1.

Zeta potential is the potential difference produced non-polar, CH 3CN will dissolve more than CH 3OH in
between the fixed charged layer and diffused layer having n-octane. Therefore, the order of solubility will be.
opposite charges around the colloidal particle. (1) KCl<CH 3OH < CH 3CN < Cyclohexane. (1)
(ii) Saturated Solution A solution in which no more
2. For tetrahedral complexes, the crystal field stabilisation
solute can be dissolved at the same temperature and
energy is lower than pairing energy, so they are not
pressure is known as saturated solution. (1)
formed in low spin state. (1)
3. Number of tetrahedral voids formed
7. (i) Cobalt (III) ion has greater tendency to form
complexes than cobalt (II) ion. Therefore, Co (II) ion
= 2 ´ Number of atoms of element being stable in aqueous solution, changes to Co (III)
Number of atoms of element ‘N’ in the ccp unit cell = 4 ion in the presence of complexing reagents and gets
Number of tetrahedral voids by nitrogen atoms = 2 ´ 4 = 8 oxidised. (1)
\ Number of tetrahedral voids occupied by atoms of (ii) Zinc has stable ground state due to its completely
2 16 filled d-orbitals. It therefore, has least tendency to form
M = ´ 8=
3 3 metallic bonds in the series, thus requires least
So, ratio of the number of atoms of N and M is enthalpy of atomisation. (1)
16
= : 4 = 16 : 12 = 4 : 3
8. Given, with 0.1mol L-1 KCl, resistance is 100 W with
3 0.2 mol L-1 KCl, resistance is 520 W conductivity of
Hence, formula would be N4 M3 . (1) 0.1mol L-1 KCl solution is 129
. S / m.
4. OH Cell constant = Resistance (R) × Conductivity (k)
H2 O = 100 ´ 0.0129
C2H5MgBr + H2C—CH2 C2H5—CH2—CH2
(A) = 1.29 cm -1 (1)
O (1)
Calculating conductivity of 0.02 M KCl solution
5. CH3 CH3
s Å – k = Cell constant / Resistance
C2H5Br
CH3—C—ONa H3C—C—OC2H5 + NaBr
= 129
. / 520
CH3 CH3 (1) = 2.48 ´ 10 -3 S cm -1
6. (i) Cyclohexane : As cyclohexane and n-octane both are Therefore, molar conductivity
non-polar. Hence, they will mix completely in all 10 3
proportions. Lm = k
M
KCl is an ionic compound while n-octane is non-polar.
10 3 ´ 2.48 ´ 10 -3
Hence, KCl will not dissolve in n-octane. =
0.02
CH3OH and CH3CN Both are polar but CH 3CN is less
polar than CH 3OH. As the solvent (n-octane) is = 124 S cm 2 mol -1 (1)
9. (i) 3-methyl aniline into 3-nitro toluene r r s r s
+ – N N N N N N
NH2 N2Cl
r
273-278K
+ NaNO2 + 2HCl + NaCl + 2H2O ¨ ¨
CH3 CH3
r
HBF4

¨
+ –
NO2 N2BF4 +
s r
N N N N
NaNO2
NaBF4+ N2 + r
Cu, D
CH3 CH3 ¨
(1)
(ii) Aniline into 1, 3, 5-tri bromoaniline (1)
NH2 NH2
10. (i) The inter halogens are generally more reactive than
Br Br halogens except F. This is because A—X bonds in
3 Br2/H2O
interhalogens are weaker than the X—X bonds in
dihalogen molecule. (1)
Br (1) (ii) Due to its low volatility, it is used to manufacture more
Or volatile acids, i.e. HF, HCl, HNO 3 , etc. from their
(i) Nitration is usually carried out with a mixture of corresponding salts.
conc. HNO 3 and conc. H 2SO 4 . So, in the presence of 2 MX + H 2SO 4 ¾® 2 HX + M2 SO 4
these acids, aniline gets protonated to form anilinium (X = F,Cl,NO 3 and M = metal) (1)
ion. Therefore, in the presence of these aniline ion. CH 3
¾ NH 2 group in aniline is o, p-directing and | 2
+ 11. (i) CH 43 ¾ 3 C ¾CH 2 ¾1COOH
activaiting, whereas the N H 3 group in aniline ions in |
m-directing and deactivating. CH 3
Now, nitration of aniline mainly gives p-nitroaniline due
IUPAC name : 3, 3-dimethyl butanoic acid. (1/2)
to steric hindrance at o-position, the nitration of
(ii) The role of HNO 3 in the nitrating mixture is to generate
anilinium ion gives m-nitroaniline. In actual practice
electrophile NO +2 that attacks on benzene. (1/2)
approx. 1:1 mixture of p-nitroaniline and m-nitroaniline
is obtained. (iii) (a) Reductive amination is a form of amination that
involves the conversion of a carbonyl group to an
NH2 NH2 NH2
amine via an intermediate imine.
+ NO2 CHO CH2NH2
+ NO2
+
– H+ H2, Raney NH3

