ii) Diaspore : Al2O3.H2O
(iii) Bauxite : Al2O3.2H2O
(iv) Cryolite : Na3AlF6
(v) Feldspar : KAlSi3O8
(vi) Mica : K2O.3Al2O3.6SiO2.2H2O
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126 General Principles and Processes of Isolation of Metals Rapid Revision & Formula Bank
ALUMINIUM
Al is most abundant metal in earth crust. Important ores are Bauxite Al2O3.2H2O; Diaspore Al2O3.H2O; Corundum
Al2O3; Feldspar KAlSi3O8; Cryolite Na3AlF6. It is usually extracted from bauxite through the following steps:
Purification of Bauxite
Bayer’s Process
(a) Red bauxite containing the impurity of iron oxide is concentrated by leaching with NaOH.
2NaOH + Al2O3 2NaAlO2 + H2O
(b) Sodium meta aluminate thus obtained is soluble in water while impurities of iron oxides remain insoluble.
The solution is diluted with water and agitated to get a precipitate of Al(OH)3.
NaAlO2 + 2H2O Al(OH)3 + NaOH
(c) On strong heating this precipitate gives alumina.
Hall’s Process
(a) Electrolysis of alumina (Hall Heroult's process) : purified alumina is then mixed with cryolite to lower
down its melting point, cryolite also increases, the conductance and molten cryolite acts as solvent.
Na3AlF6 3NaF + AlF3
AlF3 Al3+ + 3F–
At cathode : Al3+ + 3e– Al
At anode : 2F F2 + 2e–
(b) Aluminium thus obtained is refined by Hoope’s electrolytic process using molten cryolite and BaF2 as
electrolyte.
IRON
Ores : Haematite Fe2O3, Magnetite Fe3O4; Limonite Fe2O3.3H2O; Iron pyrites FeS2; Siderite FeCO3.
1. Types
(a) Pig iron or cast iron : 2 to 4.5% C with some impurities like S, Si, P, Mn. It cannot be welded.
(b) Wrought iron : purest form of Fe (0.2 - 0.5% C).
(c) Steel : 0.1 to 1.5% C along with some other elements like Cr, Mn, Ni etc.
2. Extraction from Haematite : It is concentrated by washing with water. Then it is roasted with a little of coal
in a reverberatory furnace. During roasting moisture is removed. Impurities of As, S and P are converted into
their gaseous oxides. Roasted mass is then reduced by mixing with coke and limestone in a blast furnace
in the ratio of 8 : 4 : 1 (Smelting).
THERMODYNAMICS OF METALLURGY
The method employed for extracting a metal from its ores depends on the nature of the metals and that of
the ore may be related to the position of the metal in the electrochemical series. In general, metals with
E° < – 1.5 volt yield compounds which are very difficult to reduce and electricity is usually used for the
isolation of such metals. On the other hand, noble metals with E° > 0.5 volt form easily reducible compounds.
A metal higher up in the electrochemical series should be more difficult to reduce to metallic form. As we
move down in the electrochemical series, the reduction becomes more and more easy. E° of metal provides
some idea regarding the selection of an appropriate method for extracting the metal from its compounds.
Free energy is related to standard cell potential
G° = – nF E°cell
n Number of moles electrons
F Faraday constant 96500 C.
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Rapid Revision & Formula Bank General Principles and Processes of Isolation of Metals 127
In order that the reduction of oxide, halide or sulphide ore by an element may take place simultaneously at
a given temperature and pressure, there is decrease in the free energy of the system (– G).
More the negative value of G, higher is the reducing power of an element. The free energy change ( G) is
related to the heat change ( H) as well as to the product of temperature. [ G = H – T S]
For a reaction, 2M + O2 2MO
G becomes smaller with the increase in temperature. This is because the gaseous reactant oxygen is
consumed in the reaction leading to the decrease in randomness or entropy of the system hence G becomes
negative. With further increase in temperature, T S becomes more negative value. Since the term T S is high
G is less.
Reaction becomes more feasible.
–100
–200 2Cu2O
4Cu + O 2
–300 2FeO
–1
O2
2Fe +
Change in Free Energy G , kJ mol
C + O2 CO2
–400
2CO 2
+ O2
–500 2CO 2C +
O2
o
2CO
2ZnO
–600 O2
2Zn +
–700 A
–800
l O3
2/3A 2
–900 l + O2
4/3A
–1000 2MgO
O2
2Mg +
–1100
–1200
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Chapter 19
Hydrogen and s-Block Elements
(Alkali and Alkaline Earth Metals)
HYDROGEN
Most abundant element of the universe, which was first prepared by Cavendish by the action of acids on
certain metals. Its name hydrogen was proposed by Lavoisier because it produces water when burnt in
oxygen. Hydrogen is the lightest element which is found in nature both in free state and in combined state.
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Rapid Revision & Formula Bank Hydrogen and s-Block Elements (Alkali and Alkaline Earth Metals) 129
Isotopes of Hydrogen : Hydrogen has three isotopes.
1p 1p
1p
1n 2n
1 2 3
Protium (1H ) Deuterium (1 H ) Tritium (1 H )
Non-radioactive Non-radioactive Radioactive
Physical properties of isotopes are different whereas their chemical properties are same
Physical Properties
Important physical properties of hydrogen are as follows
1. It is colourless, odourless, tasteless gas.
2. Dihydrogen has two nuclear spin isomers called ortho and para-dihydrogen.
e e e e
P P P P
Ortho-Hydrogen Para-Hydrogen
(Parallel nuclear spin) (Antiparallel nuclear spin)
Atmosphere contains 75% ortho-H2 and 25% para-H2. Ortho-H2 and Para-H2 have 1 and 0 nuclear spin
respectively. With the decrease in temperature percentage of para-form increases and it can be upto 100%.
Hard Water and Soft Water : Depending upon the behaviour of water towards soap solution. Water
may be classified as soft and hard water.
The hardness of water may be
1. Temporary hardness – due to presence of bicarbonates of calcium and magnesium.
2. Permanent hardness – due to sulphates or chloride of calcium and magnesium.
Removal of Hardness : Temporary hardness of water can be removed by following methods :
1. By boiling :
Boil
Ca(HCO3)2 CaCO3 + H2O + CO2
2. By Clark's process :
Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O
Permanent hardness can be removed by any of the following method.
1. Washing Soda : It converts soluble calcium and magnesium compounds into insoluble carbonates.
CaCl2 + Na2CO3 CaCO3 + 2NaCl
2. Permutit : The sodium ions of permutit are exchanged with calcium and magnesium ions when
hard water is passed through it.
Na 2Al 2Si 2O 8 xH 2O + Ca 2+ CaAl 2 Si 2O 8 xH 2O + 2Na +, permutit can be regenerated by
treatment of brine solution.
3. Calgon : Calcium and magnesium salts present in hard water react with calgon to give complex salt.
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130 Hydrogen and s-Block Elements (Alkali and Alkaline Earth Metals) Rapid Revision & Formula Bank
4. Ion exchange resins : Ion exchange resins are giant organic molecule of high molecular masses
which are of two types :
(a) Cation exchanger [e.g., RSO3Na]
O OH O
R R R
H2 /Pd O2
+ H2O2
O OH O
Chemical Properties
1. Oxidising property : Hydrogen peroxide acts as an oxidising agent both in acidic as well as in
alkaline medium.
In acidic medium
H2O2 + 2H+ + 2e– 2H2O; E° = 1.77 V (slow)
In basic medium
H2O2 + 2e– 2OH– ; E° = 0.87 V. (fast)
2. Reducing Property : In presence of strong oxidising agents, hydrogen peroxide behaves as a
reducing agent in both the medium.
Acidic Medium
H 2O 2 2H+ + O2 + 2e–
Alkaline medium
H2O2 + 2OH– 2H2O + O2 + 2e–
3. Acidic property : H2O2 is a weak acid (Ka = 1.55 × 10–12). It has two ionisable H atoms. It forms
two series of salts.
4. Decomposition : H2O2 is an unstable liquid
2H2O2 2H2O + O2
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Rapid Revision & Formula Bank Hydrogen and s-Block Elements (Alkali and Alkaline Earth Metals) 131
Volume Strength of H2O2
Volume strength of H2O2 solution is defined as volumes of O2 evolved at STP in ml that is obtained per ml of
H2O2 solution after complete decomposition i.e., if 1 litre solution of H2O2 gives 10 liters of oxygen at STP
volume strength of H2O2 is 10 volume.
Volume strength of H2O2 = 11.2 × M or 5.6 × N
Reaction :- 2H2O2 2H2O + O2
s-BLOCK ELEMENTS
Lithium Li 3
Sodium Na 11
Potassium K 19
Rubidium Rb 37
Caesium Cs 55
Francium Fr 87
Physical Properties
Important physical properties of Alkali metals are given below :
Flame Colouration
The alkali metals and their salts impart a characteristic colour to the flame.
Li Na K Rb Cs
Crimson red Yellow Violet Red violet Blue
Reducing Power
The reducing power of a metal is related to its oxidation potential which represents the tendency of element to
lose electron and get oxidised.
All alkali metals have low ionisation energy leading to a high oxidation potential.
(a) Reducing nature (in aq. solution) :
Li > Cs > Rb > K > Na
(b) In gaseous state
Li < Na < K < Rb < Cs
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132 Hydrogen and s-Block Elements (Alkali and Alkaline Earth Metals) Rapid Revision & Formula Bank
Chemical Reactivity
Alkali metals are highly reactive due to low ionisation energy.
Metal Hydroxides
(a) Basic strength of hydroxide increases with the increasing electropositivity of metal.
CsOH > RbOH > KOH > NaOH > LiOH.
(b) Solubility of hydroxides increases with increasing ionic character.
CsOH > RbOH > KOH > NaOH > LiOH.
(c) Li2CO3 decomposes on heating and it is insoluble in water. [ Li2CO3 Li2O CO2 ]
Beryllium Be 4
Magnesium Mg 12
Calcium Ca 20
Strontium Sr 38
Barium Ba 56
Radium Ra 88
Oxidation states
All metal show a stable oxidation state of +2.
Flame Colouration
Ca, Sr, Ba, Ra impart a characteristic colour to the flame, whereas Be and Mg do not show flame colouration
due to high ionisation energy.
[Ca – brick red], [Sr – crimson], [Ba – green], [Ra – crimson]
Reducing Nature
(a) The alkaline earth metals have the tendency to loose electrons and change into bivalent cation.
M M2+ + 2e–
Hence they act as strong reducing agents.
(b) The reducing nature increases as the atomic number increases.
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Chapter 20
p-Block Elements
The electropositive character increases from B to Al and then decreases upto Tl. It is due to ineffective shielding
caused by d and f electrons which results in the stronger nuclear pull on the electrons of outermost shell.
Compounds of Boron
1. Orthoboric Acid : H3BO3
Preparation :
Properties :
(a) Boric acid has layer type structure in which planar BO33 units are linked to one another through
Hydrogen bonds.
(b) Boric acid is a weak monobasic acid. It does not act as proton donor but acts as a lewis acid by
accepting electrons from hydroxyl ion.
H3BO3 100 C
HBO2 H2O 160 C
H2B 4 O7 H2 O Red heat
2B2 O3 H2 O
metaboric acid tetraboric acid
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134 p-Block Elements Rapid Revision & Formula Bank
OH
B
O O
Na2 HO B—O— B OH .8H2O
O O
B
OH
Preparation
4H3BO3 + Na2CO3 Na2B4O7 + 6H2O + CO2
Properties
(a) It hydrolyses in water to form alkaline solution.
(b) Borax bead Test (Test for Transition Elements)
Glassy bead + metal oxide metal metaborate (coloured)
3. Diborane: B2H6
Structure of B2H6 (Diborane)
Boron in B2H6 is sp3 hybridised.
Two bridging B – H > Terminal B – H bond
Boron is dimerised by Banana bond known as 3-centred-2electron (3c – 2e) bond.
pm
H H H H H
4
H
13
B 97° B 120° B B
pm
H H H H H H
9
11
Banana bond
Diborane
Preparation :
(a) 3LiAlH4 + 4BCl3 3LiCl + 3AlCl3 + 2B2H6
Silent Electric
(b) 2BCl3 + 6H2 Discharge
B2H6 + 6HCl
Properties :
(a) Stable at low temperature only, colourless and highly toxic.
(b) B2H6 + 6H2O 2H3BO3 + 6H2
450 K
(e) 2B2H6 + 6NH3 2B3N3H6 + 12H2
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Rapid Revision & Formula Bank p-Block Elements 135
4. B3N3H6 : Borazole also known as Borazine or Inorganic Benzene.
Preparation
B
H H
N N
B B
H N H
5. Alums : General formula, M2SO4 . M'2(SO4)3 24H2O where M is a monovalent ion like Na+, K+, NH4+ while M'
is a trivalent ion like Fe3+, Cr3+, Al3+, K2SO4. Al2(SO4)3. 24H2O-Potash alum; (NH4)2SO4. Fe2(SO4)3. 24H2O-
Ferric alum; K2SO4.Cr2(SO4)3. 24H2O-Chrome alum. Out of all these potash alum is very common. When the
crystals of potash alum are heated it swells and loses water. Anhydrous alum thus obtained is called burnt
alum.
AlCl3 Aluminium chloride exists as a dimer where two AlCl3 units are joined together with the formation
of two dative bonds (co-ordinate bonds) because AlCl3 is electron-deficient (Lewis acid).
Cl Cl Cl
Al Al
Cl Cl Cl
In AlCl3 dimer, four bond length are larger while bond length of four bonds are small.
AlCl3 is used as catalyst in Friedel Craft’s reaction, where it is a Lewis acid.
O O O
Compounds of Silicon
O Si O Si O Si O
1. Silicon dioxide (SiO2):
SiO 2 is solid at room temperature and has a three O O O
dimensional network structure as shown below O Si O Si O Si O
(a) In this structure, silicon atom is bonded to four O O O
oxygen atom which are tetrahedrally arranged around
it. O Si O Si O Si O
2. Silicones :
Silicones are synthetic organosilicon compounds containing repeated unit of R2SiO held by Si–O–Si
linkages.
Preparation : The silicones are prepared by the hydrolysis of dialkyl dichloro silane (R2SiCl2)
R R
| |
Cl Si Cl + 2H2O HO Si HO
| |
R R
R R R
R R R
R R R
Polymerisation : O Si O Si O Si O
R R R
The hydrolysis of RSiCl3, gives cross linked silicones.
Properties :
(a) Silicones are chemically inert towards oxidation, thermal decomposition or attack by organic reagents.
(b) They are water repellant and heat resistant.
3. Silicates : Silicates are the compounds in which the anions present are either discrete SiO44– tetrahedra
or a number of such units joined together through corners.
Types of Silicates : Silicates are classified into different types depending upon the number of corners of
SiO44– tetrahedron shared with other tetrahedron.
Formula
1. Orthosilicate
Ex. Zircon. SiO4
4–
(ZrSiO4)
2. Pyrosilicates 6–
Si2O 7
Ex. Thortveitite
Sc2(Si2O7)
4. Chain Silicates 2–
(SiO3 )n (Pyroxene)
Ex. Spodumene;
LiAl(SiO3)2
6. Three dimensional silicates All the four corners are shared with other
Ex. Quartz tetrahedra (SiO2)
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Rapid Revision & Formula Bank p-Block Elements 137
NITROGEN FAMILY (GROUP-15 ELEMENTS)
Characteristics of Hydrides
(a) Basic Strength : All these hydrides act as Lewis bases. They can donate an electron pair to electron
deficient species. (Lewis acids). As we go down the group, the basic character of these hydrides
decreases.
(b) Thermal Stability : Thermal stability of the hydrides of group 15 elements decreases as we go down
the group.
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138 p-Block Elements Rapid Revision & Formula Bank
OXYGEN
Preparation : Oxygen is mostly prepared by the following methods :
1. In laboratory it is prepared by heating KMnO4 or KClO3 in presence of MnO2.
Heat
2KClO3 (s) MnO 2KCl + 3O2
2
Ozone (O3)
Preparation : Ozone is prepared by subjecting pure oxygen to silent electric discharge
3O2 2O3 ; H = + 284.5 kJ mole–1.
Properties :
It is pale blue gas having a strong characteristic smell. It is neutral to litmus. It condenses to blue liquid
(b. pt 161. 2K). It condenses to a violet- black solid (melting point 80.6 K).
The important reactions are given below:
250 C
1. O3 O2 + O
2. H2S + O H2O + S
3. 2Ag + O Ag2O
4. 2Hg + [O] Hg2O (Tailing of Mercury)
5. I2 + H2O + 5[O] 2HIO3
6. It is better oxidising agent as compared to H2O2.
H2O2 + O3 H2O + 2O2
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Rapid Revision & Formula Bank p-Block Elements 139
Properties : The important properties are
1. It is a strong dibasic acid
H2SO4 H+ + HSO4– 2H+ + SO42–
2. On heating it liberates oxygen and thus it acts as a strong oxidising agent
Oxidation of non-metals
C + 2H2SO4 CO2 + 2SO2 + 2H2O
It liberates iodine from KI
Fluorine F 9
Chlorine Cl 17
Bromine Br 35
Iodine I 53
Astatine At 85
X2 F2 Cl2 Br2 I2
OXYACIDS OF CHLORINE
Different oxyacids of chlorine are
Acidic Character : Acidic Character of the same halogen increases with the increase in oxidation number of
the halogen.
