Physical Chemistry [1] / NLI

PHYSICAL CHEMISTRY-IMPORTANT POINTS

STOICHIOMETRY

Mass of one atom of an element

 Total Number of nucleons
• Relative atomic mass (R.A.M) = 1  mass of one carbon atom
12
• Y-map

Density :

density of the subs tance PM

Specific gravity  0 
density of water at4 C RT

dgas PMgas / RT Mgas Mgas

Vapour density V.D.  d  PM 
MH2

2
H2 H2 / RT

Mgas  2 V.D.
Mole-mole analysis :

Concentration terms :
Molarity (M) :

w  1000
 Molarity  M 
 mol. wt of solute   Vinml

Molality (m) :

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Number of moles of solute

Molality   1000  1000 w1 / M1w 2
mass of solvent in gram
Mole fraction (x) :

n N
 Mole fraction of solution  x1   Mole fraction of solvent  x 2  
n N nN
x1 + x2 = 1

% Calculation :

massof solute in gm
(i) %w / w   100
mass of solution ingm

massof solute in gm
(ii) %w / v   100
mass of solution ingm

Volume of solution in ml
(iii) %v / v   100
Volume of solution
Derive the following conversion :

x2  1000
Mole fraction of solute into molarity of solution M  x M  M x
1 1 2 2

MM1  1000
Molarity into mole fraction x2 =   1000  MM
2

x2  1000
Mole fraction into molality m  x1M1

mM1
Molality into mole fraction x 2  1000  mM
1

m   1000
Molality into molarity M  1000  mM
2

M  1000
6. Molarity into Molality m  1000  MM
2

M1 and M2 are molar masses of solvent and solute.  is density of solution (gm/mL)
M = Molarity (mole/lit.), m = Molality (mole / kg), x1 = Mole fraction of solvent, x2 = Mole fraction of solute
Average/Mean atomic mass :

a1x1  a2 x 2  ....  an xn
Ax 
100
Mean molar mass or molecular mass :

j n

n1M1  n2M2  ....nnMn

n Mj1
j j

Mavg.  or Mavg.  jn

n1  n2  ....nn
n
j1
j

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Calculation of individual oxidation number :
Formula : Oxidation Number = number of electrons in the valence shell - number of electrons left after bonding
Concept of Equivalent weight/Mass :

Atomic weight
For elements, equivalent weight (E) =
Valency  factor

M
For acid/base, E Where M = Molar mass
Basicity / Acidity

M
For O.A./R.A. E
no. of moles e  gained / lost

Atomic or molecular weight

Equivalent weight (E) =  v.f.  valency factor 
w.f.
Concept of number of equivalents :

Wt W W
No. of equivalents of solute =   
Eq. wt. E M/ n
No. of equivalents of solute = No. of moles of solute × v.f.
Normality (N) :

Number of equivalents of solute

Normality N 
Volume of solution  in litres 

Normality = Molarity × v.f.

Calculation of valency Factor :
n-factor of acid = basicity = no. of H+ ion(s) furnished per molecule of the acid.
n-factor of base = acidity = no. of OH– ion(S) furnished by the base per molecule.
At equivalence point :
N1V1 = N2V2
n1M1V1 = n2M2V2
Volume strength of H2O :
20V H2O2 means one litre of this sample of H2O2 on decomposition gives 20 lit. of O2 gas at S.T.P.

Valume,strengthof H2O 2
Normality of H2O2 (N) =
5.6

Volume strength H2O 2

Molarity of H2O2 (M) =
11.2
Measurement of Hardness :

mass of CaCO3
Hardness in ppm   106
Total mass of water
Calculation of available chlorine from a sample of bleaching powder :

3.35  x  V  mL 
% of Cl2  W /  g where x = molarity of hypo solution and v = mL. of hypo solution used in titration.

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ATOMIC STRUCTURE
4KZe2
Estimation of closest distance of approach (derivation) of -particle R  2
m V

The radius of a nucleus : R = R0(A)1/3cm

hc
Planck's Quantum Theory : Energy of one photon = hv =


1
Photoelectric effect : hv  hv 0  me v 2
2
Bohr's Model for Hydrogen like atoms :

h
1. mvr  n (Quantization of angular momentum)
2
2
E1 2 18 z z2 z2me4
2. En   z  2.178  10 J / atom  13.6 eV ; E1 
n2 n2 n2 n2

n2 h2 0.529  n 2 0
3. rn   2 2  A
Z 4 e m Z

2ze 2 2.18  106  z

4. v  m/s
nh n
De-Broglie wavelength :

h h
   for photon
mc p
Wavelength of emitted photon :

1  1 1
 v  RZ2  2  2 
  n1 n2 
No. of photons emitted by a sample of H atom :

n  n  1
2
Heisenberg's uncertainty principle :

h h h
x.p  or mx.v  or x.v 
4 4 4m
Quantum Numbers :
• Principal quantum number (n) = 1, 2, 3, 4....to 

nh
• Orbital angular momentum of electron in any orbit =
2
• Azimuthal quantum number (l) = 0, 1, .... to (n–1)
• Number of orbitals in a subshell = 2l + 1
• Maximum number of electrons in particular subshell = 2 × 2 (2l + 1)

h  h
• Orbital angular momentum L  l  l  1  h l l  1 h  2 
2  

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GASEOUS STATE
Temperature Scale :

CO K  273 F  32 R  R O

  
100  0 373  273 212  32 R 100   R O  where R = Temp. on unknown scale.