Aniline 150ºC
o-nitroaniline (2%) (1/2)
NO2
(b) By the Reduction of Nitriles Reduction of nitriles
p-nitroaniline (51%)
with lithium aluminium hydride (LiAlH 4 ) or catalytic
+ +
NH3 NH3 NH2 hydrogenation produces primary amines.
Containing one carbon atom more than the
+
+ NO2 NH4OH starting amine.
–H+ Raney Ni/H 2
NO2 NO2 R ¾ C ºº N ¾¾¾¾¾¾¾¾¾¾¾®
LiAlH4 or Na (Hg) / C2H 5OH
Anilinium ion m-nitroaniline (47%)
(1) R ¾ CH 2 ¾ NH 2 (1/2)
(ii) Diazonium salts of aromatic amines are more stable
than those of aliphatic amines due to delocalisation of 12. (i) Two characteristics of Barbiturates are:
the positive charge on the benzene ring as shown ● act as sealatives (to produce a calming effect)
below by the resonating structures. ● act as hyphotics (it produce sleep) (1)
 (ii) Use fo Ranitidine It acts as an antacid (controls CH 3 CH 3
hyperacidity) ½ ½ CH CHOHCH
3 3
CH 3 ¾ CH ¾ O ¾ CH ¾ C H 3 ¾¾¾¾¾®
+
Use of Paracetamol It acts as antipyretic, i.e. bring (No formed) -H
down the temperature during high fever. (1) CH 3
13. (i) CH —Br KCN
+
H3 O ½
3 CH3CN CH3COOH CH 3 ¾ CH + ¾®
+
CH 3 ¾ CH == CH 2
LiAlH4 -H Propene
(A) (B)
ether iso -propyl carbocation (1)
CH3CH2OH (1) 15. For fcc lattice of Cu, Z=4
+
aq. KOH KMnO4/H Z´M
(ii) CH3CH2Br CH3CH2OH CH3COOH d=
D
(A)
D
(B) a3 ´ Na
+
NH3 , D
We know that, 2 a = 4r
CH3CONH2 4r 4 ´ 1.278 ´ 10 -8
or a= = = 3.615 ´ 10 -8 cm
(C) (1) 2 2
14. (i) O– 4 ´ 63.55
H
=
d– (3.615 ´ 10 -8 )3 ´ 6.02 ´ 10 23 mol -1
H—C—H + CH3—CH—MgX C—CH3—CH3
H r = Antilog (0.952) = 8.95 g / cm 3
CH3 CH3 (3)
+ Or
H
(i) Type of unit cell = fcc cell
H3C—CH—CH2—HO
Length of cubic unit cell = 4.070 Å
CH3
Smallest distance between two atoms, 4R = 2 a
(ii) Acid catalysed dehydration of 1° alcohols to ethers a 4.070 ´ 10 -10 m
occurs by SN2 reaction involving nucleophilic attack Hence, shortest distance = =
2 2 2 ´ 1.41
by the alcohol molecule on the protonated alcohol
molecule. = 1.443 ´ 10 -10 m (1)
(ii) The number of neighbouring atoms = 12 (1)
Fast
(a) CH3CH2CH2 OH + H+ Z´M
H (iii) Density = 3 ;
a ´ No
—

