46

CONCEPT ESSENTIALS OF CHEMISTRY

CHEMISTRY TODAY | MAY '15

Some important formulae, trends and terms for a 'quick recap'. Class XII

Physical Che Inorganic Che Organic Che

mistry mistry mistry

The Solid State General Principles and Processes of Isolation of Elements Haloalkanes and Haloarenes
Z´M
l Density of unit cell : d = g cm -3 Main steps involved in extraction of metals : l Reactivity order : RI > RBr > RCl; 3° > 2° > 1°;
a3 ´ NA l Concentration of the ore : Hydraulic separation : SN1 reaction : 3° > 2° > 1°; SN2 reaction : 1° > 2° > 3°
l Total no. of atoms per unit cell : for oxide ores; Froth floatation : for sulphide ores; l Dipole moments :
sc bcc fcc Electromagnetic separation : for magnetic – CH3Cl > CH3F > CH3Br > CH3I
1 1 1 1 impurities/ores; Leaching : chemical method – CH3Cl > CH2Cl2 > CHCl3 > CCl4(zero)
8´ =1 8 ´ +1´1 = 2 8 ´ + 6 ´ = 4 l Conversion of ore to oxide : Calcination : for Adsorption>Isotherms
– o -Dichlorobenzene m -dichlorobenzene
8 8 8 2
carbonates and hydrated oxides; Roasting : for ~ chlorobenzene > p-dichlorobenzene (zero)
l Relation between d, a and r sulphide ores.
d a d a
sc : r = = ; fcc : r = = ; bcc : r = d = 3a l Reduction of oxide into free metal : Smelting : Alcohols, Phenols and Ethers
2 2 2 2 2 2 4 Reduction with carbon; Alumino-thermite process :
l Coordination number and packing efficiency l Acidity : Phenols > water > 1° alcohol > 2° alcohol >
Reduction with Al; Auto-reduction : for less
3° alcohol
sc : CN = 6, PE = 52.4%; bcc : CN = 8, PE = 68%; electropositive metals; Electrometallurgy :
l Distinction test of alcohols :
fcc : CN = 12, PE = 74% Electrolysis of fused oxide
l Refining of crude metal : Liquation : for metals
Alcohol Dichromate Victor Lucas
l Size and no. of voids :
(Oxidation) test Meyer’s test test
Type Size No. of Voids having low b.pts.; Distillation : for volatile metals;
1° Acid Blood red No
Octahedral 0.414 R N Poling : for metals having own oxides as impurities;
(Orange solution colour turbidity
Electrorefining : for Cu, Ag, Au, Ni, Cr, Al;
Tetrahedral 0.225 R 2N becomes green)
Zone refining : for Si, Ge, Ga.; van-Arkel method : 2° Ketone Blue Turbidity
for Ti, Zr; Chromatography : for elements available (Orange solution colour in 5 minutes
Solutions
in minute quantities. becomes green)
l Expression for concentration of a solution : 3° No reaction Colourless Turbidity
w2 ´ 1000 w ´ 1000 The p-Block Elements
M= ;N= 2 immediately
M2 ´ V(in mL) E2 ´ V(in mL) l Group 15 (Nitrogen family) : l Distinction test of phenol :
n2 n1 w2
x2 = ,x = ; ppm = ´ 106 – Bond angle, Thermal stability and Basic strength : Test Observation
n1 + n2 1 n1 + n2 Msoln. NH3 > PH3 > AsH3 > SbH3 > BiH3 FeCl3 test Violet colour
l On mixing solutions : N1V1 + N2V2 = N3(V1 + V2) ; – B.Pt. : PH3 < AsH3 < NH3 < SbH3 < BiH3 Br2 – H2O test White ppt.
M1V1 + M2V2 = M3(V1 + V2) – M.Pt.: PH3 < AsH3 < SbH3 < NH3 Liebermann's nitroso test Deep green/blue
l For liquid solutions : pA = xA × p A° ; pB = xB × p B° ; – Reducing nature : NH3 < PH3 < AsH3 < SbH3 < BiH3 (NaNO2 + conc. H2SO4) colour which changes
pA – Bond angle : PF3 < PCl3 < PBr3 < PI3 into red on dilution.
Ptotal = pA + pB; yA = , y = 1 – yA
p A + pB B – Lewis acid strength : PCl3 > AsCl3 > SbCl3; Azo dye test Orange colour

