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 mis try m istry

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