CH3—CH2—+O—H a=
4r 4 ´ 0.144
= = 0.407 nm
2 1414
.
+ = 0.407 ´ 10 -7cm
(b) CH3CH2CH2OH + CH3CH2CH2 OH2
4 ´ 197
SN2, –H2O =
CH3CH2CH2—O—CH2CH2CH3 (0.407 ´ 10 -7 )3 ´ 6.02 ´ 10 23 mol -1
(1) = 19.25g / cm 3 (1)
Under these conditions, 2° and 3° alcohols, however
give alkenes rather than ethers. The reason is that due 16. Given, WA = 2 g,WB = 25 g, K f = 4.9K kg mol -1
, DTf = 1.62 K
to steric hindrance, nucleophilic attack by the alcohol Molar mass of the solute can be found out using the
molecule on the protonated alcohol molecule does equation.
not occur. Instead protonated 2° and 3° alcohols lose W 1000
a water molecule to form stable 2° and 3° carbocations. DTf = K f ´ B ´
MB WA
These carbocations prefer to lose a proton to form
alkenes rather than undergoing nucleophilic attack by K f ´ WB ´ 1000
MB =
alcohol molecule to form ethers. DTf ´ WA
CH 3 CH 3 4.9 K kg mol -1 ´ 25 ´ 1000
½ ½ + =
H+ 162
. K ´2g
CH 3 ¾ CH ¾OH ¾® CH 3 ¾ CH ¾OH 2 ¾¾®
Protonated propan -2-ol -H 2O
Propan -2-ol (2° alcohol) . g mol -1
= 24198
CH 3 Therefore, molar mass of benzoic acid in benzene is
+½ . g mol -1
= 24198
CH 3 ¾ CH
iso -propyl carbocation Consider the following equilibrium,
(1) 2C 6H 5COOH =
(C 6H 5COOH)2
 If x represents the degree of association of the solute (i) Oxidation of SO 2 into SO 3 in the presence of
then we would have (1- x ) mol of benzoic acid left in platinum catalyst.
associated form and x / 2 as associated moles of Pt( s)
2SO 2 (g ) ¾ ¾¾® 2SO 3 (g )
benzoic acid at equilibrium. Correspondingly x / 2 as Sulphur dioxide (Oxidation) Sulphur trioxide (1)
associated moles of benzoic acid at equilibrium.
Therefore, total number of moles at equilibrium will be 19. (i) Oxidation of nitrite ion by MnO 4- in acidic medium.
x x MnO -4 + -
+ 8 H + 5 e ¾® Mn 2+
+ 4 H 2O] ´ 2
= 1- x + = 1- = 1
2 2
NO -2 + H 2O ¾® NO -3 + 2H + + 2e - ] ´ 5
Total number of moles of particles at equilibrium equals
van't Hoff factor i 2 MnO -4 + 5 NO -2 + 6 H + ¾® 2 Mn 2+ + 5 NO -3 + 3 H 2O
We know that, (1)
(ii) Acidification of K 2Cr2O 7 solution.
i = Normal molar mass / Abnormal molar mass
Cr2O 27 - + 14 H + + 6 e - ¾® 2Cr 3+ + 7H 2O
= 1.22 g mol -1 / 241.98g mol
It is used as primary standard solution in volumetric
1 - x / 2 = i = 122 g mol -1/241.98 g mol
analysis in acidic medium. (1)
122
x / 2 = 1- = 1 - 0.0504 = 0.496 (iii) Disproportionation of manganate ion in acidic
24198
. solution.
or x = 2 ´ 0.496 = 0.992 3MnO 24 - + 4 H+ ¾® 2 MnO -4 + MnO 2 + 2 H 2O (1)
Therefore, degree of associated of benzoic acid in
benzene is 99.2%. (3) 20. Alkenes/dienes and their derivatives are polymerised in
the presence of a free radical generating initiator