l Colligative properties : DTb = iK b ´ m PF3 > PCl3 > PBr3 > PI3
Aldehydes, Ketones and Carboxylic Acids
n p° - ps l Group 16 (Oxygen family) : Bond angle and
DTf = iK f ´ m; p = i RT ; = ix2
V p° Thermal stability : H2O > H2S > H2Se > H2Te l Reactivity order towards SN reactions : HCHO >
i -1 n – Volatility : H2S > H2Se > H2Te > H2O RCHO > PhCHO > RCOR > RCOPh > PhCOPh
a(disso.) = ;a = (1 - i)
n - 1 (asso.) n -1 – Acidic strength and Reducing nature : l Distinction test of aldehydes & ketones :
M C
i = c or o (where M = molar mass, H2O < H2S < H2Se < H2Te Test Aldehydes
Adsorption Isotherms Ketones
Mo Cc C = colligative property) – Stability : SF6 > SeF6 > TeF6 Schiff 's reagent Pink colour No colour
l Group 17 (Halogen family) : Adsorption
Fehling's solution Red ppt. Isotherms No ppt.
Electrochemistry – Oxidizing power : F2 > Cl2 > Br2 > I2 Tollens' reagent Silver mirror No ppt.
V 1 a l – B.Pt. and M.Pt. : HF > HCl < HBr < HI
l R= ; G = ; r = R ;k = G ´ l Acidity : Carboxylic acids > Phenols > Alcohols
I R l a – Dipole moment and Thermal stability :
HF > HCl > HBr > HI l Distinction test of carboxylic acids :
1000 1000
l Leq = k ´ V = k ´ ; Lm = k ´ V = k ´ – Bond length, Acidic strength and Reducing Test Carboxylic acids
Adsorption Phenols
Isotherms
N M
nature : HF < HCl < HBr < HI NaHCO3 Brisk effervescence of No reaction
¥ ¥
l Lcm = Lm - b C ; Leq = lc¥ + la¥ ; L m
¥
= x lc¥ + y la¥ CO2 gas
– Acidic strength : HClO < HClO2 < HClO3 < HClO4;
Lcm HOCl > HOBr > HOI; HClO4 > HBrO4 > HIO4 FeCl3 Buff coloured ppt. Violet colour
l a= ¥
; DG ° = -nFEcell
° = - RT ln K
c
Lm – Oxidizing power : HClO > HClO2 > HClO3 > HClO4
W1 E1 ° l Group 18 (Noble gases): M.Pt., B.Pt., Ease of Amines
lW = ZIt ; = ; E = E(cathode)
° - E(anode)
°
W2 E2 cell liquefaction, Solubility, Adsor ption and l Basic nature : Aliphatic amine > NH3 > aromatic
0.0591 1 0.0591 Polarizability : He < Ne < Ar < Kr < Xe amine; 3° > 2° > 1° > NH3 [in gas phase/in non-aq.
l Ecell = Ecell
° - ° =
log n+ ; Ecell log K c
n [M ] n – Thermal conductivity : He > Ne > Ar > Kr > Xe solvent]; 2° > 1° > 3° > NH3 [in aq. phase, only —CH3 subs.
amines]; 2° > 3° > 1° > NH3 [in aq. phase, only —C2H5
Chemical Kinetics d- and f-Block Elements subs. amines]

