CBSE XII Solution to Board Paper Set 1 (Delhi) Chemistry Theory Solution 1: This statement means that some

e of the physical properties of crystalline solids such as electrical resistance or refractive index show different values when measured along different directions in the same crystals. Solution 2. The Molar conductivity of a solution at a given concentration is related to conductivity of that solution, by the following relation.

A Where, m is molar conductivity and k is the conductivity of the solution.

Solution 3. Electrophoresis is the phenomenon of movement of colloidal particles under the applied electric potential. Solution 4. XeF2 is a linear molecule and adopts the following structure:

m = k

Solution 5.

The IUPAC name of the given structure is 2, 2-Dimethylbromopropane. Solution 6.

Solution 7. The solubility order of the given amines is as follows C6H5NH2 < (C2H5)2NH < C2H5NH2 Reason: The more extensive the H-bonding, the higher is the solubility. C2H5NH2 contains two H-atoms whereas (C2H5)2NH contains only one H-atom. Thus C2H5NH2 undergoes more extensive H-bonding than (C2H5)2NH. Hence, the solubility in water of C2H5NH2 is more than that of (C2H5)2NH. Further, the solubility of amines decreases with increase in the molecular mass. This is because the molecular mass of amines increase with an increase in the size of the hydrophobic part. The molecular mass of C6H5NH2 is greater than that of C2H5NH2 and (C2H5)2NH. Thus, the solubility of C6H5NH2 is less than that of C2H5NH2 and (C2H5)2NH. Solution 8. A polymer that can be decomposed by bacteria is called a biodegradable polymer. For example: poly- -hydroxybutyrate-CO- -hydroxyvalerate (PHBV) is biodegradable aliphatic polyester.

O CH CH 2 C O CH CH 2 C | || | || CH O CH CH O 3 2 3 n PHBV
Solution 9. The process of corrosion is a redox reaction that involves simultaneous oxidation and reduction reactions. It can therefore be referred to as an electrochemical reaction. In the process of corrosion, due to the presence of air and moisture, oxidation takes place at a particular spot of an object made of iron. That spot behaves as the anode. The reaction at the anode is can be written as follows. Anodic reaction: Fe (s) Fe2+ (aq) + 2e Electrons released at the anodic spot move through the metallic object and go to another spot of object. There, in the presence of H+ ions, the electrons reduce molecular oxygen. This spot behaves as the cathode. There H+ ions

come either from H2CO3 , which are formed due to the dissolution of carbon dioxide from air into water or from the dissolution of other acidic oxides from the atmosphere in water. The reaction corresponding at the cathode is written as follows. Cathodic reaction: O 2 (g) + 4H+ (aq) + 4e 2H 2O(l) Thus, the overall reaction is:

2Fe(s) + O 2 (g) + 4H + (aq) 2Fe2+ (s) + 2H 2O (l)

Also, ferrous ions are further oxidized by atmosphere oxygen to ferric ions. These ferric ions combine with moisture, present in the surroundings, to form hydrated ferric oxide (Fe2O3, xH2O) i.e., rust. Solution 10.

Ni(s) + 2Ag+(aq) Ni2+(aq) + 2Ag(s), Eo = 1.05V The galvanic cell of the given cell reaction is depicted as : Ni(s) | Ni2+ || Ag+ | Ag(s) Now, the s tan dard cell potential is Eocell = 1.05 V n=2 F = 96500 C mol1 rGo = nFEocell rGo = 2 96500 C mol1 1.05 V = 202650 Jmol1 = 202.65 kJmol1
Solution 11. The rate expression can be defined as an expression in which the rate of reaction is given as the product of the molar concentration of the reactants, with each term raised to some power, which may or may not be the stoichiometric coefficients of the reacting species in a balanced chemical equation. The rate constant can be defined as the rate of reaction when the concentration of each of the reactant is taken as unity. Example: 2NO(g) + O2 (g) 2NO2 (g) The rate expression for the above reaction can be written as follows:

Rate = k[NO]2 [O 2 ] (Experimentally determined)

Now, if the concentration of NO and O2 is taken to be unity, then the rate constant is found to be equal to the rate of the reaction.