17. The cell is represented as Mg Mg 2+(aq ) Ag+ Ag (catalyst) like acetyl peroxide, benzoyl peroxide ter-butyl
peroxide, etc. polymerisation of ethene to polythene.
To determine, Ecell nernst equation is used as
- 0.059 [Mg 2+ ] It consists of heating or exposing to light a mixture of
Ecell = E°cell = log ethene with a small amount of benzoyl peroxide (as an
n [Ag+ ]2
initiator).
Here, n = 2 This process is completed in three steps given below.
0.059 [0.130 ]
Ecell = 3.17 - log Step-I Chain Initiating Step
2 [0.0001]2
Firstly, the phenyl radical is formed by benzoyl peroxide.
= 3.17 - 0.0295 log (13 ´ 10 6 ) = 2.96 V (3) Then, phenyl radical added to the double bond of ethene
molecule (monomet) to form a new and a large free
18. (i) Role of Catalyst in a Reaction A catalyst speeds up
radical through homolysis.
the reactions by providing an alternative route for the
O O
reaction with a lower activation energy. (1)
½½ ½½
(ii) When the Catalytic Reaction Depends upon the C 6H 5 ¾ C ¾O ¾O ¾ C ¾C 6H 5 ¾®
Porous structures of catalyst and the size of the Benzoyl peroxide
reactant and the product molecules, the reaction is O
known as shape selective catalysis. (1) ½½ · ·
(iii) Types of Catalysis Catalysis can be of two types: 2C 6H 5 ¾ C ¾ O ¾® 2 C 6H 5 + 2CO 2 ­
Phenyl radical
Homogeneous Catalysis The phenomenon in
· ·
which the reactants and the catalyst are present in the C6 H 5 + CH 2 == CH 2 ¾® C 6H 5 ¾ CH 2 ¾ CH 2
same phase (i.e. liquid or gas) is known as Ethene (monomer) Big free radical (1)
homogeneous catalysis, e.g. Step-II Chain Propagating Step
(a) Inversion of sugar of hydrolysis of sugar catalysed The new big free radical thus formed in the chain initiating
by H+ ions furnished by sulphuric acid. step reacts with another molecule of ethene to form
H 2SO 4(l ) further bigger sized radical. Thus, the repetition of this
C12H 22O11(aq ) + H 2O(l ) ¾¾¾¾® sequence with new and bigger radicals tends to carry the
Sugar solution
reaction forward.
C 6H12O 6 (aq ) + C 6H12O 6 (aq ) ·
C 6H 5 ¾ CH 2 ¾ CH 2 + nCH 2 == CH 2 ¾®
Glucose
1 Fructose 3
44444244444
Solution C
C 6H 5 ¾ CH 2 ¾ CH 2 ¾ CH 2 ¾ C H 2
Heterogeneous Catalysis C
The phenomenon in which the reactants and the ¾® C 6H 5 ¾ (CH 2 ¾ CH 2 )n ¾ CH 2 ¾ C H 2
catalyst are in different phases is known as (1)
heterogeneous catalysis, e.g.
 Step-III Chain Terminating Step 23. (i) Structure of Vitamin-C
Ultimately, the growth of free radical chain may get OH
terminated by reactions which consume these free HO O
radicals by combining them in different ways to form
polythene.
HO OH
( CH2 — CH2 —
C6H5 — )n CH2 — CH2 + Functional group present = ester alcohol alkene
( CH2 — CH2 —
C6H5 — ) CH2 — CH2 (ii) Yes, it is acidic in nature.
n

