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CONCEPT PHYSICAL CHEMISTRY (Part-I)

CHEMISTRY TODAY | JULY '15

Solutions, Electrochemistry and Chemical Kinetics form the basis of physical chemistry and give an idea about the nature of
solutions, relationship between chemical energy and electrical energy in redox reactions and also the rates of reactions.

SOLUTIONS ELECTROCHEMISTRY CHEMICAL KINETICS

Expressing Concentration of Solutions Basic Terms Rate of Reaction

 Mass percentage : Grams of solute in 100 g of  Conductance : Reciprocal of resistance.  For a reaction, aA + bB  xX + yY
solution. 1 1 d[ A] 1 d[B] 1 d[ X ] 1 d[Y ]
 Strength : Grams of solute in 1 L of solution. C  ; Unit : 1 or S Rate     
R a dt b dt x dt y dt
 Molarity : Moles of solute in 1 L of solution.  Conductivity : Conductance of 1 cm3 of the  Greater the concentration of reactants, faster is the
 Normality : Gram equivalents of solute in 1 L reaction.
conductor.
of solution.  Rate becomes double for every 10° rise in
l
 Molality : Moles of solute in 1 kg of solvent.   C  ; Unit : 1 cm 1 or S cm 1 temperature.
 Mole fraction : Moles of the component/ total a
 Greater the surface area of reactants, faster is the
 Equivalent conductivity : Conductance of a
no. of moles of all components. reaction.
 Parts per million : Mass of solute in one solution containing 1 g-equivalent of an
million (106) parts by mass of solution. electrolyte dissolved in V cm3 of the solution.
  1000 Order and Molecularity
eq  ; Unit : S cm2 eq 1
Laws Normality
 Molar conductivity : Conductance of a solution  For a rate law equation, rate = k[A]a[B]b
 Henry’s law : m = Kp or p = KHx Order of reaction = a + b.
containing 1 mole of an electrolyte dissolved in  Molecularity is the number of atoms, ions or
where KH is Henry’s constant having units of V cm3 of the solution. molecules that must collide simultaneously with
pressure.
  1000 one another to result into a chemical reaction.
 Raoult’s law :
p  ps n2 m  ; Unit : S cm2 mol 1
For non-volatile solute :   x2 Molarity
p n1  n2  Electrode potential : Tendency of an electrode to
For volatile components : lose or gain electrons when it is in contact with Integrated Rate Equation and Half-Life
pA = xAp°A ; pB = xB pB° and ptotal = pA + pB
solution of its own ions.
 Cell potential or EMF of the cell : The difference Order Integrated Half-life
rate equation t1/2 =
Types of Solutions between electrode potentials of two half-cells.
0 [A]t = –kt + [A]0 [A]0/2k
 Ideal solutions : A–B interactions are of same
magnitude as A–A and B–B interactions, Types of Cells 1 ln[A]t = –kt + ln[A]0 0.693/k
Vmix = 0 and Hmix = 0. 2 1/[A]t = kt + 1/[A]0 1/k [A]0
 Non-ideal solutions : A–B interactions are of  Electrochemical cell : Device used to convert
different magnitude than A–A and B–B chemical energy of a redox reaction into 1 [ B] [ A]
2 kt  ln 0 –
interactions, Vmix  0 and Hmix  0. electrical energy. [ A]0  [ B]0 [ A]0[ B]
– Non - i d e a l s oluti ons show ing +ve  Electrolytic cell : Device which uses electricity
1 1 2n 1  1
deviations : A–B interactions are weaker to bring about a non-spontaneous redox n (n  1) kt  
than A–A and B–B interactions, Vmix reaction. [ A]n 1 [ A0 ]n 1 k (n  1)[ A]n0 1
= +ve, Hmix = +ve and resulting vapour
 Relationship between time for different fractions of
pressure is higher than that expected.
Laws a first order reaction to complete,
– Non - i d e a l s oluti ons show ing –ve
t3/4 or t75% = 2t1/2
deviations : A–B interactions are stronger
 Faraday’s first law : W = Zit 3
than A–A and B–B interactions, Vmix = t 87.5%  3t1/2  t 75%
W1 E1 2
–ve, Hmix = –ve and resulting vapour  Faraday’s second law :  t93.75% = 4t1/2 = 2t75%
pressure is lower than that expected. W2 E2
t96.87% = 5t1/2
 Azeotropes: Constant boiling mixtures.  Kohlrausch’s law : For an electrolyte AxBy,
t99.9% = 10t1/2
°m = x°+ + y°– or °eq = °+ + °–
Colligative Properties
Temperature Dependence of Rate of
 Colligative properties depend only on the Nernst Equation and Electrochemical Series Reaction and Effect of Catalyst
number of particles of solute dissolved in a
definite amount of solvent. These are :  Nernst equation : For the reaction :
n+ –
 Arrhenius equation : k = Ae–Ea/RT
– Elevation in boiling point : Boiling point M + ne  M, Ea  T2  T1 
k
of solution is higher than that of pure or log 2 
k1 2.303R  T1T2 
RT M
E  E  ln or
solvent. Tb = Tb – Tb° = Kb m nF [ M n  ]
 Activation energy
– Depression in freezing point : Freezing
point of solution is lower than that of pure 0.0591 1 = Threshold energy – Average kinetic
E  E  log n  at 298 K
solvent. Tf = T°f – Tf = Kf m n [M ] energy of reactants
– Relative lowering of vapour pressure :  For concentration cell :  Collision theory : k = PZe–Ea/RT
p  ps n 0.0591 C where P is steric factor and Z is collision
 x2  2 (for dilute solutions, Ecell  log 2 ; Ecell  +ve if C2  C1
p n1 n <<< n ) n C1
frequency.
2 1
 Catalyst increases the rate of a reaction
p  ps n2  for dilute as well as   For a reaction in equilibrium :
   without itself undergoing any permanent chemical
ps n1  concentrated solutions  0.0591
E cell  log K at 298 K change.
– Osmotic pressure :  = CRT n
 Electrochemical series : It is the arrangement of
electrodes in order of increasing standard
van’t Hoff Factor (i) and its Significance reduction potentials.
– This series helps in comparing the relative
HAVE A LOOK !
Observed value of colligative property
i oxidizing or reducing powers, relative  Different solutions having same vapour pressure
Normal value of colligative property
activities of metals and to predict spontaneity are called isopiestic solutions.
Calculated molecular mass
 of the redox reaction.
Observed molecular mass  Deliquescent substances absorb moisture because
vapour pressure of their saturated solutions is less
CHEMISTRY TODAY | JULY'15

