PHYSICAL CHEMISTRY

1. Some Basic Concepts of Chemistry

  1 gram atom = NA atoms = 6.023 × 1023 atoms
= Gram atomic mass

 1 gram molecule = NA molecules

= 6.023 × 1023 molecules = Gram molecular mass

 Mass % of an element
 Molecular Mass  Average1relative mass of one molecule
 mass of C  12 atom
12 Mass of that element in the compound ×100
= Molar mass of the compound
 Molecular mass = 2 × VD

wt. of metal
 The value of n can be obtained by the following
 Eq. wt. of metal  wt. of H displaced  1.008 relationship
2

Molecular mass
wt. of metal n
Empirical formula mass
 Eq. wt. of metal  wt. of oxygen combined  8
 Normality (N)
wt . of metal
  35.5
wt. of chlorine combined Gram equivalent of the solute W  1000
=  ,
Volume of the solution in litre GEM  V in mL
 Molecular formula = (Empirical formula)n
where GEM is gram equivalent mass of solute.
 1 amu = 1.66 × 10–24 g (amu - atomic mass unit)
Atomic mass
 Equivalent mass of an element = Valency
w
 n=
M
Molecular mass
where w is weight of substance and M is molar  Equivalent mass of an acid = Basicity
mass of substance, n is number of moles

given particles Molecular mass

 n= where n is number of moles  Equivalent mass of a base = Acidity
6.022  1023

Given volume  Equivalent mass of a salt

 n=
22.4 lit at STP
where n is number of moles
Formula mass
= Total +ve or  ve charge
 Average atomic mass

(RA At .mass)1  (RA At .mass)2  Equivalent mass of an oxidising agent

= RA(1)  RA(2)
Molecular mass
where RA is relative abundance. = Total change in oxidation number

Page: 1
 Molarity × GMM (solute) = Normality × GEM  No. of gram equivalents
(solute), where GMM is gram molecular mass.
Weight of the solute(in g)
 Normality and molarity equations : = Equivalent weight of the solute

N1V1 = N2V2
 No. of milliequivalents
M1V1 = M2V2 (For dilution)
Weight of the solute(in g)
M 1 V1 M 2 V2 = Equivalent weight of solute × 1000

n1 n2
 Strength of a solution
(For reaction where n1 and n2 are no. of moles
of the two reactants in a balanced chemical Wt. of the solute (in g)
equation) = Vol. of solution (in litres)
M3(V1 + V2) = M1V1 + M2V2
 Parts per million (ppm) of substance A (ppm)
(Final molarity on mixing two non-reacting
solutions) Mass of A
= × 106 or
Mass of solution
 Number of millimoles = Molarity × V in mL

 Number of equivalents = Normality × V in L =

Vol. of A
× 106
Vol. of solution
 Number of milliequivalents
M
= Normality × V in mL  Molality (m) =
MM 2
or

 Number of gram atoms or mole of atoms 1000

Mass of element in gram

= m
Gram atomic mass Molarity (M) =
 mM 2 
1 
 1 mole = mass of 6.023 × 1023 particles (atoms/  1000 
molecules)
where M2 = molecular mass of solute,
 1 mole atoms = Gram atomic mass (or 1 g atom)  = density
= 6.023 × 1023 atoms
n1
 1 mole molecules = Gram molecular mass (or  M
(n 1M 1  n 2 M 2 ) / 
1 g molecule) = 6.023 × 1023 molecules
= 22.4 L at STP Here, n1M1 = mass of solute,
n2M2 = mass of solvent
 1 mole ionic compound = Gram formula mass
= 6.023 × 1023 formula units i.e., n1M1 + n2M2 = mass of solution.

Page: 2
 2. Atomic Structure
1. No. of subshells in main shell = n  Nodes (n–1) = total nodes, l = angular nodes,
2. Total no.of orbitals in main shell = (n)2 (n – l –1) = Radial nodes
3. Total no. of orbitals in subshell - 2l + 1  Orbital angular momentum :
2
4. Total no. of electrons in main shell - 2n h
5. Total no. of electrons in sub shell = 2(2l + 1) (  1)  (  1)h
2π
6. No. of radial or spherical nodes = n – l – 1
14. Bohr’s model formulae
7. Nodal plane :  Radius of nth shell
It is a plane passing through nucleus where
probability of finding of electrons is zero. n2 n2
rn  0.529  Å r
No. of nodel plane = l Z Z

nh  Velocity of nth shell

8. Angular momentum of electron, mvr =
2
Z Z
vn   2.185  108 cm / s  V 
9. Orbital angular momentum of electron. n n
h
= (  1) , Z2
2  No of revolutions made by nth shell v = 3
s 1
n
= (  1)
n2
10. Magnetic moment = V
n ( n  2) B.M. n3
Where n = no. of unpaired electrons.
 No. of wave made by e – in nth shell
h
11. Spin angular momentum = S( S  1)
n3 n3
2 Tn  1.5  10 16  s  v
12. Maximum no. of lines produced when Z2 Z2
n(n  1)  IE  E  E1
electron falls to ground level, =
2
IE = –E1
13. W hen el ectron returns f rom n 2 to n1 state,
maximum no. of lines produced IE = 0 – E1 = –E1
(n  n )(n  n  1)  IEH-like atom × Z2 = I.EH atom × Z2
= 2 1 2 1
2
Z2
1 1 
 KE = 13.6  eV / atom
1 n2
 ν   RZ2  2  2  ,
λ  n1 n 2 
Z2
[R = 1.0968 × 107 m–1];  P.E. = 27.2  eV/atom
n2
hc h
E  hv  ,λ  Z2
λ 2m  K.E.  IE and TE = – 13.6 × eV/atom
n2
 No. of spectral lines produced when an
electron drops from nth level to ground level KE Ze 2 2r
 KE and TE =
TE

