Tools - For - Problem - Solving (Appendix B), R.K. Malik's Newton Classes PDF

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Appendix B
Tools for Problem

Solving
Basic Concepts and Stoichiometry
1. Density:
Mass

Volume
Units: g mL1 or g cm3

2. To convert from Celsius to Kelvin temperatures:
1 K 
TK  (TC  273.15C)  
 1C 
3. To convert from °C to °F:
 9F 
TF    TC  32F
 5C 
4. To convert from °F to C:

 5C 
TC  (TF  32F)  
 9F 
5. Scientific notation: For multiplying and dividing two scientific notations, the numericals are
multiplied or divided, while the exponents are added or subtracted.
For adding or subtracting two numbers, the exponents must be made same, so that they can be taken
out as a common factor.
6. Dimensional analysis: Using factor–label method, conversions between units can be made as
follows:
(Given quantity)  (Conversion factor)  (Desired quantity)
7. The molecular mass is defined as the sum of the atomic masses of the elements in the molecule. For
instance, in case of H2O, the molecular mass can be calculated as follows:
2  H  O  2 1.01 u  16.00 u  18.02 u
8. The formula mass is the sum of the atomic masses of the elements in the formula. For instance, in
case of Cu(NO3)2, the formula mass can be calculated as follows:
Cu(NO3 )2  Cu 2  2  (NO3 )  Cu 2  2  (N  3O)  63.55 u  2 14.01 u  6 15.995 u  187.54 u
9. Mole: Any substance that contains the same number of particles as the number of atoms in exactly 12
g of the 12C isotope of carbon.
1 12 C atom  12.000 u
1 mol of C atoms  12.000
12
g
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10. Avogadro’s constant and the relation of mole with atomic weight and molar mass: A mole of atoms
of any element has a mass in grams equal to the atomic weight of the element.
Mass of one 12C atom is 1.992648  10-23 g and 1 mol of 12C = 12 g.
So, the number of atoms present in 1 mol of 12C is
12 g 1.992648 1023 g

1 mol of 12 C 1 12 C atom
12 g 1 12 C atom
  6.023 1023 atoms mol1
1 mol of 12 C 1.992648 1023 g
where 6.023  1023 atoms mol1 is called Avogadro’s constant
11. For determining the number of particles in a sample of a pure substance by weighing the sample, you
need to know the mass of a mole of the substance and the number of particles in a mole.
Mass 
Molar mass
 Moles 
Avogadro's constant
 Atoms
(Macroscopic scale) (Atomic scale)
12. For mass–mole conversions for elements of a chemical compound, you can use the formula of the
compound to calculate the number of atoms of a given element in the sample.
Mass 
Molar mass
 Moles 
Avogadro's constant
 Molecules 
Chemical formula
 Atoms
(Macroscopic scale) (Atomic scale)
13. Percentage composition or mass percent of an element in a compound is calculated by the relation
Mass of the element in the compound
Mass % of an element  100
Molar mass of the compound
14. Stoichiometric quantities in reactions in solution
Mass of solute Mass of solute
% by mass (solute)  100  100
Mass of solute  Mass of solvent Mass of solution
Moles of solute
Mole fraction of solute 
Moles of solute  Moles of solvent
Moles of solute
Molarity 
Liters of solution
Number of moles of solute
Molality 
Mass of solvent in kg
Number of gram equivalents
N 1000
Volume in mL
Weight of solute
Milliequivalent of solute  N  V (in mL)   1000
Equivalent weight of solute
Concentration of solute per liter of solution
Formality 
Formula weight
Weight of solute (g)
Strength   N  Equiv. wt.  M  Mol. wt.
Volume of solution (L)
15. Determination of equivalent mass
(a) Hydrogen displacement method:

Mass of element Mass of element
Equivalent mass  1.008  1.008
Mass of hydrogen Volume of hydrogen displaced  0.00009

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(b) Oxide formation method:

Equivalent mass  8  8
Mass of oxide  Mass of element Mass of oxygen
(c) Chloride formation method:
Equivalent mass   35.5   35.5
Mass of chloride  Mass of element Mass of chlorine
m1 E1
(d) Metal-to-metal displacement method: 
m2 E2
(e) Double decomposition method:
Mass of AB Equivalent mass of AB Equivalent mass of A + Equivalent mass of B
= 
Mass of AD Equivalent mass of AD Equivalent mass of A + Equivalent mass of D
Mass of elements in grams

16. Atomic mass expressed in grams is known as gram atom 
Atomic mass of elements in grams
Mass of the substance in grams
Molecular mass expressed in grams is known as gram atom 
Molecular mass of substance in grams
17.
18. Gram molar volume is the volume occupied by one gram molecular mass of any gas at STP (273 K
temperature and 1 atm pressure) and is equal to 22.4 L.
Atomic mass of element
19. Equivalent mass 
Valence (n)
20. Determination of atomic mass
6.4
(a) Dulong and Petit’s law: Atomic mass (appprox.)  where specific heat is in cal g1.
Specific heat
(b) Cannizaro method: It is calculated for an element by determining the molecular mass of a
number of compounds containing that element, and then determining mass of the element in each
compound.
(c) Vapor density of a chloride:
Molecular mass  Atomic mass of M  35.5n  Equivalent mass  n  35.5n
(d) Law of isomorphism: The masses of two elements that combine with the same mass of the other
elements in their respective compounds are in the ratio of their atomic masses.
21. Relation between the stoichiometric quantities
xA 1000
(a) Relation between mole fraction and molality: m
(1  xA ) M B
1  MB
(b) Relationship between molality and molarity:  
m M 1000
where d = density of solution, m = molality, M = molarity and MB = molar mass of solute.
x 1000  
(c) Relation between molarity and mole fraction: M  B
xA M A  xB M B
Normality Molecular mass
(d) Relationship between normality and molarity:  n
Molarity Equivalent mass
(e) Molarity of dilution: The relation between molarity before and after dilution is given by

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(a) M1V1 = M2V2

(f) Molarity of mixing: When three solutions (containing same solvent and solute) of molarity M1,
M2, M3 are mixed in volumes V1, V2, V3, respectively, the molarity of mixing can be given as:
M1V1 + M2V2 + M3V3 = Mtotal (V1 + V2 + V3)
22. Relation between empirical formula and molecular formula

Molecular mass
n
Empirical formula mass
The molecular formula is the same as the empirical formula. If the molecular formula is not the same,
it will be an integral (whole number) multiple of the empirical formula.
23. Steps for calculating empirical formula are as follows:

(a) Convert percent composition into an actual mass.
(b) Convert mass into moles of each element.
(c) Find the whole number ratio of the moles of different elements.
24. The quantitative relationships among the reacting materials and the products formed are known as
stoichiometry. The sequence of calculations for solving stoichiometry problems.
25. Steps for solving limiting reagent problems

(a) Calculate the amount of product (moles or grams, as needed) formed from each reactant.
(b) Determine which reactant is limiting. (The reactant that gives the least amount of product is the
limiting reactant; the other reactant is in excess.)
(c) Once we have identified the limiting reactant, the amount of product formed can be determined. It
is the amount determined by the limiting reactant.
(d) If we need to know how much of the other reactant remains, we calculate the amount of the other
reactant required to react with the limiting reactant, and then subtract this amount from the
starting quantity of the reactant. This gives the amount of that substance that remains unreacted.
26. Theoretical and actual yield:

Actual yield
100  Percent yield
Theoretical yield
27. Double titration
Titration of the solution containing both NaOH and Na2CO3

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Milliequivalents of acid used by Na 2CO3  2b  Milliequivalents of Na2CO3

Milliequivalents of acid used by NaOH  a  b  Milliequivalent of NaOH
where a milliequivalents of acid are used in the first end point and b milliequivalents of the acid are
used at the second end point. Knowing the milliequivalents of base (Na2CO3 or NaOH) and the
volume of the solution titrated, their normality can be calculated.
Titration of the solution containing both Na2CO3 and NaHCO3:
Milliequiv. of acid used by Na2CO3  2a  Milliequiv. of Na2CO3
Milliequiv. of acid used by NaHCO3  b  a  Milliequiv. of NaHCO3
where a milliequivalents of acid are used in the first end point and b milliequivalents of the acid are
used at the second end point. Knowing the milliequivalents of the base and volume of the solution
titrated, the normality (strength) of the bases can be calculated.
28. Back titration: For an impure solid substance Z, the weight of pure Z which is reacted is given by
Molecular weight( N1V1  N 2V2 )
a
n-factor
The percentage purity of Z is given by
( N1V1  N 2V2 ) Molar mass of Z
  100
n-factor W
29. For redox titration, the molarity equation is
M1V1 M 2V2

n1 n2
where n1 and n2 are the stoichiometric coefficients of the reductant and oxidant, respectively.
30. Volume strength of H2O2 solution
Gaseous and Liquid States

1. Gas laws
1 p1 V2  T  V2 V1
Boyle’s law: p  ,  Charles’ law: Vt  V0 1  , 
V p2 V1  273.15  T2 T1
p1 T1
Gay-Lussac’s law: p  T ,  Avogadro’s law: V  n
p2 T2

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p1V1 p2V2

T1 T2
Combined gas law:
2. Equation of state/ideal gas equation/law: pV = nRT where R is the gas constant with value
R = 0.0821 L atm mol1 K1 at 1 atm pressure, 273.15 K temperature and 22.41 L volume.
R = 8.314 J K1 mol1 at 1 bar pressure (105 Pa), 273.15 K temperature and 22.71 m3 volume.
 RT
3. Molar mass of a gaseous substance: M  where  is the density.
p
4. Dalton’s law of partial pressures: ptotal  pA  pB  pC  where ptotal is the total pressure of the
mixture, and pA, pB, pC, etc. are the individual pressures of components A, B, C, etc.
k
5. Graham’s law of effusion: Effusion rate  (when compared at the same T and p)

Comparing the rates of effusion of different gases A and B, we get
Effusion rate (A) B MB

 
Effusion rate (B) A MA
where MA and MB are the molar masses of gases A and B.