l Expressions for different orders : l d-block elements : (n –1)d1–10ns0–2 l Distinction test (Hinsberg's test):
Rate law Integrated rate law Half-life – 3d series : 21Sc – 30Zn C6H5SO2Cl + 1°, 2° or 3° amines
Rate = k[A]0 [A]t = –kt + [A]0 t1/2 = [A]0/2k – 4d series : 39Y – 48Cd; 5d series : 57La, 72Hf – 80Hg KOH
Clear solution Soluble salt [1° amine]
[0 order] – 6d series : 89Ac, 104Rf – 112Cn KOH
Rate = k[A]1 ln[A]t = –kt + ln[A]0 t1/2 = 0.693 k ppt. No reaction [2° amine]
– Acidic character : MnO < Mn3O4 < Mn2O3 < MnO2 No reaction [3° amine]
[1st order]
Rate = k[A]2 < Mn2O7; Ionic character : MnO > Mn3O4 > Mn2O3
1/[A]t = kt + 1/[A]0 t1/2 = 1/k[A]0 – ArN2+X– are more stable than RN2+X–.
[2nd order] > MnO2 > Mn3O7
1 [B] [ A] – EDGs stabilise while EWGs destabilise the
Rate = k[A][B] kt = ln 0
[ A]0 - [B]0 [ A]0[B] 1/2
t = 1/k[A]0 l f-block elements : (n –2)f1–14(n –1)d0–1ns2
[2nd order] – La(OH)3 to Lu(OH)3 : Basicity decreases; La3+ diazonium salts.
1
(n - 1)kt = n-1 -
1 2n-1 - 1
Rate = k[A]n t =
to Lu3+ : Tendency to form complexes increases
[ A] [ A0 ]n-1 1/2 k(n - 1)[ A]n-1
[nth order] 0
Biomolecules
l Arrhenius equation : Coordination Compounds l Reducing sugars : All monosaccharides
Ea é T2 - T1 ù
CHEMISTRY TODAY | MAY '15

k Ligand
k = Ae - Ea /RT ; log 2 =
Central metal ion l Non reducing sugars : All polysaccharides and
ê ú
k1 2.303 R ë T1T2 û K4 [Fe(CN) 6 ] disaccharides like sucrose.
Counter ion Coordination number l Fat soluble vitamins : A, D, E and K.
Coordination sphere/entity
Surface Chemistry l Water soluble vitamins : B1, B2, B6, B12 and C
l –vely charged sols : Metals, sulphides, acidic dyes, l Spectrochemical series :
starch, clay, silk. I– < Br– < SCN– < Cl– < S2– < F– < OH– < C2O42– < Polymers
l +vely charged sols : Metal hydroxides, oxides, H2O < NCS– < edta4– < NH3 < en < NO2– < CN– < CO l Addition homopolymers : Polythene, polystyrene
basic dyes, haemoglobin. 4 l Condensation homopolymers : Nylon-6, PHB

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l Hardy–Schulze rule : Coagulation power for
–vely charged sols : Al3+ > Ba2+ > Na+
+vely charged sols : [Fe(CN)6]4– > PO43– > SO42– > Cl–
47
l m = n(n + 2) B.M.; Dt = D o ;
9 l Addition copolymers : Buna-S, Buna-N
l CFSE = (– 0.4x + 0.6y)Do where, x = no. of e–s in t2g l Condensation copolymers : Nylon-6, 6, Nylon-6, 10
orbitals, y = no. of e–s in eg orbitals. l Biodegradable copolymers : PHBV, Nylon 2- nylon 6.
CONCEPT Alcohols, phenols and ethers are the basic

ALCOHOLS, PHENOLS compounds of organic chemistry and they

find wide applications in industry as well as
in day-to-day life.