2r
  2  1
n(n  1) Ze
=
2 nh
 Angular momentum in orbit mvr =
 Heisenberg's Uncertainty Principle = (x) (p) 2
 h/4
Page: 3
 3. Chemical Bonding
 (i) % ionic character  VSEPR theory
Actual dipole moment i. (LP-LP) repulsion > (LP-BP) > (BP-BP)
= Calculated dipole moment  100
ii. NH3 Bond angle 106°45' because
(ii) Dipole moment is helpful in predicting (LP-BP) repulsion > (BP-BP) H2O  104°27'
geometry and polarity of molecule. because (LP-LP) repulsion > (LP-LB) > (BP-BP)

 Fajan's Rule: VMCA

 Hybridisation : H
2
Following factors are helpful in increasing
covalent character in ionic compounds  MO Configuration
i. Small cation Case I :

ii. Big anion 2s–2p mixing occurs (total e–  14)

iii. High charge on cation/anion 1s < *1s < 2s < *2s < 2px = 2py < 2pz <
*2px = *2py < *2pz
iv. Cation having pseudo inert gas
Case II :
configuration (ns2p6d10)
2s–2p mixing do not occurs (total e– > 14 to 20)
e.g. Cu+, Ag+, Zn+2, Cd+2
1s < *1s < 2s < *2s < 2pz < 2pz < 2px=
 M.O. Theory: 2py < *2px = *2py < *2pz

i. Bond order = 1/2 (Nb–Na)  Application of H-bonding

ii. Higher the bond order, higher is the bond Physical State (densile nature)  H-bond
dissociation energy, greater is the stability,
Melting point (mp)  H-bond
shorter is the bond length. on an atom in a
Lewis Boiling point (bp)  H-bond

= [total number of valence electrons in the free Viscosity  H-bond

atoms] – [total number of non-binding (lone
Surface Tension  H-bond
1
pair) electrons] – [total number bonding
2 Volatilty  1/H-bond
(shared) electrons]
Vapour Pressure  1/H-bond
 Relative bond strength :
sp3d2 > dsp2 > sp3 > sp2 > sp > p-p (Co-axial) > s-p > s-s > p-p (Co-lateral)

Page: 4
 4. States of Matter
 Boyle’s Law at constant temperature  Graham’s Law of Diffusion / Effusion
and amount 1
• Rate of diffusion R 
P1V1 = P2V2 = Constant d

 Charle’s Law where d is density of gas at constant

V = kT at constant pressure temperature and pressure

k is the proportionality constant depends r1 d2

upon (i) Amount of Gas (ii) Temperature • 
r2 d1
 Gay Lussac’s Law :
r1 M2
P1 P2 • 
 at constant volume r2 M1
T1 T2

 Avogadro’s Law  Dalton’s of Partial Pressure :

Vn (T and P constant) Calculate the total pressure of mixture of non-
V = K4n reacting gas and based on the law of
conservation of amount
V1/n1 = V2/n2 (Constant T and P)
P1 = PT × x1 (where P1 is a partial pressure, PT
 Ideal Gas Equation is a Total pressure, x1 is mole fraction)
PV = nRT Total pressure of Gaseous mixture at constant
Where R is Proportionality constant is also (P1 V1  P2 V2 )
known as Gas constant it is same for all Gases temperature : PT  (V1  V2 )
Value of R in different units
Aqueous Tension :Pmoist = Pdry gas + Pwater vapours
Magnitude Unit
0.0821 Litre-atm K–1 mol–1 Mass of water vapour present in certain volume of air
RH 
Maximum Mass of water vapour present in same
82.1 ML-atm K–1 mol–1 volume of air saturated by water vapour
62.1 Litre-mm-Hg K–1 mol–1
 Molecular Speed
0.083 Litre bar K–1 mol–1
8.314 Pascal m3 K–1 mol–1 2KT 2RT
Most probable speed = 
m M
8.314 × 107 erg K–1 mol–1
8.314 Joule K–1 mol–1 8RT 8KT
Average speed = 
1.987 Cal K–1 mol–1 M m
Density ; d = PM/RT
3RT 3KT
(d  P) ; (d  1/T) Root mean square = 
M m