If diffusion occurs at different pressures, pA and pB, then
1/ 2
rA  M A  pA
  
rB  M B  pB
Volume diffused (V ) Moles diffused (n) Distance travelled (l )

r  
where Time interval (t ) Time interval (t ) Time interval (t )
pdry gas  ptotal  Aqueous tension

6. Aqueous tension (liquid’s vapor pressure):
pH2O in air
7. Relative humidity: % Relative humidity  100
Vapor pressure of H2 O
nA
8. Mole fraction: xA  where xA is the mole fraction of component A, and nA, nB,
nA  nB  nC  ...  nZ
nC, …, nZ are the numbers of moles of each component, A, B, C, …, Z, respectively. The sum of all
mole fractions for a mixture must always equal 1.
9. The mole fraction of a gas in a gas mixture is simply the ratio of its partial pressure to the total
pressure.
pA  xA ptotal
10. Kinetic theory: Predictions of gas laws made by kinetic theory
It relates temperature to average kinetic energy T  Average molecular kinetic energy

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It explains the pressure–volume law (Boyle’s law) 1 1

p or V 
V p
It explains the pressure–temperature law (Gay- p T
Lussac's law)
It explains the temperature–volume law (Charles’ V T
law)
It explains Dalton's law of partial pressures ptotal  pA  pB 
It predicts an absolute zero 1
T  Average molecular knietic energy  mv 2
2
11. Kinetic energy and molecular speeds:
Speed Calculation Relation with individual velocities Relation with

temperature
Root mean It is calculated (n1v12  n2 v22  n3v32  )   ni vi2 
1/ 2
3RT
square (rms) by first taking urms    urms 
(n1  n2  n3  )   ni  M
velocity squares of
individual
velocities,
taking their
mean and then
the square root
of the mean.
Average It can be (n1v1  n2 v2  n3v3  )  ni vi 8RT
uavg   uavg 
speed of the calculated by (n1  n2  n3  )  ni M
molecules taking the
arithmetic
mean of the
speeds of
different
molecules of
the gas.
Most It is the speed It cannot be expressed in terms of speed 2RT
probable possessed by of individual molecules as in the case of ump 
M
speed of gas maximum average and root mean square speed
number of
molecules at a
given
temperature.
12. Relation between different molecular speeds: ump : uavg : urms  1:1.128 :1.224 where ump  uavg  urms
Simplifying, we get
Average speed = 0.921  Root mean square speed
Most probable speed = 0.817  Root mean square speed
3/2
 M 
v 2 e Mv
2
13. Maxwell’s speed distribution law: P(v)  4  
/2 RT
 2 RT 

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14. van der Waals Equation for deviations from ideal behavior
15. Compressibility factor (Z): The ratio of the observed volume of a gas to the calculated volume
under given conditions of temperature and pressure.
Vreal pVreal V
Z   Z  real
nRT / p nRT Videal
Z=1 Ideal gases At very low pressures, all gases
have Z close to unity. At low
pressures, the volume of gas is
large, so the volume of the gas
molecules can be neglected and
gases can behave as ideal gases.
Z<1 Real gases As the pressure increases, the
value of pV/nRT first decreases
(Z < 1), reaches a minimum
value and then increases.
Z>1 Real gases At high pressures Z > 1, so the
gases become difficult to
compress as the pressure
increases.
pV a 1
16. Boyle’s temperature or point: TBoyle   
R Rb 2Tinv
17. Virial equation: It is given by
pVm B C
Z  1   ...
RT Vm Vm2
where B, C are functions of temperature and are called first virial coefficient, second virial
coefficient and so on.
1 N
2
2 uavg  2 N
18. Collision frequency and collision number: Z   uavg  2   and N C 
2 V  V
where uavg is the average velocity of the molecules, N is the number of molecules and V is the
volume of molecules and  is the collision diameter.
1
19. Mean free path:  
N
2 2  
V 

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a 8a
20. Critical constants: Vc  3b, pc  2
, Tc 
27b 27 Rb
2a
21. Inversion temperature: Tinv 
Rb
q 35
22. Heat capacity of gases: c  CV  RR Cp 
m  T 22
H vap p H  1 1 
23. Clausius-Clapeyron equation: log p   A and log 2    
2.303RT p1 2.303R  T1 T2 
dv
24. Viscosity is the force acting on a liquid: F   A where η is the coefficient of viscosity. Units:
dx
poise
Solid State
1. Force of attraction in an ionic bond

q1  q2
F
r2
where q1 and q2 are the charges of positive and negative ions and r is the distance between them.
2. The relation between faces (F), edges (E) and interfacial angle (C) for a crystal is given by
F C  E 2
3. Crystal systems
Crystal system Edge lengths Angles Examples

Cubic a=b=c  =  =  = 90 NaCl, ZnS, Cu
Tetragonal a = b  c  =  =  = 90 White Sn, SnO2, TiO2, CaSO4
Orthorhombic a  b  c  =  =  = 90 Rhombic Sulphur, KNO3, BaSO4
Hexagonal a = b  c  =  = 90;  = 120 Graphite, ZnO, CdS
Rhombohedral a = b = c  =  =   90 Calcite (CaCO3), HgS (cinnabar)
Monoclinic a  b  c  =  = 90;   90 Monoclinic sulphur, Na2SO410H2O
Triclinic a  b  c       90 K2Cr2O7, CuSO45H2O, H3BO3
4. Bravais lattices
Crystal Class Bravais lattices
Cubic Primitive, Body centered, Face centered
Tetragonal Primitive Body centered
Orthorhombic Primitive End centered Body centered Face
centered
Monoclinic Primitive End centered
Triclinic Primitive
Rhombohedral or trigonal Primitive
Hexagonal Primitive

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5. Tetrahedral voids
If the number of atoms per unit cell in ccp or fcc structure = 4
and the number of tetrahedral voids = 8
then the number of voids = 2(the number of atoms present in ccp lattice)
6. Octahedral voids
If the number of atoms per unit cell in ccp or fcc structure = 4
and the number of octahedral voids = 4
then the number of voids = the number of atoms present in ccp lattice.
Volume occupied by atoms/spheres

7. Packing efficiency  100
Total volume of the unit cell
Radius of cation (r )
8. Radius ratio 
Radius of anion ( R)
Radius Ratio Anions Close Packing Coordination Number
0.155 to 0.225 Planar triangular 3
0.225 to 0.414 Tetrahedral 4
0.414 to 0.732 Octahedral 6
0.732 to 1.00 Body-centered cubic 8
9. Characteristic properties for primitive cubic, body centered and face centered cubic unit cells.
Characteristic Property sc bcc fcc
Relation between atomic radius (R) a  2R a  4R / 3 a  2 2R

and lattice parameter (a)
Atoms/cell 1 2 4
Lattice points/cell 1 2 4
Number of nearest neighbors 6 8 12
Packing efficiency 52% 68% 74%
10. Mass of the atoms of unit cell  Number of atoms in a unit cell (z)  Mass of an atom (M atom )
Molar mass (M )
11. Mass of one atom 
Avogadro's constant (N A )
12. Density () of unit cell of a cubic crystal
zM zM
 
Vc  N A a3 N A

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where n is the number of atoms per unit cell, M is the molar mass, NA is the Avogadro’s constant
and a is the edge length of unit cell.
Units: kg m3 or g cm3
MA MA
Primitive cubic:   1  
(2 R) N A 8N A R3
3
4M A /N A
MA 2
Face-centered cubic:   3
3
16 R 2 8 N A R
m 2M A /N A 9M A
Body-centered cubic:    3

V (64 / 9) 3R 32 3N A R3
13. Magnetic dipole moment

m = I A
where I is the current and A is the area of the loop, and such current flows counter-clockwise relative
to an observer standing along the direction of the magnetic moment.
14. Bragg’s law: n  2d sin 
15. For simple cubic crystals, the spacing between adjacent (hkl) lattice planes is given by
a
d hkl 
h  k2  l2
2
where a is the lattice constant which shows that the lattice vectors are orthogonal and of equal length,
and h, k and l are the Miller indices.
Atomic Structure
e
1. Charge-to-mass ratio of electron:  1.758820 1011 C kg1 where me is the mass of the electron.
me
2. Charge and mass of electron: e = 1.6022  1019 C and me = 9.109410  1031 kg.
3. Wavelength of the radiation:  can be defined as the distance between two maxima of either
electrical or magnetic components of the wave (crest to crest is also same). Units: meters.
4. Frequency of radiation:  is the number of waves that pass a fixed point in unit time. Units: s 1 or
Hz.
5. Wave number: The wave number   1/ is the reciprocal of wavelength. Units: m1.
6. Energy associated with regions of the electromagnetic spectrum is related to wavelengths and
frequency by the equation:
hc
E  h 

34
where h = Planck’s constant, 6.626  10 J s;  = frequency of radiation in Hz and c = velocity of
light, 2.998  108 m s1.

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Units: Joules (J)

7. Wein’s displacement law: m  T  b where b is Wein’s constant having value of 0.288 cm K, m is
the wavelength corresponding to the most intense radiation and T is the absolute temperature of the
blackbody.
8. Photoelectric work function
h  K.E.  h 0  2 mv 2  h 0
1
K.E.  h  W
where K.E. is the kinetic energy of the electron that is emitted, h is the energy of the photon of
frequency  and h0 is the minimum energy needed to eject the electron from the metal’s surface.
This is known as the photoelectric work function W and 0 is known as the threshold frequency. This
amount of energy is h0. Any energy left over (h  h0) appears as the electron’s kinetic energy.
9. Relation of wavelength with frequency

c

where c is the velocity of light (3  108 m s1)
10. Calculation of wave number in hydrogen spectra,

 1 1  1
  109677    cm
 n1
2
n22 
where  is the wavenumber, 109677 is the Rydberg’s constant with denoted by RH and n has the
values 3, 4, 5, …; thus giving a series of lines.
11. For various series of hydrogen spectra, we have

 1 1 
Paschen   R – 2  n  4, 5, 6, 7,
1 1  3 2
n 
Lyman   R  2 – 2  n  2, 3, 4, 5,
1 n   1 1 
Brackett   R  2 – 2  n  5, 6, 7, 8,
 1 1  4 n 
Balmer   R  2 – 2  n  3, 4, 5, 6,
2 n   1 1 
Pfund   R  2 – 2  n  6, 7, 8, 9,
5 n 
12. Bohr’s frequency rule states that difference in energy observed when the frequency of radiation is
absorbed or emitted is:
E E2  E1
 
h h
Units: Hz or s1
13. The angular momentum of an electron remaining in its orbit or stationary state:
nh
me vr 
2
Units: N m s or kg m2 s1 or J s

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0 n 2 h 2
14. Bohr radius: r  . For hydrogen, rn = n2a0, where a0 is Bohr radius of first stationary state =
 me2 Z
52.9 pm.
nh Ze2
15. Velocity of electron: v  
2 me r 2 0 nh
16. Moseley’s law relating frequency with atomic number:   (Z  1)2
2
17. Centrifugal force  mv
r
Ze2
18. Coulombic attractive force 
4 0 r 2
 1 
19. Energy associated with the stationary state: En   RH   n  1,2,3,
 n2 
1
K.E.  me v 2
20. Kinetic energy of electron: 2
21. Total work done in moving the electron from infinity to the point at a distance r from the nucleus:
Ze2
W 
4 0 r
 Z 2 me4
22. Total energy for an atom: Etotal 
8n 2 h 2 02
23. Energy of electron: En   RH 