HClO4 > HClO3 > HClO2 > HOCl
Reason : It is because the release of H+ ion in each case would result in the formation of ClO4–, ClO3–, ClO2–,
ClO– ions. More is the stability of resulting ion, greater will be the ease with which the ion is formed. Therefore,
the ease of formation of ions would be.
ClO4– > ClO3– > ClO2– > ClO–
Interhalogen Compounds
The halogens on account of the difference in their electronegativities combine with each other and form binary
covalent compounds of ABn type which are called interhalogen compounds. A is always bigger atom and B
is a smaller atom. n may have value 1, 3, 5 and 7 corresponding to oxidation state of halogens.
3
AB type ClF, BrF, BrCl, ICl, IBr sp hybridization, Linear shape
3
AB3 type ClF 3, BrF 3, ICl3 sp d hybridization, T-shape
3 2
AB5 type BrF5 , IF5 sp d hybridization, distorted square pyramidal shape
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Rapid Revision & Formula Bank p-Block Elements 141
NOBLE GASES - (GROUP-18 ELEMENTS)
Element Symbol Atomic Number
Helium He 2
Neon Ne 10
Argon Ar 18
Krypton Kr 36
Xenon Xe 54
Radon Rn 86
Chemical Properties :
Among group 18 members only Xenon and Krypton show chemical reactivity. The important compounds of
Xe are given below :
1. Fluorides : The common fluorides of xenon such as XeF2, XeF4 and XeF6 can be prepared by the direct
combination of xenon and fluorine under different conditions :
Ni vessel
Xe F2 XeF2
( 2 : 1) 673 K
Ni vessel
Xe 2F2 XeF4
(1 : 5 ) 673 K, 5 6 atm
Ni vessel
Xe 3 F2 XeF6
(1 : 20 ) 573 K, 50 60 atm
2. Oxides : XeO3 is the most common oxide and it is prepared by the hydrolysis of XeF4 or XeF6.
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Chapter 21
The transition elements may be defined as elements whose atoms or simple ions in their most common
oxidation state contain partially filled d-orbitals. This definition does not cover zinc, cadmium and mercury.
However, these are studied with transition elements.
The general electronic configuration of these elements is (n – 1)d1 – 10 ns0 – 2.
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Rapid Revision & Formula Bank d and f-Block Elements 143
(d) Maximum number of variable oxidation states are shown by Mn (+2, +3, +4, +5, +6, +7).
(e) The most common oxidation state for first transition series is +2 which arises from the loss of 4s
electrons (except Sc).
(f) In lower oxidation states as +2 and +3, the bonds are mostly ionic while in higher oxidation states
such as +6 or +7, the bonds are essentially covalent as in MnO4– (Mn= +7), Cr2O72– (Cr = +6)
5. Formation of Complexes :
By virtue of their small size, comparatively high nuclear or ionic charge and availability of vacant d-orbitals
of suitable energy, these metals exert strong electrostatic attraction on the ligands. The species formed
on interaction of metal and the ligand (or ligands) is known as a complex.
Formation of Coloured Compounds : The transition metal ions have unpaired d-electrons, which on
absorbing visible light can jump from one d-orbital to another i.e., d-d transitions take place. Thus when
light falls certain visible wavelengths are absorbed. The reflected light appears coloured and gives the colour
of compound. The ions having no d-d transitions are (KMnO4 & K2Cr2O7) coloured due to charge transfer
spectra. Some compounds are coloured due to polarisation e.g., AgI.
6. Catalytic Properties
Most of the transition metals and their compounds are found to act as catalysts.
Transition Metals as Catalyst : Catalytic power of transition metals is believed to operate by the
formation of interstitial compounds to adsorb and activate the reacting substances e.g. hydrogenation of
alkenes in presence of palladium or platinum is thought to take place through this mechanism.
7. Magnetic Properties
(a) Most of the transition elements show paramagnetism. Paramagnetism arises from the presence of
unpaired electrons in atoms, ions or molecules.
(b) The magnetic character is comparable in terms of magnetic moment given as n(n 2) Bohr
magnetons. In general, more is the number of unpaired electrons greater is the magnetic character.
(c) The maximum paramagnetism is seen in d5 cases, having the maximum unpaired electrons.
8. Formation of Nonstoichiometric Compounds and Interstitial Compounds
Transition metals can trap some of the small size atoms like hydrogen, boron, carbon, nitrogen, etc in
the vacant spaces between the crystal lattice forming interstitial compounds.
9. Alloy Formation
(a) Molten transition metals are miscible with one another. Therefore, on cooling a mixture of the
transition metals results in the formation of alloys.
(b) Such alloys are usually harder, have higher melting points and are more resistant to corrosion than
the parent metals.
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144 d and f-Block Elements Rapid Revision & Formula Bank
Properties of K2Cr2O7: Potassium dichromate is orange coloured compound. The important reactions are given
below
Heated
K2CrO4 + Cr2O3 + O2
KOH
K2CrO4 + H2O
Conc. Cold H2SO4
KHSO4 + CrO3 + H2O
H2SO4 conc. Heated
K2SO4 + Cr2(SO4)3 + H2O + O2
+
K2Cr2O7 H ; KI I2
+ ++
H ; Fe 3+
Fe
HCl
Cl2 + KCl + CrCl3 + H2O
SO2
K2SO4 + Cr2(SO4)3 + H2O
KCl, H2SO4 (conc.) Heated
CrO2Cl2 + KHSO4 + H2O
Heat
2MnO 2 4KOH 2O 2K 2MnO 4 2H2 O
(From KNO 3
or KClO 3 )
Step-II:
Electrolytic Oxidation
At the cathode 2H 2e H2
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Rapid Revision & Formula Bank d and f-Block Elements 145
2. Oxidising Nature in Alkaline Medium :
[2KMnO4 + 2KOH 2K2MnO4 + H2O + [O]].
In this medium KI is oxidised to KIO3 and alkenes are oxidised to glycols.
3. Oxidising Nature in Acidic Medium :
[2KMnO4 + 3H2SO4 K2SO4 + 2MnSO4 + 3H2O + 5[O]].
In this medium it oxidises
H2S + [O] H2O + S
SO2 + H2O + [O] H2SO4
H2C2O4 + [O] 2CO2 + H2O
2FeSO4 + H2SO4 + [O] Fe2(SO4)3 + H2O
2KI + [O] + H2O I2 + 2KOH
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Chapter 22
Co-ordination Compounds
CO-ORDINATION COMPOUNDS
Coordination compound may be defined as a compound that results from the combination of apparently
saturated molecules of different species and retain its identity in the solids as well as in dissolved state.
The formation of a coordination compound involves two components.
1. An acceptor : Which can accept a pair of electrons from the donor. The acceptor is usually a metal with
vacant orbitals available to accept a pair of electrons from one or more neutral molecules or anions.
In [Fe(CN)6]4–, Fe++ ion is an acceptor, which is also called as central metal ion, which acts as Lewis acid.
2. A donor : An atom or a molecule which can donate a pair of electrons is a donor. Such donor atoms or
molecules are electron rich and are called ligands, which act as Lewis bases.
Ligands may be neutral (NH3, H2O, C6H5N) or negatively charged species (:CN–,Cl–, Br–) or positively
charged
Ligand is said to be unidentate if it has only one pair of electrons that it can donate e.g., NH3
Ligand is said to be bidentate if it can bond from two positions
e.g., —
H2C H2N O=C O
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Rapid Revision & Formula Bank Co-ordination Compounds 147
1. Number of co-ordinate bonds formed with central metal/ion is known as co-ordination number of the
central species. In case of -complexes all the atoms of a -ligand are counted as co-ordination number
as in case of Zeise’s salt [Pt Cl3C2H4] co-ordination number is 5.
2. The molecules or ions bonded directly to the central ion constitute what is often termed as co-ordination
sphere, written within square brackets.
3. One more important point is the oxidation state of central metal ion. It is the charge carried by a complex ion
and is the algebraic sum of charges carried by central ion & the ligands co-ordinated to it.
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148 Co-ordination Compounds Rapid Revision & Formula Bank
ISOMERISM
1. Structural Isomerism
(a) Hydrate isomerism – Compounds which have same molecular formulae but differ in the number of water
molecule as ligands and as molecules of hydration are called hydrate isomers.
e.g., [Co(H2O)6]Cl3 & [Co(H2O)4Cl2]Cl.2H2O
(b) Ionisation isomerism – Compounds which give different ions in solution but have same molecular formulae
are called ionization isomers.
e.g., [Co(NH3)5SO4]Br & [Co(NH3)5Br]SO4
(c) Linkage isomerism – Occurs when more than one atom in a monodentate ligand functions as a donor.
e.g., [Co(NH3)5NO2]Cl & [Co(NH3)5ONO]Cl
(d) Co-ordination isomerism – This isomerism is possible when both positive and negative ions of a salt
are complex ion.
e.g., [Cr(NH3)6][Co(CN)6]
(e) Co-ordination position isomerism – This type of isomerism arises in the bridged complexes due to
difference in the attachment of ligands with the metal atom.
OH
e.g., (NH3)4Co Co(NH3)2Cl2 SO4
Cl
OH
and Cl(NH3)3Co Co(NH3)3Cl SO4
Cl
2. Stereoisomerism
(a) Geometrical isomerism is common in square planar and octahedral complexes.
Square planar complexes with general formula; [MA2X2]±n, [MA2XY]±n, [MABX2]±n, [MABXY]±n, [M(AB)2]±n
show isomerism.
Example :
NH3 NH3
Cl Cl
Co Co
Cl NH3
NH3 Cl
Cis Trans
Cl Cl
NH3 Cl
NH3 NH3
(i) e.g., Co Co
Cl Cl
Cl
en Co en en Co
(ii)
Cl en
Trans-[Co(en)2Cl2] Cis-[Co(en)2Cl2]
(c) The complex with formula [MA3X3] show facial and meridonial isomerism.
A A
A A X
X
M M
A X X X
X A
Fac-[MA3X3] Mer-[MA3X3]
3. Optical Isomerism
(a) Tetrahedral complexes with formula [M(a)(b)(c)(d)] or M(AB)2 shows optical isomerism
n
(b) Octahedral complexes having formula [M(a)2 (b)2 (c )2 ] , [M (a)(b)(c)(d)(e)(f) ], [M(AA)3 ] , [M(AA)2 b2 ] ,
[M(AA)2 b2c 2 ] containing symmetrial bidentate ligand will show optical isomerism.
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Chapter 23
Principles Related to
Practical Chemistry
Group I :
Radicals which are detected by dilute H2SO4 or dilute HCl, by liberating a gas/volatile material
(i) Carbonate
(ii) Sulphite
(iii) Sulphide
(iv) Nitrite
(v) Acetate
Group II :
Radicals which are detected by concentrated H2SO4
(i) Chloride
(ii) Bromide
(iii) Iodide
(iv) Nitrate
(v) Oxalate
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Rapid Revision & Formula Bank Principles Related to Practical Chemistry 151
Group III :
Radicals which do not give any characteristic gas with dilute and concentrated H2SO4
(i) Sulphate
(ii) Phosphate
(iii) Borate
(iv) Fluoride
(i) Cl– Colourless gas with pungent smell which fumes in air.
C 2H5OH and 3–
BO 3 Green edged blue flame of (C2H 5)3 BO3.
conc. H2SO4
3.
Conc. HNO 3 and
PO 43– A canary yellow precipitate of (NH4)3PO4.12MoO3.
(NH 4)2MoO4
Sand and –
Waxy white deposit of silicic acid i.e. H4SiO4 or Si(OH)4.
F
conc. H2SO4
Group - II :
Group - II is categorised as group-IIA and Group-IIB. The ions of this group do not react with HCl but precipitate
with H2S in dilute mineral acidic medium.
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152 Principles Related to Practical Chemistry Rapid Revision & Formula Bank
The Group-IIA sulphides of these cations are insoluble in ammonium polysulphide. The Group-IIB sulphides of
these cations are soluble in ammonium polysulphide.
Group-IIA Group-IIB
Group-III :
Group-III cations do not react with dil. HCl or with H2S in dilute acidic medium.
Group-IV :
Group-IV cations form sulphides with H2S in presence of NH4OH, these sulphides are insoluble in NH4OH.
Group-V :
Group-V cations give precipitate with ammonium carbonate in presence of NH4Cl in neutral or slightly alkaline
medium.
Group-VI :
Group Zero :
Group zero cation i.e. NH4+ reacts with NaOH to give NH3 gas
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Chapter 1
UNITS
Measurement of any physical quantity involves its comparison with a certain basic, reference standard called
unit.
Measurement = nu
Here, n is numerical value and u is unit. The numerical value is inversely proportional to the size of unit.
n × u = constant
1
n
u
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2 Physics and Measurement Rapid Revision & Formula Bank
Note : Although torque and work done by a force have same dimensional formula yet they cannot be added
as their nature is different.
Conversion of units : The numerical value of a physical quantity in a system of units can be changed to
another system of units using the equation n[u] = constant i.e., n1[u1] = n2[u2] where n is the numerical value
and u is the unit.
a b c
M L T
n2 n1 1 1 1 where the dimensional formula of the physical quantity is [MaLbTc].
M2 L 2 T2
To find a relation among the physical quantities. If one knows the quantities on which a particular physical
quantity depends and guesses that this dependence is of product type, method of dimensions are helpful in
deducing their relation.
Suppose we want to find the relation between force, mass and acceleration. Let force depends on mass and
acceleration as follows.
F = Kmbac when K = dimensionless constant, b and c are powers of mass and acceleration.
According to principle of homogeneity,
[F] = [K] [m]b [a]c
[MLT–2] = [M0L0T0] [M]b [LT–2]c
[MLT–2] = MbLc T–2c
Equating the dimension on both sides we get 1 = b, 1 = c, –2c = –2.
b = 1 and c = 1.
Precision
It is the measure of the extent to which successive measurements of a physical quantity differ from one
another.
Suppose the true value of a measurement is 35.75 and two measured values are 35.73 and 35.725. Here 35.73
is closest to 35.75, so its accuracy is more than 35.725 but 35.725 is more precise than 35.73 because 35.725
is measured upto 3 decimal places.
SIGNIFICANT FIGURES
The number of digits in the measured value about the correctness of which we are sure plus one more digit
are called significant figures.
Note : Length of an object may be represented in many ways say 5 m, 5.0 m, 500 cm, 5.00 m,
5 × 102 cm. Here 5.00 m is most precise as it contains 3 significant figures.
ERRORS IN MEASUREMENT
1. Mean Absolute Error :- If a1, a2, a3, ........ an are n measurements then
a1 a2 ...... an
am is taken as the true value of a quantity, if the same is not known.
n
a1 = am – a1
a2 = am – a2
.....................
an = am – an
| a1 | | a2 | ...... | an |
Mean absolute error, a
n
Final result of measurement may be written as :
a = am ± a
2. Relative Error or Fractional Error : It is given by
a
3. Percentage Error 100%
am
4. Combination of Errors :
(i) In Sum : If Z = A + B, then maximum absolute error in Z is given by, Z = A+ B, maximum
Z A B
fractional error in this case i.e., when two physical quantities are added then
Z A B A B
the maximum absolute error in the result is the sum of the absolute errors of the individual quantities.
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4 Physics and Measurement Rapid Revision & Formula Bank
A pB q
In more general form if Z then the maximum fractional error in Z is
Cr
Z A B C
p q r
Z A B C
Applications :
T 1 l
1. For a simple pendulum, T l1/2
T 2 l
2. For a sphere, surface area and volume are given by
4 3 A r V r
A 4 r 2, V r 2. and 3.
3 A r V r
3. When two resistors R1 and R2 are connected
(a) In series
Rs = R1 + R2 Rs = R1 + R2
∆Rs R1 R2
Rs R1 R2
(b) In parallel,
1 1 1 Rp R1 R2
RP R1 R2 R p2 R12 R22
Rp R1 R2 R1 R2
Also, Rp R1 R2 R1 R2
4. If x = 2a – 3b then, x=2 a+3 b
Vernier Callipers
It consists of two scales viz main scale and vernier scale. Vernier scale moves on the main scale. The least
count of the instrument is the smallest distance between two consecutive divisions and it is equal to
1 MSD – 1 VSD.
VS
0.9 cm
0 1
1 cm
In the figure shown, 1 MSD = 0.1 cm
1 VSD = 0.09 cm
Least count = 1 MSD – 1 VSD = 0.01 cm
Screw Gauge
It contains a main scale and a circular scale. The circular scale is divided into a number of divisions. In other
words, the complete rotation of circular scale is divided into a number of parts. The least count of a screw
gauge is pitch divided by no. of circular scale divisions.