Boyle's law and measurement of pressure :

1
At constant temperature, V
P
P1V1 = P2V2
Charles law :

V1 V2
At constant pressure, VT or 
T1 T2

Gay - lussac's law :

At constant volume , P T

P1 P2
  temp on absolute scale
T1 T2

Ideal gas Equation :

PV = nRT

w d
PV  RT or P  RT or Pm  dRT
m m
Daltons law of partial pressure :

n1RT n RT n RT
P1  , P2  2 , P3  3 and so on
v v v
Total pressure = P1 + P2 + P3 + ......
Partial pressure = mole fraction X Total pressure.
Amagat's law of partial volume :
V = V1 + V2 + V3 +.......
Average molecular mass of gaseous mixture :

Total mass of mixture n1M1  n2M2  n3M3

Mmix = Total no. of moles in mixture  n1  n2  n3

Graham's Law :

1
Rate of diffusion r  ; d = density of gas
d

r1 d2 M2 V.D2
  
r2 d1 M1 V.D1

Kinetic Theory of Gases :

1
PV  mN U2 Kinetic equation of gases
3

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1 2 3 3
Average K.E. for one mole = NA  mU   KNA T  RT
 2  2 2
• Root mean suqare speed

3RT
Urms  molar mass must be kg/mole.
M
• Average speed
Uav = U1 + U2 + U3 + ........UN

8RT 8KT K is Boltzmman constant

Uavg.  
M m
• Most probable speed

2RT 2KT
UMPS  
M m
Vander wall's equation :

 an2 
 P  2   v  nb   nRT
 v 

• Critical constants :

a 8a
Vc  3b, Pc  2
, Tc 
27b 27Rb
Vander wall equation in virial form :

 b b2 b3  a 1  a  b2 b3
Z  1   2  3  ......    1  b     ........
 Vm Vm Vm  VmRT Vm  RT  Vm2 Vm3

Reduced Equation of state :

 3 
 Pr  2   3Vr  1  8T,
 Vr 

THERMODYNAMICS
Thermodynamic processes :
1. Isothermal process : T = constant
dT = 0
T = 0
2. Isochoric process : V = constant
dV = 0
V = 0
3. Isobaric process : P = constant
dP = 0
P = 0
4. Adiabatic process : q=0
or heat exchange with the surrounding = 0(zero)
IUPAC Sign convention about Heat and Work :
Work done on the system = Positive
Work done by the system = Negative
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1st Law of Thermodynamics

U   U2  U1   q  w
Law of equipartion of energy :

f
U nRT (only for ideal gas)
2

f
E  nR ( T)
2
where f = degrees of freedom for that gas. (Translational + Rotational)
f = 3 for monoatomic
=5 for diatomic or linear polyatmic
=6 for non-linear polyatmic
Calculation of heat (q) :
Total heat capacity :

q dq
CT    J /0 C
T dT
Molar heat capacity :

q dq
C   J mole1K 1
nT ndT

R R
CP  Cv 
 1  1
Specific heat capacity (s) :

q dq
S   Jgm1K 1
mT mdT
Work Done (w) :
Isothermal Reversible expansion/compression of an ideal gas :

W  nRT in  Vf / Vi 
Reversible and irreversible isochoric processes .
Since dV = 0
So dW = – Pext. dV = 0
Reversible isobaric process :
W = P (Vf – Vi)
Adiabatic reversible expansion :
1 1
 T2 V2  T1V1
Reversible Work :

P2 V2  P1V1 nR  T2  T1 
W 
 1  1
Irreversible Work :

P2 V2  P1V1 nR  T2  T1  PV P V
W  nC v  T2  T1   Pext  V2  V1  and use 1 1  2 2
 1  1 T1 T2

Free expansion - Always going to be irrerversible and since Pext = 0

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so dW = – Pext. dV = 0
If no. heat is supplied q = 0
then E = 0 so T = 0
Application of Ist Law :
  Q  W  W  PV
  U  Q  P V
Constant volume process
Heat given at constant volume = change in internal energy

 du   dq  v

du = nCvdT

1 du f
Cv  .  R
n dT 2
Constant pressure process :
H  Enthalpy (state function and extensive property)
H = U + PV

 Cp  Cv  R  only for idealgas 

Second Law of Thermodynamics :
Suniverse  S system  S surrounding  0 for a spontaneous process.
Entropy (S) :
B
dqrev
S system  
A
T

Entropy calculation for an ideal gas undergoin a process :

irr
State A 
Sirr
 State B
P2, V2, T2

T2 V
Ssystem  nc v ln  nR ln 2 (only for an ideal gas)
T1 V1

Third Law of Thermodynamics :

The entropy of perfect crystals of all pure elements and compounds is zero at the absolute zero of temperature.
Gibb's free energy (G) : (State function and an extensive property)
Gsystem  Hsystem  TS system
Criteria of spontaneity :
(i) If Gsystem is (–ve) < 0  process is spontaneous
(ii) If Gsystem is > 0  process is non spontaneous
(iii) If Gsystem = 0  system is at equilibrium
Physical interpretation of G :
• The maximum amount of non-expansional (compression) work which can be performed.