1 
 n  1,2,3,
 n2 
 2.18 1018  13.6
24. Total energy for a hydrogen atom: E   2 J= eV
 n  n2
 Z2 
25. Total energy for hydrogen-like species: E  2.18 1018  2 J
n 
52.9(n2 )
26. Radii for hydrogen-like species: rn  . Units: pm
Z
h h
27. de Broglie’s wavelength:   
mv p
where h is Planck’s constant, m is the particle’s mass, v is its velocity and p is the momentum. de
Broglie wavelengths for subatomic particles are as follows:
Particle Electron Proton Neutron -particle Gas molecule
de Broglie 1.227 0.0286 0.0286 0.0101 h h
 nm  nm   nm   nm   
wavelength V V E V m  vrms 3mkT
h h h
28. Heisenberg’s uncertainty principle: Δx  Δpx   Δx  Δ(mvx )   Δx  Δvx 
4 4 4 m
where h = Planck’s constant = 6.626  1034 J s.
8 2 m
29. The well-known form of the Schrödinger equation: 2  ( E  V )  0
h2

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Short form of the Schrödinger equation: Ĥ  E

h2
Hamiltonian operator: Hˆ  2  V
8 2 m

30. Probability of finding an electron at a point x, y, z is  2, so 

2 dx dy dz  1
31. Properties of select particles

Particle Electric Charge (C) Mass
Kilograms (kg) Atomic Mass Units (u)
Electron 1.60  1019 9.109 382  1031 5.485799  104
Proton +1.60  1019 1.672 622  1027 1.007276
Neutron 0 1.674 927  1027 1.008665
Hydrogen atom 0 1.673 534  1027 1.007825
32. Difference between alpha ()-, beta ( )- and gamma ()-particles

Property Alpha()-particle Beta()-particle Gamma()-particle
Speed Slow Fast Moves at the speed of
light
Composition Consists of two Consists of electron. Packet of
protons and two electromagnetic
neutrons. energy.
Charge Has positive charge Has negative charge Has no charge
Origin Decay product Ejected from an Energy released when
unstable nucleus the nucleus remains
unstable after  or -
decay.
Penetration power Low Higher Highest
33. Electron transitions in the hydrogen atom and the types of radiations observed
Electron transition Name of the Region of the
From To Series Electromagnetic
Spectrum
2, 3, 4, 5, 6 1 Lyman Ultraviolet
3, 4, 5, 6 2 Balmer Visible/Ultraviolet
4, 5, 6 3 Paschen Infrared
5, 6 4 Brackett Infrared
6 5 Pfund Infrared
Humphries Infrared
series
34. Designation of a shell

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35. Quantum numbers

Principal Subsidiary Magnetic quantum Symbol
quantum quantum numbers
number number
n l m
1 0 0 1s (one orbital)
2 1 1, 0, +1 2p (three orbitals)
3 2 2, 1, 0, +1, +2 3d (five orbitals)
4 2 2, 1, 0, +1, +2 4d (five orbitals)
4 3 3, 2, 1, 0, +1, +2, 3 4f (seven orbitals)
36. Selection rules governing allowed combinations of quantum numbers
(a) The three quantum numbers (n, l and ml) are all integers.
(b) The principal quantum number (n) cannot be zero. The allowed values of n are therefore 1, 2, 3,
4, ….
(c) The angular quantum number (l) can be any integer between 0 and n  1. If n = 3, for example, l
can be either 0, 1 or 2.
(d) The magnetic quantum number (ml) can be any integer between l and +l. If l = 2, ml can be 2,
1, 0, 1 or 2.
(e) The spin quantum number (ms) refers to the two possible orientations of the spin axis of an
electron and can take the values +1/2 and 1/2.
37. The energy of all the orbitals in a given shell is the same, irrespective of the shape of the orbital.
Thus, the order of energy levels is 1s  2s  2 p  3s  3 p  3d  4s  4 p  4d  4 f
38. Aufbau’s principle: In the case of atoms, electrons occupy the available orbitals in the subshells of
lowest energy.

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<
39. Pauli’s exclusion principle: The maximum number of electrons which can be contained in the main
energy level is as follows:
Subshell Number of Orbitals Maximum
number of
Electrons
s 1 2
p 3 6
d 5 10
f 7 14
The maximum electron population per shell as per Pauli’s exclusion principle
Shell Subshell Maximum Shell Population

1 1s 2
2 2s 2p 8 (2 + 6)
3 3s 3p 3d 18 (2 + 6 + 10)
4 4s 4p 4d 4f 32 (2 + 6 + 10 + 14)
40. Hund’s rule of maximum multiplicity: Where orbitals are available in degenerate sets, maximum
multiplicity is preserved; that is, electrons are not paired until each orbital in a degenerate set has
been half-filled.

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Chemical Bonding
1. Lewis symbols for first, second and third periods are shown as follows:
2. Steps in writing a Lewis structure for molecules
3. Lewis structure of some molecules:
4. Octet rule: Atoms tend to gain or lose electrons until they have achieved an outer shell that contains
an octet of electrons (eight electrons).
5. Formal charge is the charge that each atom in a molecule would have if the electrons in the bonds
were divided equally between the two atoms. The formal charge on an atom is calculated by noting
the number of valence electrons (Va) on a neutral atom of the element and then subtracting all of the
non-bonding electrons on the atom (Na) and half of the bonding electrons on the atom (Ba). The
formal charge (FCa) on atom A is, therefore, given by the following equation.
Ba
FCa  Va  Na 
2
6. Born Lande’s equation: Lattice enthalpy for ionic compounds can be calculated theoretically as
N A Z  Z  e2 A  1  5  Z Z A   1
lattice H   1    lattice H  1.39  10   1  
4 0 r0  n   r0   n 

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where NA = Avogadro constant; A = Madelung constant, relating to the geometry of the crystal;
Z+ = charge number of cation; Z = charge number of anion; e = charge of electron 1.6022 
1019 C and 0 = permittivity of free space; r0 = distance to closest ion; n = Born exponent,
typically a number between 5 and 12.
7. Dipole moment () is equal to the amount of charge on either end of the molecule q, multiplied by
the distance between the charges r.
  qr
Units: Debye (D)
8. Percentage of polar character of a bond: This is calculated based on the difference in

electronegativity of the two bonded atoms (A  B) using the two empirical relations:
9. Pauling equation which states percentage of ionic character  18( A  B )1.4 and electronegativity is
A  B  0.208 EA  B  ( EA  A  EB B )1/ 2
10. Mulliken’s scale states that electronegativity difference is given by
(I  E)
Electronegativity ( ) 
2
11. Hanney and Smith equation which states percentage of ionic character  16( A  B )  3.5( A  B )2
12. For geometry of various compounds based on VSEPR theory, refer to Tables 5.5 and 5.6 of the
textbook.
13. In the presence of lone pair, the repulsive forces act in the following order:
Lone pair–Lone pair > Lone pair–Bond pair > Bond pair–Bond pair
14. In valence bond theory, the different types of overlap for  bonds:
(a) s–s overlap, such as in H2 molecule

(b) s–p overlap, such as in HX molecule (X = F, Cl, Br, I)
(c) p–p overlap, such as in X2 molecule (X = F, Cl, Br, I)
15. The relative strength of the  bonds increases when the intermolecular distance increases and the
order is:
2p–2p > 2p–3d > 2p–3p > 3p–3p
16. In MO theory, the order of energy of molecular orbitals has been determined mainly from
spectroscopic data. In simple homonuclear diatomic molecules, the order is:
 
1s,  *1s,  2s,  *2s,  2 p z, 22ppyx,, *2 px,  *2 pz
*2 p y
Increasing energy


17. The order of MOs shown above is correct for oxygen and heavier elements; but for the lighter
elements boron, carbon and nitrogen the 2px and 2py are probably lower than 2pz. For these atoms
the order is:
   * 2p x
1s,  *1s,  2s,  * 2s,  22 pp x,  2 p z,  * 2 p z, 
y * 2p y
Increasing energy
 

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1
18. Bond order  ( N b  Na ) where Nb is the number of electrons occupying bonding orbitals and Na is
2
the number of electrons in antibonding orbitals.
19. Stability of molecules

Based on relative number of Nb > Na Bonding is stronger and the
electrons in the bonding (Nb) and molecule is more stable.
non-bonding (Na) molecular Nb < Na Antibonding influence is stronger
orbitals and the molecule is unstable.
Based on bond order Nb > Na Positive bond order implies that
the molecule is stable.
Nb < Na or Nb = Na Negative or zero value of bond
order implies that the molecule is
unstable.
20. Hybridization: Percentage of s, p, d characters in various hybridized orbitals.
Hybridization %s %p %d
type
sp 50 50 –
sp2 33.33 66.67 –
sp3 25 75 –
3
sp d 20 60 20
sp3d2 ∼16.5 50 ∼33
sp3d3 ∼14 ∼43 ∼43
Read about the necessary conditions for hybridization in Section 5.12.
21. Types of hybridization of orbitals and their geometries

Type of Number of Shapes of Examples
Hybridization Atomic Molecules
Orbitals
Involved
dsp2 4 [d + s + p(2)] Square planar [Ni(CN)4]2
Trigonal PF5, PCl5
sp3d 5[s + p(3) + d]
bipyramidal
6[s + p(3) +
sp3d2
d(2)]
6[s + p(3) + SF6,[CoF6]3
sp3d2 d(2)] or Octahedron
[d(2) + s+ p(3)] [Co(NH3)6]3+
7[s + p(3) + Pentagonal IF7
sp3d3
d(3)] bipyramidal
22. Types of molecular orbitals formed from the linear combinations of the atomic orbitals
Atomic Orbitals Molecular Orbitals
1sA + 1sB  1s
1sA  1sB  *1s
2sA + 2sB  2s

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2sA  2sB  * 2s
2pxA + 2pxB  2 px
2pxA  2pxB  * 2 px
2pyA + 2pyB  2 py
2pyA  2pyB  * 2 py
2pzA + 2pzB  2 pz
2pzA  2pzB  * 2 pz
Thermodynamics
1. Internal energy in terms of adiabatic work done: U  U 2  U1  Wadiabatic where Wadiabatic is positive
when work is done on the system and negative when work is done by the system.
Units: joule (J). It can also be expressed in calories, where 1 cal = 4.184 J.
2. First law of thermodynamics: dU  dq  dW
Vf
3. Pressure–volume work done for a system going from state i to state f: W  V pexternal dV
i
4. The work done by the gas in an isothermal process can be expressed as