8
Vmp : Vav : Vrms = 2: : 3


Page: 5
 Kinetic Energy  Critical Constant of the Gases

3
Tc or critical temp : Tc = 8a / 27Rb
Average Kinetic Energy = KT
2 Pc or critical pressure : PC = a/ 27b2
VC or critical volume : VC = 3b
3
Total Kinetic Energy = nRT
2 PC VC 3
ZC   (For all real gases)
RTC 8
Compressibility Factor (Z)  PV PVm 
Z   
 nRT RT   Van der Waal’s Equation Real Gas
 an 2 
Ideal gases Real gases  P  2  (V  nb)  nRT where a and b are Van
 V 
• zero volume • corrected equation
2 2
• zero attractive force (P + an /V )(V – nb) = nRT
der Waal’s constant.
• PV = nRT • non-zero volume a
•Z=1 • some intermolecular force  Boyle’s Temperature : Tb 
Rb

(+)ve (–)ve
•Z>1 •Z<1
• Repulsive forces • Attractive forces
• Difficult to compress • Easy to compress
•Difficult to Liquify • Easy to Liquify

 Energy-Distance for different ion-

Covalent Interaction
Types of Interaction Energy-distance
Functions
Ionic bond 1/r
Ion-dipole 1/r2
Dipole-dipole Stationary molecules - 1/r3
Rotating molecules - 1/r6
Ion-induced dipole 1/r4
Dipole-induced dipole 1/r6
London forces 1/r6

Page: 6
 5. Chemical Equilibrium
[B]  G or a reaction under any set of conditions is
 KC =
[A]
= mol L–1 related to its value under standard conditions,
i.e. G° by the equation
PB
 Kp = P = Partial Pressure ΔG  ΔG  2.303 RT log Q
A

XB
 Under equlibrium condtions, for same number
 Kx = X = mole fraction of moles of reactants and products
A
Q = KP = KC = K and G = 0
 KP = KC(RT)ng where ng = np – nR
 ΔG  2.303 RT log K
 Predicting the extent of reaction :
 KC > 103 [Forward reaction is favoured.]  We have replaced K P by K called
thermodyanmic equilibrium constant
 KC < 10–3 [Reverse reaction is favoured.]
 10–3 < KC < 103 [Both reactants and products Significance of G°
are present in equilibrium] Significance of G° can be explained from the
 Free Energy Charge (G) following points

a) If G = 0 then reversible reaction would be (i) If G° < 0, log K > 0,  K > 1
in equilibrium, KC = 1 Hence, reaction is spontaneas in forward
b) If G = (+) ve then equilibrium will be direction.
displaced in backward direction; KC < 1 (ii) Hence G° < 0, log K > 0, K < 1
c) If G = (–) ve then equalibrium will shift in Hence, reaction is non-spontaneous or a
forward direction; reaction proceeds in the forward direction to
KC > 1 such a small proceeds in the forward direction
to such a small extent that a very small amount
 (a) KC unit (moles/lit)n
of the product is formed.
(b) KP unit (atm)n (iii) If G°= 0, log K = 0, K = 1
 Reaction Quotient and Equilibrium Constant hence, it represents equilibrium.
Consider the following reversible reaction (iv) If G° is large negative number,
A+B C+D K > > 1, the forward reaction is nearly
complete.
[C][D]
  QC 
[A][B] (v) If G° is a very small positive number,
Case I : If QC < KC then : K < < 1, then reverse reaction is nearly
complete.
[Reactants] > [Products] then the system is not
at equilibrium  Mole of Representation of Reversible
Case II : If QC = KC then : reaction.
The system is at equilibrium. i. N2 + 3H2 2NH3 K C1
Case- III : If QC > KC then :
1 1
[Products] > [Reactants] K C1  K C1 
K C2 K 2C3
The system is not at equilibrium.
Page: 7
ii. 2NH3 N2 + 3H2 K C2 iv. Decrease of pressure (from less moles to more
moles)
1 v. For exothermic reaction decrease in temp.
K C1  K C2  K C5
K 2C4 1 (Shift forward)
vi. For endothermic increase in temp. (Shift
1 3 forward)
iii. N + H2 NH3 K C
2 2 2 3
 Effect of Temperature on Equilibrium
1 1 Constant
K C2  K C3 
K C2 3 K C4 According to Von’t Hoff Equation,

1 3 k = Ae H/RT
iv. NH3 N2 + H2 K C4
2 2 Where, K = rate constant, Ea = activation energy,
R = gas constant, T = absolute temperature and
1 e = exponential constant.
K  K C2  K C2
C44 K C5 4

k
2 H  1 1
iv. 2N2 + 6H2 4NH3 K C5 log k   2.303R  T  T 
1  2 1

 Le-Chatelier's principle where, T2 > T1

i. Increase of reactant conc. (Shift reaction First case : When H = 0; K2 = K1.

forward) Second case :When H = +Ve; K2> K1
ii. Decrease of reactant conc. (Shift reaction Thirds Case :When H = – ve; K1 > K2
backward)
iii. Increase of pressure (from more moles to less
log10 K log10K
moles)
T
a) Endothermic reaction T
(Plots of logK versus T) b) Exothermic reaction

6. Ionic Equilibrium
i. Lewis Acid (e– pair acceptor)  d.o.d of strong electrolyte > weak electrolyte

CO2, BF3, AlCl3, ZnCl2, normal cation. d.o.d. dielectric constant of solvent.

