TIPS SP CRP CH-1

ATOMIC STRUCTURE
1. Mass of one mole of electrons, protons and neutrons are respectively 0.55 mg, 1.007 g
and 1.008 g

2. e/m ratio (specific charge) of electron is 1.76 108 C/g and of a proton is 9.58 104 C/g

3. If nucleus is assumed to be spherical, its density is

Mass of nucleus Mass number
=
Vol. of the nucleus 4 3
6.022 ×1023 × r
3

4. The limiting line for any series of line in hydrogen spectrum is when n2 in the Rydberg
equation is (infinity).

5. The quantum number not obtained from the solution of Schrödinger wave equation is
spin quantum number (s). It is given to account for the spin of the electron.

6. Compton effect is the decrease in the wavelength of X- rays after scattering from the
surface of an object.

Circumference of that orbit

7. No. of waves in an orbit = n
Wavelength

8. Velocity of electron in first orbit of hydrogen is 1/137th of the velocity of light.

9. Principal quantum number ‘n’ tells the main shell in which electron resides and gives
the maximum number of electron a shell can accommodate i.e. 2n2 where n = principal
quantum number.

Angular quantum number ‘ ’ represents the number of sub shells present in the main
shell and tells the shape of the sub shell its value lies between 0 to n – 1.

Magnetic quantum number ‘m’ determine the number of preferred orientation of

electron present in sub shell. Its value lies between – to + including 0.

Spin quantum number ‘s’ can have two values +1/2 and –1/2 i.e. or as an electron
can have a clock wise or anti clock wise spin.

10. The total no. of nodes in a sub shell (or orbital) are (n-1), out of which the spherical
nodes are (n-l-1) and planar or conical nodes equal to l.

11. The intensity of spectral lines in a particular series decrease with the increase in the
value of n.

12. As we go away from the nucleus the energy levels come closer i.e., with the increase in
the value of 'n' the difference of energy between successive orbits decrease. Thus,
E2 - E1 > E3 - E2 > E4 - E3 > E5 - E4 etc

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13. According to Planck’s quantum hypothesis, substances radiate or absorb energy

discontinuously in the form of smallest packet of energy called quantum (plural quanta).
The energy of a quantum given by, E = h .

14. Humphrey series is produced when the electron in the hydrogen atom jumps from outer
shells to 6th shell i.e., for these lines
1 1
v R 2 where n2 = 7,8,9 …
6 n22
These lines lie in the far infrared region

15. The number of spectral lines in hydrogen spectrum when the electron jumps from an
upper level (n2) to the lower level (n1) are = n, where n = n2-n1.

16. The orbital angular momentum ‘L’ of an electron as derived quantum mechanically is
as given below:
h
L ( 1)

= azimuthal quantum number = 0, 1, 2, 3.... corresponding to s, p, d, f…types of

orbitals respectively.
The classical analogue of the same as given by Bohr is:
h
mvr n
2
where n = 1, 2, 3….
Corresponding to 1st, 2nd, 3rd shells respectively

h h
17. =
2m,KE 2m.eV

18. Energy of an electron in any shell for hydrogen like species;

2 2me4 .Z2 2.179 10 11.Z
En = 2 2
ergs / atom
nh n2
21.79 10 19.Z 13.6 Z 2
= J / atom eV / atom
n2 n2
1312 Z
kJ / mole
n2
Where Z = atomic number.

n2 .h2 n2
19. Radius of orbit, rn 0.529A
Z.4 2 .me2 Z
rn(H) = r1 n2

Z
20. Velocity of electron in any orbit, v n 2.188 106 m/s
n

Z2
21. No. of revolution per second made by electron in an orbit = 3
1.326 1016 s 1

2 r n

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1 1 1
22. Rydberg formula R.Z2
n12 n22
Where n1 = lower level and n2 = higher level
and R is Rydberg constant of hydrogen and it is equal to 109677 cm–1. The expression
for R as derived by Bohr is as follows:
2 2me 4
R
ch3
and putting the values of universal constants, we get R = 109737 cm–1

1 1
23. Frequency 3.289 1015.Z2
n12 n22

24. In 1924, de Broglie proposed tht electron has dual nature i.e. particle as well as wave
character and de Broglie wavelength of moving charged particle may, therefore, be
h h
calculated as .
p 2eVm

25. If the wave is completely in phase, the circumference of the orbit must be equal to an
integral multiple of wave length ( )

Therefore 2 r = n

where ‘n’ is an integer and ‘r’ is the radius of the orbit

But = h/mv
2 r = nh /mv
(or) mvr = n h/2

which is Bohr’s postulate of angular momentum, where ‘n’ is the principal quantum
number.

“Thus, the number of waves an electron makes in a particular Bohr orbit in one
complete revolution is equal to the principal quantum number of the orbit”.