Pitch
Least count of spherometer and Screw Gauge =
No. of CSD
Total reading of screw gauge = Main scale reading + [(Circular scale reading) × Least count]
1. Volume m3 [M0L3T0]
2. Density kg m–3 [M1L–3T0 ]
3. Velocity ms–1 [M0L1T–1]
4. Acceleration ms–2 [M0L1T–2]
5. Angular Velocity rad s–1 [M0L0T–1]
6. Frequency s–1 or hertz (Hz) [M0L0T–1]
7. Momentum kg ms–1 [M1L1T–1]
8. Force kg ms–2 or newton (N) [M1L1T–2]
9. Work, Energy kg m2s–2 or joule (J) [M1L2T–2]
10. Power kg m2 s–3 or Js–1 [M1L2T–3]
or watt (W)
11. Pressure, Stress Nm–2 or pascal (Pa) [M1L–1T–2]
12. Modulus of Elasticity Nm–2 [M1L–1T–2]
13. Moment of Inertia kg m2 [M1L2T0]
14. Torque Nm [M1L2T–2]
15. Angular Momentum kg m2 s–1 or J.s [M1L2T–1]
16. Impulse Ns [M1L1T–1]
17. Coefficient of Viscosity kg m–1 s–1 [M1L–1T–1]
18. Surface Tension Nm–1 [M1L0T–2]
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Chapter 2
Kinematics
EQUATIONS OF MOTION
General equations of motion :
dx
v
dt
dx
vdt dx vdt = area enclosed by velocity-time graph
dv
a
dt
dv
adt dv adt = area enclosed by acceleration-time graph
vdv
a
dx
vdv adx vdv adx = area enclosed by acceleration-position graph
Equations of motion of a particle moving with uniform acceleration in straight line :
1. v = u + at
1 2 v u 1 2
2. S ut at = t vt at
2 2 2
3. v2 = u2 + 2aS
1
4. Sn th u a(2n 1)
2
1 2
5. x x0 ut at
2
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8 Kinematics Rapid Revision & Formula Bank
Here,
u = velocity of particle at t = 0
S = Displacement of particle between 0 to t
= x – x0 (x0 = position of particle at t = 0, x = position of particle at time t)
a = uniform acceleration
v = velocity of particle at time t
GRAPHS
The important properties of various graphs are given below :
1. Slope of the tangent at a point on the position-time graph gives the instantaneous velocity at that point.
(x - t) curve
Position
(x) P
dx
tan v (Instantaneous Velocity at point P)
dt
Time (t)
2. Slope of a chord joining two points on the Position-time graph gives the average velocity during the time
interval between those points.
(x - t) curve
Position (x)
xi
xf xf xi
tan v av
tf ti
ti tf
Time (t )
3. Slope of the tangent at a point on the velocity-time graph gives the instantaneous acceleration at that point.
v P
dv
tan a (Instantaneous acceleration at P)
dt
Time (t)
4. Slope of the chord joining two points on the velocity-time graph gives the average acceleration during the
time interval between those points.
vf
v
vi vf vi
tan aav Average acceleration in time interval tf – ti
tf ti
ti tf t
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Rapid Revision & Formula Bank Kinematics 9
5. The area under the acceleration-time graph between ti and tf gives the change in velocity (vf – vi) between
the two instants.
6. The area under speed-time graph between ti and tf gives distance covered by particle in the interval tf – ti.
v
speed
Shaded area = distance covered in time (tf – ti)
ti tf t (time)
7. The area under the velocity-time graph between ti and tf gives the displacement (xf – xi) between the two
instants.
v
A1
Velocity
time
Shaded area (A1 – A2) = Displacement in time (tf – ti)
A2
v
(v - t graph)
v0
dv
a v 0 tan v0
dx x x0
O x0 x
9. The position-time graph cannot be symmetric about the time-axis because at an instant a particle cannot
have two displacements.
10. The distance-time graph is always an increasing curve for a moving body.
11. The displacement-time graph does not show the trajectory of the particle.
Applications
1. If a particle is moving with uniform acceleration on a straight line and have velocity vA at A and vB at B,
v A2 v B2
then velocity of particle midway on line AB is v .
2
2. If a body starts from rest with acceleration and then retards to rest with retardation , such that total
time of journey is T, then
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10 Kinematics Rapid Revision & Formula Bank
v
(a) Maximum velocity during the trip vmax. .T
vmax
1 2 x1 x2
(b) Length of the journey L T
2 1 2
t
T
v max . T t1 t2
(c) Average velocity of the trip =
2 2( )
x1 t1
(d) .
x2 t2
1 2 h
h 0 gT (taking up as positive)
2
zulema_task@hotmail.com
2h
T
g
2h '
v 0 gT g 2gh
g
Time of flight T u
(a) Time of ascent = Time of descent =
2 2 g
u2
(b) Maximum height attained =
2g
+ +
a
u
Velocity
(g = const)
O O
t u 2u Time
g g
–g –u
– –
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Rapid Revision & Formula Bank Kinematics 11
Speed
Displacement
u u
2
2g
(Parabolic)
O
u 2 u Time O u
g g 2u Time
g g
Distance
O u 2u Time
g g
(e) Displacement of particle in complete journey = zero average velocity vav = 0
u2
(f) Distance covered by particle in complete journey =
g
u
Average speed in complete journey =
2
3. A body is thrown upward such that it takes t seconds to reach its highest point.
(a) Distance travelled in (t)th second = distance travelled in (t + 1)th second.
(b) Distance travelled in (t – 1)th second = distance travelled in (t + 2)th second.
(c) Distance travelled in (t – r)th second = distance travelled in (t + r + 1)th second.
4. A body is projected upward from certain height h with initial speed u.
(a) Its speed when it acquires the same level is u.
T
(b) Its speed at the ground level is A t=
2
x
v u2 2gh
u u Here x = 0
(c) The time required to attain same level is t =0 t =T particle follows
– 0 B same path during
h ascent and descent
2u
T=
g
(d) Total time of flight (T') is obtained by solving v = u2+2 gh
C t =T
1 u u2 2gh
h uT ' gT '2 or T '
2 g t =0
5. A body is projected from a certain height h with initial g
u
speed u downward.
h
(a) Its speed at ground level is v u2 2gh
(b) Time of flight (T)
t=T
u u2 2gh
T
g
v
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Parallelogram Law of Vector Addition : If two vectors having common origin are represented both in
magnitude and direction as the two adjacent sides of a parallelogram, then the diagonal which originates from
the common origin represents the resultant of these two vectors. The results are listed below
(a) R A B B
B sin A sin
(c) tan , tan
A B cos B A cos A
(d) If | A | | B | x (say) , then R = x 2(1 cos ) = 2 x cos and i.e., resultant bisect angle
2 2
between A and B .
A
(i) If R is perpendicular to A , then cos and A2 + R2 = B2.
B
(j) For n coplanar vectors of same magnitude acting at a point such that angle between consecutive vectors
360
are equal , the resultant is zero.
n
VECTOR SUBTRACTION
O A
( – ) A–B
–B
B sin B sin
Result : R = | A B | A2 B2 2 AB cos , tan
A B cos( ) A B cos
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Rapid Revision & Formula Bank Kinematics 13
RESOLUTION OF VECTORS
Any vector V can be represented as a sum of two vectors P and Q which are in same plane as
V P Q , where and are two real numbers. We say that V has been resolved in two component
Note : Unit vector along V is cos iˆ sin jˆ
A2 A.A
iˆ . iˆ jˆ . ˆj kˆ . kˆ 1.
A B AB sin nˆ …(i)
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A ×B
A ×B
A
B A B
(a) (b)
The direction of vector A B is the same as that of unit vector n̂ . It is decided by any of the following two rules :
(a) Right handed screw rule : Rotate a right handed screw from vector A to B through the smaller angle
between them; then the direction of motion of screw gives the direction of vector A B (Fig. a).
(b) Right hand thumb rule : Bend the finger of the right hand in such a way that they point in the direction
of rotation from vector A to B through the smaller angle between them; then the thumb points in the
Relative velocity :
Velocity of object A w.r.t. object B is v AB vA v B , v BA vB vA
1. Direction of Umbrella : A person moving on straight road has to hold his umbrella opposite to direction
vM
of relative velocity of rain. The angle is given by tan with vertical in forward direction.
vR
Umbrella
vRM
vR vR
–vM
vM
2. Closest approach : Two objects A and B having velocities vA and v B at separation x are shown in figure
vA
vB
A B
x
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Rapid Revision & Formula Bank Kinematics 15
The relative velocity of A with respect to B is given by -vB
v AB vA vB
vA vAB
vA
tan
vB
-vB
The above situation is similar to figure given below.
y is the distance of closest approach.
) on
. B ti
r.t o
y
w. f m
Now, sin vAB
A no
x
of tio
c
ire
y = x sin
(D
y
x tan xVA
y v=0
1 tan 2 VB2 VA2
A x B
3. Crossing a river :
y
v = velocity of the man in still water.
D
= angle at which man swims w.r.t. normal to bank such that B
vx = – v sin , vy = v cos
Time taken to cross the river is given by v d
v cos
d d x
t v sin A u
v y v cos
Velocity along the river
vx u v sin
d
D (u v sin )
v cos
Case I : (Shortest time)
The Minimum time to cross the river is given by
d
min (when cos = 1, = 0°, u v)
v
Distance drifted is given by
d
D u
v
Case II : (Shortest path)
To cross the river straight
drift D = 0 u – v sin =0 v
u
u
sin provided v > u
v
Time to cross the river straight across is given by
v2 – u2
d d
t
v cos v 2
u2
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16 Kinematics Rapid Revision & Formula Bank
PROJECTILE MOTION
An object moving in space under the influence of gravity is called projectile. Two important cases of interest
are discussed below :
1. Horizontal projection :
A body of mass m is projected horizontally with a speed u from a height h at the moment t = 0. The path
followed by it is a parabola.
It hits the ground at the moment t = T, with a velocity v such that
2H t=0
T x-axis
g O
v u2 2gH uiˆ gTˆj y y-axis
t = t0
The position at any instant t0 is given by H
x
x = ut0
1 2
y gt 0
2
t=T
gx 2 v
y (trajectory of particle) R
2u 2
The velocity at any instant t0 is given by
v0 uiˆ gt 0 ˆj
2H
The range R will be given by R u
g
2. Oblique projection : A body of mass m is projected from ground with speed u at an angle above
horizontal at the moment t = 0.
It hits the ground at a horizontal distance R at the moment t = T.
T
t= 2
v
uy u cos = ux
u
H
t=0 t=T
ux
R
2u y 2u sin
1. Time of flight T
g g
u y2 u 2 sin2
2. Maximum height H
2g 2g
2u x u y u 2 sin 2
3. Horizontal range R ux T
g g
gx 2
4. Equation of trajectory: y x tan
2u cos 2
2
x
or y x tan 1
R
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Rapid Revision & Formula Bank Kinematics 17
v sin
u sin – gt v
and direction of motion is such that, tan
u cos
v cos
u cos
(a) v [∵ Horizontal component is same everywhere]
cos
(b) v sin = u sin – gt
(c) When v (velocity at any instant ‘t’) is perpendicular to u (initial velocity)
= – (90° – ) u
u cos
(i) v u cot
cos(90 )
u
(ii) t v
g sin
Applications :
1. The height attained by the particle is largest when = 90°. In this situation, time of flight is maximum
and range is minimum (zero).
2. When R is range, T is time of flight and H is maximum height, then
gT 2
(a) tan
2R
4H
(b) tan
R
Rmax
3. When horizontal range is maximum, H
4
4. The horizontal range is same for complimentary angles like ( , 90° – ) or (45° + , 45° – ). It is maximum
for = 45°.
5. If A and B are two points at same level such that the object passes A at t = t1 and B at T = t2, then
y
t = t1 t = t2
A B
u
h h
t=T
t=0 x
2u sin
(i) T t1 t2
g
1
(ii) h gt1t 2
2
(iii) Average velocity in the interval AB is
vav = u cos [∵ vertical displacement is zero]
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18 Kinematics Rapid Revision & Formula Bank
6. If a projectile is projected from one vertex of a triangle such that it grazes second vertex and finally fall
down on 3rd vertex of the triangle on the same horizontal level, then tan tan tan .
7. A projectile has same range for two angle of projection. If time of flight in two cases are T1 and T2,
maximum height is H1 and H2 and the horizontal range is R. Then
1
(i) Range of projectile is R gT1T2
2
1 2 1/2
(ii) Velocity of projection of projectile is u g T1 T22
2
(iii) R = 4 H1H2
CIRCULAR MOTION
An object of mass m is moving on a circular track of radius r. At t = 0, it was at A. At any moment of time
‘t’, it has moved to B, such that AOB . Let its speed at this instant be v and direction is along the
tangent. In a small time dt, it moves to B such that B OB d .
v2 2
The radial (centripetal acceleration) is ac r
r
d
The angular acceleration is
dt
3. ac v
4. at r
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Rapid Revision & Formula Bank Kinematics 19
Uniform Circular Motion :
1. In uniform circular motion, the speed (v) of particle is remain constant ( = constant)
d
2. aT 0 and 0
dt
y
v
a
v
x
a v
a
3. Only centripetal acceleration (also called normal acceleration) exists in uniform circular motion
2 v2
ac = r
r
4. In uniform circular motion v a
y
at
a
ac
x
2
v2 2
a ac 2 at 2 r
r
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Laws of Motion
If three forces P , Q and R are acting on an object such that forces are concurrent and the object is in
P Q R
equilibrium then .
sin sin sin
P
Q
x1 = x2
v1 = v2
a1 = a2
x1 x2
x1 x2
OR x2 = 2x1
v2 = 2v1
x2 x1 a2 = 2a1
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Rapid Revision & Formula Bank Laws of Motion 21
Case III : When all the three ends are free to move
x2 x3
x1 x1
2
v2 v3
v1
2
x2 x3 a2 a3
a1
2
Note : In all the above relations downward direction is taken as positive. If any of the direction is
upward in any case then –ve sign must be incorporated in the corresponding equation.
1. A machine gun fires n bullet per second with speed u and mass of each bullet is m.
m,u
M
A v
(i) Force required by a pump to move the liquid with this speed is
dm
F v = v × Av = Av2
dt
(ii) As jet hits a vertical wall and does not rebound, the force exerted by it on the wall is, Fwall = Av2
(iii) When water rebounds elastically, Fwall = 2 Av2
(iv) For oblique impact as shown, Fwall = 2 Av2 cos
Liquid jet
v v
wall
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22 Laws of Motion Rapid Revision & Formula Bank
4. The blocks shown are being pushed by a force F. F1, F2 are contact forces between M1 & M2 and M2 &
M3 respectively
a
F M1 M2 M3
a
F2
F M3
a FBD of M3 F2 = M3a
M1 M2 M3
a
F1 F2
F1 – F2 = M2a F1 = (M3 + M2)a FBD of M2 M2
M3 M2 M3
or F2 F , F1 F
M1 M2 M3 M M M3
1 2
5. The strings are massless. Let T1 and T2 be the tensions in the two strings and ‘a’ be the acceleration.
F (M2 M3 )F M3 F F T1 T2
a , T1 , T2 M1 M2 M3
M1 M2 M3 M1 M 2 M 3 M1 M2 M3
ceiling
T T
massless
7. string M FBD of M w.r.t. ground
T
M Mg
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Rapid Revision & Formula Bank Laws of Motion 23
8. Uniform rope of mass Ms. FBD of lower portion
Tx
x
L
x Ms gx
L
The tension in the rope at a distance x from free end is given below for different cases.
(a) Stationary system
M s gx
Tx
L
Ms x
(b) If the rope is accelerating upwards, then Tx (g a)
L
Ms x
(c) If the rope is accelerating downwards, then Tx (g a ) (g a)
L
IMPORTANT PROBLEMS
Pulley mass systems massless
(i) Stationary pulley
T
M2 M1 T
a g
M2 M1 a M1 a
M1M 2 M1 g M2
T 2 g
M1 M 2 M2 g
(ii) Pulley is moving upward with acceleration a0
a0
M1M 2
T 2 (g a0 )
M1 M 2
The acceleration of each block with respect to pulley is
ar T
M2 M1 T ar
ar (g a0 )
M2 M1 a1 M1
a2 = ar – a0
a a
M1M 2 g T T
(iii) T (sin sin )
M1 M 2
M1 Fixed M2
M 2 sin M1 sin and smooth
a M2 M1
g
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24 Laws of Motion Rapid Revision & Formula Bank
aB
T
(iv)
B
T
T
2T
A aA
MAg
2aA = aB …(i)
MAg – 2T = MAaA …(ii)
T = MBaB …(iii)
Case - II :
Minimum value of F so that ‘m’ falls freely is given by m F
F = Mgcot
M
Wedge M moves with acceleration = gcot Wedge
The block falls vertically with acceleration ‘g’. smooth
Contact force between M and m is zero.
Angle of Repose
Consider a situation in which a block is placed on an inclined plane with co-efficient of friction ‘ ’. The
maximum value of angle of inclined plane for which the block can remain at rest is defined as angle of repose.
N=
s s mg cos
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Rapid Revision & Formula Bank Laws of Motion 25
Case - I : If a force F is applied on lower block
(a) F (M1 + M2)g
' ' M2
M1 F
Smooth
F
Both blocks move together with same acceleration a
M1 M2
amax = g
(b) F > (M1 + M2)g
M2 moves with constant acceleration a2 = g
F M2g
M1 moves with acceleration a1
M1
(M1 M 2 )M 2 F M2
(a) F g , both blocks move together with acceleration a with amax g.
M1 M1 M 2 M1
(M1 M 2 )M 2 g
(b) If F ,
M1
M2 F
M1
Smooth
M2
M1 moves with constant acceleration a1 g
M1
F M2g
M2 moves with acceleration a2
M2
M2 slips forward on M1.