ii. Lewis Base (e– pair donor)   Buffer solution {Henderson equation} :
NH3, ROH, ROR, H2O, RNH2 normal anions. i. Acidic, pH = pKa + log {Salt/Acid}
For maximum buffer action pH = pKa
 Dissociation of Weak Acid and Weak Base
Range of buffer pH = pKa  1
i. Weak A ci d, K a = C2/(1 – x) or Ka = C2; < < 1
ii. Alkaline  pOH = pKb + log {Salt/Base} for
ii. Weak Base, Kb = C2/(1 – ) or Kb = C2; < < 1
max. buffer action pH = 14 – pKb
1 Range pH = 14 – pKb  1
d.o.d.  µ concentration
dilution
Moles / lit of Acid or Base mixed
d.o.d.  Temperature iii. Buffer Capacity = Change in pH

Page: 8
 Relation between ionisation constant (Ki) and  Solubility Product
degree of ionisation (): Classification of salt on the basis of their
solubility
2  2C
Ki   = (Ostwald's dilution law)
(1  )V (1  ) i. Soluble, Solubility > 0.1 M
ii. Slightly Soluble, 0.01 M < Solubility < 0.1 M
If is applicable to weak electrolystes for which
 < < 1 then AgCl(s) Ag+ + Cl–
Applying the law of chemical equilibrium, we
Ki have
  KiV  or V  C 
C
[Ag  ][Cl  ]
KC  or KC × [AgCl(s)] = [Ag+] [Cl–]
Common ion effect : [AgCl(s)]
 By addition of X mole/L of a common ion, to a [Ag+] [Cl–] = KC × constant = Ksp
weak acid (or weak base)  becomes equal to Ksp = solubility product
Ka  K b  Ksp : product of molar concentrations of the
  or  [where  = degree of dissociation]
X  X  ions (formed in the saturated solution at a
given temperature) raised to the power equal
 i. If solubility product > ions product then the
to the number of times each ion occurs in the
solution unsaturated and more of the balanced equation for solubility equilibrium.
substance can be dissolved in it.
 Application of Solubility Product
ii. If ionic product > solubility product the
solution is super saturated (principle of 1. Relation Between Ksp and S
precipitation). • General form
 Salt of weak acid and strong base : 

AxBy  xA+y + yB–x
pH = 0.5 (pKw + pKa + log c) a 0 0
Kh K  K w a–S xS yS
h= ; h K (h = degree of hydrolysis)
c a Ksp = [A+y ]x [B–x]y
Salt of weak base and strong acid: = [xs]x × [ys]y = xx.sx. yy.sy
pH = 0.5 (pKw – pKb – log c) K sp  x x y y S (x  y)

Kw 2. Predicting precipitation in reactions :

h
Kb  c
(a) If Qsp < Ksp, the solution is unsaturated.
Salt of weak acid and weak base : (b) If Qsp > Ksp, the solution is supersaturated and
pH = 0.5 (pKw – pKa – pKb) precipitation takes place.
(c) If Qsp = Ksp, the solution is just saturated and
Kw no precipitation takes place.
h
Ka  K b

Page: 9
 7. Thermodynamics
 First Law of Thermodynamcis : 1. for isothermal process :
E = Q + W
P1
Expression for pressure volume work ΔS = 2.303nR log 10 or
P2
W = –PV
V2
Maximum work in a reversible expansion : ΔS = 2.303nR log10
V1
Pl
W = – 2.303 n RT log V2  2.303 nRT log P 2. For isobaric process :
V1 2

Wrev  Wirr T 
ΔS = 2.303nCP log  2 
 T1 
 qv = cvT = U, qp = cpT = H

Enthalpy changes during phase 3. For isochoric process :

transformation T 
ΔS = 2.303 nCV log  2 
i. Enthalpy of Fusion  T1 
ii. Heat of Vapourisation
4. For adiabatic process
iii. Heat of Sublimation.
 q=0 so S = 0
 Enthalpy : H = E + PV = E + ngRT
Ssys = 0
 Kirchoff's equation : Ssurr. = 0
ET2  ET1  C V (T2  T1 ) [constant V] STotal = 0

HT2  ET1  CP (T2  T1 ) [contant P]

 Entropy and Spotaneity
STotal = Ssystem + Ssurroundings
 Entropy(s) :
Case I : For a spontaneous process STotal > 0
Meassure of disorder or randomness
Case II : For non spontaneous process STotal < 0
S = SP = – SR
Case III : When process is at equilibrium STotal = 0
q rev V P In a reversible adiabatic process, as q = 0,
S   2.03 nR log 2  2.303 n R log 1
T V1 P2
Ssys =Ssurr =STotal = 0
Entropy Changes in an Ideal Gas  Free energy change :

T2 P G = H – TS, G° = nFE°cell – G =

ΔS = 2.303nCp log + 2.303nR log 1
T1 P2 W(maximum) – PV, Gsystem = –TStotal

T2 V
ΔS = 2.303nCV log + 2.303nR log 2
T1 V1

Page: 10
 H S G Reaction characteristics
– + Alwasy negative Reaction is spontaneous at
all temperature
+ – Alwasy positive Reaction is nonspontaneos at
all temperature
– – Negative at low temp. Spontaneous at high temp.
but positive at high temp.
+ + Positive at low temp. Non spontaneous at low temp.
but negative at high temp & spontaneous at high temp.

