MARKING SCHEME TERM-1 EXAMINATION 2024-25

GRADE: XII SUBJECT: CHEMISTRY

TIME: 3HRS MAX.MARKS: 70

Q. VALUE POINTS MARKS

#
SECTION A 1
1 b 1
2 a 1
3 b 1
4 c 1
5 a 1
6 c 1
7 d 1
8 c 1
9 b 1
10 d 1
11 c 1
12 b 1
13 d 1
14 a 1
15 a 1
16 d 1
SECTION B
17 Given that Henry’s law constant 2
KH=4.27×105mmHg
p=760mmHg
If X is the molar fraction/Solubility then
According to Henry’s law,
p=KHX
760=4.27×105 X
Molar fraction, X =760/4.27×105
=178×10−5
So that, the solubility of methane in benzene =1.78×10−3.

18. The reaction is: 2

2Cr(s)+3Fe2+(s)(aq)→3Fe(s)+2Cr3+(aq)
In this case number of electrons involved, n=6
Apply the equation,
 Ecell=E∘cell−2.303RT/nF x [log{(Cr3+)2/(Fe2+)3}]
Substituting the values in the above equation, we have
Ecell=0.30−0.059/6(log[10−1]2/[10−3]3=0.30−0.059/6(log104)=0.30−0.04=0.26V
OR
Kohlrausch's law of independent migration of ions states that the limiting molar
conductivity of an electrolyte can be represented as the sum individual contributions of its
cations & anions. The conductivity of a solution decrease with dilution because less ions
are present for conduction.

19. (i) Allyl chloride reacts with silver nitrate to produce allyl nitrate and a white precipitate of 2
silver chloride (AgCl). Vinyl chloride, however, does not react with silver nitrate because
of its partial double bond character, which is caused by resonance. This double bond
character prevents the release of chloride ions.

(ii) When alkyl halide reacts with lithium aluminium hydride (LiAlH4) to produce alkane,
the attacking reagent is the hydride ion (H-):
LiAlH4 is an inorganic compound that is a white solid and is often used as a reducing
agent in organic synthesis. It is very reactive with water and can release gaseous
hydrogen.
The attacking reagent is a nucleophile i.e. H- (hydride ion) which is generated from
lithium aluminium hydride. This nucleophile will substitute the halogen in the alkyl halide
and hence the reaction is known as nucleophilic substitution reaction.

20. 2
(i) 2-Methylbut-2-enal

(ii) Pent-2-enal CH3-CH2-CH=CH-CHO

21. The reagents used in the reactions are: 2

(i) Sodium borohydride (NaBH4) and
(ii) Alkaline potassium permanganate (KMnO4+ KOH)
Explanation
For the first reaction, we have the conversion of acetone (C3H6O) to a secondary
alcohol. The reagent used for this reduction is sodium borohydride, represented
as NaBH4. This reagent is effective for reducing ketones and aldehydes to their
corresponding alcohols
In the second reaction, we observe the oxidation of a primary alcohol to a carboxylic acid.
The reagent used here is alkaline potassium permanganate, denoted as KMnO4 in the
presence of potassium hydroxide (KOH). This reagent is a strong oxidizing agent and is
commonly used for oxidizing alcohols to carboxylic acids

SECTION C
22 (a) Due to the formation of hydrogen bonds by alcohols with water molecules alcohols are 3
more soluble in water than the hydrocarbons of comparable molecular masses.

(b) Nitro group is electron withdrawing group in ortho-nitro phenol which decreases
electron density on OH group and makes phenol to donate a proton easily that’s why it is
more acidic whereas, methoxy group in methoxy phenol which is electron donating group
which increases electron density on OH group and decreases acidic nature.
So, ortho-nitrophenol is more acidic than ortho- methoxy phenol. The phenoxide ion
obtained after the dissociation is stabilised by resonance in the case of o - nitrophenol.
Such stabilisation does not happen in the case of o - methoxyphenol.
 (c) Cumene is a better starting material for preparing phenol because the oxidation of
cumene with dilute acid produces phenol and acetone.
Cumene when reacts with oxygen molecule in the presence of dilute acid results in the
formation of phenol and acetone. Acetone is also an important organic compound which
is formed as a by-product and hence the reaction is much for beneficial.

23. (a) When n−butyl chloride is treated with alcoholic KOH, the formation of but−l−ene takes 3
place. This reaction is a dehydrohalogenation reaction.

(b) When bromobenzene is treated with Mg in the presence of dry ether, phenyl-
magnesium bromide is formed.

(c) Chlorobenzene (C₆H₅Cl) doesn't readily undergo hydrolysis due to the partial double
bond character of its C-Cl bond. However, it undergoes hydrolysis when heated in an
aqueous sodium hydroxide solution at a temperature of 623 K and a pressure of 300 atm
to form phenol.
The hydrolysis reaction is easier if there are electron withdrawing groups in the o- or p-
positions of the benzene ringChlorobenzene does not undergo hydrolysis under normal
conditions.