R F
mg
F
cos sin M
R
mg
Fmin at = tan–1( ) R F sin
2
1
F cos
R
mg
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26 Laws of Motion Rapid Revision & Formula Bank
axis
O r
T v
m
mv 2 2
T = Centripetal force = m r
r
Considering gravity (Conical pendulum)
l T cos
h T
r C T sin
mg
mg
Tsin = m 2r …(1)
Tcos = mg
mg
T …(2)
cos
2
T m l
h
(c) Time period = 2 (h = l cos )
g
rg ( tan )
Vmax
1 tan
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Rapid Revision & Formula Bank Laws of Motion 27
N cos
N
N sin
f cos
f mg
f sin
mg
Special Cases :
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CONCEPT OF WORK
W f .s (s s2 s1 ) f
f cos
= f s cos
= s (f cos )
s
KINETIC ENERGY
1 p2
K.E. mv 2
2 2m
WORK-ENERGY THEOREM
WTotal K.E.
or
COLLISION
One dimension
u1 u2 v1 v2
1 m1m2
KE (u1 u 2 )2 (1 e2 )
2 m1 m2
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Rapid Revision & Formula Bank Work, Energy and Power 29
Following are the important cases
1. Elastic collision e = 1
v2 – v1 = u1 – u2
m1 m2 2m2u 2
v1 u1
m1 m2 m1 m2
m2 m1 2m1u1
v2 u2
m2 m1 m2 m1
KE = 0 Final KE = Initial KE
2. Coefficient of restitution = e
u sin = v sin …(1) m
u v
eu cos = v cos …(2)
v u sin 2 e 2 cos 2
tan
tan (i.e. > )
e
t=0 m u=0
h0
h1 h2
n
(b) Speed of rebound after nth bounce = e 2gh0
1 e2
= h0
1 e 2
2h0 1 e
= .
g 1 e
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30 Work, Energy and Power Rapid Revision & Formula Bank
Tp mg cos v p2 TH
2. aC mg
m l
M M
mv p2 O TP vP
3. Tp mg cos …(2) P
l l
TL mg cos
vL mg sin
mv L2 L
4. TL mg
l
mg
5. vL 2gl , it oscillates between M and M
6. 2gl vL 5gl , it will leave the circular path somewhere between M and H.
mv H2
8. TH mg
l
9. TL – TH = 6 mg (always)
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Chapter 5
Rotational Motion
x cm
xdm y cm
ydm zcm
zdm
; ;
dm dm dm
Centre of mass of some commonly used objects.
1. Semi circular wire of radius R.
C Semi-
2R circular
OC , where C is centre of mass
wire
O
2. Semi circular disc of radius R
4R
OC Semi-
3 C
circular
3. Non-uniform rod of length L. The linear mass density disc
O
varies linearly from zero at O to maximum at B.
2L/3
2L
OC
3 O C B
L
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32 Rotational Motion Rapid Revision & Formula Bank
Differentiating v cm
w.r.t. time we get a cm as
F ext
m1 a 1 m2 a 2 ....mn a n a cm
a cm n
; or Msystem
mi
i 1
Where Fext is the vector sum of forces acting on the particles of system.
R M
MR 2 MR 2
I cm I cm
2 2
A thin rod A plate
M, L
L
ML2 ML2
Ic Ic
12 12
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Rapid Revision & Formula Bank Rotational Motion 33
A thin rod about a perpendicular A plate about one edge
axis through its end
ML2 ML2
I I
3 3
z
A Rectangular Plate
y Mass = M
Mb 2
(a) I xx l x
12
Ml 2
(b) I yy O
12
(c) Izz = Ixx + Iyy b
x
M (l 2 b 2 ) y
(d) I zz
12
z
A Thick Rod (Solid cylinder)
The axis is perpendicular to the rod and passing through the centre of mass
B A
M
L
ML2 MR 2 ML2 MR 2 R O
I AA ; IBB
12 4 3 4
B A
M, R
2 2
Icm MR 2 I cm MR 2
5 3
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34 Rotational Motion Rapid Revision & Formula Bank
2F
(1) Tangential acceleration of A is a A R (along horizontal)
M
2F
(2) Tangential acceleration of B is aB R (vertically downwards)
M
2Fr
(3) Tangential acceleration of C is aC r (along horizontal, opposite to the direction of tangential
MR
acceleration of A)
2. Hinged Rod
The rod is released from rest from horizontal position
N
L L
mg (about A)
2 A C 2
ML2 L B
I
3 2
mg
3g
I 2L
L 3g mg
(1) Linear acceleration of COM C is acm . Also, N = mg – macm =
2 4 4
3g
(2) Linear acceleration of point B is aB L
2
(3) The rod is released from unstable equilibrium position {from position A}
L 1 ML2 2
(a) When at B, Mg (1 cos )
2 2 3 u=0
A
6g L
cos
L 2
O P
(b) at C, = 0°
6g L
l B
C
3g
(c) at P, = 90°,
l
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Rapid Revision & Formula Bank Rotational Motion 35
ROLLING OF A BODY
Rolling is combination of Pure Translation and Pure Rotation Motion about Centre of Mass.
R R
vcm R vcm + R
vcm vcm
R
R vcm R vcm
vcm
vcm O O vcm O vcm
R
R vcm
vcm 180 –
Mass = m vcm R R vcm R
R
Pure translation Pure rotation Rolling
(about cm)
vcm
f
Surface at rest
kinetic friction vcm–R
vcm
f
R – vcm friction (kinetic) Surface at rest
2R
s
co
2R
2R
/2
R R
sin
2R
2R
I v=0 I v=0
(instantaneous centre of rotation) (instantaneous centre of rotation)
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36 Rotational Motion Rapid Revision & Formula Bank
1 I cm 2 1 2
K2
= 2 m v cm mv cm 1
R 2 (where k is radius of gyration)
R2 2
K2
E ET 1
R2
R2
Similarly, E E R 1
K2
Fraction of total energy Fraction of total energy
1 1 Y
Type of body K K 2 R2
translational X 1 rotational Y 1 X
2
R K 2
1. Ring or hollow 1 1
R 0.5 50% 0.5 50% 1: 1
cylinder 2 2
2 3 2
2. Spherical Shell R 0.6 60% 0.4 40% 2:3
3 5 5
3. Disc or solid R 2 1
0.666 66.67% 0.333 33.33% 1: 2
cylinder 2 3 3
2 5 2
4. Solid sphere R 0.714 71.4% 0.286 28.6% 2:5
5 7 7
Note : Above values X and Y are independent of mass and radius of the body. They only depend on the
type of body.
Applications
1. A force is applied at the distance h from centre of mass as shown in figure
h
F1
R F
aC.M h
K2
M1
R 2 fr
2
F (K hR ) Rough ground
fr N (must be less than mg for Rolling)
K2 R2
K2
If h friction is backward
R
K2
hfriction become forward
R
2. If force is applied at centre of mass then (h = 0)
F FK 2 F
So, a and fr
K2 K 2 R2 R2
M 1 1
2 K 2
R
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Rapid Revision & Formula Bank Rotational Motion 37
3. If force is applied at highest point (h = R)
2F
aC.M.
K2
M 1
R2
R2 K 2
fr K 2 R2 F , forward direction
4. (i) (ii)
fr
R
C F
R Rough inclined plane
in
fr
mgs
F =
Rough horizontal
surface
a
R
R
(iii) (iv) a
T T R
R
T
a a
m
F = mg F=mg
F
a= I
m c.m.2
R
Ic.m.a
fr or T =
R2
In the situations described above, the linear acceleration of the moving object can be calculated by same
formula, the value of F, and moment of inertia will depend on the kind of problem.
Also consider the following situation.
F
a=
I R
(m1 m2 )
R2 T1 T2
Ia
T2 – T1 =
R2 m1
Here, F = (m2 – m1) g = Net pulling force m2
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38 Rotational Motion Rapid Revision & Formula Bank
1 2 1 2
By conservation of energy, mgh I mv cm
2 2
(Total energy) (Rotatory) (Translatory)
Icm K2
Let 1 2 = 1 (where k is radius of gyration)
MR R2
R
mg sin g sin g sin
1. acm =
Icm K2 fr )
m 1 ping
p
sin i
2
R R2 sl h
mg ( no
gh
vcm rou s
2gh K2 g co
2. v cm = 2gh 1 m
R2
1 2h mg sin
3. Time . ∵ Force of friction fr
sin g R2
1
K2
i.e., t
mg sin
4. Force of friction fr
R2
1
K2
5. Instantaneous power P = (mg sin )v
R2
tan 1 1
6. Maximum angle of inclination for pure rolling, max
2
K
ANGULAR MOMENTUM
The general formula for angular momentum about any point is
L Mv cmR I
Case - I : Pure translation
| LO | Mv cm h
LC = 0
z
M
C
vcm
h
O x
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Rapid Revision & Formula Bank Rotational Motion 39
Case - II : Rolling body
Lc = Ic
LA = IC + MvcmR
LO = Ic + Mvcmb
LB = Ic – Mvcma
LD = Ic
B
z a
D C
vcm
R
b
A
O x
Case - III : Centre of mass is fixed
Put vcm = 0 in the above results so L0 = LA = LC = IC
Case - IV
Lc = – Ic
LA = – IC + MvcmR
LO = – Ic + Mvcmb
z
C
vCM
R
b
A
x
O
Case - V
Lc = Ic
LA = IC
LO = Ic – Mvcmb vCM
C
R
A
x
O
b
Note : In all above situations, anticlockwise sense has been assigned a negative sign.
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Chapter 6
Gravitation
g
g 2
h
1
Re
g
If h = Re , g
4
2h
If h < < Re then g g1
Re
x
g g 1
Re , at the centre of earth g = 0, weight = 0
angle of latitude
GM
I rˆ
r2
2. Gravitational potential
W GM
V V (units J/kg)
m r
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Rapid Revision & Formula Bank Gravitation 41
GM
Ii = 0, Vi =
R
GM GM
Is = 2
, Vs
R R
Io = GM , Vo GM
r2 r
|I| V
r=R r
O r O
r=R
GM
R
GMr GM 3GM 3
Ii = 3
, Vi 3
(3R 2 r 2 ) At centre Vc VSurface
R 2R 2R 2
GM GM
Is , Vs
R2 R
GM GM
Io 2
, Vo
r r
|I| V
|Imax|
1
I r I r=R
r2 O r
O r hyperbolic
r=R VS `
3 parabolic
Vs Vc
2
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42 Gravitation Rapid Revision & Formula Bank
3. Gravitational intensity and potential on the axis of uniform ring of mass M radius R at distance x from
centre.
GMx GM
I 3
,V
2
(R x2 ) 2 R 2
x2
R 2GM
At centre I = 0. I is maximum at x ; Imax =
2 3 3R 2
R
V 2 x
|I|
R x GM
–
2 R
4. Neutral point : The point P at which gravitational field is zero between two massive bodies, is called
neutral point.
M1 P M2
M1 M2
r12 r22
r1 r2
GM e m
Energy required to escape = Escape energy = + = Binding energy.
Re
ESCAPE VELOCITY
2GM e 8 2
ve GRe 2gRe
Re 3
KEPLER’S LAWS
(1) All planets revolve around the Sun in elliptical orbit having the Sun at one focus.
If e = eccentricity of ellipse then distance of the planet from the Sun at perigee is
rp = (1 – e)a
and distance of the planet from the Sun at apogee is
ra = (1 + e)a (a = semi major axis)
Ratio of orbital speeds at apogee and perigee is
va rp 1 e
vp ra 1 e
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Rapid Revision & Formula Bank Gravitation 43
Ratio of angular velocities at apogee and perigee is
2 2
a rp 1 e
p ra 1 e
vp
ea rp Perigee
Apogee ra
a
Sun
va
2a
(2) A planet sweeps out equal area in equal time interval i.e., Areal speed of the planet is constant
dA 1 L
vr = constant (L represents angular momentum of planet about the Sun)
dt 2 2m
(3) Square of time period is proportional to cube of semi-major axis of the elliptical orbit of the planet.
i.e., T 2 a3
SATELLITES
Important results regarding satellite motion in circular orbit.
1. Orbital Velocity (v0) : Gravitational attraction of planet gives necessary centripetal force.
GM
v0
r
GM gRe2
v0 (h = height above the surface of earth)
r Re h
ve 2v 0
2. Time Period : The period of revolution of a satellite is
T
2 r
2 r
r r3
2
v0 GM GM
For a satellite orbiting close to the earth’s surface (r ~ Re), the time period is minimum and is given by
Re3 Re
Tmin 2 2
GM g
R
Thus, for any satellite orbiting around the earth, its time period must be more than 2 or
g
84.6 minutes.
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44 Gravitation Rapid Revision & Formula Bank
3. Potential Energy (U), Kinetic Energy (K) and Total Energy (E) of satellite
GMm
U
r
GMm
K
2r
GMm
E [K = –E & U = 2E ]
2r
GM1M 2
(1) F , where r is distance between them (i.e., r = r1 + r2)
r2
V2
(2) M1r1 = M2r2 M1 M2
cm
V1 r1 r2
GM1M 2 M1V12
(3)
r2 r1
GM1M 2 M 2V22
(4) 2
r r22
M2r M1r
(5) r1 , r2
M1 M 2 M1 M 2
G
V1 M2 ,
(M 1 M 2 )r
G
V2 M1
(M1 M 2 )r
when M1 = M2
GM
V1 V2
2r
r
r1 = r2 =
2
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Chapter 7
Properties of Solids and Liquids
Strain Stress
l ‘A’ (area)
(1) Longitudinal strain = (1)
l
F
l
l
Normal Stress (Tensile) = F/A
V
(2) Volumetric strain = (2)
V
r 2
A=4 r
A(area) L
L
(3) Shear strain = (3)
L F
F
Tangential Stress or Shear Stress = A
MODULI OF ELASTICITY
Shear stress F FL
(3) Modulus of rigidity or shear modulus or G
Shear strain A A L
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46 Properties of Solids and Liquids Rapid Revision & Formula Bank
Applications :
Fl YA
1. For a wire Y F l
A l l
i.e. a wire behaves like a spring of spring constant (k)
YA 1
k i .e., k
l l
2. When this wire is stretched by applying an external force F, and l is extension produced, then
(a) Work done by external force = F l
1
(b) Work done by restoring force = F l
2
1
(c) Heat produced = F l
2
1
(d) Elastic potential energy stored = F l
2
1 F l 1F l
Energy density U
2 volume 2 Al
1
= stress × strain
2
1 (stress)2 1
= Y (strain)2
2 Y 2
3. A rod of mass m and length l hangs from a support
Area of cross-section = A
Extension produced due to its own weight,
l
Mgl gl 2
l = ( = density of wire)
2 AY 2Y
l
F Y, A F
Heated
If = Rise in temperature
l
Compressive strain =
l
Compressive stress = Y × strain = Y
F=Y ×A
Note : If the rod is placed on horizontal frictionless surface, then stress developed on heating is zero.
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Rapid Revision & Formula Bank Properties of Solids and Liquids 47
Poisson’s Ratio
Consider a uniform bar being stretched by applying two forces at its ends.
R R– R
F F
l
l+ l
l
Longitudinal strain =
l
R
Lateral strain =
R
R /R
Poisson’s ratio,
l /l
(a) Theoretically – 1 0.5
(b) Practically 0 0.5
(c) When density of material is constant = 0.5
1h1 = 2h2
P0 P0
h2 h1 1
A B
2. When the U tube accelerates horizontally, difference of levels of liquid satisfies the relation,
a h
tan
g L
L
a
h
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48 Properties of Solids and Liquids Rapid Revision & Formula Bank
L
2 2 2
L h L
Here h and tan tan .
2g L 2g
Excess pressure
If Po = Atmospheric pressure
Pi = Inside pressure
then Pi – Po = Excess pressure
Liquid drop
PO
(1) Pi
r
2T
Pi = Po +
r
Soap bubble
PO
Pi
(2)
4T
Pi – Po =
r
Air bubble
Po
Pi
(3) r
2T
Pi = Po +
r
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Rapid Revision & Formula Bank Properties of Solids and Liquids 49
(4) Capillary tube, concave meniscus
O
R
r PO
Pi
Capillary tube,
Concave Meniscus
2T
(a) Pi Po
R
Fc
(b) Fa
2
(5) Capillary tube, convex meniscus.
PO
r
Pi
R
o
Convex Meniscus
2T
(a) Pi Po
R
Fc
(b) Fa
2
Combining of Bubbles
1. If the soap bubble coalesce in vacuum, then Po = 0
r2 = r12 + r22
2. If two soap bubbles come in contact to form a double bubble then
r = radius of interface, r1 > r2
1 1 1
r r2 r1
The interface will be convex towards larger bubble and concave towards smaller bubble because
P2 > P1 > P0.
r2
P2
r1
P0
P1
Radius ‘r’
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50 Properties of Solids and Liquids Rapid Revision & Formula Bank
CAPILLARY ACTION
Rise or fall of liquid in a tube of fine diameter. O
R
Ascent formula r
2T 2T cos
h
R g r g
Energy of a Liquid
Various energies per unit mass :
1. Potential energy/mass = gh
1 2
2. Kinetic energy/mass = v
2
P
3. Pressure energy/mass =
Energy Heads
Various energy heads per unit mass :
1. Gravitational head = h
v2
2. Velocity head =
2g
P
3. Pressure head =
g
BERNOULLI’S THEOREM
It is based on conservation of energy.