 Isothermal process  Characteristics of Internal energy

1. T = 0 2. U  0 Ideal gas Real gas
3. q  0 4. H  0 U = f(T) only U =f (T, P or V)

 Adiabatic process When T is constant When T is constant

U = 0, H = 0 U  0, H  0
1. T  0 2. U  0
3. q  0 4. H  0  dU   dU 
  0   0
 dV T  dV T
 Graphical representation of thermodynamic
processes  Concept of Heat Capacity

q
(1) 1) Isobaric process Heat Capacity (s) C =
T
2) Isothermal process
P q
(2)
3) Adiabatic process Specific Heat Capacity (s) s =
mΔT
(4) (3)
4) Isochoric process
V q
Molar Heat Capacity (Cm) Cm =
nT
for expansion:
WIsobaric> WIsothermal > WAdiabatic > WIsochoric  Work Done in Adiabatic Process
for compression : As q = 0
WIsobaric> WAdiabatic > WIsothermal > WIsochoric U = W = nCVT
 Work for Osothermal Process W = nCV(T2 – T1)
For expansion for compression nR
W =   1 (T2  T1 )
1. V2 > V1 1. V1 > V2
2. W = – ve 2. W = +ve  Relation between CP and CV :
3. W = –Pext. (V2–V1) 3. W = + Pext. (V1–V2) CP – CV = R
4. W = – Pext. V 4. W = + Pext. V
5. Wmax.no. of moles

Page: 11
 8. Solid State
Total No.
of atoms
Unit Cell Corners Body Face per unit
cell
SCC 1/8 × 8 = 1 ---- ---- 1
BCC 1/8 × 8 = 1 1 ---- 2
FCC/CCP 1/8 × 8 = 1 ---- 6 × 1/2 = 3 4
End
Centred 1/8 × 8 = 1 ---- 2 × 1/2 = 1 2

Seven Primitive cells their Possible variations as centred unit cells

Possible Axial distances Axial angles
Crystal system variations or edge lengths
Cubic Primitive
Body-centred a=b=c  = 90°
Tetragonal Primitive, a=bc  = 90°
Body-centred
Orthorhombic Primitive, a  a c  = 90°
Body- centred,
Face-centred,
End-centred
Rhombohedral Primitive a=b=c   90°
or Trigonal
Hexagonal Primitive a = b c = 90°,  = 120°
Monoclinic Primitive, a  b c = 90°,  120°
End-centred
Triclinic Primitive a  b c   90°

S.C. B.C.C. F.C.C. H.C.P.

No. of atom 1 2 4 6
P.E. 52.4% 68% 74% 74%
Void space 47.6% 32% 26% 26%
C.N. 6 8 12 12
No. of T.V. 0 0 8 12
No. of O.V. 0 0 4 6

a 3a a a
Relationship between r r r r=
2 4 2 2 2
edge length and radius
Type of Packing AAA Type ABCABC Type ABAB AB type

Page: 12
 • Max No. of O.V. in one body diagonal = 1
ZM
• d
N A  aq a
• 1st Nearest distn betn two O.V. =
d = density z = number of atom in a unit cell. 2

NA = 6.022 × 1023 • Distn betn edge center’s O.V. & Body center’s

Square Close Packing a

O.V. =
2
• The spheres in the adjacent row lie just one
over & show a horizontal & vertical alignment
 3
• Co-ordn 4 • Diamond = = 0.34
6
• Packing fraction = 78.5%
Defects in Crystal Structure :
Hexagonal Close Packing
Imperfection of Solids
• The spheres in every second row are seated in 2 Types
the depression.
• Co-ordn 6 Electronic imperfections Atomic imperfections
or
• Packing fraction = 90.75% (91%) Point Defects
Tetrahedral Void
• Co-ordn = 4 Stoichiometric Non-Stoichiometric Impurity
defect defect defects
rvoid
• Radius Ratio= r  0.225
sphere Vacancy Interstitial Schottky Frenkel
defects defects defects defects
• T.V’s. Location at body diagonal density
density  density  density  (constant)
• Max No. of T.V. in one body diagonal = 2
Shown by Shown by
• 1st Nearest distn betn two T.V. = a/2 non-ionic solids ionic solids

a Metal excess defect Metal deficiency defect

• 2nd Nearest distn betn two T.V. = 2
density 

 Radius ratio and co-ordination number (CN)

3a
• 3nd Nearest distn betn two T.V. =
2 Limiting radius ratio CN Geometry
[0.155  0.225] 3 [Plane triangle]
3a [0.255  0.414] 4 [Tetrahedral]
• Distn betn Corner atom & T.V. =
4 [0.414  0.732] 6 [Octahedral]
• Ratio betn T.V. & O.V. = 2 : 1 [0.732  1] 8 [bcc]