AND ETHERS
Chemical properties
l Cleavage of O—H bond : Ease of reaction depends on stability
Physical properties of alkoxide ion.
B.pt. µ No. of C-atoms Acidity : Phenols > Water > 1° alcohol > 2° alcohol > 3° alcohol
l Cleavage of C—OH bond : Ease of reaction depends on stability of
Solubility µ Branching carbocations.
Order of reactivity : 3° alcohol > 2° alcohol > 1° alcohol
ALCOHOLS l Reactions involving whole alcohol molecule :
443 K
(CnH2n+1OH) C C
413 K
Dehydration : R—OH + conc. H2SO4 ROR
142 pm
:O: 96 pm 383 K
RO—SO2OH
H 513 K
ROR
C 108.9° H Preparation R—OH + Al2O3 633 K
H sp3 l RX + KOH(aq.) ® ROH + KX C C
H conc. H2SO4/H2O [O] [O]
Oxidation : Alcohol Aldehyde/Ketone Carboxylic acid
(Markovnikov's addition)
Cu/273 K
l C C RCH2OH Dehydrogenation : 1° alcohol Aldehyde
Alkene (i) B2H6 in THF
Cu/273 K
(ii) H2O2, OH – 2° alcohol Ketone
(Anti-Markovnikov's addition) Cu/273 K
Dehydration : 3° alcohol C C
l HCHO H2/Pt or Pd or Ni
RCH2OH
Reduction

or 1° Alcohol
RCHO
NaBH4 or LiAlH4
or Distinction tests
or R CH R l Dichromate test (oxidation) : 1° alcohol ® Acid with same
or Na/C2H5OH
Grignard's

R number of C-atoms; 2° alcohol ® Ketone with same number of

reagent

C O OH
R
Carbonyl 2° Alcohol C-atoms; 3° alcohol ® No reaction under normal conditions.
(i) RMgX/Dry ether
compounds or l Victor Meyer’s test : 1° alcohol ® Blood red colour;
(ii) H2O/H + R3C—OH
2° alcohol ® Blue colour; 3° alcohol ® Colourless.
3° Alcohol
(i) LiAlH4 or B2H6/ether l Lucas test : 1° alcohol ® No turbidity; 2° alcohol ® Turbidity in
l RCOOH RCH2OH
PHENOLS Carboxylic acids
(ii) H3O + 5 minutes; 3° alcohol ® Turbidity appears immediately.
(C6H5OH)
109° Some important alcohols
H Methanol : Prepared by catalytic hydrogenation of carbon
: :

l
O
136 pm monoxide or water gas. It is used as a solvent, preservative,
Physical properties
sp2 substitute for petrol, etc.
l Pure phenols are colourless liquids or solids.
l Form intermolecular hydrogen bonds hence, soluble in water. l Ethanol : Prepared by the hydration of ethene or by the fermentation
of molasses. It is used as an antiseptic, power alcohol, in beverages, etc.

Preparation
NaOH NaOH dil. HCl Chemical properties
l C6H5SO3H –H O C6H5SO3Na 573-623 K, C6H5ONa –NaCl
2 l Electrophilic substitution of phenols : Halogenation,
–Na2SO3, –H2O
dil. H2SO4, D
sulphonation, nitration, Friedel—Crafts alkylation, etc. occur at
– +
C6H5 N2Cl + H2O C6H5OH o- and p- positions due to activating effect of —OH group.
–N2, –HCl
Phenol
623 K, 320 atm dil. HCl
C6H5Cl + NaOH C6H5ONa –NaCl
–NaCl, –H2O
1. O2 Tests to distinguish phenols from alcohols
C6H5CH(CH3)2 FeCl3 test : Gives violet colour
2. H+, H2O l
Cumene
l Br2 – H2O test : Gives white ppt.
ETHERS l Liebermann’s nitroso test : Gives blue colour which turns red on
(CnH2n + 2O dilution
l Ammonia/Sodium hypochlorite test : Gives blue colour
where n > 1)
141 pm
:O: Classification l Azo dye test : Gives orange colour
H H l Simple or symmetrical : Same alkyl groups are attached to
H C 111.7° C H oxygen, ROR.
H sp3 H Physical properties
l Mixed or unsymmetrical : Different alkyl groups are l Dipolar due to slightly polar C—O bonds.
attached to oxygen, ROR¢.
l B.pts. are lower than isomeric alcohols due to lack of hydrogen
l Aliphatic ethers : R and R¢ both are alkyl groups.
l Aromatic ethers : Either one or both R and R¢ are aryl groups. bonding.
l Solubility in water (soluble due to formation of
H–bonds with water)
l Fairly soluble in organic solvents.
Chemical properties
l Reaction of ethereal oxygen :
l Lighter than water.
R +
ROR + HCl(conc.) O – H Cl– Preparation
R
:

conc. H2SO4, 413 K

2ROH
l Cleavage of C – O bond : or Al2O3, 523 K ROR
373 K
R – OR + HX R – OH + R – X D Ether
RX + RONa
– In case of alkyl aryl ethers, phenol and an alkyl halide are obtained. (Williamson synthesis) –NaX
dil. H2SO4 l Williamson synthesis involves SN2 mechanism in case of 1° alkyl
ROR + H2O 2R – OH halides.
D
ROR + PCl5 D 2R – Cl l In the case of 2° and 3° alkyl halides, elimination takes place.
l Reactions involving alkyl group : l Dehydration of alcohols for the formation of ethers follows the order :
– Formation of peroxides with air and light. 1° > 2° > 3°
– Substitution products obtained on halogenation.

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l Electrophilic substitution reactions : Uses
Aryl alkyl ethers give o- and p-substituted products due to +R effect of Ethers are used as industrial solvents, heat transfer medium (diphenyl
alkoxy group (–OR). ether), flavouring agents and in perfumes.
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 46
CHEMISTRY TODAY | JUNE '15
CONCEPT SOME BASIC CONCEPTS OF CHEMISTRY
Introduction of most fundamental and important tools of chemistry which help in various calculations.

SI Units Law of Conservation of Mass Masses

 SI system has seven base units pertaining to Matter can neither be created nor destroyed.  Atomic mass unit (amu or u) : Mass exactly
seven fundamental scientific quantities : equal to 1/12th of the mass of an atom of
C-12 isotope.
Physical quantity SI unit Law of Definite Proportions
 Atomic mass of an element : Average
Length (l) metre (m) A given compound always contains exactly the relative mass of its atoms as compared to an
same proportion of elements by weight.
Mass (m) kilogram (kg) atom of C-12.
 Average atomic mass : Given for isotopes.
Time (t) second (s) Xi Ai where Xi = % abundance
Law of Multiple Proportions 
Electric current (I) ampere (A) X i Ai = atomic mass
If two elements can combine to form more than  Gram atomic mass : Atomic mass of an
Thermodynamic kelvin (K)
one compound, the masses of one element that element expressed in grams.
temperature (T)
combine with a fixed mass of the other element,  Molecular mass : Sum of atomic masses of
Amount of substance (n) mole (mol) are in the ratio of small whole numbers. all the elements present in a molecule.
Luminous intensity (Iv) candela (cd)
Gay Lussac’s Law of Gaseous Volumes Mole Concept
 SI system allows the use of prefixes to
indicate the multiples or submultiples of a When gases combine or are produced in a Mole : Collection of 6.022 × 1023 particles
unit : chemical reaction they do so in a simple ratio In case of
by volume provided all gases are at same atomic substances :
deci - 10–1 deka - 101 temperature and pressure. 1 mole = Gram atomic mass = 1 gram atom
centi - 10–2 hecto - 102 = 6.022 × 1023 atoms
molecular substances :
milli - 10–3 kilo - 103
Avogadro's Law 1 mole = Gram molecular mass
micro - 10–6 mega - 106 = 1 gram molecule
nano - 10–9 giga - 109 Equal volumes of gases at the same temperature = 6.022 × 1023 molecules
pico - 10–12 tera - 1012 and pressure should contain equal number of gaseous substances :
molecules. 1 mole = 22.4 L at STP