For an ideal, non-viscous and incompressible liquid,
P1 v 12 P2 v 22
gh1 gh2 = constant
2 2
2(P1 P2 )
Q a1a2
(a12 a22 )
P1, a1
P2, a2
v1 v2
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Rapid Revision & Formula Bank Properties of Solids and Liquids 51
Case - (b) :
Venturimeter
2g (h1 h2 )
Q a1a2
a12 a22
h1
h2
a1 v1 v2 a2
(a) Speed of efflux v e 2gh (If a << A). This is known as Toricelli’s theorem.
If a is comparable to A then
A2
ve 2gh 2
A a2
h
H
ve 2gh
A 2
t h1 h2
a g
t H [Put h1 = H, h2 = 0]
1h1
(d) ve 2g h2 in the situation shown in figure
2
h1 1
2 ve h2
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52 Properties of Solids and Liquids Rapid Revision & Formula Bank
R 2 h( H h)
H
Rmax = H when h
2
h
H
(f) H
Reynold’s Number
vD Inertial Force
NR
Viscous force
vD
2000 vc 2000 (Critical velocity)
D
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Rapid Revision & Formula Bank Properties of Solids and Liquids 53
Viscosity and Viscous Force
Plate F
v
dv
F A
dy
Units of : SI 1 Pa.s = 10 poise = 1 decapoise
C.G.S 1 dyne/cm2-s = 1 poise
Poiseuille’s Equation
Volume flow rate across a tube with pressure difference between its ends is,
dV Pr 4
Q
dt 8 l
STOKES LAW
When a small spherical body of radius r is moving with velocity v through a perfectly homogeneous medium
having coefficient of viscosity , it experiences a retarding force given by
F=6 rv.
Important case :
(1) A body of radius r released from rest in a fluid
If = density of body
= density of liquid or fluid
Terminal velocity is given by,
2 r 2g
vT ( )
9
Thermal Expansion
When the temperature of a body increases, its all dimensions (length, area, volume) increase.
(1) Coefficient of linear expansion is given by
L
L
L = L0 (1 + ), is the change in temperature in °C or K & L0 is initial length
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54 Properties of Solids and Liquids Rapid Revision & Formula Bank
m m
(1 ) = 0(1 – )
θ 0
An Isotropic body expands equally in all directions and we can obtain the following relations
3
=3 , =2 or , =
1 2 3 2
CALORIMETRY
(1) Specific heat capacity or Gram specific heat (c) : If Q heat is given to a substance of mass ‘m’, and
rise in temperature is , then
Q
c= (cal/g°C)
m
(2) Molar heat capacity (C) :
C = Molar mass (M) × specific heat capacity
M. Q Q
C = Mc = =
m n
Q m
C :n= is number of moles
n M
(3) Heat capacity of an object is defined as product of mass and specific heat.
(4) In general if Q heat is given to a substance of mass ‘m’ which increases its temperature by then
Water
Specific heat C = 1 cal/gm/°C = 4.2 J/gm/°C = 4200 J/kg/°C
Lf = 80 cal/gm = 336 J/gm
Lv = 540 cal/gm = 2268 J/gm
For ice : Cice = 0.5 cal/g °C = 2100 J/kg °C
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Rapid Revision & Formula Bank Properties of Solids and Liquids 55
Law of Conduction
Consider a rod of length l, cross sectional area A, with its ends maintained at temperatures T1 & T2
(T1 > T2). In steady state
l
T1
A Q
A
T2
x
dx
Rate of heat flow across any section is given by
dQ dT
H= – kA
dt dx
dT
Here k = Thermal conductivity and is known as temperature gradient i.e. rate of change of temperature
dx
with distance. k depends only on the nature of the material.
S.I. units of thermal conductivity is Wm–1K–1
T1 T2
A k dQ/dt
dQ (T1 T2 )
In steady state kA
dt l
l l l
Thermal resistance, R as in current electricity R
kA A A
k
constant a substance which is good conductor of heat (silver) is also a good conductor of
T
electricity (mica & human body is exception to above law)
where is electrical conductivity
Composite Rod :
(1) Series
In steady state
dQ/dt dQ/dt
l1 l2 l1 l2 A A
R k1 k2
k 1A k2 A kA T1 T2
Where k = effective thermal conductivity given by l1 T l2
For same area of cross section,
l1 l 2 .......... ln
k
l1 l 2 ln
..........
k1 k 2 kn
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56 Properties of Solids and Liquids Rapid Revision & Formula Bank
2k1k 2
k = k k2
1
Temperature of junction
k1 k2
T1 T2
l1 l2
T .
k1 k2
l1 l2
k1T1 k 2T2
T
k1 k 2
(2) In parallel l
Q
dQ dQ1 dQ2 dQ1
A1 k1
dt dt dt dt
T1 T2
dQ2
A2 k2
1 1 1 k ( A1 A2 ) k1A1 k 2 A2 dt
R R1 R2 l l l
where k = effective coefficient of thermal conductivity given by
k1A1 k 2 A2
k
A1 A2
k1 k2
Example, for two slabs of equal area k =
2
STEFAN’S LAW
The radiant energy emitted by a perfectly black body per second per unit area (emissive power) is directly
proportional to the fourth power of the absolute temperature of the body.
R T4 R = T4
Power
R P = A T4 ( = 5.67 × 10–8 Wm–2 K–4)
Area
dT 3 (T 4 T04 ) r
The rate of fall in temperature is given by
dt sr
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Rapid Revision & Formula Bank Properties of Solids and Liquids 57
Newton’s Law of Cooling
If the temperature T of a body is not much different from surrounding temperature T0, then rate of cooling of
a liquid is directly proportional to the difference in the temperature of liquid T and temperature of surroundings
(T0) i.e.
Rate of – dT – dT
dt dt
cooling
T T – T0
kT0
dT
Rate of cooling (T T0 )
dt
dT
– = (T – T0)
dt
Results
(1) Tf = T0 + (Ti – T0)e– t, where Ti is initial temperature, Tf is temperature after time t.
Ti T0
(2) Another form t log
Tf T0
Ti
m mass of body
dT 4 A T03 T0
(3) (T T0 ), c specific heat
dt mc A surface area
emissivity
t
T1 T2 T1 T2
T0
t 2
ln(T1 – T0)
Above formula gives time ‘t’ taken by the body to cool down from T1 to T2. T0 is temperature of surrounding.
(5) If temperature of a body changes from 1 to 2 in time ‘t’ and changes from 2 to 3 in next time then
2 – 0 3 – 0
= ( = temperature of environment)
1 – 0 2 – 0
0
(6) If equal masses of two liquids having same surface area and finish, cool from same initial temperature to same
final temperature with same surrounding, then
t1 k2 c1
= = ; c1 & c2 are specific heats
t2 k1 c2
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58 Properties of Solids and Liquids Rapid Revision & Formula Bank
b
m
T
where b is a constant known as Wien's constant
Results
Spectral emissive
power (e )
A1
1 T2 A1 T14
T1
2 T1 A2 T24
T2
1 2
A2
The Sun
R The Earth
T 4R 2
I = (Power radiated)(Area) = = S, where S is called solar constant [S = 1.4 kW / m2]
r2
1
14
r 2 S 1.5 108 2 1.4 103
4
So, T 2 5800 K
R 7 105 8
5.67 10
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Chapter 8
Kinetic Theory of Gases
and Thermodynamics
1 M 2
or P = v rm s Vrms = Root mean square velocity
3 V
1 Nm 2
or P v N = Number of molecules
3 V
2
P v rms = density of gas
3
3 kT
vrms = , k = Boltzmann’s constant, m = mass of one molecule in kg
m
8RT 8P v1 v 2 v3 ......... v n
(ii) Average speed vavg = Mw n
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60 Kinetic Theory of Gases and Thermodynamics Rapid Revision & Formula Bank
(iii) vmp = Most probable speed is defined as the speed corresponding to which there are maximum number of
molecules.
= Density of gas
2RT 2P 2 kT
v mp = Mw = Molecular weight
Mw m R = Gas constant
P = Pressure of gas
Order of magnitude : vrms > vavg > vmp
m = Mass of one molecule
8
v rms : v av : v mp 3 : : 2 –
~ 3 : 2 .5 : 2
f
(iii) Cv R
2
Degrees of f U CP
Gas U nR T CV CP=CV + R
freedom (f) 2 n T CV
3 3 3 5 5
Monoatomic nR T R R
(Translational) 2 2 2 3
3(Trans) + 5 5 7 7
Diatomic nR T R R
2(Rot) 2 2 2 5
Non-Linear 3 (Trans) + 3 4
3nR T 3R 4R
Poly atomic (Rot) 3
2
(ii) mix 1
fmix
fmix R
Cvmix
2
Cpmix Cvmix R
Thermodynamic Process
(1) Melting process : (Change of state, solid to liquid)
Q= U+W
mLf = U + 0 [W = 0 as volume remains nearly constant]
(2) Boiling process : (Change of state, liquid to vapours)
mLv = U + P[V2 – V1]
V2 = volume of vapours
V1 = volume of liquid
When 1 g of water vapourises isobarically at atmospheric pressure. U = 2091 J, P = 1.01 × 105 Pa,
V1 = 1 cm3, V2 = 1671 m3.
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Rapid Revision & Formula Bank Kinetic Theory of Gases and Thermodynamics 61
(3) Isochoric process : Volume is constant
dV = 0 W=0 [dV = change in volume]
Q = nCV T = U
U
CV
n T
(4) Isobaric process : Pressure is constant
P = constant, dW = PdV
W = P V = nR T
Q = nCP T = U + W
nCP T = nCV T + nR T
CP = CV + R
U W Q U W Q
or
f 2 f 2 1 1
U 1
Fraction of total heat converted to internal energy =
Q
W 1
Fraction of total heat converted to work is,
Q
nRT
So P
V
Work done in isothermal process
V V
W Q nRT loge 2 2.303 nRT log10 2 = 2.303 nRT log P1
V1 V1 10
P2
(6) Adiabatic process : Heat exchanged (Q) is zero
PV = K [Equation of adiabatic process]
As Q = 0, nC T = 0 or C = 0
Also, 0 = nCV T + W [by first law of thermodynamics]
nR
Now, W U i.e. W = – nCV T = – (T – T1)
–1 2
nR T
W
1 x
R
Molar heat capacity C CV
1 x
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(8) Cyclic process : System returns to its initial state (P, V & T)
For the overall process T = 0 U=0
Q= W
Indicator Diagram :
P-V graph of a process is called indicator diagram. Area under P-V graph represents the work done in a process.
Small work done, dW = PdV
P1
P2
V1 V2 V
CARNOT ENGINE
Heat supplied = Q1
Heat rejected = Q2 Q1 – Q2 = W
W Q1 Q2
% efficiency, 100 100%
Qsupplied Q1
Heat Supplied Q1 Q1
Coefficient of performance,
W total W Q1 Q2
T1
T1 T2 (for ideal pump)
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Chapter 9
Periodic Function
If f(t + T) = f(t) then function ‘f’ is periodic with period T.
Harmonic Motion
When oscillatory motion of a particle can be expressed in terms of sine or cosine functions, it is said to be
a harmonic motion.
k
a x
m
d 2x k d 2x 2
x 0 or x 0 (This equation represents the differential equation of S.H.M. )
dt 2 m dt 2
dx
v A cos t
dt
or, v A sin t , maximum speed = A
2
v A2 x2
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64 Oscillations and Waves Rapid Revision & Formula Bank
(b) Acceleration
dv 2
a A sin t , maximum acceleration = A 2
dt
a=A 2sin( t+ )
i.e., acceleration leads velocity by . Acceleration and displacement are in opposite phase.
2
(c) Dependence of acceleration with position, is a = – 2x
A A
O t x
T T 3T –A A
2 2
–A –A x2 v2
1
A2 ( A )2
v a
+A
O t x
T T 3T
2 2
2
–A slope = –
2
tan =
a
a
2
+A 2
A
O t v
T T 3T A
2 2
–A
2 v2 a2
1
( A )2 ( A 2 )2
Energy in SHM
Salient points regarding energy in SHM :
Displacement T f
KE T/2 2f
PE T/2 2f
Total Energy 0
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1 2
1. KEavg m A2 .
4
1 2
2. KEmax = m A 2 at mean position.
2
3. KEmin = zero at extreme position.
1 2
4. PEavg = m A2 .
4
1 2
5. PEmax = m A 2 at extreme position.
2
1 2A2
6. Total energy, E = m which is constant i.e. doesn’t depend on x
2
7. Both kinetic and potential energy vary parabolically with x.
E
1
m 2
A2 TE
2
PE
TE = Constant
TE = (1/2)m 2A2
KE
x x = –A x=A x
A T
8. PE = KE at x and t . (Starting from mean position towards +x).
2 8
SIMPLE PENDULUM
l
Time period of oscillation of simple pendulum of length l for small angular amplitude is given by T 2
g
where g is the effective acceleration due to gravity, directed along the length of pendulum when it is at mean
position.
T 1 l
1. If length ‘l’ is changed, .
T 2 l
T 1 g
2. If gravity ‘g’ is changed, .
T 2 g
l
Effective g = | g a | , where a is pseudo acceleration. T 2
g
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66 Oscillations and Waves Rapid Revision & Formula Bank
1
T 2
1 1
g
l Re
OSCILLATION OF SPRING
Horizontal Oscillations
The spring is pulled/pushed from x = 0 to x = x0 and released.
k
M M
Smooth x=0 x = x0
M
(2) Time period T 2
k
COMBINATIONS OF SPRINGS
Series Combination :
k1 k2 k
(1)
M M
Smooth Smooth
1 1 1 k1k 2 M
k T 2
k k1 k 2 or Effective spring constant, k1 k 2 , k
1 1 1
(2) k k1 k2
k1
Effective spring constant, k
k1k 2
k1 k 2
k
k2
M M M
T 2
k
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Parallel Combination
M
(1) Effective spring constant, k = k1 + k2 , T 2
k
k1 k
k2 M M
Smooth Smooth
M
(2) Effective spring constant, k = k1 + k2 T 2
k
k1 k2 k
M M
Smooth Smooth
Physical Pendulum
Figure shows an extended body (called physical pendulum) pivoted about point O, which is at a distance d
from its centre of mass.
O
d
cm
mg
I
Time period of oscillation, T 2 I = moment of inertia of the body about pivoted point.
mgd
L h
then, T = 2 2
g g
l
T 2
g (sin sin )
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68 Oscillations and Waves Rapid Revision & Formula Bank
Superposition of SHMs
Consider two SHMs along the same line
If y1 = a1 sin t a2
A
y2 = a2 sin ( t + )
then, equation of resultant SHM is given by,
a1
y = y1 + y2 = A sin ( t + )
a2 sin
where, A a12 a22 2a1a2 cos & tan 1
a1 a2 cos
Damped Oscillations
If there is any dissipative force like viscous force in SHM, then the amplitude of the particle decreases with
time such type of oscillations are known as damped oscillations.
x
d 2x dx
(i) Differential equation for damped oscillation m b kx 0,
2 dt
dt
where b = Coefficient of damping.
(ii) Displacement-time equation, x = A(t) sin( t + )
b
t
(iii) Amplitude of damped oscillation, A(t ) A0 e 2m , where A0 = Initial amplitude.
2
2 b k
(iv) Angular frequency of damped oscillation, 0 2m , where 0
m
=natural frequency.
T stress 2 T D2
v A
density D 4
T
v= A
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(b) Transverse wave in a long bar is given by
Y
v where Y = Young’s modulus, = Density of material
= density
(ii) In gases v . is bulk modulus of the gas. This value is not a fixed value for gases
P
Taking isothermal process =P v
Put P = 1 atm, = 1.23 kg/m3 v = 280 m/s (more than 15% error)
Case - II : Corrected by Laplace
For Adiabatic = P
P
v . Taking = 1.4, we get, For air v 20 T
v = 330 m/s
RT P
v= =
M
1 1
(2) v or v (If temperature is kept constant)
M
(3) Velocity of a wave depends on medium, not on the frequency of source
(4) v T
(5) Velocity of sound in humid air is more because its density is less than that of dry air.
(6) Velocity of sound in humid hydrogen is less than in dry hydrogen due to similar reason.
SOUND WAVES
These are mechanical and longitudinal waves. They propagate in form of compressions and rarefactions.
Particle displacements can be represented by wave function
S = A sin( t – kx)
As particles oscillate, pressure variation takes place according to the wave function.
P = P0 cos( t – kx), P0 = maximum pressure variation
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70 Oscillations and Waves Rapid Revision & Formula Bank
Characteristic of Sound
Loudness : Sensation of sound produced in human ear is due to amplitude. It depends upon intensity, density
of medium, presence of surrounding bodies,
(a) Intensity of Wave
I = 2 2f 2A2 v
1 2
= A2 v
2
I f 2 and I A2
(b) Intensity Level or (Sound Level) ( )
T = Mg
(tension in wire)
l
Mg
n 2l
l or
2 n
T
Velocity v where ‘ ’ is mass per unit length of wire.
v nv n T
n
2l 2l
Open V V V
n 1:2:3:4
2l l 2l
st nd
I Harmonic 2 Harmonic nth Harmonic
V 3V V
Closed ( 2n 1) 1:3:5:7
4l 4l 4l
st
I Harmonic 3 Harmonic (2n –1) Harmonic
rd th
Note : Even numbered (i.e., 2nd, 4th .....) harmonics do not exist in close organ pipe.