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G  dWnonexp  dH  TdS.
Standard Free Energy Change (G0) :
1. G0 = –2.303 RT log10 K
2. At equilibrium G = 0
3. The decrease in free energy (–G) is given as :

V2
G  Wnet  2.303 nRT log10
V1

4.  Gf0 for elemental state = 0

5. G0f  Gproducts
0 0
 GReac tants

Thermochemistry :

Change in standard enthalpy H0  Hm,2

0
 H0m,1
= heat added at constant pressure. = CPT.
If Hproducts > Hreactants
 Reaction should be endothermic as we have to give extra heat to reactants to get these converted into products

and if Hproducts  Hreac tan ts

 Reaction will be exothermic as extra heat content of reactants will be released during the reaction.

Enthalpy change of a reaction : Hreaction  Hproducts  Hreac tan ts

0
Hreactions  H0products  Hreac
0
tants

= positive – endothermic
= negative – exothermic
Temperature Dependence of H : (Kirchoff's equation) :
For a constant volume reaction

H02  H10  CP  T2  T1 

where CP  CP (products) – CP (reactants)

for a constant volume reaction

E02  E10   C V .dT

Enthalpy of Reaction from Enthalpies of Formation :

The enthalpy of reaction can be calculated by

H0r   B Hf,0 products   B H0f, reac tantsB is the stoichiometric coefficient.

Estimation of Enthalpy of a reaction from bond Enthalpies :

 Enthalpy required to   Enthalpy released to 

   
H   break reac tan t int o    form products from the 
 gasesous atoms   gasesous atoms 
   
Resonance Energy :

H0resonance  H0f, experimental  H0f, calculated

 H0c, calculated  H0c, exp erimental

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CHEMICAL EQUILIBRIUM
At equilibrium :
i) Rate of forward reaction = rate of backward reaction
ii) Concentraion (mole/litre) of reactant and product becomes constant.
iii) G = 0
iv) Q = Keq.

Equilibrium constant (K) :

rate cons tan t of forward reaction K

K  f
rate cons tan t of backward reaction K b

Equilibrium constant in terms of concentraction (KC) :

Kf [C]c [D]d
 KC 
Kb [A]a [B]b

Equilibrium constant in terms of partial (KP) :

[PC ]c [PC ]d
KP 
[PA ]a [PB ]b

Equilibrium constant in terms of partial (Kx) :

x cC x Dd
Kx 
x aA x Bb

Relation between KP & KC :

KP = KC . (RT)n.

Relation between KP & KX :

KP = Kx (P)n.

K2 H  1 1 
• log    
K1 2.303R  T1 T2  ; H = Enthalpy of reaction

Relation between equilibiurm constant & standard free energy change :

Go = –2.303 RT log K

Reaction Quotient (Q) :

[C]c [D]d
The values of expression Q 
[A]a [B]b
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Degress of Dissoication () : : 117/N/57, Kakadeo, Kanpur. Ph.: (0512) 2505235, 2505236, 9151550550
 = no. of moles dissociated / initial no. of moles taken
= fraction of moles dissociated out of 1 mole.
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Note : % dissociation = × 100

molecular weight of equilibrium mixture

Observed molecular weight of An(g) = total no. of moles

Dd M  Mo
  T
(n  1)  d (n  1)Mo

External factor affecting equilibrium :

Le Chatelier's Principle :
It a system at equilibrium is subjected to a disturbance or strees that changes any of factors that determine the state
of equilibrium, the system will react in such a way as to minimize the effect of the disturbance.

Effect of concentration :
If the concentration of reactant is increased at equilibrium then reaction shift in the forward direction.
If the concentration of product is increased then equilibrium shift in the backward direction.

Effect of volume :
If volume is increased pressure decreases hence reaction will shift in the direction in which pressure increases that
is in the direction in which number of moles of gases increases and vice versa.
If volume of increased then, for
n > 0 reaction will shift in the forward direction
n < 0 reaction will shift in the backward direction
n = 0 reaction will not shift.

Effect of pressure :
• If pressure is increased at equilibrium then reaction will try to decrease the pressure, hence it will shift in the direction
in which less no. of moles of gases are formed.

Effect of inert gas addition :

i) Constant pressure :
If inert gas is added then to maintain the pressure constant, volume is increased. Hence equilibrium will shift in the
direction in which larger no. of moles of gas is formed
n > 0 reaction will shift in the forward direction
n < 0 reaction will shift in the backward direction
n = 0 reaction will not shift.
ii) Constant volume :
Inert gas addition has no effect at constant volume.

Effect of Temperature :
Equilibrium constant is only dependent upon the temperature.

1 Ho  So
If plot of nk vs is plotted it is a straight line with slope =  , and intercept =
T R R
• For endothermic (H > 0) reaction value of the equilibrium constant increases will the riese in temperature.
• For exothermic (H < 0) reaction value of of the equilibrium constant decreases will increase in temperature.
• For H > 0, reaction shifts in the forward direction will increase in temperature.

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• For H < 0, reaction shifts in the backward direction will increase in temperature.
• If the concentration of reactant is increased at equilibrium then reactions shift in the forward direction.
• If the concentration of product is increased then equilibrium shifts in the backward direction.