Vf
Wrev  2.303nRT log
Vi
5. Work done in case of free expansion: W = 0
6. Enthalpy change at constant pressure: H  U  pV  U  ng RT where ng is the change in
the number of moles of gaseous substances.
 T 
7. Joule–Thomson coefficient:     . The temperature at which  = 0 is called inversion
 p  H
temperature.
Units: K Pa1
8. Heat and heat capacity: q  CT where q is heat in J and C is heat capacity in J g1 K1 and T is
temperature in K.
9. Heat and specific heat capacity: q  c  m  T where c is specific heat capacity in J g1 K1.
C
10. Molar heat capacity: Cm  where n is the number of moles and Cm is molar heat capacity in J
n
mol1 K1
 U 
Heat capacity at constant volume: CV   
11.  T V
 H 
Heat capacity at constant pressure: C p   
12.  T  p
Relation between CV and Cp: C p  CV  R where R is gas constant.
13.
14. For solids and liquids, there is no volume change, so V = 0, therefore, H  U  C p  CV

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15. Heat of reaction at constant volume in a bomb calorimeter: U  qV as no expansion work is

done.
16. Enthalpy of reaction: r H  Enthalpies of products  Enthalpies of reactants
r H   ai H products   bi H reactants
or i i
For reactions at constant volume, the change in enthalpy can be expressed as:
17. (H 2  H1 )  C p (T2  T1 )
For reactions at constant volume, the change in enthalpy can be expressed as:
18. (U 2  U1 )  CV (T2  T1 )
19. Born–Haber cycle for calculating lattice energy for formation of NaCl:
Na + (g)  Cl (g)  Na + Cl (s)
1
 Lattice H o  f H o +sub H o +ion H o +  bond H o +eg H o
2
qrev
20. A finite change in entropy can be given by: S  . Units: J K1.
T
When heat is absorbed, q is positive and ΔS is also positive indicating an increase in entropy of the
system.
fus H
21. Entropy of fusion: fus S  Sliquid  Ssolid  where Tm is the melting point of the solid.
Tm
 vap H
22. Entropy of vaporization:  vap S  Svapor  Sliquid  where Tb is the boiling point of the liquid.
Tb
sub H
Entropy of sublimation: sub S  Svapor  Ssolid 
23. T
24. Gibbs energy in terms of enthalpy and entropy, G  H  T S
25. Gibbs energy in terms of equilibrium constant: r G  RT ln K  2.303RT log K
o
H surroundings H system
Entropy change in terms of enthalpy change: Ssurroundings  
26. T T
Magnitude of the Gibbs energy change for a reaction to predict the useful work:
27.
(G) p,T  Wuseful work
Gibbs energy change for a reaction: Gº  Gproducts  Greactants
o o
28.
r G  G  RT ln Q
o
or
where ln Q is the natural logarithm of the reaction quotient. At equilibrium,  r G o = 0, so Q = K.
Units: atm for gaseous reactions; mol L1 for reactions in solution.
29. Relation between enthalpy, entropy and equilibrium constant:
22.  r Gº  r H  T r S  RT ln K  2.303RT log K
o o
30. Application of first law of thermodynamics to various processes:

 1
(a) For an adiabatic expansion of an ideal gas: T2V2  TV1 1
 1
or TV  1  constant or pV   Constant
q p  U  pV  H
(b) For an isobaric process in an ideal gas: W  p(V2  V1 )  pV and
(c) For an isochoric process in an ideal gas, V = 0: U  q p  pV  q p

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V p
(d) For an isothermal process: W  2.303nRT log V or W  2.303nRT log p
2 1
1 2
31. Kirchhoff’s equation is used to calculate heat of reaction at a temperature provided it is known at
another temperature keeping the same pressure. It is given by
HT 2  HT 1
 C p
T2  T1
32. At constant volume, it is given by
UT 2  UT 1
 CV
T2  T1
W q2  q1
33. Efficiency of the Carnot heat engine:   q  q2
2
34. For an isolated system, Stotal  Ssystem  Ssurrondings . For the relation between change in entropy
and change to be spontaneous, refer Section 6.17.
35. Factors Affecting Entropy
Quantity Change Effect on entropy

Volume Increase Increase
Temperature Increase Increase
Physical state Solid to gas or Liquid to Increase
gas
Number of particles Increase Increase
36. Gibbs energy and spontaneity:
Enthalpy Entropy Gibbs Energy Reaction

H < 0 S > 0 G < 0 Spontaneous
H > 0 S < 0 G > 0 Non-spontaneous
H > 0 S > 0 G < 0 at high Spontaneous at high
temperature temperature
G > 0 at low Non-spontaneous at low
H < 0 S < 0 G < 0 at low Spontaneous at low
G > 0 at high Non-spontaneous at
temperature high temperature
37. Relation between enthalpy, entropy and equilibrium constant:

 r Gº  r H o  T r S o  RT ln K  2.303RT log K
38. For important implications of this expression, see Section 6.20.

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Solutions
1. Common types of solutions
Solute + solvent Solution Example

Solid in solid Solid Alloys, gemstones etc.
Solid in liquid Liquid Sugar in water
Solid in gas Gaseous Camphor in nitrogen gas
Liquid in solid Solid Mercury with
sodium/silver
Liquid in liquid Liquid Ethanol in water
Liquid in gas Gaseous Water in air
Gas in solid Solid Solution of hydrogen in
palladium
Gas in liquid Liquid O2 dissolved in water
Gas in gas Gaseous Air
2. Solubility:
Mass of solute
Solubility  100
Mass of solvent
where there is an equilibrium between solute and solvent Solute (undissolved) Solute (dissolved)
3. Mass percentage (W/W) of a solution:
g solute g solute
Mass percent  100  100
g solute  g solvent g solution
4. Volume percentage (V/V) of a solution:
Volume of liquid in question
Volume percent  100
Total volume of solution
5. Mass by volume percentage (W/V) of a solution:
g solute
Mass by volume percent  100
mL solution
6. Parts per million/billion:
g(solute) g(solute) g(solute)
100%  % 106 ppm  ppm 109 ppb  ppb
g(solution) g(solution) g(solution)
7. Molarity of a solution:
Number of moles of solute Mole
Molarity  M  
Liter of solution Liter
Units: molar (M) = mol L1
8. Mole fraction of substance A:
nA
xA 
nA  nB  nC  nD   nZ
where nA, nB, nC, , nZ are the numbers of moles of each component, A, B, C, , Z, respectively.
The sum of all mole fractions for a mixture must always be equal to 1. The mole percent is obtained
by multiplying the mole fraction by 100%.

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9. Molality of a solution:
Number of moles of solute Mole
Molality  m  
Kilograms of solvent Kilogram
Units: molal (m) = mol kg1
10. Formality of a solution:
Formality 
Formula weight
11. Normality of a solution:
Normality 
Equivalent weight of solute
Units: normal (N)
12. Henry’s law:
Cgas  KH pgas (KH is constant)
where Cgas is the concentration of the gas and pgas is the partial pressure of the gas above the solution.
C1 C2

Also expressed as p1 p2
and p  KH x
13. Raoult’s law:

p1  p1o x1
where p1 is the partial pressure of one component, p1o is the partial pressure of the pure component
and x1 is the mole fraction of that component.
14. Dalton’s law of partial pressures:
ptotal  p1o  ( p2o  p1o ) x2
15. For a two-component system, the law is expressed as above. Here, ptotal is the total pressure over
solution phase, p1o and p2o are the partial pressures of the individual components and x2 is the mole
fraction of the second component.
16. Vapor pressure of ideal binary liquid solution:
1 p o  ( pBo  pAo ) yA 1  1 1 
 A o o
 o   o  o  yA
pT pB pA pB  pA pB 
17. Colligative properties and determination of molar mass
Colligative Property Expression Molecular Mass

Determination
p A  pA p A  pA nB wB  M A
o o
Relative Lowering of Vapor nB
  
Pressure p
o
A
nA p
o
A
nA M B  wA
Elevation of Boiling Point Tb  Kb m 1000  wB  K b

MB 
where Tb  wA

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 T  RTb*2 M A
Kb   b  
 m m0 1000  H vap
Depression in Freezing Point Tf  Kf m 1000  wB  K f

MB 
where Tf  wA
 T  RTf*2 M A
Kf   f  
 m m0 1000  H fusion
Osmotic Pressure V  nRT wB RT

MB 
 V
18. vant Hoff factor (i)
Observed value of colligative property

i
Calculated value of colligtive property
p A  pA
o
nB
Relative lowering of vapor pressure: p  o
i
p A
nA
Elevation of boiling point: Tb  i(Tb  T )  iKb m
b
o
Depression of freezing point: Tf  i(Tfo  Tf )  iKf m

nB
Osmotic pressure:   i RT
V
Chemical Equilibrium
1. For the hypothetical reaction A  B C  D , the expression for equilibrium law can be written as
kf [C][D]
KC  
kb [A][B]
where KC is the equilibrium constant, kf and kb are the rates of forward and backward reactions.
Units: (mol L1)n
1
2. Equilibrium constant for reverse reaction: KC 
KC
3. The relation between reaction type and the equilibrium constant can be summarized as
Reaction aA  bB  cC  d D cC  dD  aA  bB naA  nbB  ncC  ndD
Equilibrium constant KC
K 
1 KC  KCn
C
KC
4. For gaseous reactions in homogeneous equilibrium, the concentration or active masses can be
replaced by partial pressures to give
[ pC ]c  [ pD ]d
Kp 
[ pA ]a  [ pB ]b
where pA, pB, pC and pD are the partial pressures of A, B, C and D, respectively, and Kp is called the
pressure equilibrium constant.