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End correction (e) :
The antinodes are formed slightly out side the open end. The distance of antinode from open end of the pipe
is called end correction. It depends on radius of pipe. (e = 0.6 r)
Thus, we have,
For closed organ pipe For open organ pipe
l + 2e
l+e
(2n 1)V nV
4(l e) 2(l 2e )
Resonance Tube: ‘ ’
If resonance is obtained first at length l1.
l1
then at length l2, then
l2
= 2(l2 – l1)
a2 sin
y = y1 + y2 = A sin ( t – kx + ), where A a12 a22 2a1a2 cos and tan 1
a1 a2 cos
Resultant Intensity is given by
I I1 I 2 2 I1I 2 cos
DOPPLER’S EFFECT
If a wave source and a observer are moving relative to each other, the frequency observed by the receiver (f) is
different from the actual source frequency (f0) given by,
v v0
f f0
where v = speed of sound, v0 = speed of observer, vs = speed of source
v ∓ vs
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Chapter 10
Electrostatics
ELECTRIC FIELD
Electric Field due to a Point Charge (Q) :
+Q P( q )
1 Q qˆ F 1 Q ˆ
F i , E i
4 0 r2 q 4 0 r2 r F, E x-axis
1 Q ˆ
E i
4 0 r2
Application
(i) Direction of Electric Field at Various Points (when charge Q is placed at origin) :
y-axis
1 Q ˆ
EB 2
j 1 Q xiˆ yˆj
4 0 y EP rˆ , where rˆ
B 4 0
2
r x
2
y2
P
1 Q ˆ y
r
EC i
4 0 x2
–x-axis x-axis
C Q A
x x 1Q ˆ
EA i
y 4 0 x2
1 Q ˆ
ED 2
j
4 0 y
–y-axis
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Rapid Revision & Formula Bank Electrostatics 73
Qx +Q
Eaxis 2
4 0 (R x 2 )3/2
Ecentre = 0 E
x P
R
At x = , E is maximum.
2
q –q
–q +q
+q +q
ELECTRIC DIPOLE
An arrangement of two equal and opposite charges separated by some distance.
–q +q
2a
2pr
E axial 2
4 0 (r a 2 )2
2p
E axial 3
4 0r
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74 Electrostatics Rapid Revision & Formula Bank
E axial
3. For an ideal dipole E equatorial (For same distance from centre of dipole).
2
4. Electric field at any point in the plane of a short dipole
P is a point in x-y plane at a distance r from the centre of dipole, such that OP makes an angle with
dipole moment.
p si n Enet
Eeq 3
4 0r
2 p cos
y-axis Eax 3
4 0r
P Enet
r
s
co
p Eeq
O Eax
p x-axis
p sin P
1 p
(a) Enet 1 3 cos 2
4 0 r3
E eq1 1
(b) tan tan tan tan
E ax 2 2
(c) The net electric field makes an angle + with dipole moment.
1
(d) When E p + = 90° tan 2
Electric Dipole Placed in a Uniform Electric Field (Torque on dipole in uniform electric field)
Case-1 : p | | E Case-2 : p | | ( E )
E E
p qE –qE
–qE qE
–q +q +q p –q
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Rapid Revision & Formula Bank Electrostatics 75
E +q E
+q qE qE
2a
2a –qE 2a sin
–qE
–q –q
In vector form p E
(c) Translational equilibrium but not in (c) Translational equilibrium but not in
rotational equilibrium. . rotational equilibrium.
ELECTRIC FLUX
The number of field lines that pass through a surface is directly proportional to flux of electric field through
that area.
In general, E . dA
N m2
Units : or V-m
C
Important cases :
A
A E
E A
E
= EA =0
= EA cos
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76 Electrostatics Rapid Revision & Formula Bank
(4) E
Lateral
surface R
A
Base
h
E
base E.A E R2
R Base
A
E
base =0
1
φentered E R2
2
R2
leaving E
2
(6) E
A O
Base
base E R2
curved E R2
Electric Flux
Some frequently asked cases :
q a
2 q
cube
q 0
q
1. a square
6 0 2. q
each face
6 0
a
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Rapid Revision & Formula Bank Electrostatics 77
E H q
ABCD = = DCHG = BCHE
F 24
q G
0
q q
3. q 4. cube
B C cube =
2 0
8 0
A D
q
5. cube
4 0
Important results for fields due to different bodies (derived by Gauss Law)
kQ
1. Point charge Q : 2 .
r
2. Shell of charge with charge Q and radius R : kQ (outside) and zero (inside).
r2
kQr kQ
3. Sphere of charge with charge Q and radius R : (inside) and (outside).
R 3 r2
2k
4. Infinite line of charge with linear charge density : (perpendicular to line charge).
r
1 1
V2 – V1 = V = KQ r
r1
2
KQ
2. Potential due to a point charge Q at a distance r is V .
r
Kp cos
3. Potential due to a dipole at distance r at angle is V q1
r2 r1
Kq1 Kq2 Kq3 r2
4. Potential due to system of point charges is VP . P
r1 r2 r3 q2
r3
x2
q3
If V and E are functions of x, then V2 V1
E dx .
x1
x2 y2 z2
In general, V2 V1
x
1
E x dx y 1
Ey dy z
1
Ez dz
V V V
1. Ex , Ey , Ez .
x y z
dV
2. If V is a function of single variable r, E .
dr
r31 r23
1 q1q2 q 2q3 q3q1
U
4 0 r12 r23 r31
q1 q2
r12
CAPACITOR
It is a device used to store electric energy in the form of electric field.
CAPACITANCE
Capacitance of a conductor is measure of ability of conductor to store electric charge and hence electric energy
on it.
When charge is given to a conductor its potential increases. It is found that
V Q
or, Q V
Q = CV
where C is the capacitance and its unit is farad (F).
C depends on
Shape and size of conductors and their relative placement w.r.t. each other.
Medium surrounding the conductor.
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Rapid Revision & Formula Bank Electrostatics 79
Capacitance of Isolated Spherical Conductor
C=4 0r
+ –
E
Qd d
2. Potential difference between the plates = A + –
0 0
+ –
0A
3. Capacitance = d
d
Plate area = A
2
Q A QE
4. Force of attraction between the plates =
2A 0 2 0 2
1
(a) Induced charge Qi Q 1 , K is dielectric constant. –Qi +Qi
K +Q –Q
(b) Capacitance, C 0A .
t
(d t)
K
(d) The capacitance of a parallel plate capacitor is C. If its plates are connected by an inclined conducting
rod, the new capacitance is infinity.
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80 Electrostatics Rapid Revision & Formula Bank
Spherical Capacitor
1. Potential difference between plates
b a
V KQ
ba –Q
2. Electric field at any point P between plates +Q
r P
a
KQ
E b
r2
3. Potential at any point P between plates
KQ KQ
V
r b
4 0ab
4. Capacitance C
b a
4 0b 2
5. If the inner surface is grounded, capacitance C
b a
Cylindrical Capacitance of a Long Capacitor
Potential difference between plates
2KQ b
V l n
l a
Dielectric Polarisation
When a dielectre slab is placed between the plates of capacitor its polarisation take place. Thus a charge
–Qi, appear on its left face and +Qi appears on its right face.
+Q –Qi +Qi –Q
1
Qi Q 1
k
Q Q E0
E0 ;E
A 0 A 0k k
E0 E
0A
1. C
t1 t2 t3 t4
K1 K2 K3 K4
+ K1 K2 K3 K4 –
t1 t2 t3 t4
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Rapid Revision & Formula Bank Electrostatics 81
For two dielectrics,
d
If t1 t2
2
0A 2 0A + K1 K2 –
C
d d 1 1
d
2K1 2K 2 K1 K 2
2K1K 2 0 A 2K1K 2
C K eq d/2 d/2
K1 K 2 d K1 K 2
0 [K1A1 K 2 A2 K 3 A3 ]
2. C A1
d K1
A2
+ K2 –
A3 K3
A A/2
If A1 A2 K1 A/2
2
A A
0 K1 K2
2 2
C
d A/2 K2 A/2
K1 K 2 0 A K1 K 2
C K eq
2 d 2
COMBINATION OF CAPACITORS
1. Capacitors in Series (three capacitors)
Q Q Q
V1 V2 V3
C1 , C2 and C3
V = V1 + V2 + V3 C1 C2 C3
1 1 1
V Q
C1 C2 C3 V1 V2 V3
Q V
V
Ceq
1 1 1 1
Ceq C1 C2 C3
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82 Electrostatics Rapid Revision & Formula Bank
Q Q
V1 V2 C1 C2
C1 C2
V
1 1 1
Ceq C1 C2 V1 V2
C1C2
Ceq Q = CeqV
C1 C2
C2 C1
V1 V V2 V
C1 C2 C1 C2 C1 Q1
3. Capacitors in Parallel
C2 Q2
Q1 = C1V, Q2 = C2V, Q3 = C3V V
Q = C1V + C2V + C3V C3 Q3
1 Q2 1
U CV 2 QV
2 2C 2
Sharing of Charge
Case-1 : Two capacitors charged to potentials V1 and V2 are connected end to end as shown
C1V1 C2V2 V1
(a) Final common potential V
C1 C2 A
C1C2 C1
(b) Charge flown through key (V1 V2 ) in the direction A to B. V2
C1 C2
B
C1C2 C2
(c) Loss of energy = (V1 V2 )2
2(C1 C2 )
C1C2
(b) Loss of energy = (V1 V2 )2 V2 C2
2(C1 C2 )
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Rapid Revision & Formula Bank Electrostatics 83
Inserting a Dielectric Slab
1 When battery is disconnected (isolated) (charge is constant)
Q0 = initial charge
C0 = initial capacitance
V0 = initial potential
E0 = initial energy
(a) New capacitance = KC0
Q0 V0
(b) New potential difference = KC K
0
2
1 V E0
(c) New energy stored = (KC0 ) 0
2 K K
1
(d) E (KC0 ) (V0 )2 = KE0
2
4 3 4
(a) n r0 R3
3 3
R n1/ 3r0
(b) C = n 1/3C0
R
(c) Total charge = nQ0
nQ0 nQ0
(d) V n 2 / 3V0
C n1/ 3C0
1 Q2 (nQ0 )2
(e) Total energy = 2 C = n5/3 U0
2n1/ 3C0
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Chapter 11
Current Electricity
2. Parallel Grouping
R1
R2 Rp
1 1 1 1
Rp R1 R2 R3
R3
Illustrations :
R
nR/(n + 1)
1.
nR
R1 R1 R2
R1 + R2
2.
R2
R1
R2 R3 R2 Rp
3.
A R1 B R3 1 1 1 1
Rp R1 R2 R3
Cell Terminology
1. EMF (E)
The potential difference across the terminals of a cell when no current is being drawn from it.
2. Internal Resistance (r)
The opposition to flow of current inside the cell.
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Rapid Revision & Formula Bank Current Electricity 85
3. Terminal Potential Difference
I R I
It is the potential difference across the terminals of a cell
when current is supplied by it.
E = IR + Ir, V = IR V
E – V = Ir .... (i)
E r
E V
r = R Cell
V
E1 E2 E3
+ – r1 + – r2 + – r3 n cells
i
(c) Current i
E i
r R i
Note : If polarity of m cells are made reverse in the series combination of n identical cells then
equivalent emf Eequivalent = (n – 2m)E and internal resistance requivalent = nr
2. Parallel Grouping :
E1 r1
E1 E2 E3
......
r r2 r3 E2
(a) Eequivalent = 1 r2
1 1 1
........
r1 r2 r3 E3 r3
1 n cell
(b) requivalent =
1 1 1 i
......
r1 r2 r3 En rn
(c) If all cells have equal emf. E and internal resistance r then
Eequivalent = E R
r
requivalent =
n
E
Current i
r
R
n
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86 Current Electricity Rapid Revision & Formula Bank
mnE
i
mR nr
i will be maximum if mR = nr
KIRCHHOFF’S LAWS
1. Junction Rule : It is based on conservation of charge.
I I1
I = I1 + I2
I2
Note : By convention rise in potential is taken as positive and fall in potential is taken as negative.
METER BRIDGE
It is based on Wheatstone bridge principle. It is used to find an unknown resistance.
Unknown
R X
D
G
100 –
A B C
E
( )
P R
When there is no deflection in galvanometer then bridge is called balanced and for balanced bridge ,
Q S
R X 100
Unknown X R
100
Note : Location of null point is independent of resistivity or area of cross-section of wire AB.
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Rapid Revision & Formula Bank Current Electricity 87
INSTRUMENTS
1. Ammeter
(a) Shunt resistance is added in parallel to the galvanometer coil to make it into an ammeter.
ig
Shunt resistance S G .
i ig
2. Voltmeter
(a) A large resistance is added in series to the galvanometer coil to make it into a voltmeter.
V
R G
ig
R-C CIRCUIT
1. Charging
C R
E K
Key K is closed at t = 0.
Current starts flowing and charge of capacitor starts increasing.
At any instant t, q is charge on capacitor. I is current in the circuit.
(a) q = q0 [1 – e–t/RC] where q0 = EC is maximum charge
q I
–t
E t / RC RC
(b) I e = I0e q0
R I0
0.63q0
0.37 I0
t t
RC RC
At t = 0, I = E/R
+ –
+ – R
+ –
+ –
+ –
q0
K
Key K is closed at t = 0
(a) q = q0e–t/RC
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88 Current Electricity Rapid Revision & Formula Bank
dq q0 q
(b) I I = +I0e–t/RC where, I 0
dt RC q0
(c) RC = time constant ( )
at t = 0, q = q0 0.37 q0
at t = RC, q = 0.37 q0 0.135 q0
t
at t = 2RC, q = 0.135 q0 RC 2RC
(d) The charge and potential difference both decay exponentially like radioactive decay with half-life
= 0.693 RC
I 2Rt
H in calories, where J = mechanical equivalent of heat = 4.186 or 4.2 J/cal
J
t 2
In general of a variable current I passes through a resistor, heat produced across R in time t is H
0 I Rdt
R=r R
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Chapter 12
Magnetic Effects of Current
and Magnetism
BIOT-SAVART LAW dB
Magnetic field due to current carrying element is given by r P
idl sin dl
0
dB
4 r2
i (dl r) i
0
dB 3
4 r
The direction of magnetic field due to small element dl is in the direction of dl r
Units : 1. S.I. unit of magnetic field is tesla (T)
2. CGS unit of magnetic field is gauss.
3. 1 gauss = 10–4 tesla.
0i 2
B (cos 1 cos 2)
4 r
i r
P
0i
or B (sin sin )
4 r
1
0i
= = 0 or , B
1 2
2 2π r
, 0, B 0i
= 0°, = 90°, or
1 2 2 4 r
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90 Magnetic Effects of Current and Magnetism Rapid Revision & Formula Bank
CIRCULAR LOOP
1. At the centre of a current loop
0 idl sin 90
dB 2
dl
4 r
r
0i 0i i
B
4 r 2 dl 4 r 2
2 r
0i
B (Outward).
2r
i i
(Outward field perpendicular to the plane of loop) (Inward field perpendicular to the plane of loop)
2. On the axis of a loop
I
R
B (towards right perpendicular to the plane of loop)
x
0 2 I R2 0 2M
B
4 (R 2 2 3/2
x ) 4 (R 2 x 2 )3 / 2
0 2M
For x >> R, B [Current carrying loop acts as an magnetic dipole]
4 x3
where M = I × R2 is called magnetic dipole moment
M IA
I
I
1. 2.
P P
r r
0I 0I
BP [sin ] BP [sin sin ]
4 r 4 r
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Rapid Revision & Formula Bank Magnetic Effects of Current and Magnetism 91
to b
r P
a O I
3. I 4.
0I 8 0I a2 b2
BP [sin 1] B0
4 r 4 ab
8 2 0I
when a = b B0
4 a
i
r
i i
5. O 6.
O
i
0i
B0
4r
Magnetic field at O
3 0 i
B0 where ‘a’ is length of each side of regular hexagon
a
i
i
i1
b
a i O
7. O 8.
0i 1 1 i
B0
4 a b i2
B0 = 0 (for any value of )
i
i 3
i/3 O
i i r r i
9. 3 10.
i
At the centre of At O, B = 0
cube, B = 0
i1 r1 O r2 i2
11. 12.
r r
O
At O, B = 0, such that 0 I
i1 i2r B0
r1 r ; r2 2r 2
i1 i 2 i1 i 2 ( is radian)
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92 Magnetic Effects of Current and Magnetism Rapid Revision & Formula Bank
I I
r r
13. O I 14. O I
I I
0I 0I 0I
B0 B0
2 r 4r 4r
I P
15.
BP = 0 (at point P)
Upward Inward
Current Current
i1 i2
dl
B
B .d i 0 ( i1 i2 )
B.dl 0 i enc
Here B.dl implies the integration of scalar product B. dl around a closed loop called an Amperian loop.
The current ienc is the net current encircled by the loop.
dl Amperian loop
B·dl 0I
0I
B
2 r
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Rapid Revision & Formula Bank Magnetic Effects of Current and Magnetism 93
(2) Magnetic field inside a long straight current carrying conductor
i R
r Amperian loop
Amperian loop r
dl , B dl
R
B
I
I r2
nR 2
I
B·dl 0
nR 2
r2
0 r
B i.e. Bin r
2 R2
Graphical variation of magnetic field
B
–R
x
R
SOLENOID
A long solenoid having number of turns/length ‘n’ carries a current I.