Vapour Pressure of Liquid :

Partial pressure of H2 O vapours

Relative Humidity = Vapour pressure of H O at that temp.
2

Thermodynamics of Equilibrium :
G = Go + 2.303 RT log10 Q

 K1  Ho  1 1 
Vant Hoff equation - log      
 K 2  2.303 R  T2 T1 

IONIC EQUILIBRIUM
1. OSTWALD DILUTION LAW :

[H ][A  ] [C][C ] C 2

* Dissociation constant of weak and (Ka), K a   
[HA] C(1   ) 1  

Ka
If  << 1, then 1 –   1 or Ka = c2 or    Ka  V
C

Kb
* Similarly for a weak base,   . Higher the value of Ka / Kb, strong is the acid/base.
C

Acidity and pH Scale :

 pH = – log aH, (where aH is the activity of H+ ions = molar concentration for dilute solution).
[Note : pH can also negative or > 14]
pH = –log [H+]; [H+] = 10–pH
pOH = –log [OH–]; [OH–] = 10–pOH
pKa = –log Ka; Ka = 10–pKa
pKb = –log Kb; Kb = 10–pKb

PROPERTIES OF WATER :
1. In pure water [H+] = [OH–] so it is neutral.
2. Moler concentration / Molarity of water = 55.56 M.
3. Ionic product of wate (Kw) :
Kw = [H+] [OH–] = 10–14 at 25o (experimentally)
pH = 7 = pOH  neutal
pH < 7 or pOH > 7  acidic
pH > 7 or pOH < 7  basic
4. Degree of dissoication of water :

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no. of moles dissociated 10 7

  = 18 × 10–10 or 1.8 × 10–7%
total no. of moles initially taken 55.55

5. Absolute dissociation constant of water :

[H ][OH ] 107  10 7

Ka  Kb    1.8  10 16
[H2 O] 55.55
pKa = pKb = – log (1.8 × 10–16) = 16 – log 1.8 = 15.74
Ka × Kb = [H+] [OH–] = Kw

Note : for a conjugate acid-base pairs

pKa + pKb = pKw = 14 at 25oC
pKa of H3O+ ions = –1.74
pKb of HO– ions = –1.74.
* pH Calculation of Different Types of Solutions :
a) Strong acid solution :
i) If concentration is greater than 10–5 M
In this case H+ ions coming from water can be neglectd.
ii) If concentration is less than 10–5 M
In this case H+ ions coming from water cannot be neglectd.

b) Strong base soluiont :

Using similar method as in part (a) calculate first [OH–] and then use [H+] × [OH–] = 10–14

c) pH of mixture of two strong acids :

Number of H+ ions from I-solution = N1V1
Number of H+ ions from II-solution = N2V2
N1V1  N 2 V2
[H ]  N 
V1  V2

d) pH of mixture of two strong bases :

N1V1  N 2 V2
[OH ]  N 
V1  V2

e) pH of mixture of a strong acid and a strong base :


N1V1  N 2 V2
If N1V1 > N2V2, then solution will be acidic in nature and [H ]  N 
V1  V2

 N2 V2  N1V1
If N2V2 > N1V1, then solution will be basic in nature and [OH ]  N  V1  V2

f) pH of a weak acid (monoprotic) solution :

[H ] [OH ] C 2
Ka  
[HA] 1 

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Ka
If  << 1 (1 – )  1  Ka C2    (is valid if  < 0. 1 or 10%).
C

On increasing the dilution  C     and [H ]   pH 

g) pH of a solution of a polyprotic weak acid :

1
pH 
2

pK a1  logC 

RELATIVE STRENGTH OF TWO ACIDS :

[H ] furnished by  acid c k a1 c1


 1 1 
[H ] furnished by  acid c 2  2 k a2 c 2

h) pH of a mixture of two weak acid (both monoprotic) soluitons :

K a1 1
(1  1) and ( 2  1)  
K a2 2

[H ]  C11  C2  2  C1K a1  C2K a2

** If water is agin considered third weak acid in solution of two weak acid then

[H ]  K a1 C1  K a2 C2  K w

CwKaw = 10–14 = Kw

[H ]  C1K a1  C 2K a2  10 14

i) pH of a mixture of weak acid (monoprotic) and a strong acid solution :

If [SA] = C1 and [WA] = C2, then [H+] from SA = C1 and [H+] from WA = C2
Let HA is a weak acid.

C1  C12  4K a C2
[H ] 
2

** If a strong acid of low conc. is added in water then [H+] of solution can be calcualted as

C1  C12  4K w
[H ] 
2
* SALT HYDROLYSIS :

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Hydrolysis of ployvalent anions or cations :

For [Na3PO4] = C
Ka1 + Kh3 = Kw
Ka1 + Kh2 = Kw
Ka3 + Kh1 = Kw
Generally pH is calclated only using the first step Hydrolysis

Ch2
K h1   Ch2
1 h

K h1 K w  K a3
h  [OH ]  ch  K h1  c  [H ] 
c C

1
So, pH = [pK w + pK a3 + logC]
2
Hydrolysis of Amphiprotic Anion. (Cation is not Hydrolysed e.g., NaHCO3, NaHS, etc.

 pK  pK a2 

pH HCO3   a1
2
 
 
b) Similarly for H2PO4– and HPO42– amphiprotic anions.

 pK  pK a2   pK a1  pK a2 
pH H PO    a1  and pHHPO42    
 2 4  2   2 

K a1 K a2 K a3
H3PO4   H2PO 4   HPO42    PO34 ionisation,

K w  
K w  
Kw 
Kh  Kh 2  Kh 
1 K a1 K a2 1 K a3

1
The pH of H3PO4 = (pKa1 – log C)  Ka1 >> Ka2 >> Ka3
2

1
pH of NaH2PO4 = (pKa1 – pKa2)
2

1
pH of Na2HPO4 = (pKa2 – pKa3)
2

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1
pH of Na3PO4 = (pKw – pKa3 + log C)  Sec hydrolysis can neglect.
2

BUFFER SOLUTION :
a) Acidic Buffer : e.g., CH3COOH and CH3COONa. (weak acid and salt of its conjugate base).