26. According to Heisenberg’s uncertainty principle, it is impossible to define both

position and momentum of a microscopic particle simultaneously with accuracy i.e.
h h h
x p , x m v or x v .
4 4 4 m

27. Aufbau Principle suggests that orbitals of lower energy are filled first, filling of electrons
proceeds until the electrons equal to the atomic number are not accommodated i.e.
a) The orbital for which the value of (n + l) is the lowest is filled first
b) When two orbitals have same (n + l) value, then the orbital having lower value of n is
filled first.

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28. According to Pauli’s Exclusion Principle, no two electrons in an atom can have same
values of all four quantum numbers. If two electrons have same values of three quantum
numbers then the fourth particularly spin quantum number will be different.

29. According to Hund’s rule, electron pairing in p, d, and f orbitals cannot occur until each
orbital of a given sub shell contains one electron each or is singly occupied.

30. Einstein’s Photoelectric equation is K.E. = h – h 0, where 0 is the threshold

frequency.

31. The negative potential at which the photoelectric current becomes zero is called cut off
potential or stopping potential.

STOICHIOMETRY
In this chapter we will discuss the calculations based on chemical equations. It has been
classified into two parts:

1. Volumetric Analysis

2. Gravimetric Analysis

1. Volumetric Analysis
Equivalent Weight: It is the weight of a substance which accepts or donates one mole of
electrons.

Molecular weight (or ) Atomic wei ght (or ) Ionic weig ht

Equivalent weight =
n factor

Calculation of ‘n’ Factor for Different Class of Compounds

1. Acids: n = basicity
H3PO4 n = 3
H3PO3 n = 2
H3PO2 n = 1

2. Bases: n = acidity

eg. Ammonia and all amines are monoacidic bases

3. Salt: (Which does not undergo redox reactions)

n factor = Total cationic or anionic charge

4. Oxidizing Agents or Reducing Agents : ‘n’ factor = change in oxidation number Or

number of electron lost or gained from one mole of the compound.

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Law of Chemical Equivalents: In a chemical reaction the equivalents of all the species
(reactants or products) are equal to each other provided none of these compound is in excess.

N1V1 = N2V2 ( when normalities and volumes are given)

W NV
= (When weight of one substance in given)
E 1000

Relation between percentage weight by weight (a), sp. gravity (d) and strength in gm / litre (s)
S = 10 ad

Back Titration
This is a method in which a substance is taken in excess and some part of it has to react with
another substance and the remaining part has to be titrated against standard reagent.

Double Titration

This is a titration of specific compound using different indicators. Let us consider a solid mixture
of NaOH, Na2CO3 and inert impurities.

When the solution containing NaOH and Na2CO3 is titrated using phenolphalein indicator
following reaction takes place at the phenolphthalein end point –

NaOH + HCl NaCl + H2O

Na2CO3 + HCl NaHCO3 + H2O

1
Here, eq. of NaOH + eq. of Na 2CO3 = eq. of HCl
2 (n 2 )

When methyl orange is used, Na2CO3 is converted into NaCl + CO2 + H2O.

Hence, eq. of NaOH + eq. of Na 2CO3 = eq. of HCl

(n 2 )

Above titration can be carried out using phenolphthalein and methyl orange in continuation as
well as separately. Accordingly we apply law of equivalents to calculate percentage composition
of the mixture.

Note: Phenolpthlein indicates end point when Na2CO3 is converted into NaHCO3

Volume Strength of H2O2

x volume of H2O2 means x litre of O2 is liberated by 1 volume of H2O2 on decomposition
2H2O2 2H2O + O2

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68 gm 22. 4 lit at STP

68 x 17 x
x litre of O2 is released from gm of H2O2 =
22.4 5.6
17x
Strength, S =
5.6
S 17 x x
Normality = = =
E 5.6 17 5.6
1 x
Molarity = Normality =
2 11.2

Gravimetric Analysis
In gravimetric analysis we deal with different types of relations like weight - weight, weight -
volume, or volume - volume relationship between reactants or products of the reaction.

CHEMICAL KINETICS
Rate of Reaction: Consider the general reaction

P + 2Q 3R.

In the above reaction, two moles of Q disappear for every mol of P reacting and three moles of
R are formed for each mol of P disappears.

d[P] 1 d[Q] 1 d[R]

rate of reaction = .
dt 2 dt 3 dt

Negative sign indicates the consumption of the reactants and positive sign indicates the
production of the product.

Characteristics of First Order Reaction

i) Unit of Rate constant : (time)-1

General unit : (mole/litre)1-n time-1

n = order of a reaction.

ii) Time required for the completion of same fraction of initial concentration is independent
of initial concentration.

iii) Half life period : Time period in which half of the reaction is completed is known as
half - life period.