0 nI
Bend (near one end)
2
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94 Magnetic Effects of Current and Magnetism Rapid Revision & Formula Bank
F q (v B )
F = qvB sin
F is perpendicular to both v & B and is in the direction of v B when q > 0 and opposite to v B when
q < 0.
mv 2 mv p 2km p2
F qvB r (k is kinetic energy). As k .
r qB qB qB 2m
Results
1. During revolution its speed is constant
2. During revolution its kinetic energy is constant
3. Work done by the magnetic force is zero
4. Velocity and momentum change continuously in direction, not in magnitude.
2 r 2 m
5. T (Independent of speed and radius)
v qB
v sin
r
B
v cos
pitch
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Rapid Revision & Formula Bank Magnetic Effects of Current and Magnetism 95
The particle moves in a helical path such that
mv sin 2 m
r ,T , Pitch = v cos ×T
qB qB
Case-3 : If charged particle is moving parallel or anti-parallel to field B then force is zero and it moves in
a straight line
Cyclotron
A cyclotron is a machine used to accelerate charge particle (like proton, deutron, -particle). It uses both
electric and magnetic field. Speed of particle is increased by electric field.
qB
Cyclotron frequency
2 m
q 2B 2Rmax
2
K max
2m
To accelerate electrons Betatron and Synchrotron are used. A synchrotron accounts for the variation in mass
with speed. A Betatron uses the induced electric field produced by a time varying magnetic field to accelerate
charged particles.
B
I = Current through the conductor, = Length of the conductor
Bsin
F IB sin
F I ( B)
The direction of is always in the direction of current.
F = BI(2R)
BI(2R)
× × × × × × × × × ×
× × × F = BIL
iLB I I
L
× × × × × × × × × × × × O × ×
(1) i (2) (3) (4) T
R
I O R
× 2IBL × L
L × × × × × × × × × ×
× × i × ×
iLB
× × × × × × × × × ×
BI(2R)
Net F = 0
T = BIR
(tension in the wire)
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96 Magnetic Effects of Current and Magnetism Rapid Revision & Formula Bank
to
F F I1 I2
I1 I2
Attraction Repulsion
r
to
0 I1I 2
F (force/unit length) is given by F .
2 r
0 I1I 2
The force on a segment of length ‘l’ is l
2 r
Force on a small current carrying segment placed near long and perpendicular current carrying wire.
0 i1i 2 l
log 1
d
FPQ
2
PQ 0
Principle
When a current carrying coil is suitably placed in a magnetic field, torque acts on it. In moving coil
galvanometer radial field is used which is obtained from magnet having concave shape poles. In this type of
field plane of the coil is always parallel to the magnetic field so maximum torque acts on it.
Pointer Scale
g
p rin
S
N Coil
S
Soft iron
core
Cylinder
= NIAB [ = 90° due to radial field] ( Angle between M and B )
=C ( = Angle of twist)
where is angle turned by the pointer and C is restoring torque/twist in the suspension wire.
C
I
NBA
NBA
Current sensitivity =
I C
NBA
Voltage sensitivity =
V IR CR
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Rapid Revision & Formula Bank Magnetic Effects of Current and Magnetism 97
MAGNETISM
BAR MAGNET
Magnetic field due to a Bar Magnet
B
2. B equatorial is antiparallel to M .
1 1
as tan tan cot tan or tan 2.
2 2
B
mB
N
2l
= mB × 2l sin
S
= m × 2l × B sin mB
= MB sin
Results :
1. M B , max = MB [when = 90°],
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98 Magnetic Effects of Current and Magnetism Rapid Revision & Formula Bank
MB
Angular frequency ;
I
I
Time period T 2
MB
L/2 L/2
-1
se
ca T = T/2 T = T/2
1. Cut into two halves
ca
se L
-2
T =T
A/2
T =T
A/2
I
where T 2
MB
2. Two bar magnets having magnetic moments M1, M2 and moment of inertias I1, I2 are joined as shown.
I1
I1 I 2 M1
(a) T1 2
(M1 M 2 )B
M2
I2
I1 I 2
(b) T2 2
(M1 M 2 )B
I1
M1
T22 T12 M1
T22 T12 M2 M2
I2
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Rapid Revision & Formula Bank Magnetic Effects of Current and Magnetism 99
EARTH’S MAGNETIC FIELD
The basic components of earth’s magnetic field at a place are shown
Geographic meridian
1. = Angle of declination
2. = Angle of dip/inclination BH
3. BH = B cos BV
Magnetic
B
meridian
4. BV = B sin
5. BH2 + BV2 = B2
BV
6. tan
BH
7. When the dip circle is not in magnetic meridian and dip circle is at an angle of 1 to magnetic meridian.
1
s
co
BH Apparent angle of dip = 1
1
BH
= True dip
BV B
[ = True dip angle, 1 and 2 = apparent dip angle in two arbitrary perpendicular)
BV
tan 1 (apparent dip) [Vertical component remains same]
BH cos 1
tan
tan 1
cos 1
B0
1. Magnetic Intensity (Magnetising Force) : H
0
Pole strength ∵ M m l
I
area ∵ V A l
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100 Magnetic Effects of Current and Magnetism Rapid Revision & Formula Bank
3. Magnetic Induction or Magnetic Flux Density (B) : Number of magnetic field lines crossing per unit
area normally through a magnetic substance.
B = B0 + 0I
B0 applied magnetic field
B= 0H + 0I
0 I magnetic field due to magnetisat ion
B= 0 (H + I)
I
4. Magnetic Susceptibility : m (no unit)
H
B
5. Magnetic Permeability : B= H
H
From above B = 0(H + I)
H= 0 (H + I)
I
1
0 H
Curie Law
Magnetic susceptibility of paramagnetic material is inversely proportional to its absolute temperature.
1
m
T
Variation of I with H
1. Diamagnetic 2. Paramagnetic
I
H
H
I
3. Ferromagnetic (Hysteresis)
OB = Retentivity (residual magnetism even after magnetising field is reduced to zero)
OC = Coercivity (reverse magnetic field required to reduce residual magnetism to zero)
Area ABCDEFA = Energy loss/cycle during magnetisation and demagnetisation.
I
A I
B
C
O H H
F
D E
Steel
(High coercivity, high retentivity) Soft iron
(Low coercivity, low retentivity)
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Chapter 13
Electromagnetic Induction
MAGNETIC FLUX
B.A BA cos ( = Angle between B and A )
A
B
k
v
l A(+) B(–)
B(–)
A(+) O R e = Bvl sin
e = Bv(2R)
A(–)
e = Bvl
4. 5. 6.
A B
A(+) r
A B B(–)
l (–) O
(+) R
1 1 2 1 2
e= Bl2 e= BR = 0 eOA = Br
× 2 × 2 ×
AB
× 2 ×
×
Disc Part of Disc
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102 Electromagnetic Induction Rapid Revision & Formula Bank
7. 8. 9.
× × (B) × × × A ×
A D
R
v v v
l R l
O
B C
B
A D
I =0 I
I =0
Bvl Bvl R
2BvR 2BvR Bvl
I
B C
Bvl
× × × × × I ×
R
10.
× × × ×
I
v r
R1 l R2 R1 R2
Bvl
× × × × Bvl
I
Sliding rod also has a R1R2
resistance ‘r ’ r
R1 + R2
11. 12.
× × × × × ×
× × × × × × v
× × × × × × i
× ×R× × × × b a
× × × × × ×
× × × × × ×
Einduced = 0 0 iv a
ln 1
Ring 2 b
0 N1N 2 A
M
l
N1 = Number of turns in one solenoid
N2 = Number of turns in other solenoid l
A = Area of cross-section of narrower solenoid
l = Length of solenoid
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Rapid Revision & Formula Bank Electromagnetic Induction 103
r I a
r
R b
r b
0 r2 8 a2 b2 2 0 r b
(a) M (b) M r (c) M a log
2R 4 ab 2 r
(For r << a, r << b)
Energy in Inductor
1 2 1 B2 I
Energy U B LI , Energy density =
2 2 0
Combination of Inductors
1. Inductor in series
L1 L2
2. Inductor in parallel
L1
L2
1 1 1
L L1 L2 (Neglecting mutual induction)
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104 Electromagnetic Induction Rapid Revision & Formula Bank
R L
At t = 0 the switch S
is closed
i
S
E t=0
E t
L
i i e . Here
R R
Graph for variation of current (i) with time (t) is shown here.
i
E/R
E
0.63
R
t= t
E r
E 1/r
r r
LC OSCILLATIONS
A charged capacitor is connected to an inductor and switch
is closed at t = 0. +
+
–
– S
–
+ –
+ –
The charge and current vary sinusoidally as, + –
q = q0 cos t [∵ at t = 0, q = q0] L
i = i0 sin t [∵ at t = 0, i = 0]
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Rapid Revision & Formula Bank Electromagnetic Induction 105
Graphical representation of this variation is as shown.
i q
t t
q0 1 1
i0 , , is frequency of LC oscillations
LC LC 2 LC
2
1 2 qmax
The maximum charge and maximum current in LC oscillation are related as LI max
2 2C
qmax Imax LC
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Chapter 14
Alternating Current and
Electromagnetic Waves
t t
1 1
E mean
t
Edt , Imean
0
t
Idt
0
t t
1 1 2
2
E rms E 2 dt , Irms
2
I dt
t t
0 0
E0
I0 Generator
R
2. Inductive Circuit L
I = I0 sin ( t – /2)
E0
I0
X L , where XL = L = 2 fL
E = E0 sin t
Capacitive Circuit + –
+ –
–
1. I = I0 sin ( t + /2) + –
+ –
+ –
E0 1 1
2. I0 E = E0 sin t
X C , where XC =
C 2 fC
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Rapid Revision & Formula Bank Alternating Current and Electromagnetic Waves 107
SERIES LCR CIRCUIT
I L C I R I
V1 V2
E = E0 sin t
E0
V = rms value of applied voltage
2
Phase Relationship
I and VR are in same phase in case of resistance.
VL leads I by 90° in case of inductor.
VC lags behind I by 90° in case of capacitor.
I R2 ( XL XC )2
(a) Impedance = Z R2 ( XL X C )2
R R
(b) Power factor = cos
Z R 2
( XL X C )2
T
1
T 0
Pav EIdt
E 0 I0
Pav cos
2
E0 I0
. cos
2 2
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108 Alternating Current and Electromagnetic Waves Rapid Revision & Formula Bank
ELECTROMAGNETIC WAVES
Electromagnetic waves are non-mechanical waves. They transport energy and momentum and carries
information. They are transverse in nature and hence they can be polarised.
An electromagnetic wave is the one constituted by oscillating electric and magnetic fields which oscillate
in two mutually perpendicular planes; the wave itself propagates in a direction, perpendicular to both the
directions of oscillations of electric and magnetic fields.
E0
x-axis
(direction of propagation
B0 is E × B )
B (Transverse in nature)
1. Both electric and magnetic field vary in phase with each other.
2. Ey E0 sin( t kx ) jˆ, Bz B0 sin( t kx )kˆ, speed v
k
1 1
3. In vacuum, c . In a medium v .
0 0
c
Refractive index of the medium r r .
v
E E0 Erms
4. = c (speed) =
B B0 Brms k
1 2 1 B02 1 2 1 B02
5. Average energy density Uav 0E0 0E0
2 2 0 4 4 0
E B EB
S or S . Here E B represents the direction of flow of energy.
0 0
7. Intensity : Average rate of flow of energy per unit time per unit area in the direction of wave propagation.
Erms Brms 1 E 0 B0
I = Sav =
0 2 0
I
I = c × Uav or U av
c
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Rapid Revision & Formula Bank Alternating Current and Electromagnetic Waves 109
P
For a point source of power P, Intensity at a distance r from the source is I .
4 r2
I P
Now U av
c 4 r 2c
1 2 P P
0E0 2
E0
2 4 r c 2 r 2c 0
E0 P 0
B0
c 2 r 2c
8. Radiation pressure (for normal incidence)
(a) For perfectly absorbing surface P = I/c
(b) For perfectly reflecting surface P = 2I/c
(c) For all other surfaces I/c < P < 2I/c
(d) For a surface of reflectance r
I
P (1 r )
c
9. The direction of wave propagation is always along E B and E, B, c are always perpendicular.
10. Speed of electromagnetic waves only depends upon the medium. All the electromagnetic waves travels
with equal speed (i.e. 3 × 108 m/s) in vacuum.
11. When a electromagnetic wave travels from one medium to another then its speed changes but frequency
remains same.
c
12. Speed of electromagnetic waves in any medium = [where is the refractive index of the
electromagnetic waves]
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Chapter 15
Optics
PLANE MIRROR
Following are some important points regarding image formation by plane mirror :
Real object
O I
Virtual image
u0 v0
du dv
2. , i.e., speed of object w.r.t. mirror is equal to speed of image w.r.t. mirror. For example, if object
dt dt
is at rest and mirror is moving with velocity x towards object then velocity of image will be 2x.
3. For extended object, it can be seen that height of object = height of image.
Height of image
Magnification = 1
Height of object
A A
B B
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Rapid Revision & Formula Bank Optics 111
4. Image is laterally inverted, i.e., it has front back reversed.
y y
x x
5. Keeping incident ray fixed, if a plane mirror is rotated by an angle , reflected ray rotates by an angle 2 .
6. For two mirrors inclined at an angle ‘ ’. Number of images formed by the mirrors for a point object are
360 360
(a) 1 , if = even number
360 360
(b) 1 , when = odd and object is placed symmetrically.
360 360
(c) , when = odd and object is placed unsymmetrically.
R
1. f where,
2
f = Focal length
u = Object distance
2. 1 1 1 v = Image distance
f v u I = Size of image
O = Size of object
I v f v f
3. m
O u f f u
4. Magnification is negative for inverted image and positive for erect image.
5. If object O is moving with velocity v0 as shown in figure then velocity of image vimage = –m2v0
O
v0
. .
1 1 1
.
v u f
dv v 2 du
dt u 2 dt
vimage = –m2v0
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112 Optics Rapid Revision & Formula Bank
6. If object is moving with velocity v0 as shown in figure then velocity of real image vimage = mv0
v0
P
1. At infinity C F Real inverted, very small
[m (0–)]; at focus or
M in focal plane.
O M
I M
O
(m < + 1) between P and F
P I F C
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Rapid Revision & Formula Bank Optics 113
Laws of Refraction (Snell’s Law)
Consider a light ray crossing a series of media as shown.
sin = Constant
3
3
OP PI
(By Snell’s law)
2 1
1 1
PI OP x
2 2 P
∵ 1 < 2, PI < OP
x I
x 1 Shift = x 1
1
Shift
2
O
Glass-slab
O
Different results for refraction by glass slab are :
x
1. Incident and emergent rays are parallel. i Medium 1 (air)
O
t sin(i r ) Medium 2
2. l = lateral displacement = r ‘ ’
cos r glass
l
for small values of i, sin(i – r) i – r and r 0.
incident ray
i 1 emergent
l = t i ti 1 ray
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114 Optics Rapid Revision & Formula Bank
4. O O 5. t O O
‘ ’ 1
1 ‘ ’ t 1–
t 1–
t
If an object is placed at distance x from plane mirror then image will be formed at distance of x from mirror.
O I
Now if a glass slab of thickness t is introduced between object and mirror then image will shift toward object
by 2t 1 1
O I I
shift
t
x
Critical Angle
If a ray is travelling from optically denser medium to optically rarer medium, then critical angle may be defined as
the angle of incidence in denser medium corresponding to which angle of refraction in rarer medium is 90°.
If 1 = refractive index of rarer medium
Normal
2 = refractive index of denser medium
1
and ic = critical angle
r = 90°
then 2sin ic = 1 sin 90°
Grazing
ic emergence
1
sin i c 2(> 1)
2
O P C I
2 1 2 1
u R
v u R v
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Rapid Revision & Formula Bank Optics 115
Some Important Relations for Lenses
Converging (Convex) lens Diverging (Concave) lens
f>0 f<0
1 1 1
1. Lens formula
v u f
v f f v
3. In lenses, m
u f u f
4. A convex mirror or a concave lens can form a real image if object is virtual as shown.
P I
real image I O F C O O
virtual
object
5. If an object moves along the axis of a convex lens from infinity towards its focus with a constant speed, then
v2
vi = m2v0, for a lens vi = v0
u2
6. If an object moves perpendicular to axis of a convex lens with a velocity v0 then vi = mv0
LATERAL MAGNIFICATION
AB vB vA
mL
AB uA uB
uA
For short object A B
uB
p
dv
mL B A
du vA
vB
v2
For a concave mirror, mL
u2
v2
For a convex lens, mL
u2
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116 Optics Rapid Revision & Formula Bank
Case 1 Case II
O I O I P
u v
C u v
Final image is real and inverted and coincides with O Final image is real and erect and coincides with O
1 2 1 1
For a thin lens, P (Power ) 1
f 1 R1 R2
O I I1
(R1) v
1 2 (R1) 1
u v
COMBINATION OF LENSES
1. In contact : P1 P2
1 1 1
f f1 f2
2. P = P1 + P2 – dP1P2
P1 P2
1 1 1 d
f f1 f2 f1f2 (Applicable only for parallel rays)
f1 f2
where d is the separation between two lenses in air
d
Silvering of Lenses
1. When a convex lens is silvered it will behave like a concave mirror.
2. When a concave lens is silvered it will behave like a convex mirror.
3. Case-1 : When one face ( of radius of curvature R2) of a double convex lens is silvered
Peq = 2Pl + Pm R2
1 1 1 2 R1
2( 1)
Feff R1 R2 R2
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Rapid Revision & Formula Bank Optics 117
PRISM AND DISPERSION
A
Angle of prism
A
i e
r1 r2
Incident Emergent ray
ray
B C
Base
Note :
1. The variation of with i is unsymmetrical.
2. Under minimum deviation, ray passes symmetrically through the prism.
3. If prism is isosceles or equilateral, refracted ray is parallel to base of prism under minimum deviation.
A
4. If A > 2C or cosec
, there will be no emergent light whatever may be the angle of incidence.