[Salt]
pH  pK a  log [Henderson's equation]
[Acid]
b) Basic Buffer : e.g., NH4OH + NH4Cl. (weak base and salt of its conjugate acid).

[Salt]
pOH = pKb + log
[Base]

Buffer Capacity (index) :

Total no. of moles of acid / alkali acided per litre

Buffer capacity =
Change in pH

dx (a  x) (b  x)
Buffer capacity =  2.303
dpH ab

INDICATOR :
HIn H+ + In–

 [Hn]
or [H ]  KHn  [n ]

[n] [Ionsied form]

 pH  pKHn   pH  pKHn  log
[Hn] [Unionised form]

SIGNIFICATION OF INDICATORS :
• Extent of reaction of different bases with acid (HCl) using two indicators :
Phenolphthalein Methyl Orange
NaOH 100% reaction is indicated 100% reaction is indicated
NaOH + HCl  NaCl + H2O NaOH + HCl  NaCl + H2O
Na2CO3 50% reaction upto NaHCO3 100% reaction is indicated
stage is indicated
Na2CO3 + HCl  NaHCO3 + NaCl Na2CO3 + 2HCl  2NaCl + H2O + CO2
NaHCO3 No reaction is indicated 100% reactions is indicated
NaHCO3 + HCl  NaCl + H2O + CO2

ISOELECTRIC POINT :

[H ]  K a1K a2

pK a1  pK a2
pH 
2

SOLUBILITY PRODUCT :
KSP = (xs)x (yx)y = xx.yy.(s)x + y
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CONDITION FOR PRECIPITATION :

If ionic product KI.P > KSP precipitation occurs.
If KI.P = KSP saturated solution (precipitation just begins or it just prevented).
*ELECTROCHEMITRY*
ELECTRODEPOTENTIAL
For any electrode  oxidiation potential = - Reduction potential
Ecell = R.P of cathode - R.P. of anode
Ecell = R.P of cathode + O.P of anode
Ecell is always a +ve quantity & Anode will be electrode of low R.P.
Ecell = SRP of cathode - SRP of anode.
 Greater the SRP value greater will be oxidising power.
GIBBS FREE ENERGY CHANGE :

  G = -nFEcell
 G0 = -nFE0cell
NERNST EQUATION : (Effect of concentration and temp of an emf of cell)
 G =  G0 + RTlnQ (Where Q is reaction quotient)
 G0 = -RTlnKeq

0 RT
E cell  Ecell  ln Q
nF

0 2.303RT
E cell  Ecell  logQ
nF

0 0.0591RT
Ecell  Ecell  logQ [At 298 K]
n
At chemical equilibrium
 G = 0; Ecell = 0
0
nFcell
 log K eq 
0.0591

0 0.0591
E cell  log K eq
n
For an electrode M(s)/Mn+

2.303RT 1
EM  / M  EM0  /M  log n 
nF M 

Concentration Cell : A cell in which both the electrodes are made up of same material.
For all concentraiton cell E0cell = 0.
(a) Electrolyte Concentration Cell :
eg. Zn(s)/Zn2+(c1) | | Zn2+(c2)/Zn(s)
(b) Electrode Concentration Cell :
eg. Pt, H2(P1 atm)/H+(1M0/H2(P2 atm)/Pt
DIFFERENT TYPES OF ELECTRODES :

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0.0591
1. Metal - metal ion Electrode M(s)/Mn+ M n   ne   M (s ) E  E0  log M n  
n
2. Gas-ion Electrode Pt/H2(atm)/H+(XM)
1

1 PH2 2
 
as a reduction electrode H (aq )  e  H 2 (atm) E  E 0  0.0591log
2 H  

3. Oxidation-reduction Electrode Pt/Fe2+, Fe3+

Fe 2  
as a redcution electrode Fe3+ + e-  Fe2+ E  E 0  0.0591log  3  
Fe 

4. Metal-Metal insoluble salt Electrode eg. Ag/ACl, Cl-

as a reduction electrode AgCl(s) + e-  Ag(s) + Cl-

 ECl  / AgCl / Ag  ECl0  / AgCl / Ag  0.0591log C  

CALCULATION OF DIFFERENT THERMODYNAMICS FUNCTION OF CELL REACTION

  G = -nFEcell

 dG 
 S    (At constant pressue)
 dT  P

 d  G   d 
 S      nF   Ecell  
 dT P  dt P

 E 
  T  = Temperature cofficient of e.m.f of the cell.
 P
E = a + bT + CT2 + ...............

 ΔCP of cell reaction

dH
CP 
dT

d
CP   H 
dT

d 2Ecell
CP  nFT
dT 2
 ELECTROLYSIS :
(a) K+, Ca+2, Na+, Mg+2, Al+3, Zn+2, Fe+2, H+, Cu+2, Ag+, Au+3

increa sing order of deposition


(b) Similarly the anion which is stronger reducing agent (low vlaue of SRP) is librated first at the node.