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 TIPS SP CRP CH-7

0.693
t½ = .
k

The radioactive disintegration follows first order kinetics, thus for any radioactive
disintegration

2.303 a
= log
t a x

= disintegration constant

Arrhenius Equation
In 1889, Arrhenius suggested a simple relationship between the rate constant k for a reaction
and the temperature T.

k = Ae-Ea/RT

Ea
i) log k = log A
2.303RT

k2 Ea T2 T1
ii) log
k1 2.303R T1T2

Kinetics of Some Complex Reactions

1. Side or Concurrent Elementary Reactions

B
k1
A
k2
C

The differential rate expressions for the above two reactions are
d[B]
r1 k1 [ A ]
dt
d[C]
r2 k 2 [A]
dt
The overall-rate of disappearance of A is given as

d[ A ]
r1 r2 k1 k 2 [ A ] k[ A ] ----- (i)
dt

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The first-order rate constant k is the sum of the two rate constants k1 and k2 of the two
side reactions. Equation (i) can be integrated to get the integrate rate expression. Thus,
we have
[ A ]t t
d[ A ]
k dt
[ A ]0
dt 0

[ A ]0
or ln kt k1 k 2 t
[ A ]t

Since the rate of formation of products B and C are given by

d[B]
k 1 [A] t
dt
d[C]
k 2 [ A ]t
dt

It follows that the ratio of concentrations of B and C at any instant will be given by

[B] k1
[C] k2

Hence, if the ratio of B and C is determined at any instant (or at the end of the
experiment) and k1 + k2 is determined from the kinetic study, it is possible to determine
the individual rate constant k1 and k2.

2. Consecutive or Sequential Reactions

Consider the following consecutive reaction:

k1 k2
A B C

Let the initial concentration of A be [A]0 and let after time t, the concentrations of A, B
and C be [A], [B] and [C], respectively. It is obvious that

[A]0 = [A] + [B] + [C] … (1)

The differential rate expressions are

d[ A ]
k 1[ A ] . … (2)
dt
d[B]
k1[ A ] k 2 [B] … (3)
dt
dC
k 2 [B] …(4)
dt

On integrating Equation, (2) we get

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 TIPS SP CRP CH-9

[A] = [A]0 exp ( k1t) …(5)

Substituting [A] from equation (5) into equation (3), we get
d[B]
k1[ A ]0 exp( k1t ) k 2 [B]
dt
On integrating the above linear differential equation of first-order, we get
k1
[B] [ A ]0 exp k1t exp k 2t … (6)
k2 k1

Substituting equations (5) and (6) in equation (1), we get

k1
[A]0 = [A]0 exp( k1t) + [A]0 [exp( k1t) exp( k2t)] + [C]
k2 k1

1
or [C] = [A]0 1 k 2 exp k 1t k1 exp k 2t
k2 k1

Maximum Concentration of B:

k1
[B] [ A ]0 exp k1t exp k 2t …(6)
k2 k1

d[B]
At the maximum concentration of B, we will have 0
dt

Hence, differentiating equation (6) with respect to t, we get

d[B] k
[ A ]0 k1 exp k1t k 2 exp k 2t
dt k2 k1

Now, equating it to zero, we get, k 1 exp k 1t max k 2 exp k 2 t max 0

k1
or exp k 1 k 2 t max
k2

k1
or ln k1 k 2 t max … (7)
k2

1 k1
or tmax = ln …(6)
k1 k2 k2

Substituting equation (7) in equation (6), we get

k2 / k1 k2
k
[B]max [A]0 2 IONIC EQUILIBRIUM
k1

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1. Calculation of pH

pH of a Weak Monobasic Acid Solution

HA H+ + A–
C 0 0 … initially (mole L–1)
C(1– ) C C … At equilibrium (mole L–1
2
[H ][ A ]
Ka = C = 2C ( 1)
[HA ] (1 )
(For this approximation to apply 0.1)
K
[H+] = C = C a = k A C
C
1
pH = –log (Ka C)1/2 = - [log Ka + logc]
2
1
= [pKa – logC]
2
pH + pOH = pKw

pOH of a weak mono acidic base solution

BOH B+ + OH–
C(1 – ) C C … At equilibrium
2
C 2
Kb = C
(1 )
[OH–] = C = Kb C
1
pOH = [pKb – logC]
2
pH 14 pOH

pH of a mixture of two weak mono basic acids

HA H+ + A– HB H+ + B–
C1 (1 – 1) (C1 1 + C2 2) C1 1 C2(1 – 2) (C1 1 + C2 2) C2 2
Using same approximations, 1 and 2 can be calculated and hence H+ ion concentration of the
solution also.

pH of a solution of strong acid/strong base

Strong acid remains completely ionised in solution ( = 1) and hence.
[H+] = molarity of solution basicity of acid
= Normality of solution.
Similarly, [OH–] = Molarity of the solution acidity of strong base
= Normality of solution

However, if the solution of acid or base be very dilute (Normality 10–7), it is imperative to add
H+ ion concentration of water to that of the acid itself after considering common ion effect of acid
or base on the ionization of water.