Solution 12. (i) The Shorter N O bond in NO 2 is due to the existence of resonance in NO 2 . The resonating structure can be drawn as follows.

Due to resonance in NO 2 , the two bonds are equivalent. This leads to a decrease in bond length. Thus, the N O bond length in NO 2 resembles a double bond. Now, the resonating structure for NO 3 can be drawn as:

As seen from the above resonating structure of NO 3 , the three oxygen atoms are sharing two single bonds and one double bond. So the real N-O bond length resembles a single bond closely. This explains the existence of shorter bond length of the N-O bond in NO 2 than in NO 3 . (ii) The kinetic inertness of SF6 can be explained on the basis of its structure.

As seen from the above structure, the six fluorine (F) atoms protect the sulphur atom from attack by the regents to such an extent that even thermodynamically most favourable reactions like hydrolysis do not occur. OR (i) In gaseous and liquid state, PCl5 has a trigonal bipyramidal structure. In this structure, the two axial P Cl bonds are longer and less stable than the three equatorial P Cl bonds. This is because of the greater bond pair bond pair repulsion in then axial bonds. Hence, all the bonds in PCl5 are not equivalent. Because of stronger S-S bonds as compared to O-O bonds, sulphur has a greater tendency for catenation than oxygen.

(ii)

Solution 13. (i) In aqueous solution, Cu+ ion undergoes oxidation to Cu2+ ion. The relative stability of different oxidation states can be seen from their electrode potentials.

Cu + (aq) + e Cu (s), Cu 2+ (aq) + 2e Cu(s),

E o(red) = 0.52V E o(red ) = 0.34V

(ii)

Due to more reduction electrode potential value of Cu+, it undergoes oxidation reaction quite feasibly. Hence, Copper (I) ion is not known in aqueous solution. The actinoids show a larger number of oxidation states because of very small energy gap between the 5f, 6d and 7s sub-shells. Hence all their electrons can take part in bond formation.

Solution 14. Riemer-Tiemann reaction: Riemer-Tiemann reaction involves the treatment of phenol with chloroform in the presence of aqueous sodium hydroxide at 340 K followed by hydrolysis of the resulting product to give 2-hydroxybenzaldehyde (salicylaldehyde). The chemical reaction can be represented as follows. (i)

(ii)Friedel-Crafts acetylation of anisole: Friedel-Crafts acetylation of anisole involves the treatment of anisole with either acetyl chloride or acetic anhydride to give 2-methoxyacetophenone (as a mirror product) and 4methoxyacetophenone (as a major product), the chemical reaction can be represented as follows.

Solution 15. (i) Phenol on reaction with concentrated HNO3 results in the formation of picric acid.

(ii)

2-Methyl propene can be obtained from 2-methyl propanol by the reaction of the later with alc. KOH

Solution 16. The -form of glucose and -form of glucose can be distinguished by the position of the hydroxyl group on the first carbon atom. In open chain -glucose, the hydroxyl group on the first carbon atom is towards the right whereas, in the closed ring - glucose, the hydroxyl group on the first carbon atom is below the plane of the ring. On the other hand, in open chain -glucose, -glucose, the hydroxyl group on the first carbon atom is towards the left whereas, in the closed ring glucose, the hydroxyl group on the first time atom is above the plane of the ring. The structures of open and closed -form and - form of glucose can be drawn as follows.

Solution 17. I.

Primary structure of proteins: Each polypeptide chain in a protein has amino acids linked with each other in a specific

II.

sequence. This sequence of amino acids is said to be the primary structure of proteins. Secondary structure of proteins: The secondary structure of proteins refers to the shape in which a long polypeptide can exist. The two different secondary structure possible are -Helix structure and pleated sheet structure. -Helix structure: In -Helix structure, a polypeptide chain forms all possible hydrogen bonds by twisting into a helix with NH group of each amino acid residue and hydrogen bonded to >C=O of an adjacent turn of helix. -Helix structure: In a -pleated structure, all peptide chains are stretched out of nearly maximum extensions and then laid side by side which are held together by intermolecular hydrogen bonds. Uses of Bakelite: (a) It is used for making combs. (b) It is used for manufacturing electrical switches. (ii) Uses of Nylon 6: (a) It is used for making tyre cords. (b) It is used for making fabrics and mountaineering ropes.