 For solute undergoing association :

n than that of water vapours in air at that
  (1  i) ; i 1 Commercial Cells/Batteries temperature.
(Degree of association) n 1
 For solute undergoing dissociation :  Primary cells cannot be recharged e.g., dry cell,  Efflorescent substances lose their water of
i 1 mercury cell. crystallisation because their hydrated crystals have
  ; i 1 vapour pressure larger than that of water vapours in
(Degree of dissociation) n  1  Secondary cells can be recharged e.g., lead air.
 Modified colligative properties : storage battery, Ni–Cd storage cell.
p  ps  Association generally occurs in non-aqueous
 Fuel cells convert the energy produced during
 ix2 ; T = iK m, T = iK m; solvents (non-polar) because high dielectric
p b b f f combustion of fuels into electrical energy constant of water helps in the dissociation of the
 = iCRT directly e.g., H2–O2 fuel cell. associated molecules.
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‰ Calculation of Lattice Enthalpy–Born Haber Cycle ‰ Fajan’s Rule :
 Born Haber cycle is based on Hess’s law of
constant heat summation and it correlates + – + –
the energy changes taking place in various
steps involved in the formation of ionic Cation Anion
compounds.
According to Fajan’s Rules, the magnitude of
 The steps can be represented in the cycle as :
covalent character in the ionic bond depends upon
IE the extent of polarization caused by cation.
M(g) M(+g)
Heg + In general,
X(g) X(–g)  Smaller the size of cation, larger is its polarizing
Hs
1
power.
Hd U
2  Among two cations of similar size, the polarizing
Hf
1
M(s) + 2 X2(g) MX(s) power of cation with noble gas configuration
ns2np6nd10 is larger than cation with noble gas
1 configuration ns2np6.
DHf = DHs + IE + DHd + DHeg + U
2 e.g., polarizing power of Ag + is more
where, DHf = Enthalpy of formation,
than K+.
DHs = Enthalpy of sublimation,
IE = Ionisation energy,  Larger the anion more will be its polarisibility.
DHd = Enthalpy of dissociation, Valence Shell Electron Pair Repulsion Theory
DHeg = Electron gain enthalpy (VSEPR)
and U = Lattice energy.
‰ According to this theory the best arrangement of
‰ Covalent bond : It is formed by mutual sharing of
a given number of electron pairs is the one that
one or more electron pairs between two atoms so
minimizes the repulsion among them.
that each atom involved in bonding attains nearest
noble gas configuration in order to gain stability. ‰ Repulsive interactions between the pairs of electrons
 The sharing of one, two and three electron pairs are in the order :
between two atoms gives rise to the formation lone pair–lone pair > lone pair–bond pair >
of single, double and triple bond respectively. bond pair–bond pair
 Covalent bond formed between two similar Valence Bond Theory
atoms is called non-polar bond because shared
‰ A bond is formed between two atoms when the
pair of electrons is attracted equally by two
new forces of attraction are greater than forces of
atoms.
repulsion.
 Covalent bond formed between two dissimilar
atoms is called polar bond because shared pair ‰ In terms of orbital overlap concept, the formation