2. Buffer Mixture

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Two types:
i) Acid Buffer, e.g., CH3COOH + CH3COONa
ii) Base Buffer, e.g., NH4OH + NH4Cl
Henderson’s equation for calculating pH of buffer mixture
[salt ]
pH = pKa + log … For acid buffer
[ Acid]
[salt ]
pOH = pKb + log … For base buffer
[Base ]

Buffer Capacity
Amount of acid or base added to buffer solution to charge its pH by unit. It is the capacity of a
buffer solution to resist the change in pH on addition of acid or alkali.
d(b )
Buffer capacity ( ) =
d(pH)
Where b is no.of mole(s) of acid or base added to one litre solution and d(pH) is change in pH.
Buffer solution registers maximum buffer capacity when [acid] or [base] = [salt]
pKa and pKb for a conjugate acid – base pair
HA H+ + A–
Acid (weak) base conjugate (strong)
A– + H2O HA + OH–
[ A ][H ] [HA ][OH ]
Ka Kb = = [H+] [OH–] = Kw
[HA ] [A ]
So, pKa + pKb = pKw = 14 (at 25°C)
For example, pKa of CH3COOH is 4.75 so pKb of CH3COO– ion will be 14 – 4.75 = 9.25.

3. Salt Hydrolysis

i) Salt of weak acid with a strong base like CH3COONa, Na2CO3 etc.
It is the anion of the salt that interacts partially with solvent water to furnish tree OH–
ion in solution thereby rendering the solution faintly alkaline.
A– + H2O HA + OH–
( weak acid )

Initially: C mole L–1, constant 0 0

At equilibrium: C (1 – h), constant Ch Ch
2
[HA ][OH ] Ch Ch h KH
KH = C h2C h
[A ] C(1 h) (1 h) C
Other ionic equilibria existing side by side in this solution:
[H ][ A ]
HA H+ + A–, Ka =
[HA ]
H2O H+ + OH–, Kw = [H+] [OH–]
K Kw Kw
KH = w , h = , [OH–] = Ch = K C
Ka K aC a

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1/ 2
– Kw
pOH = – log[OH ] = – log C
Ka
1
or pOH = [pKw – pKa – logC]
2
Using this equation pOH may be calculated.

ii) Salt of strong acid with a weak base like NH4Cl, FeCl3 etc.
Hydrolysis if this salt means partial interaction of cation of the salt to furnish free H+ ion in
solution thereby rendering the solution faintly acidic.
B+ + H2O BOH + H+
( weak acid )

C(l-h) constant Ch Ch … At equilibrium

KH K
h , KH = w
c Kb
Kw
[H+] = Ch = C
Kb
1
pH = [pKw – pKb – logC]
2
With the help of this equation, pH can be calculated

iii) Salt of Weak acid with a weak base like CH3COONH4

Both cation and anion of the salt interacts with solvent water to furnish free H+ and OH– ions
in solution which combine to form freshly ionised water molecule. The resulting solution may
be either faintly acidic, alkaline or neutral depending on [H+] [OH–], [H+ [OH–] or [H+] =
[OH–] i.e., Ka Kb, Ka Kb or Ka = Kb
CH3COO– + NH4 + H2O CH3COOH + NH4OH
At equilibrium: C(l-h) C(l-h) Ch Ch
2
Ch Ch h
KH = h2
C(l h)C(l h) 1 h
Other ionic equilibria existing here are:
[CH3COO ][H ]
CH3COOH CH3COO– + H+, Ka =
[CH3COOH]
[NH4 ][OH ]
NH4OH NH4 + OH– , Kb =
[NH4OH]
H2O H+ + OH–, Kw = [H+] [OH–]
Kw Kw
KH = , h
Ka Kb K a Kb
From acetic acid dissociation equilibrium
K q [CH3COOH] Ch K w Ka
[H+] = Ka Ka h =
[CH3COO ] C(l h) Kb
1
pH = –log [H+] = [pKw + pKa – pKb]
2

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pH of a solution of the salt of a weak acid with a weak base is independent of the
concentration of salt solution. Knowing Kw, Ka and Kb, pH can be calculated.
1
When Ka = Kb, pH = pK w = 7
2
When Ka Kb, pH 7
When Ka Kb, pH 7

4. Solubility Product

In a saturated solution of AxBy (sparingly soluble salt), following equilibrium exists.