• Ratio betn T.V. & O.V. at 1 body digaonal=2:1  Relationship between radius of void (r) and
3a the radius of the sphere (R): r (tetrahedral)
• Distance Between O.V. & T.V. =
4 = 0.225 R; r (octahedral) = 0.414 R

Octahedral Void  Paramagnetic : Presence of unpaired electrons

[attracted by magnetic field]
• Co-ordn = 6
 Ferromagnetic :
r
• Radius Ratio= void  0.414 Permanent magnetism []
rsphere
 Antiferromagnetic :
• O.V’s. Location at body center & as well as
edge center Net magnetic moment is zero []
Page: 13
 9. Solutions
Pressure of the Gas (or) Henry’a Law : number of equivalents
 Normality (N) = volume of the solution in litres
 The mass of a gas dissolved per unit volume
of solvent is proportional to the pressure of
number of moles
the gas at constant temperature.  Molairty (M) = volume of the solution in litres
 m  p or m = kp where k is Henry’s constant
 The partial pressure of the gas is proportional  Raoult's law
to the mole fraction of the gas (x) in the P = pA + pB = p° AXA + p° BXB
solution” and it is expressed as p = KHx Here
 Characteristics of an ideal solution :
KH is the Henry’ s law constant.
(i) sol V = 0 (ii) sol H = 0
PP  K H Xgas PP  K Hso lub ility  Relative lowering of vapour pressure
Partial pressure of HCl/torr

1000 PA  PA PA  PA nB

= PA
; PA = X B
= nA  nB
500
 Colligative  Number of particles ions/moles
of solute properties
 Depression of freezing point, Tf = Ktm

0 0.010 0.020  Elevation in boiling point with relative

Mole fraction of HCl in its lowering of vapour pressure
Solution in cyclohexane
1000K b  p  p 
Tb   
1 1 M 1  p  (M1 = mol. wt. of solvent)
KH  Solubility 
Solubility Temp
 Osmotic pressure (P) with depression in
Solubility  p
dRT
massGas  p freezing point Tr P = Tr × 1000K
f

nGas  p  Relation between Osmotic pressure and other

colligative properties :
Positive Deviation Negative Deviation
a) Acetone + Ethanol a) Acetone + Aniline PA0  PA dRT
i.   Relative lowering of vapour
PA0 MB
b) Acetone + CS2 b)Acetone + CHCl3
c) Acetone + C6H6 c) CH3OH+CH3COOH pressure

d) H2O + CH3OH d) H2O + HNO3 dRT

ii.   Tb  Elevation in boiling point
1000K b
e) H2O + C2H5OH e) CHCl3+C2H5O–C2H5
f) CCl4 + toulene f) H2O + HCl dRT
iii.   Tf  Depression in freezing point
g) CCl4 + CHCl3 g)CH3COOH+Pyridine 1000K f

h) CCl4 + CH3OH h)CHCl3 + Normal molar mass Observed colligative property

i  Observed molar mass  Normal colligative property
i) + C2H5OH

Page: 14
 n Solute association
 Degree association a = (1 – i)
n 1
&
If a solute is associated in solutions, n
i 1 molecules associate and  is the degree of
degree of dissociation ()  association,
n 1
nA An
Abnormal Molar mass
Initial moles 1 0
 Electrolytes undergo ionisation in aqueous
Number of moles after dissociation 1– n
solutions as a result number of particle in the
solution increases hence magnitude of
1i
colligative properties increases. 
Degree of ionisation, 1 1
n
van’t Hoff’s factor (i) =

observed colligativ e properties Colligative properties with Van’t Hoff factor :

a) i = calculated colligativ e property (or) Inclusion of van’t Hoff factor modifies the
equations for colligative properties as,
Calculated molar mass of solute • Relative lowering of vapour pressure of
b) i = experimental molar mass of solute (or)
solvent,

total number of moles of particles p  p

 iX solute
after dissociation or association p
c) i = number of moles of particles
before dissociation or association Depression of freezing point, Tf = iKfm
Elevation of boiling point, Tf = iKbm
Normal / actual / Calculate / Original M wt of solute
d) i  Abnormal / Observed / Theorical M of solute Osmotic pressure of solution,  = iCST
wt

Solute dissociation (or) Ionisation

If a solute is dissociated or ionised in solutions
to give ‘n’ ions and ‘  ’ is the degree of
ionisation,
An  nA
Initial moles 1 0
Number of moles after dissociation
1  n

i 1
Degree of ionisation, α 
n1

Page: 15
 10. Electrochemistry
 Faraday’s 1st Law  Under standard conditions (Eo)
Eocell = EoRP(cathode) – EoRP(anode) (or)
The mass of substance deposited at an electrode
is directly proportional to charge pass through Eocell = EoOP(anode) – EoOP(cathode) (or)
it. Eocell = EoOP(anode) + EoRP(cathode)
Mass  Charge (Q)  Nernst Equation
WQ
E = E  0.0591 log 10 [Pr oducts ]
W = ZQ (Z = electrochemical equivalent) n [Re ac tan ts ]