Solution 18. (i)

Solution 19. Given, silver crystallizes in fcc unit cell

So, r =

a 2 2

Where e is the radius of the silver atom and a is the edge length Now, edge length = 400 pm = 400 1010 cm Thus,

r=

4001010 cm 21.414

= 141.441010 cm = 141.4 pm
Thus, the radius of the silver atom was found to be 141.4 pm Solution 20. (a)The plot of [N2O5] v/s t is as follows

[N2O5] (M) 0.400 0.289 0.209 0.151 0.109

Time (min) 0.00 20.0 40.0 60.0 80.0

log[N2O5] -.03979 -0.5391 -0.6798 -0.8210 -0.9625

From the plot, log [N2O5] v/s t, we obtain

Slope = =

0.70 (0.60) 40 20 0.70 + 0.60 0.10 = 20 20 k 2.303

Also, slope of the line of the plot =

k 0.10 = 2.303 20 0.10 2.303 = 0.01151 or k = 20 or, k = 1.15 103 min1

(b) After 100 min

k=

[N O ] 2.303 log 2 5 o t [N 2O5 ]t 2.303 0.400 log t 0.098

After 100 min k=

= 0.1406 min1
(c) The initial rate of reaction

r = k[N 2O5 ] = 1.15 103 0.400 = 4.6 104 s1

Solution 21. (i) Production of high vacuum: Traces of air can be adsorbed by charcoal from a vessel, evacuated by a vacuum pump to give a very high vacuum. (ii) Heterogeneous catalysis: The gaseous reactants are adsorbed on the surface of the solid catalysts. As a result, the concentration of the reactants increase on the surface and hence the rate of the reaction increases. (iii) Froth floatation process: This process is used to remove gangue from sulphide ores. The basic principle involved in this process is adsorption. In this process, a mixture of water pine oil is taken in tank. The impure powdered sulphide ore is dropped in through hopper and the compressed air is blown in through the agitator is rotator is rotated several times. As a result, froth is formed and the sulphide ores get adsorbed in the froth. The impurities settled down and are let out through an outlet at the bottom. The froth formed is collected in froth collector tank. After sometime, the ore particles in the froth collecting tank start settling gradually, which are then used for further metallurgical operations. OR

(i)

(ii)

(iii)

A micelle is an aggregate of surfactant molecules dispersed in a a liquid. A micelle in aqueous solution forms as aggregate such that the hydrophilic head regions are in the centre of micelle. Peptization is the process of conversion of a precipitate into a colloidal sol by shaking it with the dispersion medium in the presence of an electrolyte. The electrolyte used in this reaction is known as a peptizing agent. Desorption is the process of removing an adsorbed substance from the surface through which it was adsorbed.

Solution 22. (i) Vapour phase refining : Vapour phase refining is the process of refining metal by converting it into its volatile compound and then, decomposing it to obtain a pure metal. The basic principle involved in this process are: (a) The metal should form a volatile compound with an available reagent, and (b) The volatile compound should be easily decomposable so that the metal can be easily. Nickel, zirconium, and titanium are refining using this method. (ii) Electrolytic refining of a metal is the process of refining impure metals by using electricity. In this process, impure metal is made the anode and a strip of pure metal is made the cathode. A solution of a solution salt of the same metal is taken as the electrolyte. When an electric current is passed, metal ions from the electrolyte are deposited at the cathode as pure metal and the impure metal from the anode dissolves into the electrolyte in the form of ions. The impurities present in the impure metal gets collected below the anode. This is known as anode mud.