AxBy(s) xA+ + yB–

+ x – y
Ksp = [A ] [B ] , Ksp = Solubility product of AxBy
Thus, for satd solution of AgCl
Ksp = [Ag+] [Cl–]
In satd solution of Ag2SO4
Ksp = [Ag+]2 [ SO24 ]

Relation between solubility(s) and solubility product Ksp

Let S be the solubility of AxBy in mole L–1. If AxBy be sparingly soluble, whole of AxBy passing
into solution will remain completely ionised so.
AxBy(s) xA + yB
xs ys

In satd solution
[A+]x [B–]y = Ksp
(xs)x (ys)y = Ksp
or xx yy sx+y = Ksp
K sp
or S= x y x y
x y

Solubility Product Principle

For Unsaturated solution: Ionic product Ksp

Saturated solution: Ionic product = Ksp
Super saturated solution: Ionic product Ksp
Ionic product means [A+]x [B–]y

Since super saturation is the condition of precipitation so for precipitation of any salt, the ionic
product must exceed the solubility product.

Solubility of a salt when Acid – Base Reaction occur simultaneously or the anion or
cation of the salt gets hydrlysed.

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Let us consider CH3COOAg, a salt of weak acid with a strong base. The solubility of
CH3COOAg be S mole L–1
CH3COOAg(S) CH3COO– + Ag+
s s
The acetate ion will get hydrolysed as
CH3COO– + H2O CH3COOH + OH–-
Initially: S 0 0
At equilibrium: S (l – h) Sh Sh
S–x x x
(Where Sh = x)

So, [CH3COO–] [Ag+] = Ksp

or (S – x) S = Ksp
x2 K x2
KH = , or w
s x Ka s x
Knowing Ksp, Kw and Ka, S and x can be calculated.

Solubility of a salt in a Buffer

Solubility of a solute in acidic or basic buffer can be determined if value of Ksp is given. For
example solubility of Mg(OH)2 basic buffer of pH = 12 i.e. [OH–] = 10–2g – ion L–1, is S mole L–1
(say)
Ksp = [Mg2+] [OH–]2 = S (10–2)2
S = 104 Ksp

Theory of acid-base indicator

An acid-base indicator is a weak organic acid or base which possesses different colour in its
ionised and unionised form due to change in structure from benzenoid to quinonoid upon
ionisation in solution.

HIn H+ + I
Colour A Colour B

[H ][In ]
= Kin
[HIn]
HIn]
or [H+] = K in [
[In ]
[HIn]
or pH = pKin – log
[In ]
Let for colour A to predominate: [HIn] 10 [In–] then pH pKin + 1. Similarly, for collur B to
prevail pH pKin + 1Thus, an indicator will change its colour when pH of solution changes
abruptly from pKin – 1 to pKin + 1, called indicator range or pH – range of the indicator (Kin =
indicator constant, a constant at constant temperature)

CHEMICAL EQUILIBRIUM

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Kf
1. a) Equilibrium constant =
Kb
Kf = rate const for forward reaction
Kb = rate const for backward reaction
b) Heat of reaction
H = activation energy of forward reaction - activation energy of backward reaction

2. Relation between Kp and Kc is Kp(RT) n. When n = 0, Kp = Kc. When n = Positive, Kp >

Kc and when n = Negative, Kp < Kc. The equilibrium constant has a constant value at
constant temperature. Concentration, pressure, temperature and catalyst are the
important factors which influence the equilibrium state.

3. If a system at equilibrium is subjected to a change of pressure, temperature or

concentration, the equilibrium gests shifted in such a way as to counteract the effect of
that change. This is called Le- Chatelier's principle.

4. Increase in the concentration of any reactant always favours the forward reaction and so
the equilibrium gets shifted to the right. Similarly, decrease in concentration of the
products favours backward reaction. Hence equilibrium can be shifted accordingly by
increasing the concentrations of the reactants or by decreasing the concentration of the
products so that it may proceed more nearly to completion.

5. Pressure has no effect on the reaction in which there is no change in the number of
moles of the reactants and products. Increase in pressure at equilibrium favours the
reaction which takes place with decrease in volume or number of moles. Increase in
temperature at equilibrium favours endothermic reaction.

6. A catalyst increase forward reaction and the backward reaction to the same extent.

7. The value of equilibrium constant at two different temperature are related by the
K H 1 1
following equation log 2 T 2 > T1
K1 2.303R T1 T2
a) If a reaction is exothermic (it is attended by the evolution of heat), increase in
temperature will shift the equilibrium in the direction of the reactants and in now
characterised by a lower value of equilibrium constant K.
b) If a reaction is endothermic (it is attended by the absorption of heat), increase in
temperature will shift the equilibrium in the direction of products and it is now
attended by an increase in the value of equilibrium constant K.
c) Conversely, lowering of temperature cause the equilibrium constant K to increase in
the case of exothermic reaction and lowering of temperature causes the equilibrium
K to decrease in the case of endothermic reaction.

8. Addition of an inert gas such as He at constant volume has no effect upon the position of
equilibrium. For example, total pressure in N2O4 2NO2 system could be
changed without changing the volume by adding helium which would increase the total
number of moles of the gas and hence the total pressure.
2
nNO 2
Since volume remains constant, we have Kc = .
nN2O 4 V
The ratio (nNO2)2/(nN2O4) remains constant. Thus position of equilibrium is not affected
by the addition of helium.