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Units: (atm)n
5. Relation between pressure equilibrium constant and concentration equilibrium constant:
ng
K p  KC  RT
Value of ng Effect on Kp and KC

When the number of moles of products is equal to Kp = KC
that of the reactants, that is, n = 0
When the number of moles of products is more Kp > KC
than that of the reactants, that is, n > 0
When the number of moles of products is less than Kp < KC. Here n = 1.
that of reactants, that is, n < 0
[C]c [D]d
6. Reaction quotient (Q) for a reaction aA  bB cC  dD : Q  or in terms of pressure
[A]a [B]b
(pC )c (pD ) d
Q
(pA ) a (pB )b
7. Relation between QC and KC values and the direction of reaction:
QC and KC values Relative concentration Direction of net reaction

QC > KC Products more than reactants From right to left
QC < KC Reactants more than products From left to right
QC = KC Equilibrium concentrations No net reaction
 RTV V w
8. Vapor density   
2nRT 2n 2n
In a closed vessel, the vapor density will be inversely proportional to the number of moles of the
gaseous species as  is a constant.
(Vapor density)initial Total moles at equilibrium

(Vapor density)eq Initial moles
9. Degree of association and dissociation:
Moles associated Moles dissociated

(Association)   (Dissociation) 
Initial moles Initial moles
10. Relationship of degree of association/dissociation with vapor density
 D  d  n 
(Association)     
 d  1  n 

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Dd
(Dissociation)  
(n  1)d
where (vapor density)initial = D and (vapor density)eq = d.
11. Relationship between ΔG and ΔGo in terms of reaction quotient Q: G  Go  RT ln Q
For a reaction in equilibrium, ΔG = 0 and Q = KC, therefore,

G o
G o   RT ln K  ln K    K  eG / RT
o
RT
If ΔGo < ΔGo/RT > 0 eG

o
/ RT
> 1 or K > 1 This implies that the reaction is
0 spontaneous and it proceeds in the
forward direction to an extent that
products are present predominantly.
If ΔGo > ΔGo/RT < 0 eG
o
/ RT
< 1 or K < 1 This implies that the reaction is non-
0 spontaneous and it proceeds in the
forward direction to a small extent,
such that very small quantities of
products are formed.
12. Effect of temperature on equilibrium constant:
K p2 H  1 1 
log    
K p1 2.303R  T1 T2 
Ionic Equilibrium
1. Degree of dissociation or ionization:
Number of molecules present as ions


Total number of molecules of the electrolyte

At infinite dilution 

2. Dissociation/ionization constant
 2C
KC 
1
[A  ][B ] C  C C 2
3. Ostwald’s dilution law: K   
[AB] C (1   ) (1   )
where AB is electrolyte, C is the initial concentration and  is the degree of dissociation.
K
4. For a weak electrolyte,  is very small as compared to 1, so K  C 2     KV
C
5. Acid–Base concepts:

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Concept/Theory Acids Bases

Arrhenius Produce H+ ions in water Produce OHions in water.
Brönsted–Lowry Proton donor Proton acceptor
Lewis Can accept a pair of Can donate a pair of
electrons in the formation of electrons in the formation of
a coordinate covalent bond. a coordinate covalent bond.
6. Indication of conjugate pairs
Acid Base Conjugate Acid of Conjugate Base of

Base Acid
Strong Strong Weak Weak
Strong Weak Weak Strong
Weak Strong Strong Weak
Weak Weak Strong Strong
7. Percentage ionization of the acid or base, is defined as follows:
Moles ionized per liter

Percentage ionization  100%
Moles available per liter
[H  ][A  ]
8. Acid dissociation or ionization constant for reaction HA H  A : K a 
[HA]
 2C
Acid dissociation constant (Ka) and degree of dissociation (): Ka  mol L1
9. 1
[BH  ][OH  ]
Base dissociation or ionization constant for reaction B  H2O BH  OH : K b 
10. [B]
(C ) 2 C 2
11. Base dissociation constant (Kb) and degree of dissociation (): K b  
C (1   ) 1  
12. The ionization constant of water and its ionic product: Kw  [H3O ][OH ]
Ka  Kb  Kw or pKa  pKb  pKw  14.00 (at 25 C)
13. Relation between Ka and Kb:
14. The pH scale:
pH   log[H ] or [H ]  10 pH

pOH   log[OH ] or [OH ]  10 pOH
pH  pOH  pKw  14.00 (at 25 C) or [H+] + [OH] = 1014
15. Activity can be defined in terms of molar concentrations:

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[H + ]
aH 
mol L1
[H + ]
pH  log aH   log
mol L1
16. pH calculation of a mixture of two or more weak monobasic acids in water:
pH   log(H )  log Ka1 C1  Ka2 C2
where Ka  Ka (HA) and Ka  Ka (HB) .
1 2
17. pH of mixture of strong acids in water:

[H ]total milliequivalents  NAVA  NBVB  milliequivalents of acids.
[H  ]total milliequivalents
[H  ]  and hence pH   log[H ]molarity .
Total volume
18. Hydrolysis constant and degree of hydrolysis:

Ch 2
Kh 
1 h
where h is the degree of hydrolysis.
19. Degree of hydrolysis is independent of concentration of solution and the pH is:
pH  7  12 (pKa  pKb )
Kw 1 1
20. Salt of a weak acid and a strong base: K h  and pH  7  pKa  log C
Ka 2 2
Kw 1 1
21. Salt of a strong acid and a weak base: K h  and pH  7  log C  pK b
Kb 2 2
Kw 1 1
22. Salt of a weak acid and a weak base: K h  and pH  7  log Ka  pK b
Ka Kb 2 2
23. Salt of strong acid and strong base does not undergo salt hydrolysis. The pH in such cases is
1
pH  pK w
2
24. Henderson–Hasselbalch equation:
[Salt]
pH of an acidic buffer: pH  pKa  log
[Acid]
[Salt]
pH of a basic buffer: pOH  pK b  log
[Base]
25. Buffer capacity or buffer index: Suppose a buffer solution is having volume 1 L containing x mol
of acid and y mol of salt, then we have pH as
y 1 y
pH  pKa  log10  pKa  ln
x y 2.303 x  y
y(x  y )
The buffer index is given by B.I.  2.303 
x
[Salt]
The maximum value of buffer index occurs when  1.
[Acid]
26. Buffer range: From Henderson equation we have

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(pKa  1) < pH < (pKa + 1)

Beyond this range, the buffer index is very small for any practical application.
27. Solubility product constant for reaction:

Ax By xA y   yBx
[A y  ]x [Bx ] y  K[A x B y ]  KK   Ksp
where K is the equilibrium constant of the reaction and K is the equilibrium constant in saturated
solution.
1/ x  y
 Ksp 
28. Solubility product and solubility: S   x y 
.
x y 
29. Solubility increases with increase in [H+] or decreases in pH in case of salts of weak acids:
1/ 2
 K  [H  ]  
S   a  Ksp 
 Ka  
30. For indicators, acid ionization constant, KIn, is given by
[H  ][In  ]
K ln 
[HIn]
31. Henderson equation for phenophthalien based on Ostwald’s theory of indicators
[Ph  ][H  ]
K In 
[HPh]
[Ph  ]
pH  pK In  log10
[HPh]

At the equivalence point, we have [Ph ] = [HPh] and pH = pKIn.
[Me ][OH]
For methyl orange, K 
[MeOH]
[Me ]
pOH  pK In  log10
[MeOH]
32. Value of equilibrium constant changes with change in temperature:
H  1 1 
log K 2  log K1    
2.303R  T2 T1 
33. Acid–Base titrations:
M AVA  M BVB
Strong acid vs. strong base: [H  ] 
VA  VB
M AVA  M BVB M AVA
Weak acid vs. strong base: [H  ]  Ka and [OH  ]  K b
VA  VB VA  VB
M BVB  M AVA
[OH  ] 
VA  VB
Redox Reactions

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1. Difference between oxidation and reduction
Oxidation Reduction
It is addition of oxygen or electronegative element It is addition of hydrogen or electropositive
to a substance. element to a substance.
It is removal of hydrogen or electropositive It is removal of oxygen or electronegative
element. element.
It is caused by loss of electrons. It is caused by gain of electrons.
2. Activity series: Important observations from activation series

(a) An element will be displaced from its compounds by any metal below it in the table.
(b) Metals below hydrogen in the series can displace hydrogen from solutions containing H+, while
metals above hydrogen do not react.
(c) For metals below hydrogen in the activity series, there is a parallel between the ease of oxidation
of the metal and the speed with which it reacts with H+.
3. For rules for assigning oxidation number, see Section 10.4.

4. Fractional oxidation number: The element for which fractional oxidation number is observed is
present in different oxidation states. For example, in Fe3O4, the formula leads to an oxidation number
8/3; in Pb3O4, the oxidation state of Pb is +8/3; in C3O2, the oxidation state of C is +4/3.
5. Types of redox reactions: The various types of redox reactions are combination reaction,
decomposition reaction, displacement reaction and disproportionation reaction. For their
characteristics and example, refer to Section 10.5.
6. Balancing redox reactions – steps involved
Oxidation Number Method Half-Reaction Method (Ion–Electrode

Method)
1. Represent each reactant and product with correct 1. Divide the skeleton equation into half-
formula. reactions
2. Identify the atoms whose oxidation states have 2. Balance atoms other than H and O
changed.
3. Make sure the number of N atoms and S atoms 3. Balance oxygen by adding H2O to the side
are equal on both sides, and note the increase (or that needs O
decrease) in the oxidation number for the number
of atoms involved.
4. Draw a bridge between the same atoms whose 4. Balance hydrogen by adding H+ to the side
oxidation states have changed, indicating the that needs H
electrons gained or lost.
5. Multiply the molecule, atoms or ions oxidized or 5. Balance the charge by adding electrons
reduced by an appropriate number so as to make
the increase in the oxidation number of the atom(s)
oxidized equal to the decrease in the oxidation
number of the atom(s) reduced.
6. Balance the rest of the equation by inspection. 6. Make the number of electrons gained equal
to the number lost and then add the two half-
reactions
7. Cancel anything that is the same on both
sides

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Additional steps for basic solutions

8. Add to both sides of the equation the same
number of OH as there are H+.
9. Combine H+ and OH to form H2O.
10. Cancel any H2O that you can.
7. Stoichiometry of redox reactions: If the stoichiometric coefficients of the reductant and oxidant are
n1 and n2, respectively, then in a volumetric estimation, the molarity equation may be written as
M1V1 M 2V2

n1 n2
1.
8. Equivalent weight calculation:
(a) Equivalent weights of oxidants and reductants:
Fe2(SO4)3 as oxidizing agent (COOH)2 as reducing agent
Fe3  1e  Fe2 C2 O24  2CO2  2e
1 mol of Fe2(SO4)3  2 mol of Fe2+ 90