Scientific Notation Dalton's Atomic Theory Percentage Composition

 A number is represented as x × 10n  Matter consists of indivisible atoms. It shows mass of a constituent in 100 parts of a
 n is –ve if decimal is moved towards right  All the atoms of a given element have compound.
and n is +ve if it is moved towards left. identical properties including identical Mass % of an element
mass. Atoms of different elements differ in Mass of that element in the compound
  100
mass. Molar mass of the compound
Significant Figures  Compounds are formed when atoms of
different elements combine in a fixed ratio.
 These are all certain digits with last digit
 Chemical reactions involve reorganisation
uncertain. Empirical Formula
of atoms. These are neither created nor
 All non-zero digits are significant .  It is the simplest whole number ratio of
destroyed in a chemical reaction.
 Zeros preceding to first non-zero digit are different atoms present in a compound.
not significant.  Steps to obtain empirical formula :
 Zeros between two non-zero digits are
significant. Stoichiometry % age Change to
Molar ratio 
 Zeros on the right side of the decimal are At. mass
 It deals with calculations based upon
significant.
chemical equations.
Molar ratio
 Various steps involved in calculations are : Simplest molar ratio 
Minimum molar ratio
Dimensional Analysis – Write balanced chemical equation.
– Write the relative number of moles or Change to
 Required unit = Given value × conversion relative masses of reactants and products
factor Write the numbers below Simplest whole
involved below their formulae. number ratio =
the symbols of elements
 Some useful conversion factors : – In case of gases write 22.4 L at STP in Simplest ratio × Integer
Length – 1Å = 10–8 cm = 10–10 m place of 1 mole. Empirical formula
1 nm = 10–9 m, 1 pm = 10–12 m – Apply unitary method to make required
Volume – 1 L = 1000 mL calculations.
= 1000 cm3 = 1 dm3 = 10–3 m3
Molecular Formula
Pressure – 1 atm = 760 mm or torr
= 101325 Pa  It is the formula showing exact number of
Limiting Reagent
1 bar = 105 Nm–2 = 105 Pa atoms present in a molecule.
Energy – 1 calorie = 4.184 J The reactant which gets consumed completely  Molecular formula = n × empirical formula
1 eV = 1.6022 × 10–19 J and limits the amount of product formed is
1 J = 10 7 ergs called limiting reagent.
CHEMISTRY TODAY | JUNE '15

Reactions in Solutions
wsolute
 Mass percent (%) =  100
wsolution
HAVE A LOOK !
nA nB
 Mole fraction (xA) = ,x 
 Mass is the quantity of matter contained in the substance and is constant whereas weight varies nA  nB B nA  nB
from place to place. w2  1000
 Molarity (M) =
 Exact numbers have an infinite number of significant figures. M2  V (in mL)
 Molar volume of a gas is 22.7 L at 1 bar and 0°C. w2  1000
 Molality (m) =
 The number of molecules in 1 mL of a gas at STP is known as Loschmidt number. M2  w1(in g)
47

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 46

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 on s 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,  Eff lorescent 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

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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.
47
 States of matter are distinguished by the strength of the bonds holding the

CONCEPT molecules of the matter together. Gases, liquids and solids are all made up
of microscopic particles, but the behaviour of these particles differs in the
STATES OF three phases.

MATTER Crystal Lattice and

Unit Cell
l Crystal lattice : The regular arrangement of
constituent particles in a three dimensional space.
l Unit cell : The smallest repeating unit of space lattice.
l Types of unit cells :
d a
Classification – Simple cubic : Particles at the corners only, r = = ,
2 2
Amorphous
l solids : Constituent Z = 1, efficiency = 52%, C.No. = 6.
particles are not arranged in regular – Body centred : Particles at the corners as well as body centre,
pattern. d 3a
– short range order and isotropic in nature. Z = 2, r = = , efficiency = 68%, C.No. = 8
2 4
– supercooled liquids or pseudo solids. – Face centred : Particles at the corners as well as face centres,
l Crystalline solids : Constituent particles are d a
Z = 4, r = = , efficiency = 74%, C.No. = 12
arranged in definite geometric pattern. 2 2 2
– long range order and anisotropic in nature. l If N is no. of spheres in ccp then tetrahedral voids = 2N,
– true solids. having radius = 0.225 R and octahedral voids = N,
l Crystalline solids can be molecular solids, having radius = 0.414 R.
ionic solids, metallic solids or covalent
solids depending upon the nature
of intermolecular forces.