9. Standard free energy change of a reaction and its equilibrium constant are related to
each other at temperature T by the following relation:

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G 2.303RT log K p
G H T S
When G = -ve, the value of equilibrium constant will be large positive quantity and
when G is positive, the value of K is less than 1, i.e. low concentration of products at
equilibrium state.

10. Degree of dissociation from density measurements: Degree of dissociation in the case of
reversible reactions in which there is increase in the number of molecules can be
determined by measuring density of the reaction mixture at equilibrium. Let d be the
observed density at a particular temperature when degree of dissociation is x and D be
the vapour density when there is no dissociation.
D d
x ; Where n is the number of molecules of products.
n 1d

ELECTROCHEMISTRY
1. Faraday’s first law of electrolysis

Weight of substance liberated quantity of electricity passed

W Q W ZQ W Zit (Z= electrochemical equivalent)

E
Z (Eequivalent weight )
96500

2. Faraday’s second law of electrolysis: For the same quantity of electricity passed
through solutions of different electrolytic cells connected in series, weight of substance
produced is directly proportional to their equivalent weight.

w1 E1
W E
w2 E2

3. One faraday (96500 coulombs) of electricity deposits one gram equivalent weight of the
substance.

weight deposited
E 96500
quantity of electricity coulomb
W
E 96500
Q
W Q it
E 96500 96500

1
4. Conduc tance (C) [units of conductance ohm–1 or mohos or siemens (s)]
R

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5. If ‘ ’ is the distance between the electrodes and ‘a’ is the area of cross section of
electrode.

R ( ) (Where is specific resistance or resistivity)

a

1 1
C
R a a

Where = specific conductance or conductivity is referred to as cell constant.

a

1000
6. a) Equivalent conductance eq
Normality
1000
b) Molar conductance m
Molarity

7. For sparingly soluble salt like AgCl, PbSO4, BeSO4 etc.

1000
Solubility in mol/litre (s) = 0
m

8. According to Kohlrauch law for an electrolyte. AmBn

0 0 0
c

0 0 0
m m n

Where 0 and 0
are the ionic conductivities at infinite dilution for cation and anion
respectively.

c
m
9. Degree of dissociation of an electrolyte at conc. (C), 0
m

10. E0cell 0
ERP(cathode) 0
ER.P.(anode)

11. For the cell reaction

aA bB mC nD
2.303RT [C]m [D]m
Ecell E0cell log
nF [A]a [B]b
0.0591 [C]m [D]n
Ecell E0cell log at 298K (Nernst Equation)
n [A]a [B]b

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2.303RT 0.0591
12. E0cell logk E0cell logK (at 298K)
nF n

(K = eqm. Constant for cell reaction)

13. G nFE and G0 nFE0

14. The decreasing order of the discharge potential or the increasing order of deposition for
some cations and anions are in the following order.
Cations: K , Na , Ca2 , Mg2 , Al3 , Zn2 , H , Cu2 , Ag , Au3
Anions SO24 , NO3 , OH , Cl , Br , I

15. If two half cell reactions having potentials E10 and E02 are combined to give third half cell
reaction having a potential E03 then
G03 G10 G02
n1E10 n2E02
E03
n3
0 0
If n1 n2 n3 , E 3 E 1 E02

16. Temp. co efficiency of the emf of the cell

dEcell H Ecell
dT P nFT T

17. Enthalpy change:

dEcell
H nF T Ecell
dt P

dEcel
18. Entropy change S nF
dT p

THERMOCHEMISTRY
Heat of reaction at constant pressure = H

Heat of reaction at constant volume = E

H E ngRT

ng = difference in number of moles of gaseous products and reactants.

T2
Kirchoff’s Law: H2 H1 Cp dT = Cp (T2 T1 ) , assuming Cp remains almost
T1

constant within the small temperature range T1 to T2.

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Cp Cproducts Creac tan ts

T2
E2 E1 Cv dT Cv (T2 T1 )
T1

Cv = Cvproducts - Cvreactants

First Law of Thermodynamics

Qp E ( w)

Work Pext Vfinal Vinitial Pext (V2 V1 ), Pext = external pressure = final
pressure of gas.

v2
Any reversible work = pdV
v1

Isothermal and reversible work for n moles of an ideal gas

V2 P1
nRT ln nRT ln
V1 P2

Adiabatic work = nCv (Ti Tf )

Adiabatic Reversible Relations

1-y
r r-1 y
PV = constant TV = constant TP = constant

dE
For an ideal gas 0
dV T

dE a
For a real gas
dV T V2

Joule Thomson co efficient J T

1 H 1 2a
b
Cp P T Cp RT

1 dV
Coefficient of thermal expansion ( )
V dT P

1 dV
Coefficient of compressibility
V dP T

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2
VT
Cp Cv (for any substance solid, liquid or gas) =

for an ideal gas Cp Cv R for one mole.