of electrons is more attracted towards more of a covalent bond between two atoms results by
electronegative atom. pairing of electrons present in the valence shell
‰ Coordinate bond : It is a special type of covalent having opposite spins.
bond in which shared pair of electrons is donated ‰ A s-bond is formed by head-on overlap of orbitals
by one atom called donor atom to the other atom
(stronger bond) while a p-bond is formed by
called acceptor.
sidewise overlap of orbitals (weaker bond).
‰ Percentage ionic character :
Hybridisation
 Pauling scale :
% ionic character = 18(cA – cB)1.4 ‰ It is the process of intermixing of orbitals with
 Hannay and Smith equation : slightly different energies so as to redistribute their
% ionic character = 16(cA – cB) + 3.5 (cA – cB)2 energies giving another set of orbitals (called hybrid
 Dipole moment (m) = q × d orbitals) with same energy, size and shape.

48 chemistry tODAy | JULY ‘15

  The structure of any molecule can be predicted on the basis of hybridisation by formula :
No. of hybrid orbitals (H)
  Charge   Charge  
 No. of valence   No. of  
1 present   present   1
=   electrons of  +  monovalent  −  +  ⇒ H = [V + M − C + A]
2   central atom   atoms   on the   on the   2
   
  cation   anion  

Value of H (Hybrid orbitals) 2 3 4 5 6 7

Type of hybridisation sp sp2 sp3 sp3d sp3d2 sp3d3
‰ Shapes of Some Simple Molecules
Types of No. of No. of No. of Types of Geometry of molecule Examples
molecules electron bond pairs lone pairs hybridisation
pairs involved
AB2 2 2 0 sp Linear BeF2, [Ag(NH3)2]+,
HgCl2
2
AB3 3 3 0 sp Trigonal planar BF3, AlCl3, NO3–,
CO32–
AB2L 3 2 1 sp2 V-shaped or bent SnCl2, PbCl2
AB4 4 4 0 sp3 Tetrahedral CH4, SiF4, CCl4,
NH4+
AB3L 4 3 1 sp3 Trigonal pyramidal NH3, PX3
(X = F, Cl, Br, I)
AB2L2 4 2 2 sp3 V-shaped or bent H2O, OF2, SCl2
3
AB5 5 5 0 sp d Trigonal bipyramidal PF5, PCl5, SbCl5
AB4L 5 4 1 sp3d See saw SF4, TeBr4
3
AB3L2 5 3 2 sp d T-shaped ClF3, XeOF2
3
AB2L3 5 2 3 sp d Linear XeF2, ICl2–, I3–
AB6 6 6 0 sp3d2 Octahedral SF6, [SbF6]–
AB5L 6 5 1 sp3d2 Square pyramidal IF5, ClF5, BrF5
3 2
AB4L2 6 4 2 sp d Square planar XeF4, ICl4–
AB7 7 7 0 sp3d3 Pentagonal bipyramidal IF7
AB6 L 7 6 1 sp3d3 Distorted octahedral XeF6
Resonance Molecular Orbital Theory
‰ It is the phenomenon in which a molecule can ‰ The electrons in a molecule are present in the
be represented by more than one electronic various molecular orbitals.
arrangement none of which explains the known ‰ The atomic orbitals of comparable energy and
properties of the compound. proper symmetry combine to form molecular
orbitals.
‰ The actual structure of the compound is intermediate
of the various electronic arrangements and is called ‰ The electron in a molecular orbital is influenced by

resonance hybrid. two or more nuclei depending upon the number of

atoms in the molecule, thus a molecular orbital is
‰ The difference between the energy of resonance polycentric.
hybrid and the most stable contributing structure is
‰ The number of molecular orbitals formed is equal
called resonance energy. to the number of combining atomic orbitals.