(Q = Charge in Coulombs)
  nE 
& E Cell  Eright  Eleft & K eq . = antilog 
W=ZIt  0.0591 
I = current in Ampere G = – nFEcell &
t = time in seconds G°= – nFE°cell = – 2.303 RT logKc
W = Z Q (Q = 1C) Remember
 G 
then W=Z & Wmax= + nFE° & G = H + T  T 
 P
1 F charge deposits
 Application of Nernst Equation
1 g eq of any substance
To find the Ecell of concentration cells
EIt
So W= sec of substance 0.059 C 
F Ecell = log10  2  (for concn cell Eocell = 0)
n  C1 
= No. of faradays
To find the pH of concentration cell
 Faraday’s 2nd Law
For the measurement of Eq. constant (K)
If equal electricity is passed through two or
more cells connected in series then the mass
0.059
of substance deposited is directly proportional E 0cell = log 10K C
n
to equivalent mass
 Calculation of pH of an electrolyte by using a
W1  E1 calomel electrode :
W2  E2
E cell  0.2415
pH =
W1 W2 0.0591

E1 E2
 Thermodynamic efficiency of fuel cells :

 eq  G  nFE cell
 Degree of dissociation :     For H2 – O2 fuel cells it is 95%.
0eq H H

 P = KH.X
 Kohlraush's law : 0m  x0A  y0B

Page: 16
 Summing-up the Units of Different Quantities
S.N. Physical Symbol Expression Commonly used Units SI Units

V
1. Resistance Rq R= omh () omh ()
I

1
2. Conductance G R= omh–1 (–1) seimen(S)
R

a
3. Specific resistance  = ohm cm ohm m
1

l 1 l l
4. Conductivity k kG   ohm–1 cm–1 (–1 cm–1) S m–1
a Ra p

k
5. Equivalent eq  eq  ohm–1 cm2 eq–1(–1 cm2eq–1) S m2 eq–1
normality

conductivity

k
6. Molar conductivitym m  ohm–1 cm2 eq–1(–1 cm2eq–1) S m2 mol–1
molarity

l
7. Cell constant G* G*  cm–1 m–1
a

Effect of dilution on
Conductance  Increases
m & eq  Increases
Conductivity  Decreases
Debye–Huckel–Onsager equation :
m = m – b C (or) eq =oeq – b C
m = Molar conductance at given concentration
m = Molar conductance at infinite dilution
C = concentration in molarity.
b = Constant value depends on type of electrolyte, solvent & temp.
• With dilution the Degree of dissociation of weak electrolyte increases, so m increases.

Page: 17
 11. Chemical Kinetics
 Rate of reaction = Rate of disappearance of A
Decrease in concentration of A Increase in concentration of B
 = Rate of appearance of B 
Time interval Time interval
Order Integrated rate equation Unitss of k Straight line t1/2 proportional
obtained by to
plotting t vs
1
0 k
t
[A0 ]  [A] mol L–1 s–1 a–x a

2.303 a
1 k log s–1 log (a – x) independent of a
t ax

x 1 1
2 k or L mol–1 s–1
ta(a x) (a  x) a

2.303 b(a x) 1
k log L mol–1 s–1
t(a  b) a(b x) a

1  1 1  1 1
n k  n 1
 n 1  Ln–1 mol1–n s–1
t(n  1)  (a  x) a  (a x)n 1 a n 1

 Some important graphs of diffrent order of reactions are given below :

(a) Plots of rate vs concentrations

Zero order 1st order 2nd order 3rd order

Rate
Rate
Rate

Rate

Concentration Concentration (Concentration)2 (Concentration)3

(b) Plots of integrated rate equations

Zero order First Order Second Order Third Order

Intercept = [R]0
Slope = – k Slope 
k Slope = k Slope = k
2.303
log [R]

[R] 1 1
[R] [R]0
} Intercept = 1/[R] 0 } Intercept = 1/[R] 0
2

Time ‘t’ Time ‘t’ Time ‘t’ Time ‘t’

(c) Plots of half-lives vs initial concentration

Zero order 1st order 2nd order 3rd order

t1/2 t1/2 t1/2 t1/2

Initial conc. (a) Initial conc. (a) 1/a 1/a2

Page: 18
 If reaction completion is given in percent, then This is an equation of straight line of the form
take initial concentration (a) 100 and if reaction y = mx + c.
completion is given in fraction, then take initial If we draw a graph between log k and (1/T),
concentration as 1. we get a straight line with slope equal to
Questions based on t1/2 can be solved by another
E a
method also based on following diagram. .
2.303R
 Order of reaction It can be fraction, zero or
any whole number.
 Molecularity of reaction is always a whole Ea
Slope =
number. It is never more than three. It cannot 2.303R

log k
be zero.
 First Order Reaction :
1
2.303 a 0.693 T
k log 10 & t 1 / 12  [A]t  [A]0 e kt
t ( a  x) k
Ea can be calculated by measuring the slope of
a
 Zero Order Reaction : x = kt and t1/ 2  the lines. Ea = –slope × 2.303 R
2k
If k1 and k2 are rate constants at temperatures
The rate of reaction is independent of the T1 and T2 respectively then,
concentration of the reacting substance.
 Time of nth fraction of first order process, k2 Ea  T2  T1 
log   
k 1 2.303R  T1T2 
 