C6H5 —(CH2 — CH2—)n CH2 — CH2 The common name is ascorbic acid.
(iii) The values associated with passage is scientific
C6H5 —( CH2 — CH2 —
)n CH2 — CH2 (1) knowledge. (4)

21. (i) Cr = 4 s1 3 d 5 24. Let, the order of the reaction with respect to A be x and
with respect to B be y.
3d 4s 4p Therefore, rate of the reaction is given by
Since, Co is strong field ligand it will pair up the electrons. Rate = k[ A] x [B] y
According to the question,

Co Co Co Co Co Co
6.0 ´ 10 -3 = k [0.1]x [0.1] y …(i)
2 3 -2 x y
Hybridisation = d sp and diamagnetic in nature. (1) 7.2 ´ 10 = [0.3] [0.2 ] …(ii)
(ii) In K 4 Fe(CN)6 , oxidation state of Fe is + 2. 2.88 ´ 10 -1 x
= k [0.3] [0.4] y
…(iii)
In K 3Fe(CN)6 , oxidation state of Fe is +3. -2 x y
2.40 ´ 10 = k[0.4] [0.1] …(iv)
Therefore, configuration is
Fe 2+ = d 6 = t 2 g 6 Dividing equation (iv) by (i), we obtain (1)
-2 x y
2.40 ´ 10 k [0.4] [0.1]
Fe 3+ = d 5 = t 2 g 5 =
-3
6.0 ´ 10 k [0.1]x [0.1] y
CFSE K 4Fe(CN)6 = - 0.4 ´ 6D 0 = - 2.4D 0
[0.4]x
CFSE K 3Fe(CN)6 = - 0.4 ´ 5D 0 = - 2.0 D 0 Þ 4=
[0.1]x
Therefore, K 4Fe(CN)6 is more stable than K 3Fe(CN)6 .
(1) (4)1 = 4 x
(iii) The crystal field splitting, D 0 , depends upon the field x =1 (1)
produced by the ligand and charge on the metal ion.
Some ligands are able to produce strong fields in Dividing equation (iii) by (ii), we obtain
which case, the splitting will be large whereas others 2.88 ´ 10 -1 k [0.3]x [0.4] y
=
produces weak fields and strength. This series is 7.2 ´ 10 -2 k [0.3]x [0.2 ] y
known as spectrochemical series. y
e.g., I- < Br - <SCN - <Cl - <F- <OH - <C 2O 24 - æ 0.4 ö
4= ç ÷
è 0.2 ø
<H 2O<NCS - <EDTA 4 - <NH 3 <en<CN - <CO (1)
4 = 2y
22. (i) In Mond's process, the crude Ni is heated in the
stream of CO to form volatile nickel carbonyl, Ni(CO)4 . (2 )2 = 2 y
This Ni(CO)4 when heated higher, it will decomposed Þ y =2 (1)
to give pure metal as
450- 470 K Therefore, the rate law is
330-350K
Ni + 4 CO ¾¾¾® Ni(CO)4 ¾¾¾® Ni + CO Rate =k [ A][B]2
(1)
Pure
(ii) Zinc dust is used to precipitate silver metal from From experiment I, we obtain
sodium argent to cyanide. The solution of sodium
6.0 ´ 10 -3 mol L-1 min -1
argent to cyanide combines with zinc dust and forms k=
sodium tetracyanozincate and silver metal. (0.1mol L-1 )(0.1 mol L-1 )2
Zn + 2Na[Ag(CN)2 ] ¾® Na 2 [Zn(CN)4 ] + 2 Ag (1) = 6.0 L2 mol -2 min -1
(iii) Copper is extracted from copper matte which From experiment II, we obtain
contains iron as impurity. Silica is added to remove
this impurity as iron silica in the form of fusible slag. 7.2 ´ 10 -2 mol L-1 min -1
k=
FeO + SiO 2 ¾® FeSiO 3 (1) (0.3 mol L-1 )(0.2 mol L-1 )2
Impurity Iron silicate
(Slag) = 6.0 L2 mol -2 (1)
From experiment III, we obtain
2.88 ´ 10 -1mol L-1min -1
k= = 6.0 L2mol -2min -1
(0.3 mol L-1 )(0.4 mol L-1 )2
From experiment IV, we obtain
2.40 ´ 10 -2 mol L-1 min -1
k= = 6.0 L2 mol -2 min -1
(0.4 mol L-1 )(0.1mol L-1 )2
Therefore, rate constant, k = 6.0 L2 mol -2 min -1
Or
Given that
Activation energy, Ea = 209.5 kJ mol -1
Multiply by 1000 to convert in joule,
Ea = 209500 J mol -1
Temperature, T = 581K
Gas constant, R = 8.314 J K -1mol -1
According to Arrhenius equation
K = Ae - Ea / RT
e - Ea / RT represents the number of molecules.