SO42 , NO3 ,OH  ,Cl  , Br  , I 


increa sing order of deposition

FARADAY'S LAW OF ELECGTROLYSIS :

First Law :

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w = zq w = Z it Z = Electrochemical equivalent of substance
Second Law :

W W1 W2
= Constant   ...............
W E E E1 E2

W i  t  current efficiency factor


E 96500

actual mass deposite / produced

CURRENT EFFICIENCY = Theoritical mass deposited / produced  100

 CONDITION FOR SIMULTANEOUS DEPOSITION OF Cu & Fe AT CATHODE

0 0.0591 1 0 0.0591 1
ECu 2
/ Cu
 log 2   EFe 2
/ Fe
 log 2
2 Cu 2 Fe
Condition for the simultaneous deposition of Cu & Fe on cathode.
CONDUCTANCE :

1
 Conductance =
Re sis tan ce
 Specific conductance or conductivity :

1
(Reciprocal of specific resistance) K

 Equivalent conductance :

K  1000
E  unit : - ohm-1 cm2 eq-1
Normality
 Molar conductance :

K  1000
M  unit : - ohm-1 cm2 mol-1
molarity

l
specific conductance = conductance x
a
KOHLRAUSCH'S LAW :

Variation of λ eq / λM of a solution with concentration :

(i) Strong elecrolyte

Mc  M  b c

(ii) Weak electrolytes :   n   n  where  is the molar conductivity

n+ = No of cations obtained after dissociation per formula unit
n- = No of anions obtained dissociation per formula unit
APPLICATION OF KOHLRAUSCH LAW :

1. Calculation of λ M0 of weak electrolytes :

M0 CH3COOHI   M0 CH3COONa   M0 HCl   M0 NaCl 

2. To calculate degree of diossociation of a week electrolyte

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mc c 2
  ; K eq 
m0 1   
3. Solubility (S) of sparingly soluble salt & their Ksp

1000
Mc  M  K 
so lub ility
Ksp = S2.
 IONIC MOBILITY : It is the distance travelled by the ion per second under the potential gradient of 1 volts per cm. It's
unit is cm2s-1v -1.
Absolute ionic mobility :

c0  c ; a0  a

c0  F c0 ; a0  F a0

v
Ionic Mobiliy  = v / l  ; v  speed; (v/l)  potential gradient

Transport Number :

 c   a 
tc   , ta   
 c  a   a  c 
Where tc = Transport number of cation & ta = Transport Number of anion
*SOLUTION & COLLIGATIVE PROPERTIES*
1. OSMOTIC PRESSURE :

(i)    gh
where  = density of soln., h = equilibrium height.
(ii) Vont-Hoff Formula (For calcualtion of O.P.)
 = CST

n
 = CRT = RT (just like ideal gas equation)
V
 C = total conc. of all types of particles.

 n1  n2  n3  ........
= C1 + C2 + C3 + .............. 
V
Note : If V1 mL of C1 conc. + V2 mL of C2 conc. are mixed.

 C V  C2V2 
  1 1  RT
 V1  V2 
Type of solution :
(a) Isotopic solution - Two solutions having same O.P.

 1   2 (at same temp.)

(b) Hyper tonic - If  1   2  1st solution is hypertonic solution w.r.t. 2nd solution.
(c) Hypotonic - 2nd solution is hypotonic w.r.t. 1st solution
Abnormal Colligative Properties : (In case of association or dissociation)

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VANT HOFF CORRECTION FACTOR (i) :

exp/ observed / actual value of colligative property ex. / observed no. of particles / conc.
i = =
Theoritical value of colligative property Theoritical no. of colligative property

observed molality theoretical molar mass ( formula mass )

=
Theoritical molality exp erimental / observed molar mass( apparent molar mass )

 i>1  dissociation.
i<1  association

 exp.
 i
 theor

   iCRT

   i1c1  i 2 c2  i 3c3 ........ RT

Relation between i & α (degree of dissociation) :

i = 1 + (n-1) α Where, n= x + y

Relation b/w degree of association β & i

1 
i = 1+  - 1 β
n 
2. RELATIVE LOWERING OF VAPOUR PRESSURE (RLVP) :
Vapour pressure : Psoln. < P
Lowering in VP = P - Ps =  P

P
Relative lowering in vapour pressure RLVP =
P
Raoult's law :- (For non - volatile solutes)
Experimentally relative lowering in V.P = mole fraction of the non volatile solute in solutions.

P  Ps n
RLVP =  X solute 
P nN

P  Ps n

Ps N

P  Ps M
 (molality )  (M = molar mass of solvent)
Ps 100

If solute gets associated or dissociated

P  Ps i .n

Ps N

P  Ps M
 i   molality  
Ps 1000

 According to Raoult's law

(i) p1 = p10X1 where X1 is the mole fraction of the solvent (liquid)

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p10  p1
(ii) An alternate form   x2
p10

P P
 Ostwald - Walker Method : Experiment or lab determination of or P
P s

P  Ps loss in wt. of solvent


Ps loss in wt . if solution

P  Ps loss in wt . of solvent

P gain in wt . of dehydrating aget

3. ELEVATION IN BOILING POINT :

Tb  i  Kb m

RTb2 RTb2 M
Kb  or Kb 
1000  Lvap 1000  Hvap

 Hvap 
Lvap   
 M 
4. DEPRESSION IN FREEZING POINT :

 Tf  i  K f .m

RTf 2 RTf 2 M
Kf = molal depression constant = 
1000  Lfusion 1000  Hfusion

RAOULT'S LAW FOR BINARY (IDEAL) MIXTURE OF VOLATILE LIQUIDS :