SOLID STATE Imperfections in Solids

Defects in stoichiometric crystals :
l
– Schottky defect : Arises when equal number of
cations and anions are missing from the lattice sites and
results in decrease in density of the crystal.
– Frenkel defect : Arises due to dislocation of smaller ion from its
normal site to interstitial site and does not affect the density.
l Defects in non-stoichiometric crystals :
– Metal excess defect :
Magnetic Arises when a negative ion is missing from its lattice site, leaving
Properties a hole which is occupied by an electron (F-centre).
l Diamagnetic substances : Weakly repelled When an extra cation is at interstitial site and electrical neutrality
by external magnetic field. e.g., N2, NaCl, Zn, Electrical is maintained by electron present in another interstitial site.
TiO2, etc. Properties – Metal deficiency defect :
l Paramagnetic substances : Weakly attracted by l Conductors : Conductivity range, Arises when metal shows variable valency and is characterised
external magnetic field. e.g., O2, Cu2+, Fe3+, Cr3+, etc. 104 to 107 ohm–1 m–1 by missing of a cation from its lattice site and the presence of a
l Insulators : Conductivity range, 10–20 to cation having higher charge in the adjacent site.
l Ferromagnetic substances : Show permanent When extra anion is at interstitial site and
magnetism even in the absence of external magnetic field. 10–10 ohm–1 m–1
l Semiconductors : Conductivity range, 10–6 electrical neutrality is maintained by extra
e.g., Ni, Fe, Co, etc. charge on adjacent metal ion.
l Antiferromagnetic substances : Have zero net to 104 ohm–1 m–1
dipole moment due to presence of equal number of – n-type semiconductors : Group 14 elements
domains in the opposite directions. e.g., MnO. doped with group 15 elements, free electrons
l Ferrimagnetic substances : Possess very increase conductivity.
small net magnetic moment due to – p-type semiconductors : Group 14
unequal number of domains in elements doped with group 13
the opposite directions. elements, holes increase GASEOUS
e.g., Fe3O4. conductivity.
STATE
A substance
l exists in gaseous state
if the thermal energy of molecules pre-
dominates over the intermolecular forces.
l Gas laws :
1
– Boyle’s law : P µ (at constant T and n)
V
– Charles’ law : V µ T (at constant P and n)
– Gay Lussac’s law : P µ T (at constant V and n)
LIQUID – Avogadro’s law : V µ n (at constant P and T)
STATE – Dalton’s law of partial pressures : Ptotal = pl + p2 + ... + pn (at constant V and T)
l A substance exists in liquid Pdry gas = Pmoist gas – aq. tension
state if the intermolecular forces lie r d2 M2
between gaseous and solid states. – Graham’s law of diffusion : 1 = =
r2 d1 M1
l Properties of liquids :
l Ideal gases : Follow gas laws in all conditions of temperature and pressure.
– Vapour pressure : Pressure exerted by vapours in
– Follow ideal gas equation; PV = nRT
equilibrium with the liquid at a particular temperature.
l Real gases : Follow gas laws only at high temperature and low
– Boiling point : Temperature at which the vapour pressure of a
pressure.
liquid becomes equal to the atmospheric pressure.
– Follow van der Waals equation;
– Surface tension : Tangential force acting along the surface of a liquid
æan2 ö
at right angle to a line of one unit length drawn on the surface of ç P +(V - nb) = nRT
the liquid. èV 2 ÷ ø
– Viscosity : Measure of resistance to flow. l Critical constants and van der
l Eotvos equation : Relates surface tension (g
), Waals constants :
a
temperature (T) and critical temperature Vc ==3b, Pc ,
(Tc) of liquid to its density (d) and 27b2
molar mass (M), 8a
2/3
Tc =
æd ö 27 Rb
g = k(Tc - T)ç ÷
èMø

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