 45
n = 2, so Equiv. weight = 2
So n = 2 for 1 mol of Fe2(SO4)3
and
400
 200
Equiv. weight = 2
(b) Equivalent weight based on medium
KMnO4 as oxidizing agent in Na2S2O3 as reducing agent in acidic

acidic medium medium
MnO4  8H  5e  Mn 2  4H2O 2S2 O32  S4 O62 +2e
n = 5, so Equiv. weight = n = 2/2 = 1 for 1 mol of Na2S2O3, so
158 158
 31.6  158
5 Equiv. weight = 1
KMnO4 as oxidizing agent in Na2S2O3 as reducing agent in
alkaline medium alkaline medium
MnO4  8H  5e  Mn 2  4H2O S2 O32  10OH  2SO42  5H2 O  8e
n = 5, so Equiv. weight = n = 8 for 1 mol of Na2S2O3, so
158 158
 31.6  19.75
5 Equiv. weight = 8
(c) Equivalent weight based on dilution
conc. HNO3 dil. HNO3

NO3  2H  1e  NO2  H2 O NO3  4H  3e  NO  2H2O
63 63
 63  21
n = 1, so Equiv. weight = 1 n = 3, so Equiv. weight = 3

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(d) Equivalent weight of a substance undergoing disproportionation: For substance AX undergoing

disproportionation, we have
Mol. wt. of AX in  Mol. wt. of AX in
Effective mol. wt. of AX oxidation half-reaction reduction half-reaction
Equivalent weight  
Number of e transferred Number of e transferred
(i) When number of transferred electrons is same: For reaction H2 O2  H2O  O2 ,
68
Equivalent weight 
 34
2
(ii) When number of transferred electrons is different: For reaction Br2  OH  Br   BrO3  H2O
479.4
Equivalent weight   47.94
10
9. n-factor calculation: The n-factor of oxidizing agent or reducing agent is calculated depending upon
the change in oxidation state of the species considered. For calculating n-factor for different cases,
refer Section 10.9.
o
10. Overall cell potential of a redox reaction: Ecell  Eox
o
 Ered
o
. Units: volts (V).
11. Redox titrations:
Titration Redox Reactions Indicator Used End Point

agent
KMnO4 MnO4 ion MnO4  5Fe2  8H  Mn 2  5Fe3  4H2 O KMnO4 as self- Marked by
against as oxidizing
(Oxidizing agent) (Reducing agent) indicator pink
acidic 2KMnO4  3H 2SO4  5H 2 C2 O4  K 2SO4  2MnSO4 coloration.
agent
solution 8H2 O  10CO2
(e.g.,
oxalic
acid)
K2Cr2O7 Cr2 O72 ion Cr2 O72  14H  6e  Cr 3  7H2O Diphenylamine Marked by
against intense blue
as oxidizing Cr2 O72  14H  6Fe2  2Cr 3  6Fe3  7H2O
Mohr salt agent coloration.
Iodometric Cu2+ as 2Cu 2  4I  Cu 2 I2  I2 Starch Marked by
Oxidizing
titration in oxidizing agent intense blue
which free agent S O2 I  2S2 O32  S4 O6 2  2I coloration.
2 3 2
I2 liberated as reducing Reducing
agent
from KI is agent
determine
d by
titrating
against
Cu2+ ions
Iodimetric I2 as an Thiosulphate: I 2  2S2 O32  S4 O6 2  2I Starch Marked by
titrations oxidizing Reducing
agent
intense blue
involve agent in coloration.
the direct neutral or Sulphite: I2  SO32  H2O  2I  SO42  2H
Wiley Physical Chemistry for JEE (Main & Advanced): Appendix B 33

Copyright  Wiley India
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titration of slightly Arsenite: I2  AsO32  H2 O  2I  AsO42  2H

iodine acidic Antimonite: I2  SbO33  H2O  2I  SbO42  2H
with a medium
reducing Thiosulphat
agent es, sulphites,
arsenites or
antimonites
as reducing
agents
Electrochemistry
A
1. Electrical resistance (R) and specific resistance ():   R 
l
where l is the length of the conductor, A is the cross-sectional area of conductor and R is the electrical
resistance.  is called the specific resistance or resistivity.
Units: ohm m
1 A
2. Electrical conductance (G): G  
R l
where l is the length of the conductor, A is the cross-sectional area of conductor, R is the electrical
resistance and  is called the specific resistance or resistivity.
Units: Siemens (S) or ohm1 or mho.
1 l
3. Specific conductance ():   
R A
Units: S m1 or ohm1 m1
l
Cell constant (G*): G* 
4. A
Thus, the cell constant (G*) is the ratio of length (l) to the cross-sectional area (A).
Units: m1
I 2 Rx R3 RR
5. Wheatstone bridge for calculating unknown resistance:    Rx  1 3
I1 R1 R2 R2

Molar conductance:  m  V 
6. 1000  C
where m is the molar conductance,  is the conductivity of the solution and C is the molar
concentration of the solution.
Units: S m1 L mol1
7. Equivalent conductance:
  V

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where  is the equivalent conductance,  is the conductivity of the solution and V is the volume of the
solution containing 1 g-equiv. of the substance. In terms of concentration,


1000  C
Units: S m2 g-equiv.1
8. Kohlrausch law: m  0m  k C

where k is a constant that is specific for a given solvent, at a given temperature, but varies with the
type of electrolyte, C is the concentration and  0m is the molar conductivity at infinite dilution.
According to Kohlrausch’s law: 0m  v 0  v 0
where m0 , 0 and 0 are limiting molar conductivities of the electrolyte, cations and anions,
respectively and v+ and v are the number of cations and anions, respectively.
Debye–Huckel–Onsager equation: m  0m  ( A  B0m ) C
9.
where A and B are the Debye-Huckel constants. If a solution is at infinite dilution, that is, C is almost
zero then m  0m .
Number of moles of electrolyte dissociated x
10. The degree of dissociation () of any electrolyte:   
Initial number of moles of electrolyte n0
x m
Relation between degree of dissociation and molar conductivity:   
n0  0m
11.
12. The dissociation constant for weak electrolyte at concentration C:
C 2 C  2m Cm
2
K  
1     0m ( 0m   m )
( 0m )2 1  0m 
 m 
13. Electrochemical conventions:
14. The emf of a cell is given by: Ecell  ERight  ELeft
Units: Volts (V).

15. Hydrogen electrode: Pt,H2 (1 atm) | (1.0 M)HCl

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2H (aq)  2e H2 (g)

16. Calomel electrode: Pt, Hg(l), Hg2Cl2 (s) | KCl( x M) saturated with Hg2Cl2
Hg 2 Cl2 (s) Hg 22  2Cl
Hg 22  2e 2Hg
Hg 2 Cl2 (s)  2e 2Hg  2Cl 
17. The standard Gibbs energy of the reaction: G  RT ln K

o
Units: Joule (J)
18. Mathematical relationship between Gibbs energy change and emf of the cell:
G  nFEcell
19. Calculation of cell potential and other thermodynamic parameters from Gibbs–Helmholtz equation:
 (G)   E 
 T   nF  T 
 p  p
  E  
H  nF  E  T   
  T  p 
H  G  E 
S   nF  
T  T  p
20. The Nernst equation for a galvanic cell:

RT RT [C]c [D]d
Ecell  Ecell
o
 ln Q  Ecell
o
 ln
2F 2 F [A]a [B]b
21. Equilibrium constant from Nernst equation:
2.303 RT
o
Ecell  log Keq
nF
22. Types of electrodes:
Type Reactions Type Reactions
Metal–Metal n
Anode: M(s)  M (aq)  ne

Metal insoluble–metal AgCl(s) Ag+  Cl
ion half-cell n  salt anion half-cell Ag+ (aq)  e
Cathode: M (aq)  ne  M(s)
Ag (s)

AgCl(s)  e Ag (s)  Cl
Gas–Gas ion Anode: Amalgam electrode Zn 2 ( x M)  2e Zn(Hg)

half-cell H2 ( p atm)  2H (C M)  2e
Cathode:
2H (C M)  2e  H2 ( p atm)
Redox half- C6 H4 (OH)2 C6 H4O2  2H  2e

cell

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aproducts
Variation of G with temperature: G  G 0  RT ln
23. areactants
where T is the temperature on Kelvin scale and aproducts and areactants are activities of products and
reactants.
25. Concentration cells:

2.303RT p
Electrode concentration cell: Ecell  log 1
(a) nF p2
Examples are Pt, H2 ( p1 ) | HCl( x M) | H2 ( p2 ),Pt , Hg–Pb(C1 ) | PbSO4 (aq) | Hg–Pb(C2 ) , etc.
2.303RT a
Electrolyte concentration cell: Ecell  t  log 2
(b) nF a1
where for all practical purposes, a2 C2 ; a1 C1 and t is the transport number (or transference
number).
Examples are , etc.
(c) Applications are
(a) Determination of valency of ions
2.303RT C
Ecell  log 2
nF C1
(b) Determination of the solubility of a sparingly soluble salt
0.0591 C
Ecell  log 2
n x
(c) where C1 = x is the concentration of the saturated solution, C2 = 0.1 M, n = 1 and F = 96500
C. From this, x can be calculated. From the value of x, Ksp, and hence S can be calculated.
26. Faraday’s laws:
(a) First law:
Amount of substance formed Amount of electricity passed

at one of the electrodes through the cell
or w = ZQ = ZIt
where Z is the electrochemical equivalent of that substance, I is the current, t is the time and
Q is the charge.
w It
 Number of equivalents 
Also, E 96500
Application of first law: Thickness of the coated layer in electroplating can be found using
the first law as
I t  E
(l  b  h cm3 )   g =
96500
(b) Second law:
Wt. of M1 deposited Eq. wt. of M1 w1 w2
 
Wt. of M 2 deposited Eq. wt. of M 2 E1 E2
or
27. Products formed in electrolysis depend upon nature of electrolyte, nature of electrodes, standard
electrode potentials of oxidizing and reducing species; and concentration of solution used.