24 Use the relation : ΔTf=iKfm, where I is van’t Hoff factor. 3

Given that m=0.01,ΔTf=0.068ºC,Kf=1.86Kkgmol−1
Substituting the values in the above equation, we have
 0.068k=1×86Kkgmol−1×0.01molkg−1
or i=0.068/(1.86×0.01)=3.6559....(i)
AlCl3→Al3++3Cl−
1-x x 3x
i=(1+3x)/1
From (i) and (ii), we have
1+3x=3.6559 or 3x=2.6559 or x=0.8853
Percentage of dissociation =0.8853×100=88.53

Calculation of cell constant 3

25. Conductivity of 0.1 M KCl = 1.29 x 10 -2 Ω-1 cm-1
Resistance = 85 ohm
Conductivity:

Conductivity of unknown electrolyte K,

26. (a) 3
 (b)

(c)

27. (a) CH3COCH3 in the presence of dilute NaOH: 3

(CH3)3C−CH−CH2COCH3
|
OH

(b)HCN

(c) Conc. NaOH

(CH3)3C−CH2OH and (CH3)3C−COONa

28. (i) pKb of aniline is more than that of methylamine. 3

In aniline, the lone pair of electrons on N atom is in resonance with benzene ring. Hence, it
cannot be easily donated to an acid. This decreases its basicity. In methyl amine,
the +I effect of methyl group increases the electron density on N atom so that the lone pair
of electrons on N atom can be easily donated to an acid. Hence, methylamine is more
basic than aniline. Higher is the basicity, lower is the pKb and vice versa.

(ii) Ethylamine is soluble in water whereas aniline is not. With increase in the molecular
weight, the solubility decreases. Aniline has higher molecular weight than ethylamine.

(iii) Primary amines have higher boiling points than tertiary amines because primary
amines undergo intermolecular hydrogen bonding, while tertiary amines do not.
Primary amines have two hydrogen atoms on the nitrogen atom, which allows them to form
hydrogen bonds with other molecules. This intermolecular hydrogen bonding requires more
energy to break, so primary amines need more heat to boil, giving them a higher boiling
point. Tertiary amines, on the other hand, have no hydrogen atoms on the nitrogen atom,
so they can't form hydrogen bonds. As a result, they have lower boiling points than primary
amines with similar molecular weights.

(i) d 4
29. (ii) b OR a
(iii) b
 (iv) c
30. (i) Substrates that form more stable carbocations react faster in SN1 reactions. 4
Thus, CH2=CHCH2Cl and (CH3)3CCl will react faster with OH- than CH3CH2CH2Cl and
CH3Cl, respectively. Additionally, H2O being polar protic favours SN1 reactions by
stabilizing the carbocation.
(ii) Phenyl magnesium bromide is generated when bromobenzene is reacted with Mg in
the presence of dry ether. Ether is used as a solvent in Grignard reactions because it
reacts with Grignard reagents to form a stable complex. The magnesium-halogen bond is
ionic and solvates the carbon-oxygen bond of ether, which increases the Grignard
reagent's ability to react.
(iii) (a)

(iii) (b)

(iv) (a) 1-Propene

(iv)(b) 4-Chloro-acetaphenone

SECTION E
31. 5
(i) Carbylamine reaction
Carbylamine reaction is used as a test for the identification of primary amines. When
aliphatic and aromatic primary amines are heated with chloroform and ethanolic potassium
hydroxide, carbylamines (or isocyanides) are formed. These carbylamines have very
unpleasant odours. Secondary and tertiary amines do not respond to this test.
For example,

(ii) Diazotisation
Aromatic primary amines react with nitrous acid (prepared in situ from NaNO 2 and a
mineral acid such as HCl) at low temperatures (273-278 K) to form diazonium salts. This
conversion of aromatic primary amines into diazonium salts is known as diazotization.
For example, on treatment with NaNO2 and HCl at 273−278 K, aniline produces
benzenediazonium chloride, with NaCl and H 2O as by-products.

(iii) Hoffmann bromamide reaction

When an amide is treated with bromine in an aqueous or ethanolic solution of sodium
hydroxide, a primary amine with one carbon atom less than the original amide is produced.
This degradation reaction is known as Hoffmann bromamide reaction. This reaction
involves the migration of an alkyl or aryl group from the carbonyl carbon atom of the amide
to the nitrogen atom.

For example,

(iv) Coupling reaction

The reaction of joining two aromatic rings through the −N=N−bond is known as coupling
reaction. Arene diazonium salts such as benzene diazonium salts react with phenol or
aromatic amines to form coloured azo compounds.

It can be observed that, the para-positions of phenol and aniline are coupled with the
diazonium salt. This reaction proceeds through electrophilic substitution.
 (v) Ammonolysis
When an alkyl or benzyl halide is allowed to react with an ethanolic solution of ammonia, it
undergoes nucleophilic substitution reaction in which the halogen atom is replaced by an
amino (−NH2) group. This process of cleavage of the carbon-halogen bond is known as
ammonolysis.

When this substituted ammonium salt is treated with a strong base such as sodium
hydroxide, amine is obtained.