Number of molecules = e - Ea / RT = e -209. 5 / 8. 314 ´ 581
. ´ 10 -19 (1)
= 1/ anti ln (43.4) = 147
(ii) (a) Rate of a chemical reaction at a given
temperature may depend on the concentration of
reactants and products. The representation of
rate of reaction in terms of concentration of the
reactants is called the rate law, rate equation or
rate expression.
Consider a general reaction,
aA + bB ¾® cC + dD (1)
where, a, b, c and d are the stoichiometric
coefficients of reactants and products.
The rate expression for this reaction is
Rate µ [ A] x [B] y
where, exponents x and y are determined
experimentally and may be or may not be equal to
the stoichiometric coefficient (a and b) of the
reactants. Above equation can also be written as:
Rate = k [ A]x [B] y
d [R ]
- = k [ A]x [B] y
dt (1)
This form of equation is known as differential rate
equation, where k is the proportionality constant
called rate constant. Rate constant (k ) is equal to
the rate of reaction when molar concentration of
reactants is unity. Its units depends upon the
order of reaction.
(b) (a) L-1mol s -1
Order of reaction = 0 (zero)
-1 -1
(b) L mol s
Order of reaction = 2 (two)
25. (i) Since, the byproduct of roasting of sulphide ore
is SO 2 . It also turns lime water milky. Therefore, gas ‘B’
must be SO 2 .
As the gas B is obtained when amorphous solid ‘A’
burns in air therefore, amorphous solid ‘A’ must be
sulphur, S 8 .
(ii) (a) HF>HCl>HBr >HI
(1) Thermal stability is directly proportional to bond
dissociation energy. As we move from fluorine to
iodine, atomic size decreases. Therefore, H — X
bond length increases. This causes the H — X
bond dissociation energy to decrease. Hence,
H — X bond breaks easily.
(b) The decreasing order is
Ne>Kr > Xe>Rn>He.
As we go down the group, size of atom increases
and ‘He’ is smaller in size, and the effective
nuclear charge is very high. So, much energy is
required by the ‘He’ atom to put electron in its
configuration. (5)
Or
(i) (a) In the solid state, PCl 5 exists as an ionic solid
[PCl 4 ]+ , [PCl 6 ]- .
Hence, ionic in nature.
(b) Ozone is thermodynamically less stable than
oxygen, because its decomposition into oxygen
results in the liberation of heat (DH is negative)
and increase in entropy (DS is positive). These
two effects results in large negative Gibbs energy
change (DG ) for its conversion into oxygen.
(c) Most of the reactions of fluorine are exothermic
(due to the small and strong bond formed by it
with other elements). It forms only one oxoacid
while other halogens form a number of oxoacids.
Hydrogen fluoride is a liquid (b.p 293 K) due to
strong hydrogen bonding.
(ii) (a) I2 + 2NaCl O 3 ¾® 2NaIO 3 + Cl 2
(b) I2 + S 2O 23 - ¾® S 4O 26 - + I-
(c) P4 + SOCl 2 ¾® 2PCl 3 + 4SO 2 + 2S 2Cl 2
(d) XeF2 + PF5 ¾® [XF]+ [PF6 ]- (5)
26. (i) (a)
H3 C 1 CH3
6 2
CH3
5 3
4
Cyclohexanone 2,2,6-trimethyl cyclohexanone
In 2, 2,6-trimethyl cyclohexanone, three methyl group
are present at a-position with respect to the ketonic
(‚
ƒ C == O ) group. Therefore, these groups cause
steric hindrance during the nucleophilic attack of CN -
ion so, cyanohydrin is not formed. Due to the absence
of methyl group in cyclohexanone, there is no steric
(1)
hindrance and cyanohydrin is formed. (1)
(b) Resonance in semicarbaside