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28. Transport (transference) number: The fraction of the total current carried by the cation or anion is
termed as transport number.
Current carried by the cations
t   Q m v
Total current carried by both the ions
Current carried by the cations
t   Q m v
Total current carried by both the ions
where t+ + t = 1.
v v
For electrically neutral solution, t  and t 
(v  v ) (v  v )
t v 
Relation with molar conductance:     
t v 
(0 )
To calculate ionic conductance: t 
0
Ionic velocity V
29. Ionic mobility    m2 V 1s 1
Potential gradient dV /dt
30. Chemical composition of rust: Fe2O3xH2O(s)
31. Batteries
(a) Primary cells
Leclanche cell: Zn + 2MnO2 + H2O  Zn 2+ + Mn 2O3 +OH
Alkaline dry cell: Zn + 2MnO2  ZnO + Mn 2O3
Weston Cadmium Cell: Cd(s)  HgSO4 (s)  Cd2 (aq)  2Hg(l)  SO42 (aq)
Mercury cell:
Silver Button cell:

(b) Secondary cells
Lead storage cell (lead acid battery):
During discharging: Pb(s)  PbO2 (s)  2H2SO4 (aq)  2PbSO4 (s)  2H2O(l)
On recharging: 2PbSO4 (s)  2H2O(l)  Pb(s)  PbO2 (s)  4H+ (aq)  2SO42 (aq)
Nickel–Cadmium battery: Cd + 2NiO(OH) + 2 H2O  2Ni(OH)2 + Cd(OH)2
III
Lithium battery: Li  MnO2  Li Mn O2
32. Fuel cells: Fuel  Oxidant  Oxidation product  Reduction product
Hydrogen–oxygen fuel cell: 2H2  O2  2H2O

nFE
Efficiency of fuel cell: Efficiency of cell 
H
Chemical Kinetics
1. The rate of a reaction

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(Conc. of X at time tfinal  Conc. of X at time tinitial ) (Conc. of X)

Rate with respect to X  
(tfinal  tinitial ) t
Units: mol L1 s1

For a reaction A  B,
Decrease in concentration of A [A]
Rate of disappearance of A  
Time t
Increase in concentration of B Δ[B]
Rate of appearance of B  
Time t
2. Average and instantaneous rates:
Δ[A] Δ[B]
ravg  
Δt Δt
3. d[A] d[B]
As t  0, ravg  rinst or rinst  
dt dt
4. Rate law for a reaction aA + bB  Products
Rate  k[A]x [B]y

where k is the rate constant, and x and y are orders with respect to A and B, respectively. The
exponents x and y may or may not be equal to the stoichiometric coefficients (a and b of the reactants)
d[A]
5. Differential rate equation:   k[A]x [B] y
dt
6. Units of rate constant depending upon the order of the reaction:
dx
 k[Concentration of reactant]n
dt
dx 1
k 
dt [Concentration]n
 dx  1
For zero-order reaction, k      mol L1 time1
 dt  [Concentration]
0
 dx  1 mol L1 1
For first-order reaction, k        time1
1
time mol L1
 dx  1 mol L1 1
For second-order reaction, k        L mol1time1
2
time (mol L1 )2
1  2n 1  1 
Half-life period: t1/ 2   
7. k (n  1)  a n 1 
Units: s or min or h
8. Summarized expressions:

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Order of Differential rate law Integrated rate law Half life Units of
reaction rate
constant
Zero d[A] kt  [A0 ]  [A] [A 0 ] mol
 k
dt 2k L1s1
First d[A] [A0 ] ln 2 s1
 k[A] kt  ln
dt [A] k
Second d[A] 1 1 1 L mol1

 k[A]2 or  k[A][B]
2
kt   (for same reactant)
dt [A] [A 0 ] k[A 0 ] s1
Third d[A] 1  ([A0 ]  [A])(2[A0 ])  3 L2 mol2

 k[A]3 or  k[A]2 [B] kt  k[A 0 ]2
dt   2 s1
2[A0 ]2  [A0 ]2 
or  k[A][B]2 or  k[A][B][C]
(for same reactant)
 [14 C] 
9. Radioactivity: Rate  k (14 C) and ln  14   kt1/2
 [ C]0 
10. Consecutive reactions: A   B  C

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

Differential rate equations:  k1[A]  k1[A]  k2 [B]  k2 [B]
dt dt dt
Integrated rate equations: [ A]  [ A]0 e k1t
k1
[B]  [A 0 ](e k1t  e k2t )
k2  k1
 k 
[C]  [A 0 ] 1  1 (e k1t  e k2t )  e k1t 
 k2  k1 
 k1t  k2t
Case I When k1 >> k2: [B]  [A0 ](e  e )
k1 k
Case II When k2 >> k1: [B]  [A 0 ](e k1t  e k2t )  1 [A 0 ] e k1t
k2 k2
11. .
12. Parallel reactions:

d[A] d[B] d[C]
Differential rate equations:   (k1  k2 )[A]  k1[A]  k2 [A]
dt dt dt
 ( k  k )t
Integrated rate equations: [A]  [A]0 e 1 2
k1[A]0
[B]  [1  e( k1 k2 )t ]
(k1  k2 )
k [A]
[C]  2 0 [1  e( k1 k2 )t ]
(k1  k2 )

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The ratio of products, called the branching ratio, is at all times.

[B] k1

[C] k2
kf
13. Reversible or opposing reactions: A kb
B
d[A] d[B]
Differential rate equations:   kf [A]  kb [B]
dt dt
Integrated rate equations: [A]  Aeq  xeq exp[(kf  kb ) t ]
[B]  Beq  xeq exp[(kf  kb ) t ]
14.
15. Determination of Order of Simple Reaction – Experimental Methods

(a) Initial rate method: n1A + n2 B  n3C  Products
(r0 )1  k[A0 ]1x [B]y [C]z and (r0 )2  k[A0 ]2x [B]y [C]z
log (r0 )1 (r0 )2 

x
(r0 )1 [A0 ]1x  [A0 ]1  (r0 )1 [A ]
    log   log 0 1   
x
(r0 )2 [A0 ]2 [A 0 ]2  (r0 ) 2 [A 0 ]2 log [A 0 ]1 [A 0 ]2 
(b) Graphical method:
dx
For first order:  k (a  x)
dt
dx
For second order:  k (a  x) 2
dt
If plot log (a  x) vs. t is a straight line, the reaction follows first order. If the plot of 1/(a  x)
versus t is a straight line, the reaction follows second order. In general, for a reaction of nth order,
a graph of 1/(a  x)n1 vs. t must be a straight line.
(c) vant Hoff differential method: for two different initial concentrations A1 and A2,
 dA1   dA 2 
log10    log10  
n=  dt   dt 
 log10 A1  log10 A2 
where dA1/dt and dA2/dt are determined from concentration vs. time graphs and the value of n
can be obtained.
(d) Half-life method: For the same reaction, the half-lives are determined at two different
concentrations and related to the order of reaction.
Rate constant at T2 kT2

16. Temperature coefficient (Q10 )  
Rate constant at T1 kT1
17. Activated complex theory: The difference in activation energy is mainly responsible for observed
difference in rates of reactions.
The threshold energy ET = ER + Ea where ER is the energy of the reactant.
Ea(forward) = Ea(backward) + H
For exothermic reaction, Ea(forward)  H = Ea(backward)

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For endothermic reaction, H = Ea(forward)  Ea(backward)
18. Calculation of activation energy:
k2 Ea  1 1  T1T2 k 
log     or Ea  2.303R log  2 
k1 2.303R  T2 T1  T2 – T1  k1 
Units: Joule (J)
19. Arrhenius equation: k  Ae E /RT a
where k is the rate constant for the reaction and A is the proportionality constant that is known as
Arrhenius factor or frequency factor.
kcat 1
20. Effect of catalyst: log  [ Ea(uncat)  Ea(cat) ]
kuncat 2.303 R T
   2  ( M 2  M1 )
2
21. Collision frequency: Z1,2  n1*n2*  1  8 RT

 2  M1M 2
where Z is the number of molecules colliding per cm3 per second in the reacting system containing 1
mol L1 of reactant; 1 and 2 are the molecular diameters of the respective molecules; M1 and M2
their molecular masses; n1* and n2* the numbers of the respective molecules per cm3 at temperature T.
22. Fraction of molecules activated:
n Number of molecules activated

 e Ea /RT 
n* Total number of molecules
23. Relation between Z and rate constant k: k  ZeEa /RT
24. Probability factor, P is introduced to allow the disparity between calculated and observed rate
constants:
k  PZe Ea / RT
*
where P may have the values ranging from unity to 109. It is also known as the steric factor and takes
into account the proper orientation of the collision.
Surface Chemistry
x x
1. Freundlich adsorption isotherm:  kp1/n or  kC1/n
m m
x 1
log    log k    log p
m n

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x 1
For solutions, log    log k    log C
m n
x k1k2 p
2. Langmuir adsorption isotherm: 
m 1  k1 p
p 1 p
or  +
( x / m) k1k2 k2
At low pressure, the amount of gas adsorbed is directly proportional to the pressure of the gas
x
 k1k2 p
m
At high pressure, adsorption attains a constant value.
x
 k2
m
At intermediate pressure, the extent of adsorption does not increase as fast as the pressure.
x kk p
 1 2
m (1  k1 p)
3. Brunauer, Emmett and Teller proposed a theory (BET theory) for multilayer adsorption
V Cx

Vm (1  x)[1  (C  1) x]
where x = p/po, where p is the pressure of the gas at temperature T and po is the saturated vapor
pressure of the gas at the same temperature.
x 1 (C  1) x
 
V (1  x) CVm CVm
It is possible to determine the parameters Vm and C from plot of x/V(1  x) versus x and thus get the
volume of gas required to form a monolayer.
Vm
4. Surface area of solids: V 
1  1/ k1 p
From Vm value and density of liquefied adsorbate (such as nitrogen), the surface area occupied by a
single molecule of adsorbate on the surface can be estimated. The area of one molecule of nitrogen
under these conditions is taken as 16.2  1020 m2.
Surface sites used to adsorb the gas
5. Sites occupied per molecule of gas =
Molecules of gas
6. Enzyme catalysis occurs by the following mechanisms:
(a) Büchner’s mechanism: Enzyme  Substrate  Enzyme  Substrate complex  Enzyme  Product
(b) Lock and key hypothesis: The specificity of an enzyme (the lock) and its substrate (the key)
comes from their geometrically complementary shapes. Refer Figure 13.10 in the textbook.
(c) Induced-fit model: The flexible nature of enzyme helps explain enzyme binding specificity and
the ability of enzyme to convert reactants into products. An enzyme is a dynamic catalyst
7. Types of colloid dispersion:

Dispersed Dispersion Medium Name Example

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Phase
Gas Gas –a –
Liquid Gas Liquid aerosol Fog, perfume spray
Solid Gas Solid aerosol Smoke, dust
Gas Liquid Foam Fire extinguisher foam,
shaving foam
Liquid Liquid Emulsion Milk, mayonnaise
Solid Liquid Sol, paste Toothpaste,
crystallization
Gas Solid Solid foam Expanded polystyrene,
cushion foam
Liquid Solid Solid emulsion (gel) Opal, pearl
Solid Solid Solid suspension Pigmented plastics
(sol)
a
A gas-in-gas system is not a colloid, it is a mixture.
8. Classification of colloids: The colloids are classified into lyophilic, lyophobic, multimolecular,
macromolecular and associated colloids. For characteristics and examples, refer to Section 13.11 of
the textbook.
9. Kraft temperature (Tk): The temperature above which micelle formation takes place.
10. Critical micelle concentration (CMC): The concentration above which micelle formation takes
place.
11. Helmholtz electrical double layer: The combination of two layers of charges around the colloidal
particle. The first layer of charges is firmly held to the colloidal surface while the second layer of
charge is diffused.
12. Electrokinetic potential or zeta potential: The potential difference is set up between the two layers
in Helmholtz electrical double layer because of the fixed and diffused charges of opposite signs.
13. Hardy–Schulze Rule: The greater the polarizing power of the flocculating ion added, the greater is
its power to cause precipitation. The ions carrying the charge opposite to that of sol particles are
effective in causing coagulation of the sol.
14. Coagulating power of an electrolyte is directly proportional to the valence of the active ions (ions
causing coagulation).
15. Gold number: The number of milligrams of the protective colloid that will just prevent the
coagulation of 10 ml of a gold sol on the addition of 1 ml of 10% sodium chloride solution. The
smaller the value of gold number, the greater is the protecting power of the protective collloid.
1
Protective power of colloid 
Gold number
Nuclear Chemistry
1. Representation of atom:
2. Elementary particles:

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4 0 1 1
2 He 1e 1p 0n
 -particle Electron or  -particle Pr oton Neutron
3. Kasimir Fajans and Frederick Soddy rules:
(a) Emission of an -particle produces an element which is four mass units lighter and the atomic
number decreases by two.
(b) When a -particle is emitted the mass number remains the same. However, the atomic number
increases by one:
 219  215  211  211  207  207
223
88 Ra 
 86 Rn 
 84 Po 
 82 Pb 
 83 Bi 
 81 Tl 
 82 Pb
(c) Radioactive elements that fall in the same place in the periodic table are different forms of the
same element.
4. Different combination of protons and neutrons in a nuclide

(a) Nuclide: A particular combination of protons and neutrons.
(b) Isotopes: Nuclides with the same number of protons.
(c) Isobars: Nuclides with the same mass number.
(d) Isotones: Nuclides with the same number of neutrons.
(e) Isodiaphers: Radioactive nuclides with same (N  Z) or (A  2Z) values.
(f) Isosters: Molecules with same number of atoms as well as electrons.
5. Stability: Stability of a nucleus depends on the number of protons and neutrons present
(a) Harkin’s rule: Elements of even atomic number are more stable and more abundant than
neighboring elements of odd atomic number. 1H is a notable exception.
(b) Magic numbers: Nuclei with 2, 8, 20, 28, 50, 82 or 126 neutrons or protons are particularly
stable and have a large number of isotopes. The numbers 114, 164 and 184 should also be
included in the series of magic numbers. When both the number of protons and the number of
neutrons are magic numbers the nucleus is very stable.
(c) Neutron to proton ratio: Nuclei with n/p ratios appreciably higher or lower than the stable ratio
are radioactive. When they decay they form nuclei closer to the line of maximum stability.
(i) If the n/p ratio is high, the isotope lies above the curve. Such a nucleus will decay in such a
way that it reduces the n/p ratio and forms a stable arrangement, thus, emitting a -particle.
(ii) If the n/p ratio is high, the isotope lies below the curve. Such a nucleus will decay in such a
way that it reduces the n/p ratio and forms a stable arrangement, thus, emitting a positron.
6. Modes of radioactive decay:

238
(a) Alpha decay: 92 U 90234
Th + 24 He ( - decay)
(b) Beta decay: Three different modes of  -decay can be observed in nature

19 K 20 Ca + 1e [negatron ( ) emission]
40 40 0
19 K + 1e 18 Ar + hν (electron capture)

40 0 40

19 K 18 Ar + 1e [positron(  )emission]
40 40 0
Gamma emission: 6027 Co 27 Co +  ( -ray emission)

m 60
(c)
Spontaneous fission: 98 Cf  54 Xe + 44 Ru + 40 n
252 140 108 1
(d)
7. Mass defect: Difference between the mass of an atom and the sum of the masses of its protons,
neutrons, and electrons.
Mass defect  Predicted mass  Observed mass
8. Binding energy of a nuclide can be calculated from its mass defect with Einstein's equation that
relates mass and energy.

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E= mc2
Binding energy for a nuclide
Binding energy per nucleon 
Total number of protons and neutrons it contains
The binding energy per nucleon ranges from about 7.5 to 8.8 MeV for most nuclei, and largest for
56
Fe, which is the most stable nuclide in the periodic table.
d( N )
9. Rate expression for radioactive decay: Rate    k(N )
dt
10. Disintegration or decay constant ( ): Fraction of the total number of atoms disintegrating per
second. This constant is represented by .
dN
 dt
N
dN
When time t = 1 s, 
N
On integration, N  N0et  N  N010t /2.303
where N0 is the initial concentration.
11. Time required for decay of any specific fraction: t1/ n  [ N0 ]0
N0  N N
12. Fraction of atoms () decayed in time t:   1  1  e  t
N0 N0
ln 2 0.693
13. Half-life: t1/2  
 
In general, for n number of half-life times (nt1/2),
14. Amount of radioactive substances present = ( 12 )n N0
15. Amount of radioactive substances decomposed = 1  ( 12 )n N0
16. Average life: The sum of lives of all atoms divided by the total number of atoms
Total life time of all atoms
Average life ( avg ) 
Total number of atoms
1
 avg 

If t = 1/, N  0.37 N0
17. Relation of average life with half-life: t1/2  0.693  avg   avg  1.44t1/2
18. Radioactive equilibrium: When the rate of decay of radioactive substance to form element B is same
as the rate of formation of C from B.
N1 2 1/ 1 ( avg )1
  
N 2 1 1/ 2 ( avg )2
N1 (t1/2 )1

or
N 2 (t1/2 )2
Case 1 (transient equilibrium): When 1 < 2 and (t1/2)1 ≈ (t1/2)2
N1 2  1

N2 1

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2.303  
tmax  log10  2 
2  1  1 
Case 2: When 1 > 2 and (t1/2)1 < (t1/2)2
When the parent element has shorter half-life time than the daughter element, steady state is not
achieved.
19. Parallel decay: For the reaction


A 1
B

2
C
Total rate of disintegration of A is
  1  2
Decay constants for each process can be expressed as
1  [Fractional yield of B]  
2  [Fractional yield of C]  
20. Units of radioactivity: The units of radioactivity are Curie(Ci), Rutherford (Rd) and Becquerel (Bq).
The conversion factors are
(mCi) = 103 Ci or microcuries (μCi) =106 Ci
(mRd) = 10 Rd (103 dps) or micro-Rutherford (μRd) =106 Rd (1 dps)
3
1 Ci = 3.7  1010 disintegrations s1 = 3.7  1010 Bq
21. Units of absorbed dose: The units of absorbed dose are Gray (gy), Rad, Sievert (Sv) and Roentgen
equivalent for man (Rem). The conversion factors are:
1 Gy = 100 rad
1 rem = 102 Sv
22. Radioactive series:
Thorium (4n) series
Neptunium (4n + 1) series
Uranium (4n + 2) series
Actinium (4n + 3) series
where the numbers in brackets indicate that the parent and all the members of a particular series have
mass numbers exactly divisible by four, or divisible by four with a remainder of one, two or three.
There is no natural cross-linking between the four series, although this can be performed artificially.
23. Nuclear reactions

Particle capture reaction: 13 Al  
Al  01n  28
27
13
Particle-particle reaction: 147 N  01n  146 C  01 H

33 As  1 H  25 Mn  1 H  12 0 n
Spallation reaction: 75 2 56 1 1
235
Fission reaction: 92 U  10 n  139 94 1
56 Ba + 36 Kr + 30 n
Fusion reaction: 78 Li  11 H  2 24 He  Energy
24. Nuclear reactions in the sun
Step 1: H  H  H  Positron  Neutrino
1 1 2
Step 2: H  H  He   -ray
2 1 3
Step 3: He  He  He  H  H
3 3 4 1 1

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The net energy released is 26 MeV. These reactions are responsible for 85% of the Sun’s energy. The
remaining 15% can be accounted for by the following reactions:
Step 1: He  He  Be   -ray
3 4 7
Step 2: Be  Electron  Li  Neutrino

7 7
Step 3: B  2 He  Positron  Neutrino

8 4
25. Radiation biological effectiveness (RBE): rems = rads  RBE

26. Relation between exposure rate and the distance from the source:
1 I1 d22
Radiation   
d2 I2 d12
where I1 and I2 are the exposure rates. This relation is also called inverse square law

Ph.: 0651-2562523, 9835508812, 8507613968

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Tools for Problem

Units: g mL1 or g cm3

4. To convert from °F to C:

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(a) Hydrogen displacement method:

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(b) Oxide formation method:

Mass of elements in grams

21. Relation between the stoichiometric quantities

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(a) M1V1 = M2V2

22. Relation between empirical formula and molecular formula

23. Steps for calculating empirical formula are as follows:

25. Steps for solving limiting reagent problems

26. Theoretical and actual yield:

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Milliequivalents of acid used by Na 2CO3  2b  Milliequivalents of Na2CO3

30. Volume strength of H2O2 solution

Gaseous and Liquid States

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Effusion rate (A) B MB

where MA and MB are the molar masses of gases A and B.

Volume diffused (V ) Moles diffused (n) Distance travelled (l )

pdry gas  ptotal  Aqueous tension

10. Kinetic theory: Predictions of gas laws made by kinetic theory

It relates temperature to average kinetic energy T  Average molecular kinetic energy

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It explains the pressure–volume law (Boyle’s law) 1 1

11. Kinetic energy and molecular speeds:

Speed Calculation Relation with individual velocities Relation with

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1. Force of attraction in an ionic bond

Crystal system Edge lengths Angles Examples

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Volume occupied by atoms/spheres

Relation between atomic radius (R) a  2R a  4R / 3 a  2 2R

Number of nearest neighbors 6 8 12

Packing efficiency 52% 68% 74%

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Units: kg m3 or g cm3

13. Magnetic dipole moment

14. Bragg’s law: n  2d sin 

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Units: Joules (J)

9. Relation of wavelength with frequency

10. Calculation of wave number in hydrogen spectra,

11. For various series of hydrogen spectra, we have

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23. Energy of electron: En   RH 

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Short form of the Schrödinger equation: Ĥ  E

31. Properties of select particles

32. Difference between alpha ()-, beta ( )- and gamma ()-particles

34. Designation of a shell

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35. Quantum numbers

36. Selection rules governing allowed combinations of quantum numbers

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Shell Subshell Maximum Shell Population

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2. Steps in writing a Lewis structure for molecules