chemistry tODAy | JULY ‘15 49

‰ The bonding molecular orbital has lower energy  Intermolecular H-bonding makes the
and greater stability than the corresponding anti- compound more viscous and increases the
bonding molecular orbital. surface tension.
‰ The molecular orbital gives electron probability  Stability of proteins and nucleic acids is due to

distribution around a group of nuclei in a H-bonding.

molecule. Metallic Bonding
‰ The molecular orbitals are filled in accordance ‰ Metallic bond is electrostatic force of attraction
with Aufbau principle obeying the Pauli’s exclusion between positively charged kernels (nuclei with
principle and the Hund’s rule. core electron) and mobile electrons which holds the
metal atoms together.
‰ The order of energies of molecular orbitals for
‰ Strength of metallic bond increases with increase
simple homonuclear diatomic molecules like
in the number of mobile electrons and increase in
O2, F2 and Ne2 is s1s, s*1s, s2s, s*2s, s2pz,
effective nuclear charge.
p2px = p2py, p*2px = p*2py, s*2pz
‰ The order of energies of molecular orbitals for SELF CHECK
diatomic lighter elements like B2, C2 and N2 is 12. Assuming 2s-2p mixing is not operative, the
s1s, s*1s, s2s, s*2s, p2px = p2py, s2pz, paramagnetic species among the following is
p*2px = p*2py, s*2pz (a) Be2 (b) B2 (c) C2 (d) N2
‰ The stability of molecules can be determined by bond (JEE Advanced 2014)
order, higher the bond order higher is the stability. 13. Which one of the following properties is not shown
It can be calculated as : by NO?
1 (a) Its bond order is 2.5.
Bond order = (Nb – Na)
2 (b) It is diamagnetic in gaseous state.
[Nb = No. of bonding electrons, Na = No. of (c) It is a neutral oxide.
antibonding electrons] (d) It combines with oxygen to form nitrogen
‰ Higher the bond order, higher is the bond dioxide.
dissociation energy and smaller is the bond length. (JEE Main 2014)
Hydrogen Bonding 14. In which of the following pairs of molecules/ions,
‰ The attractive force which binds hydrogen atom of both the species are not likely to exist?
one molecule with the electronegative atom (F, O or (a) H2–, He22+ (b) H2+, He22–
N) of another molecule is called hydrogen bond. (c) H2–, He22– (d) H22+, He2
‰ Intermolecular hydrogen bonding : It is formed (JEE Main 2013)
between the two different molecules of the same KEY POINT
or different compounds e.g., in case of HF, ROH or • After the formation of coordinate bond,
H2O, etc. hybridisation of donor atom is not affected
‰ Intramolecular hydrogen bonding : The bond whereas that of acceptor gets changed.
is formed between hydrogen atom and an • p-bonds are always formed in addition to
electronegative atom (F, O or N) within the same s-bonds.
molecule e.g., in o-nitrophenol. An intramolecular • Shape of the molecule is decided by s-bonds
hydrogen bond results in the cyclization of the only.
molecules and prevents their association. • s-orbitals can form s-bonds only.
‰ Applications of H-Bonding • Strongest H-bond exists in KHF2, [F—H---F]–.
 Intermolecular H-bonding increases the
boiling point while intramolecular H-bonding 
decreases the boiling point. anSWer KeyS (Self checK)
 Intermolecular H-bonding increases the 1. (a) 2. (b) 3. (d) 4. (c) 5. (c)
solubility of covalent compounds in water while 6. (a) 7. (d) 8. (a) 9. (c) 10. (b)
the intramolecular hydrogen bonding decreases
11. (a) 12. (c) 13. (b) 14. (d)
the solubility.

50 chemistry tODAy | JULY ‘15