PA = XAP0A  PB = XBP0B
if P0A > X0B  A is more volatile than B
 B.P. of A < B.P. of B
 According to Dalton's law
PT = PA + PB = XAP0A + XBP0B
XA' = mole fraction of A in vapour about the liquid/solution.
XB' = mole fraction of B
PA = XAP0A = XA'PT
PB = XB'P0T = XBP0B

1 X 'A XB'
= +
PT PA0 PB0
Graphical Representation :

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A more volatile than B (P0A > P0B)

Ideal solutions (mixtures) : Mixtures which follow Raoult's law at all temperature.
A --------- A   A --------B,
B -------- B

Hmix  0 : Vmix  0 : Smix = +ve as for process to proceed : Gmix  ve

eg. (1) Benzene + Toluene.
(2) Hexane + heptane.
(3) C2H6Br + C2H5I.
Non - Ideal solutions : Which do not obey Raoult's law.
(a) Positive deviation :-
(i) PT, exp > (XAP0A + XBP0B)
A   A
(ii) B   B  A    B (B-weaker force of attraction)\

(iii) Hmix  ve energy absorbed

(iv) Vmix  ve (1L + 1L > 2L)

(v) Smix  ve

(vi) Gmix  ve

eg. H2O + CH3OH
H2O + C2H5OH
C2H5OH + hexane
C2H5OH + cyclohexane
CHCl3 + CCl4  dipole, dipole interaction becomes weak.

(b) Negative deviation

(i) PT exp < XAp0 < XBp0

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A   A
(ii) B   B  A    B
strong force of atraction.
(iii) H  ve

(iv) Vmix  ve (1L + 1L < 2L)

(v) Smix  ve

(vi) Gmix  ve

eg. H2O + HCOOH
H2O + CH3COOH
H2O + HNO3

Immiscible Liquids :
(i) Ptotal = PA + PB

(ii) PA  PA0 X A  PA0 [Since, XA = 1]

(iii) PB  PB0 X B  PB0 [Since, XB = 1]

(iv) Ptotal  PA0  PB0

PA0 nA
(v) 
PB0 nB

PA0 WAM B
(vi) 
PB0 M AWB

nA RT nB RT
PA0  ; PB0 
V V

B.P. of solution is less than the individual B.P.'s of both the liquids.

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Henry Law :
This law deals with dissolution of gas in liquid i.e. mass of any gas dissolved in any solvent per unit volume is
proportional to pressure of gass in equilibrium with liquid.
mp
m = kp

weight of gas
m
volume of liquid

*SOLID STATE*
 Clasification of Crystal into Seven System
Crystal system Unit cell Dimension and Angles Bravais Lattices

Cubic a = b = c;       900 SC, BCC, FCC

Orthorthombic a  b  c;       900 SC, BCC end centred & FCC

Tetragonal a = b  c;       900 SC, BCC

Monoclinic a  b  c;     900   SC, end centred

Rhombohedral a = b = c;       900 SC

Triclinic a  b  c;       900 SC

Hexagonal a = b  c;     900 ,   1200 SC

 ANALYSIS OF CUBICAL SYSTEM
Property SC BCC FCC

a 3a a
(i) atomic radius (r) a = edge length
2 4 2 2
(ii) no. of atoms per 1 2 4
unit cell (Z)
(iii) C. No. 6 8 12
(iv) Packing efficiency 52% 68% 74%
(v) No. voids
(a) octahedral (Z) __ __ 4
(b) Tetrahedral (2Z) __ __ 8
 NEIGHBOUR HOOD OF A PARTICLE :
(I) Simple Cubic (SC) Structure :
Type of neighbour Distance no. of neighbours
nearest a 6 (shared by 4 cubes)

(next)1 a 2 12 (shared by 2 cubes)

(next)2 a 3 8 (unshared)
(II) Body Centered Cubic (BCC) structure :
Type of neighbour Distance no. of neighbours

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3
nearest 2r  a 8
2
(next)1 =a 6

(next)2 = a 2 12

11
(next)3 = a 24
2

(next)4 = a 3 8
(III) Face Centered Cubic (FCC) structure :
Type of neighbour Distance no. of neighbours

a  38
nearest 12=  
2  2 

 38
(next)1 a 6=  
 4 

3
(next)2 a 24
2

(next)3 a 2 12

5
(next)4 a 24
2

Z M
 DENSITY OF LATTICE MATTER (d) = N  a 3 
A  
where NA = Avogadro's No. M = atomic mass or molecular mass.
 IONIC CRYSTALS

 r 
C.No. Limiting radius ratio  r 
 
3 0.155 - 0.225 (Triangular)
4. 0.225 - 0.414 (Tetrahedral)
6. 0.414 - 0.732 (Octahedral)
8 0.732 - 0.999 (Cubic)
 EXAMPLES OF A IONIC CRYSTAL
(a) Rock salt (NaCl) Coordination number (6 : 6)
(b) CsCl C.No. (8 : 8)

2
Edge length of unit cell : asc   r  r 
3
(c) Zinc Blende (ZnS) C.No. (4 : 4)

4
afcc 
3
r
Zn 2
 rS 2 
(d) Fluorite structure (CaF2) C.No. (8 : 4)

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4
afcc 
3
r
Ca2
 rF  
 Crystal Defects (Imperfections)

*CHEMICAL KINETICS & REDIOACTIVITY*

 RATE/VELOCITY OF CHEMICAL REACTION :

c mol / lit .
Rate = = = mol lit-1 time-1 = mol dm-3 time-1
t sec
Types of Rates of chemical reaction :