2.303  1 
t1/ n  log  Ea
k  1  1  Factor e  RT in the Arrhenius equation is known
 n 
as ‘Boltzmann factor’.
 Amount of substance left after 'n' half lives =
Activation Energy
[A]0
2n The minimum amount of energy absorbed by
the reactant mole ules so that their energy
 Arrhenius gave a mathematical expression to
becomes equal to threshold energy is called
deduce the relationship between rate constant
activation energy.
and temperature.
Or, we can say that it is the difference between
k  Ae  Ea /RT
threshold energy and the average kinetic
energy possessed by reactant molecules.
where, A is frequency factor and it is constant
Ea is activation energy Activation energy = Threshold energy –
R is gas constant, T is temperature Average kinetic energy of reactant.
On taking log on both sides Ea
Arrhenius equation : log k =   log A
2.303RT
Ea
ln k = ln A –
RT This is an equation of straight

Ea
Arrhenius equation : log k =   log A
2.303RT

Page: 19
 ET Activation complex
Threshold
energy Activation
Ea energy
ER
Average kinetic Energy evolved
energy of reactants
H
EP
Energy 

Products

Progress of reaction

Rate constant at (T+10°)

Temperature coefficient (n) = Rate constantat T

12. Surface Chemistry

 Emulsion : Colloidal soln. of two immiscible liquids [O/W emulsion, W/O emulsion]
 Emulsifier : Long chain hydrocarbons are added to stabilize emulsion.
 Lyophilic colloid : Starchy gum, gelatin have greater affinity for solvent.
 Lyophobic colloid : No affinity for solvent, special methods are used to prepare sol.
[e.g. A s2S3, Fe(OH)3 sol]
 Preparation of colloidal solution :
i. Disperision methods ii. Condensation method
 Properties of colloidal solution :
i. Tyndal effect ii. Brownian movement
iii. Coagulation iv. Filtrability
 Positively charged colloid Negatively charged colloid
Hydrated metallic oxide Metal Cu, Ag, Au, Sol
Al2O3.xH2O, CrO3.xH2O, Fe2O3.xH2O Metallic sulphides As2S3, Sb2S3, CdS sol
Basic dye stuffs methylene blue sol, Acid dy stuff eosin, congo red
Haemoglobin (blood)
Oxide TiO2 Sol Sols of starch, gum gelatin, clay
 Hardy Schulze Rule- This rule states that the precipitating effect of an ion on dispersed phase of
opposite charge increases with the valency of the ion.
• The higher the valency of the flocculating ion, the greater is its pricipitating power. Thus for the
precipitation of As2S3sol (–ve) the precipitating power of Al3+, Ba2+, and Na+ ions is in the order Al3+ >
Ba2+ > Na+.
• Similarly for precipitating Fe(OH)3 sol (positive) the precipitating power of [Fe(CN)6]–3, SO42– and Cl–
ions is in the order
[Fe(CN)6]3– > SO42– > Cl–

Page: 20
• The minimum concentration of an electrolyte i. Freundlish adsorption isotherm :
in milli moles required to cause precipitation
For physisorption, Freundlish explained the
of 1 litre sol in 2 hours is called
variation in adsorption due to the change in
FLOCCULATION VALUE. The smaller the
pressure graphically and mathematically as
flocculating value, the higher will be the
follows :
coagulating power of the ion.
Here Adsorbate - Gas and Adsorbent - Solid
1
Flocculation value  Flocculation power
C D
 x
 Gold Number m B
 
• The number of a hydrophilic colloid that will
A
jsut prevent the precipitation of 10 ml of P
standard gold sol on addition of 1 ml of 10%
NaCl solution is known as Gold number of Case-I At low pressure (A B)
that protector (Lyophilic colloid). x
P
• The precipitation of the gold sol is indicated m
by a colour change from red to blue when the Case-II At high pressure (C D)
particle size just increases.
x
 P0
• The smaller the gold number of a protective m
Lyophilic colloid, greater is its protection
Case - III At intermediate pressure (B C)
power.
• Note : Gelatin and startch have the maximum x
 P1/n [Where n = 1 to ]
& minimum protective powers. m

1 x
The resultant condition  KP1/n
• Protection Capacity  Gold number m
At low pressure n = 1
 Effect of temperature :
At high pressure n = 
x At intermediate pressure 1 < n < 
 Extent of Adsorption  m 
 
 The value of (1/n) ranges from 0 to 1.
x  Mass of adsorbate Here,
m  Mass of adsorbent x  Mass of adsorbate
m  Mass of adsorbent
At constant At constant
x pressure x pressure p  pressure of adsorbate gas
m m K and n  Constants that depends on the
nature of adsorbate and adsorbent.
Temperature  Temperature 
[A] Physisorption [B] Chemisorption

 Effect of pressure :
The variation in extent of adsorption with
change in pressure at constant temperature can
be explained with the help of some graphs
called as adsorption isotherms.

Page: 21