2
5. A = 2C is called limiting value of angle of prism.
6. If A < C, total internal reflection at second face can never take place.
7. In case, one face is silvered, for incident ray to retrace its path after
A
reflection from 2nd face.
r2 = 0 r1 = A
i r1 sin i
sin A
8. Angle of deviation is maximum when angle of incidence = 90º.
9. A thin hollow prism as shown produces zero deviation.
Dispersion
B C D A V
A 2 4 6
... [Cauchy’s formula]
R
R
= ( – 1)A
White Y
As, < ray
V R V
V > R
V< R
= angular dispersion = V R ( V R )A
V R
= mean refractive index =
2
( V R )A V R d
Dispersive power
( 1)A 1 1
d = difference in refractive index
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118 Optics Rapid Revision & Formula Bank
Combination of Prisms
= 1 + 2, = 1 + 2
=0
( V R )A ( V R )A 0
Chromatic Aberration
This is the phenomena observed when different colours come to focus at different points on the principal axis.
This defect can be removed by using an achromatic lens combination.
b c
As, a 2 4
White light
and R> Y > v
fV fY fR
R< Y < v
1 1 1
fR > fY > fv as ( 1)
f R1 R2
Achromatic Combination
A combination free from chromatic aberration is achromatic combination.
1. Lenses in contact
1 1
Power P P1 P2
f1 f2
1 1 d
2. P P1 P2 dP1P2
f1 f2 f1f2
1f2 2 f1
Condition for achromatism d .
1 2
f1 d f2
f1 f2
(b) = d
1 2
2
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Rapid Revision & Formula Bank Optics 119
OPTICAL INSTRUMENTS
1. Simple Microscope / Magnifying Glass : It uses a single convex lens of focal length f
D
m , where u is distance of object
u
Case-1 :
F
B
f
(Final image at infinity)
D
For relaxed eye, u f , image at m= >0
f
Case-2 :
A
B F B
D
(Final image at least distance of distinct vision)
D
For strained eye, image is at D m= 1 >0
f
2. Compound Microscope
It uses two convex lens objective (fo) and eyepiece (fe)
uo = object distance from objective (uo is close to fo)
vo = image distance from objective (close to length of tube)
vo
Magnification by objective mo = (–ve)
uo
D
Magnification by eyepiece me =
ue
Magnification for microscope
vo D
m = mo × me =
uo ue
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120 Optics Rapid Revision & Formula Bank
Case-1 :
Eyepiece
Objective lens
B Fe
F0
vo D LD
Relaxed eye : m
uo fe fo fe
Length of tube L = V0 + fe
Case-2 :
Eyepiece
Objective lens
Fe B
B
A
(Final image at least distance of distinct vision )
vo D L D
Strained eye : m 1 1
uo fe fo fe
fe D
Length of tube V0
fe D
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Rapid Revision & Formula Bank Optics 121
3. Astronomical Telescope : fo is focal length of
objective and fe is focal length of eye-piece.
fo
For relaxed eye i.e., normal adjustment. m
fe
Length of tube L = fo + fe
Objective
Eyepiece
Fo Fe
B
C1 C2
fo fe
Case-2 :
Objective
Eyepiece
B Fe B Fo
A
D
(Final image at least distance of distinct vision)
fo fe
For strained eye : m 1
fe D
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122 Optics Rapid Revision & Formula Bank
WAVE OPTICS
1. 2.
Plane
Plane Converging Diverging
wavefront
wavefront wavefront wavefront Diverging
wavefront
3.
Plane Plane
wavefront wavefront
SUPERPOSITION OF WAVES
B
Wave-1 : y1 = A sin t
Wave-2 : y2 = B sin ( t + ) R
B sin
where tan
A B cos
and R A2 B2 2 AB cos
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Rapid Revision & Formula Bank Optics 123
Relation between phase difference and path difference
For the two points A and B on a wave,
AB =2
XAB = A B
2
x
Interference
Phenomenon of redistribution of energy on account of superposition of waves is known as interference.
Coherent Sources
Condition for sustained interference-Sources must be coherent i.e., phase difference between them must be
constant.
S1
M y
D
d D
O 2d
d
S C 4I0
x N d
=D
S2
D
Screen
yd y
For small x ∵ sin tan
D
D
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124 Optics Rapid Revision & Formula Bank
DIFFRACTION
Diffraction is the phenomenon of light observed due to superposition of secondary wavelets starting from different
points of a wavefront which is not blocked by an obstacle or which are allowed by an aperture (of size
comparable to the wavelength of light).
In other words you can say diffraction is the phenomena of entering of light in the region of geometrical shadow,
due to bending around obstacle edges.
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Rapid Revision & Formula Bank Optics 125
a
1. x sin
2
2. For ‘O’ waves from all points in the slit travel about the same distance and are in phase.
a
3. At P, waves r1 and r2 have a phase difference x sin .
2
a
4. When sin 1 , there will be destructive interference.
2 2
when a sin 1 = , first minima will be formed at P.
5. In general a sin n = n is position of nth minima.
6. Angular position of first minima 1 sin 1
a
2
7. Angular spread of central maximum is 2 = 2 sin 1 . If << a, then angular spread = .
1
a a
2 D
10. Width of central maximum =
a
D
11. Width of other fringes = .
a
4I 0
12. If I0 is the intensity of central maximum, then intensity of nth maxima is I n
(2n 1)2 2
I0 : I1 : I2 : : 1 : 0.045 : 0 : 016.
13. The intensity of fringe goes on decreasing in case of diffraction while it remain nearly same in the interference.
Polarization
Polarization is a phenomenon exhibited by transverse waves only.
Polarizer Analyser
A
C
Polarization by Reflection
Unpolarized
light
Air Reflected fully
polarized
Air i i Reflected, partially ip ip
polarized
Medium
Medium ( ) r ( ) r
Refracted
Refracted
1
tan i p
sin i c
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Chapter 16
Dual Nature of Matter and
Radiation, Atoms and Nuclei
h h h
2. de-Broglie wavelength of a particle .
mv p 2mEk
where p = mv is momentum of particle
Ek = kinetic energy.
3. For an electron accelerated through V volts.
h 12.27 150
Ek eV Å or Å
2meV V V
0.286
4. For a proton accelerated through V volts, Å
V
0.101
5. For an -particle accelerated through V volts, Å
V
nh h 2 r
6. For an electron revolving in nth orbit of Bohr’s Hydrogen atom, mvr , .
2 mv n
X-RAYS
Variation of intensity (I) of X-rays with wavelength :
Intensity (I)
K
K
min Wavelength ( )
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128 Dual Nature of Matter and Radiation, Atoms and Nuclei Rapid Revision & Formula Bank
1. At certain sharply defined wavelength, the intensity of X-rays is very large as marked K and K . These
are known as characteristic X-rays.
2. At other wavelengths intensity varies continuously. These are known as continuous X-rays.
hc 12400 Å
min , where V is applied voltage in volts.
eV V
4. The minimum wavelength does not depend on the material of target. It depends only on the accelerating
potential.
5. Continuous X-rays are due to continuous loss of energy of electrons striking the target through successive
collisions.
6. Characteristic X-rays are due to the transition of electrons from higher energy level to the vacant space
present in the lower energy level.
hc
7. Wavelength of K , ( transition from L to K )
EL EK
hc
8. Wavelength of K , (transition from M to K )
EM EK
For K X-ray,
3Rc
a=
4
b=1
Diffraction of X-Rays
Davisson and Germer’s accidental discovery of the diffraction of electrons was the first direct evidence confirming
de Broglie’s hypothesis that particles have wave properties as well.
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Rapid Revision & Formula Bank Dual Nature of Matter and Radiation, Atoms and Nuclei 129
PHOTOELECTRIC EFFECT
The emission of electrons from a metallic surface when illuminated with light of appropriate wavelength
(or frequency) is known as photoelectric effect. It was discovered by Hertz in 1887.
Light of frequency
Cathode or and intensity I
photosensitive Anode
metal
e
Photoelectrons
A
V
Potential divider
Work Function ( ) : It is the minimum energy of photon required to liberate an electron from a metal surface.
Threshold Frequency ( 0) : The frequency of incident radiation below which photoelectric effect does not take
place. h 0 = .
Stopping Potential (V0) : The smallest negative value of anode potential which just stops the photocurrent
is called the stopping potential.
If the stopping potential is V0 then eV0 = KEmax = Maximum kinetic energy of photoelectrons emitted.
The following important points should be kept in mind :
1. The kinetic energy of photoelectrons varies between zero to KEmax.
2. If ( > 0) is frequency of incident photon, h 0 is work function then h – h 0 = KEmax. This is Einstein’s
photoelectric equation. Here h is Planck’s constant.
3. Efficiency of photoelectric emission is less than 1%. It means it is not necessary that if the energy of
incident photon is greater than work function electrons will definitely be ejected out.
4. If frequency of incident radiation ( ) is doubled, stopping potential (V0) or kinetic energy maximum (K.E.max)
gets more than doubled.
5. If on a neutral ball made up of metal of work function , radiation of frequency (greater than threshold
frequency) is incident, number of photoelectrons emitted from the ball before the photoelectric emission
(h )4 0R
stops is given by n .
2
e
6. Saturation current depends upon intensity of incident light whereas stopping potential depends upon
frequency of light as mentioned in graphs also.
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130 Dual Nature of Matter and Radiation, Atoms and Nuclei Rapid Revision & Formula Bank
V0 Photocurrent
Metal 1 I2 IS1 and IS2
Metal 2 IS2 saturation
I1
IS1 currents
Stopping
potential I2 > I1
Slope = h/e = tan
= constant
2 > 1
1. 2.
1
Frequency
e 0 0
V0
0 > 0 Stopping Retarding potential
2
potential
e
Saturation Photocurrent
Photocurrent
2
2 > 1
3. 4. 1
Intensity : Constant
I
Intensity –VS2 –VS1
nh
i.e., mvr
2
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Rapid Revision & Formula Bank Dual Nature of Matter and Radiation, Atoms and Nuclei 131
E3
E2
E1
Nucleus
E2 – E1 = h
where, E2 = higher energy state
E1 = lower energy state
and = frequency of photons of radiation/emitted absorbed.
r Electron
+
Nucleus
+Ze
1 (Ze) e mv 2
...(i)
4 0 r2 r
nh
Angular momentum about the nucleus, mvr ...(ii)
2
(a) Velocity of electron in nth orbit
Putting value of mvr from equation (ii) into equation (i),
1 nh
Ze 2 v
4 0 2
Z e2 Z
v .v 0 ...(iii)
n 2 0 h n
where,
c
v0 = 2.2 × 106 m/s
137
v0 1
where c = 3 × 108 m/s = speed of light in vacuum, = fine structure constant
c 137
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132 Dual Nature of Matter and Radiation, Atoms and Nuclei Rapid Revision & Formula Bank
Z e 2 nh
m r
n 2 0 h 2
n2 0h2 n2
r 2
.r0 ...(iv)
Z me Z
where,
r0 = 0.53 Å.
(c) Total energy of electron in n th orbit
From equation (i)
1 Ze 2
K.E. mv 2
2 8 0r
1 (Ze ) ( e )
and P.E. 2 K.E.
4 0 r
P.E. = – 2 K.E.
Total energy, E = K.E. + P.E. = – K.E.
Z 2 me 4 Z2
E .E 0
n 2 8 02 h 2 n2
2 r n3
T .T0
v Z2
where,
T0 = 1.51 × 10–16 s.
(e) Frequency of revolution in nth orbit
1 Z2
f .f0
T n3
where,
f0 = 6.6 ×1015 Hz.
(f) Magnetic field at the centre due to revolution of electron
0I 0e 0e v
B
2r 2r T 2r 2 r
2
v Z Z Z3
B B 2 B
r 2 n n n5
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Rapid Revision & Formula Bank Dual Nature of Matter and Radiation, Atoms and Nuclei 133
(g) Wavelength of photon
1 1 1 2
R 2 Z
n1 n22
where,
R = Rydberg constant
1 –1
912 Å
BINDING ENERGY
The amount of energy needed to separate the constituent nucleons to large distances is called binding energy.
If the nucleons are initially well separated and are brought to form the nucleus, this much energy is released.
10
Binding energy per nucleon (MeV)
56
32 Fe 100
Mo
O S
127
16
I 184 197
W An 238
U
8
4 18
He O
14
N
6 6
Li
4
3
H
2
2
H
0
0 50 100 150 200 250
Mass number (A)
Likewise, the low B.E. per nucleon for heavy nuclei indicates that if a single heavy nucleus breaks up into
middle mass nuclei, energy will be released. Release of energy in fission process is based on this fact.
Note : 1. Binding energy per nucleon is practically constant for 30 < A < 170.
2. B.E. per nucleon is lower for both light nuclei (A < 30) and heavy nuclei (A > 170).
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134 Dual Nature of Matter and Radiation, Atoms and Nuclei Rapid Revision & Formula Bank
RADIOACTIVITY
Law of Radioactive Disintegration
dN
N
dt
dN
N ( is decay constant)
dt
t
N N0e
dN t
Activity A N0e
dt
λt
A A0 e
ln 2 0.693
T1/ 2
Let N0 be the initial number of active nuclei and N be the number of active nuclei remaining after n half lives
0
then N .
2n
Application : Let R1 be activity of radioactive substance at t = T1 and R2 be the activity at t = T2, then
R1 = N1 and R2 = N2
Number of nuclei disintegrated in (T2 – T1) is
R1 R2 (R1 R2 )T
N1 N 2
ln 2
where T is the half life of radioactive substance.
Average Life (Tav)
1 T1/2
Tav or Tav = 1.44 T1/2 or T1/2 = 0.693 Tav
ln 2
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Chapter 17
Electronic Devices and
Communication Systems
DIODE AS RECTIFIER
A device to convert ac into dc.
1. Half Wave Rectifier
I0
I0 Irms
I0 2
Input RL Output I0
Imean
Irms
Step down form factor 1.57
transformer Imean
Important points :
a. Input frequency = Out put frequency.
b. Maximum Efficiency = 40.6%
2
ac component Irms
c. Ripple factor r 2
1 1.21 .
dc component Imean
0.406 RL
d. Efficiency of half wave rectifier
rf RL
I0 I0
Input I0 Irms
Output
RL 2
2I 0
Centre tap Imean
transformer
a. Out put frequency = 2 × input frequency
b. Maximum Efficiency = 81.2%.
c. Ripple factor r = 0.48.
0.812 RL
d. Efficiency of full wave rectifier
rf RL
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136 Electronic Devices and Communication Systems Rapid Revision & Formula Bank
JUNCTION TRANSISTOR
Symbols used for transistors are shown here :
PNP NPN
P N P N P N
h h e h h e e h e e
h h h h h h
e h e e e e e e
e e
h
e
h e h
e
h
h h eh e
Emitter BaseCollector Emitter BaseCollector
E C E C
B B
Ie Ib Ic
PNP NPN
Ic Ic
Ib RL Ib RL Output
Output Ie
Ie
Input
Vi
V0
Ic
2. DC current gain .
Ib
Ic
3. AC current gain ac .
Ib
V0
4. AC voltage gain Av .
Vi
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Rapid Revision & Formula Bank Electronic Devices and Communication Systems 137
RL
6. Resistance gain Rg (Ri = input resistance).
Ri
1 1
7. 1
8. < 1, >1
Ic
9. Transconductance g m
Vi
COMMUNICATION SYSTEMS
Communication of information to each other is a basic human activity. For example, one person wishes to tell
something or give a message to another person sitting near him. Then he speaks and transmits sound waves
through air medium or channel. The other person receives the message by listening through his/her ears. In
modern communication systems the information is first converted into electrical signals or electromagnetic waves
and then sent electronically. This has the advantage of speed, reliability and possibility of communicating over
long distances.
The key to communication system is to obtain an electrical signal voltage or current which contains the
information. For example, a microphone can convert speech signals into electrical signals. Similarly, pressure
can be sensed by piezoelectric sensor which gives pressure in terms of electrical signal. A signal is defined
as a single-valued function of time (that conveys the information) and which, at every instant of time
has a unique value.
Transmission
Generation
of
Transmitter Receiver
Information
Signal
Channel
Note : In an AM-wave the difference between upper side band and lower side band (which is equal
to 2fm) is known as the band width.
Graphically, the carrier frequency and the side bands can be shown as :
Amplitude
Ac
mAc
2
f (Hz)
(fc – fm) fc (fc + fm)
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138 Electronic Devices and Communication Systems Rapid Revision & Formula Bank
Q
d h
A P B
O
Ra y pat h of tr ans mi tted wav es fol lowi n g
space-wave (or line of sight) mode of propagation.
The transmitter is located at the ground on a tall lower.
Range
r : Radius of earth
d= 2rh h : Height of transmitting antenna
This distance is of the order of 40 km.
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