H nC v (T2 T1 ) … for n moles of an ideal gas undergoing adiabatic

and reversible change

Second Law of Thermodynamics

dq qrev
S ds
T T

Entropy change

i) During heating or cooling of solid or liquid of mass m and specific heat

T2
S mc ln
T1

ii) During isothermal expansion of gases

V2 P1
S nRln nRln
V1 P2

iii) Non isothermal expansion

T2 V2 T2 P2
S n Cv ln R ln n Cp ln R ln
T1 V1 T1 P1

Lt
iv) Transition of state S [Lt = latent heat of transition]
T

v) Free mixing S XiR ln Xi per mole

vi) S 0 for adiabatic process

G H T S

( G)
G H T
T p

Putting isothermal expansion of a gas

V1 P2
GT RT ln RT ln
V2 P1

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During isothermal pressure change of solid (liquid)

GT V(P2 P1 )

Clausius Clapeyron equation

P2 L v T2 T1
ln
P1 R T1T2

dP Lt
Clapeyron equation
dT T(V2 V1 )

lt
1 1
T
2 1

Lt = latent heat of transition/ mole but lt is same in/grams, 2 and 1, are densities in state 2 and
1 respectively.

G H T S

At equilibrium under the condition of constant P and T i.e. the laboratory condition, G 0 and
hence

H T S

H
S
T

A reaction to be feasible: G 0 i.e. G must be negative.

LIQUID SOLUTION
1. Solution: A solution is homogeneous mixture of two or more components whose
concentration can be varied with in a limit or mixture of solute (dispersed phase +
dispersion medium) and solvent is combindly called as solution.

2. Solubility: The amount of solute which is dissolved in 1000gm of a solvent is called as

solubility to make a saturated solution.

Hsolution Hlattice energy Hhydration energy

If Hydration Energy Lattice energy, solute goes in solution and Hsolution becomes
negative.

3. Vapour pressure of liquid: It is the pressure exerted by vapour when they are in
equilibrium with the liquid at a given temperature. It depend on

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i) Nature of liquid
ii) Temperature
iii) Purity of the liquid

More is the force of attraction between liquid molecules, lower is the vapour pressure
and vice versa.

4. Vapour pressure of a solution: When a miscible solute is added to a pure solvent it

results in the formation of a solution. Some solute will replace the molecules of solvent
from the surface, therefore escaping tendency of solvent molecule decreases. This
causes a lowering in vapour pressure.

ps p0

5. Ideal solution: These are the solutions in which solute solute and solute solvent
interactions are almost similar to solute solvent interactions. They obeys Raoult’s Law
for all range of concentrations and temperatures.

Hmix 0
Vmix 0
e.g. Hexane + heptane

6. Non ideal: In such solutions solute solvent interactions are different than solute solute
and solvent solvent interactions. They does not follow Raoult’s Law at all
concentrations.
Hmix 0
Vmix 0
They shows two types of deviations:
i) If Hmix 0 and Vmix 0 then non ideal solution show positive deviation.
ii) If Hmix 0 and Vmix 0 then non ideal solution show negative deviation.

7. Raoult’s Law

a) If components are volatile

PA X APA0
PB XBPB0
PTotal = PA PB
= XAPA0 XBPB0
= X APA0 (1 XA )PB0
PTotal = X A PA0 PB0 PB0
b) If only (A) component solvent is volatile vapour pressure of solution Ps XAPA0
c) Mole fraction in vapour phase
PA
yA
PT

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8. Relative lowering in vapour pressure

P0 Ps
XB (mole fraction of solute)
P0

9. Elevation in Boiling Point

Tb Kb m

Kb Wsolute 1000
Msolute
Tb Wsolvent

10. Calculation of molal elevation constant

RT02 M0RT02
Kb
1000L v 1000 Hv
T0 = Boiling point of pure liquid (solvent)
Lv = Latent heat of vaporisation per gm of solvent
Hv = Latent heat of vaporization per mole of the solvent
M0 = Molecular mass of solvent
R = Gas constant
= 8.314JK 1mol 1 if L v or Hv are in Joules
= 2 cal deg 1 mol 1 if L v or Hv are in calories

11. Calculation of molal depression constant

RT02 M0RT02
Kf
1000 f 1000 Hf
T0 = Freezing point of pure liquid (solvent)
M0 = Molecular mass of solvent
Hf = Latent heat of fusion per mole of the solvent
Tf = Latent heat of fusion per gm of the solvent