Though primary amine is produced as the major product, this process produces a mixture
of primary, secondary and tertiary amines, and also a quaternary ammonium salt as
shown.

32 (i) Lead storage battery is a secondary cell that can be charged by passing a current. 5
Reactions occurring in the lead storage battery while operating (during discharge) are:

At cathode: PbO2+SO42−+ 4H++2e−→PbSO4+2H2O

At anode: Pb+SO4 2−→PbSO4+2e−

Overall reaction: Pb+PbO2+2H2SO4→2PbSO4+2H2O.

(ii)
OR

Step 1: Identify the half-reactions

The given reaction is:
Au(s)+Ca2+(aq1M) →Au3+(aq1M) +Ca(s)

We can break this down into two half-reactions:

1. Oxidation half-reaction (at the anode):
Au(s)→Au3+(aq)+3e−

2. Reduction half-reaction (at the cathode):

Ca2+(aq)+2e−→Ca(s)
Step 2: Determine the standard reduction potentials
Given:
- EºAu3+/Au=+1.50V

- EºCa2+/Ca=−2.87V

Step 3: Calculate the standard cell potential (E°cell)

The standard cell potential can be calculated using the formula:
Eºcell=Eºcathode−Eºanode
Here, since the oxidation reaction is at the anode, we take the reduction potential of Au as
the anode and the reduction potential of Ca as the cathode:
Eºcell=EºCa2+/Ca−EºAu3+/Au
 Eºcell =(−2.87V)−(+1.50V)
Eºcell =−4.37V
Step 4: Calculate the number of electrons transferred (n)
To balance the number of electrons in the half-reactions, we need to find the least common
multiple of the electrons transferred:
- Oxidation of Au: 3 electrons
- Reduction of Ca: 2 electrons
The least common multiple of 3 and 2 is 6. Thus, we will multiply the oxidation half-reaction
by 2 and the reduction half-reaction by 3:
- Oxidation: 2Au(s)→2Au3+(aq) +6e−
- Reduction: 3Ca2+(aq)+6e−→3Ca(s)
So, n=6.

Step 5: Calculate ΔG°

Using the formula:
ΔG∘=−nFEºcell
Where:
- F=96500C/mol (Faraday's constant)
Substituting the values:
ΔGº=−6×96500C/mol×(−4.37V)
ΔGº =6×96500×4.37
ΔGº =2530230J/mol

Step 6: Determine spontaneity

To determine if the reaction is spontaneous, we check:
1. If ΔGº <0: The reaction is spontaneous.
2. If Eºcell>0: The reaction is spontaneous.
From our calculations:
- ΔG∘=2530230J/mol (which is positive)
- Eºcell =−4.37V (which is negative)
Since both conditions are not satisfied, the reaction is not spontaneous.

Answer
(a) ΔG∘=2530230J/mol
(b) The reaction is not spontaneous.

(ii) Yes, the tarnish due to silver sulphate will be removed by placing the tarnished ware in
an aluminium pan. Actually, aluminium is is a stronger reducing agent than silver.
Therefore, it will reduce silver ions (Ag+) to metallic silver. It being silvery white in colour
will get slowly deposited on the walls of the silver ware and the tarnish will be removed.
Al(s)+3Ag+(aq) →Al3+(aq) +3Ag(s)

Alternatively,
Eºcell=Eºcathode−Eºanode= (−0.71)−(−1.66)=0.95 V is positive.
The redox reaction is feasible and the tarnish will be removed.
33 (A) =CH3COCH2CH3 Butan-2-one 5
(B) =CH3−(OH) CH−CH2−CH3 Butan-2-ol
( C) =CH3−CH=CH−CH3 But-2-ene
(D) =CH3CHO Ethanal

Ketones react with 2, 4-DNP reagent to form orange red precipitate. Ketones do not reduce
Tollen’s reagent. Methyl ketones (containing CH3CO−group) give iodoform test. Hence the
above structure of (A).

CH3−CO−CH2−CH3----NaOH/l2−−−−>CHI3 (Iodoform)+CH3CH2COONa (Sodium-

propionate)
CH3−CO−CH2----NaBH4/2[H]−−−>CH3−CH(OH)−CH2 −CH3 (Butan-2-ol)

(b) (i) Oxidation of propanal is easier than propanone

Propanol is easily oxidised to propanoic acid on treatment with common oxidising agents
like nitric acid, potassium permanganate or potassium dichromate.
Oxidation of propanone involves breaking of carbon-carbon bond and therefore requires
drastic conditions.
(ii) α− hydrogen of aldehydes and ketones is acidic in nature

The species obtained after the removal of H+ is stabilised by resonance.

OR
(a) (i) Cyanohydrin of cyclobutanone

(ii) Hemiacetal of ethanal

(b) (i) CH3−CH=CH−CH2−CHO Pent-3-enal

(ii) CH3CHO Ethanal
(c)
Tollens. Reagent Test: Propanal on treatment with ammoniacal silver nitrate gives a bright
silver mirror. This test is not given by propanone.

Fehling.s Solution Test: Propanal on heating with Fehling solution gives a reddish-brown
precipitate. Propanone does not give this test.