NH2—NH—C—NH2 NH2—NH—C — NH2

Semicarbaside has two amino (NH 2 ) group, out of which one is involved in resonance as shown above.
Electron density on this NH 2 decreases and it does not act as an nucleophile. But the other NH 2 group (attached to NH)
has lone pair of electrons which are not involved in resonance. So, their pair is available for the nucleophilic attack on
carbonyl group (‚ ƒ C == O ) of aldehydes and or ketones. (1)
(c) Esterification is a reversible reaction,
H 2SO 4
RCOOH + R ¢ OH = RCOOR ¢ + H 2O
Ester
When the sufficient amount of products are formed, the rate of forward reaction decreases and the reverse reaction
begins. To avoid this condition, i.e., in order to shift the equilibrium in forward direction, the concentration of products
(ester and / or water) should be decreased (in accordance to Le-Chatelier's principle). So, water should be removed
continually. (1)
(i) Propanal acts as both nucleophile and elctrophile.
OH CH 2
½ 5½ 1 4
2 3
CH 3CH 2CHO + CH 3CH 2CHO ¾® C H 3 C H 2 CH ¾ CH ¾ C HO
3-hydroxy 2-Methylpentanal
(ii) Butanol serves as both nucleophile and electrophile.
OH CH 2CH 3
6 5 4 ½ ½ 1
CH 3CH 2CH 2CHO + CH 3CH 2CH 2CHO ¾® C H 3 C H 2 C H 2 ¾ 3 CH ¾ 2 CH ¾C HO
2-ethyl -3-hydrohexanal
(iii) Propanal serves as electrophile and butanal as nucleophile.

OH CH 2CH 3
5 ½ ½ 4 1
CH 3CH 2CHO + CH 3CH 2CH 2CHO ¾® C H 3 C H 2 ¾ 3 CH ¾ 2 CH CHO
Propanal Butanal 2-ethyl -3-hydroxypentanal
(iv) Butanal serves as electrophile and propanal as nucleophile.
OH OH 3
6½ ½
5 1 4
CH 3CH 2CH 2CHO + CH 3CH 2CHO ¾® CH 3 CH 2 CH 2 ¾ 3 CH ¾ 2 CH ¾C HO
Butanal Propanal æ 1 ö
3-hydroxy-2-methyl hexanal ç 4 ´ = 2÷
è 2 ø
Or
(i) (a) Benzoic acid to 3-phenylpropan-1-ol
COOH COCl CHO

SOCl2 H2/Pd
+CH3CHO
Reduction

Dil. NaOH, D

CH2CH2CH2OH CH==CH CHO

H2Ni

(1)
(b) Benzoic acid to m-nitrobenzyl alcohol
COOH CH2OH CH2OH

LiAlH4/H2O Conc. HNO3

NO2 (1)
 (c) Propanone to Propene
O OH
Reduction Conc. S2HO4
CH3—C—CH3 + LiAlH4 CH3—C—CH3 CH3CH=CH2
Propene (1)
(ii) (a) Cross Aldol Condensation
It is carried out between the two different aldehydes or ketones. It gives a mixture of four products.
If both the reactants contain a-hydrogen atoms, the reaction gives a mixture of four products due to self condensation
and cross-condensation.
(i ) NaOH
CH3CHO + CH3CH2CHO ¾¾® CH3—CH CH—CHO + CH3CH2—CH C—CHO
(ii ) D
But-2-enal
(From two molecules CH3
of ethanal)
2-methylpent-2-enal
(From two molecules of propanal)

Simple or self aldol products

+
CH3—CH C — CHO + CH3CH2—CH CHCHO
Pent-2-enal
CH3
2-methylbut-2-enal
(From one molecule of ethanal
and one molecule of propanal)
Cross aldol products
(1)
Ketones can also used as one component in the cross aldol. Cross aldol condensation reactions are of great
synthetic use even if one of the carbonyl compound do not possess a-H atoms.
O
–
OH
CHO + C — CH3 ¾¾® CH CH C
293 K
Benzaldehyde O 1, 3-diphenylprop-2-en-1-one
Acetophenone (Benzalacetophenone)
(Major product)
(b) Haloform Reaction
Acetaldehydes and methyl ketones are oxidised by sodium hypohalite solution to give haloform. This is called
haloform reaction.
O O
|| Cl 2 , OH - ||
R ¾ C ¾ CH 3 ¾ ¾¾¾ ¾® R ¾ C ¾O - + CHCl 3
-
ClO

Hypohalites are XO - , where X = Cl, Br, I.

This reaction is used to distinguish between higher ketones and methyl ketones.
This test is also given by CH 3 —CH—CH 3 , 2° alcohol (at C 2 ) as CH 3 ¾C H ¾R
½ |
OH OH (1)