12. Mole fraction of a component in the vapour phase

Partial pressure of that component PA

yA =
Total vapour pressure PT

13. Various relations of colligative property

P0 Ps dRT
P0 M2
M2 = Molecular mass of solute

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dRT
Tb
1000 K b
dRT
Tf
1000 K f
1000K b P0 Ps
Tb
M0 P0
1000K f P0 Ps
Tf
M1 P0

Abbreviation
= Osmotic pressure
M2 = Molecular mass of solute
Tb = Elevation in boiling point
Tf = Depression in freezing point
M0 = Molecular mass of solvent
P0 Vapour pressure of solvent
Ps = Vapour pressure of solution

14. Relation between mole fractions of one component of ideal solution in the vapour phase
and liquid phase.

PA0 1 PB0 PA0

1
PB0 y A
XA PB0
1 1
Graph of vs should be linear with
XA yA
PA0 PB0 PA0
Slope = and intercept =
PB0 PB0
Where X A = mole fraction in liquid phase of component A.
XB = mole fraction in liquid phase of component B
PB0 = vapour pressure of pure liquid B
0
P =
A vapour pressure of pure liquid A
yA = mole fraction of component A in vapour phase
yB = mole fraction of compound B in vapour phase

15. Relation between total pressures mole fraction of one component in vapour phase.
1 1 PB0 PA0
yA
PTotal PB0 PA0PB0
1
Graph between vs y A should be linear.
PTotal

16. Van’t Hoff Factor (i) = It is accountant for anomalies

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Observed colligative property

i=
Calculated colligative property
1
Colligative property
Mobserved
Calculated Molar Mass
i
Observed Molar Mass
P0 Ps
iXB XB = mole fraction of solute
P0
Tb i K b m m = molality
Tf i Kf m V = volume of solution
n
i solute RT n = no. of moles
V
i = 1 non electrolytes (glucose, sucrose, urea, protein)
i 1 solute which dissociates (KCl, KNO3 , CaCl2 )
i 1 Solute which associates (RCOOH,C6H5 OH)

17. i = a(m – 1) + 1 For solutes which dissociates

i 1
a m = fraction of solute after dissociation
m 1
For e.g. KCl (m = 2)

18. For solutes which associates in medium

i 1
a
1/ m 1
m = fragment which get associates

19. Silica garden: When a small crystal of CuSO4 or NiSO4 is added to 5% sodium silicate
solution. This is to be known as chemical garden or silica garden. It is produced due to
diffusion of metal ion from crystal to form precipitate of metal silicate. This precipitate act
as a semi permeable membrane around the crystal. Osmosis takes place water flows
from dilute sodium silicate to stronger salt solution. After sometime membrane burst and
more metal ions are free, again process repeats and this growth of crystal looks like a
plant.

20. Henry’s Law: The mass of gas dissolved by a unit volume of a solvent at constant
temperature is directly proportional to the pressure of the gas with which it is in
equilibrium

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Graph between pressure and solubility

x2 P
x2 KH x 2
x2 mole fraction of gas dissolved

Equilibrium
K H = proportionality constant

pressure
Solubility

SOLID STATE
1. Amorphous substance are isotropic, while crystalline substances are said to be
anisotropic.

2. The reverse of crystallisation is the fusion or melting of the solid.

3. A crystal may have one or more planes and one or more axes of symmetry, but it has
only one centre of symmetry. A cubic crystal, such as NaCl possesses a total of 23
elements of symmetry.

4. The unit cell is the smallest unit of a crystal, which when repeated, in three dimensions,
will generate the crystal.

5. In a cubic system of crystals, there are three types of Bravais lattices, depending upon
the shapes of the unit cell viz., simple cubic, face centred and body centred lattices.

6. Close packing means an arrangement in which a given number of equal spheres occupy
the minimum amount of space.
Limiting radius ratio (r+/r–) Co ordination number
0.155 2
0.155 – 0.225 3
0.225 0.414 4
0.414 – 0.732 4
0.414 – 0.732 6
0.732 – 0.999 8

7. Structural relationship for cubic lattices

Simple BCC FCC
Lattice points per unit cell 1 2 4
No. of nearest neighbours 6 8 12
Distance between nearest neighbours a 3a a
2 2
Atomic radius a 3a a
2 4 2 2
Occupied volume (P.F.) 52.3% 68% 74%

8. Density of cubic crystal is given by

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M Z
NA a3
M – molecular mass of the substance
Z – no. of formula units per unit cell of the crystal
NA – Avogadro’s number
a edge length of the cubic cell

9. Schottky defect is observed in the crystals, of KCl, NaCl, CsCl, KBr etc. Frenkel defect is
observed in crystals of CaF2, ZnS, AgI and AgBr etc. and is less common than Schottky
defect. Metal excess defect because of anion vacancies, occurs e.g. in yellow coloured
NaCl and due to cation vacancies, occurs in NiO, FeO and FeS etc. Metal excess defect
due to interstitial cation occurs in Zinc oxide (ZnO).

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