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Some important formulae, trends and terms for a 'quick recap'. Class XII
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.
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CONCEPT Alcohols, phenols and ethers are the basic
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
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
:
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)
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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.
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.