For a reaction R 
 P

Total change in concentration

Average rate =
Total time taken

 c  dc d R  d  P 
Rins tan tan eous  lim     
t  0 t
  dt dt dt

 RATE LAW (DEPENDENCE OF RATE ON CONCENTRATION OF REACTANTS) :

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Rate = K(conc.)order - differential rate equation or rate expresion
Where K = Rate constant = specific reaction rate = rate of reaction when concentration is unity
unit of K = (conc)1-order time-1
Order of reaction :

m1A + m2B 
 products.
p q
R   A   B  where p may or may not be qual to m1 & similarly q may or may not be equal to m2.

p is order of reaction with respect to reactant A and q is order of reacion with respect to reactant B and (p+q) is
overall order of the reaction.
 INTEGRATED RATE LAW :
C0 or 'a' is initial concentration and Ct or a-x is concentraiton at time 't'
(a) Zero order reactions :
Rate = k[conc.]0 = constant

C0  Ct
Rate = k = or Ct = C0 - kt
't '

C0
Unit of K = mol lit-1 sec-1, time for completion =
k

C0 C C0
at t1/2, Ct  , so kt1/2 = 0  t1/2 =  t1/2  C0
2 2 2k
(b) First order reaction :

(i) Let a 1st order reaction is, A 

 productss

2.303 a 2.303 C0
t log or k  t log C
k ax t

ln 2 0.693
 t1/2   = independent of initial concentraiton.
k k

1
t Avg .   1.44t1/2
k
Graphical Representation :

2.303 2.303
t logCt  logC0
k R

(c) Second order reaction :

2nd order reaction Two types

A + A 
 productss A+ B 
 products

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a a a b 0
(a-x) (a-x) a-x a-x

dx 2 dx
 dt  k (a  x )  k (a  x )  b  x 
dt

1 1 2.303 b(a  x )
  kt k log
(a  x ) a t (a  b) a(b  x )
(d) Psuedo first order reaction :

 For A + B  Prodcutss [Rate = K[A]1[B]1]

2.303 b(a x)
 k log
t (a  b) a(b  x )
Now if 'B' is taken in large excess b >> a.

2.303 a
k log
bt ax

 'b' is very large can be taken as constant

2.303 a 2.303 a
  kb  log   k '  log , k' is pseudo first order rate constant
t ax t ax
 METHOD OF DETERMINE ORDER OF A REACTION :
(a) Initial rate method :
r = k[A]a[B]b[C]c if [B] = constant
[C] = constnat
then for two different initial concentrations of A we have
a
a a
r01   A0 1 
r01  k  A0 1 , r02  k  A0 2    
r02   A0  
 2 
(b) Using integrated rate law : It is method of trial and error.
(c) Method of half lives :

1
for nth order reaction t1/ 2  R n 1
 0
(d) Ostwald isolation Method :
rate = k[A]a[B]b[C]c = k0[A]a
 METHOD OF MONITOR THE PROGRESS OF THE REACTION :
(a) Progress of gaeous reaction can be monitored by measuring total pressure at a fixed volume &
temperature or by measuring total volume of mixture under constant pressure and temperature
2.303 P  n  1
k  log 0 {Formula is not applicable when n =1, the value of n can be fractional also.}
t nP0  Pt

(b) By titration method :

2.303 V
1.  a  V0 a  x  Vt k  log 0
t Vt

2. Study of acid hydrolysis of an easter.

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2.303 V  V0
k log 
t V  Vt

(c) By measuring optical rotation produced by the reaciton mixture:

2.303     
k log  0 
t  t    
 EFFECT OF TEMPERATURE ON RATE OF REACTION

Kt  10
T.C. =  2 to 3 (for most of the reactions)
Kt

Arhenius theory of reaction rate,

SHR = Summation of enthalpies of reactants

SHP = Summation of enthalpies of reactants
DH = Enthalpy change during the reaction
Ea1 = Energy of activation of the forward reaction
Ea2 = Energy of activation of the backward reaction
EP > Er  endothermic
EP < Er  exothermic

H   EP  Er  = enthalpy change

H  Eaf  Eab

E threshold  Eaf  E r  Eb  E p

Arhenius equation :

k  Ae  Ea RT

r  k [conc.]order

d ln k E
 a2
dT RT

 Ea  1
logk      log A
 2.303R  T
If k1 and k2 be the rate constant of a reaction at two different temperature T1 and T2 respectively, then we have

k2 Ea  1 1 
log    
k1 2.303R  T1 T2 

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Ea
* ln k  ln A 
RT

Ea  0

* T  , K  A
Reversible reaciton :

kf  Af e  Eat / RT

kb  Ab e  Eab / RT

Kf  Af   Eat  Eab  /RT

K eq   e
K b  Ab 

H A 
In K eq    ln  f 
RT  Ab 

 B   K1 Ea1 k1  Ea2 k2
C  K2  Ea  k1  k2

(ii) REVERSIBLE 1ST ORDER REACTION (both forward and backward )

Kf a
x
Kf  K b

1 e  f b 
 k k t

1  X eq . 
kf  kb  ln  
t  X eq.  X 

(iii) SEQUENTIAL 1St ORDER REACTION :

[ A]  [ A]e  k1t


x  a 1  e  k1t 

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K1a 1 K1
y e  k1t  e  k2 t   t B (max)   K  K  ln K
K 2  K1  1 2 2

CASE -I K1 >> K2

CASE - II K1 << K2

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