Anode : Cathode :

M M n + + ne M n + + ne M

(iii)

In the process of leaching, the finely divided silver is treated with dilute solution of sodium cyanide while a current of air is continuously passed. As a result, silver pass into the solution forming solution dicyanoargenate(I) while the impurities remain unaffected which are filtered off.

Ag 2S + 4NaCN

2Na[Ag (CN )2 ]

Na 2S

Sodium dicyano arg enate (I)

Solution 23. (i) (ii) (iii)
2 + 5C2 O 4 + 2MnO 2Mn 2+ + 8H 2O + 10CO 2 4 + 16H

2KMnO4 K 2 MnO4 + MnO2 + O2

2 Cr2O7 + 8H+ + 3H 2S 2Cr3+ + 7H 2O + 3S

Heated

Solution 24. (i) K4[Mn(CN)6] Name: Potassium hexacyanomanganate(II) Stereochemistry Does not show geometric or optical isomerism Magnetic behaviour Paramagnetic (ii) [Co(NH3)5Cl] Cl2 Name: Pentaamminedchloridocobalt (III) chloride Stereochemistry Does not geometric isomerism but is optically active Magnetic behaviour Paramagnetic (iii) K2[Ni(CN)4] Name: Potassium tetracynoinickelate (II) Stereochemistry Does not show geometric or optically isomerism Magnetic behaviour Diamagnetic

Solution 25.

(i)

(ii)

Haloalkanes can easily dissolve in organic solvents of low polarity because the new forces of attraction set up between haloalkanes and the solvent molecules are of same strength as the forces of attraction being broken. A mixture of equal amounts of two enantiomers is known as racemic mixture. For example: When a 3o halide undergoes substitution with KOH, the reaction proceeds through SN1 mechanism forming the racemic mixture in which one of the products has the same configuration as a reactant, while the product has an inverted configuration.

(iii)

The SN1 substitution reaction involves the formation of carbocation, which is not affected by the presence of bulky groups. Thus, C6H5CH(C6H5)Br will be more reactive towards SN1 substitution reaction forming racemic mixture.

Solution 26. (a) The basicity of amines depends on the +I effects of the alkyl group. The presence of CH3 group in alkylamine increases the electron density on the nitrogen atom and thus increases the basicity. Hence, alkylamine is more basic than ammonia CH3NH2 > NH3 (b) (i)

(ii)

Solution 27. (i) Detergents: A detergents is a surfactant or a mixture of surfactants having cleaning properties in dilute solution. Commonly, detergent refers to alkylbenzenesulphonates. For example: Sodium dodecylbenzene sulphonate (ii) Food preservatives: Food preservatives are chemicals that prevent food from spoilage due to microbial growth. Table salt, sugar,

vegetable oil, sodium benzoate (C6H3COONa), and salts of propanoic acid are some examples of food preservatives. (iii) Antacids: Any drug that is used to counteract the effects of excess acid in the stomach and raise the pH to an appropriate level is called an antacid. Example: Omeprazole Solution 28. (a) Molartiy is defined as the number of moles of solute dissolved per litre of solution. Mathematically M =
Number of moles of solute Volume of solution in litres (dm3 )

Molality of a solution is defined as the number of moles of solute dissolved in 1000 grams of solvent. Mathematically, m =
Number of moles of the solute Mass of solvent in kg

While molarity decreases with an increase in temperature, molality is independent of temperature. This happens because molality involves mass, which deos not change with a change in temperature, while molarity involves volume, which is temperature dependent. (b) Given w2 = 10.50 g w1 = 200g Molar mass of MgBr2 (M2) = 184 g Using the formula,
Tf =
1000 k f w2 w1 M2 1000 1.86 10.50 200 184 19.530 = 0.53 200 184

Now, Tf = To - Tf = 273 0.53 = 272.47 K OR

(a) Osmosis : The process of flow of solvent molecules from pure solvent to solution or from solution of lower concentration of solution of higher concentration through a semi permeable membrane is called osmosis. Osmotic pressure : The pressure required to just stop the flow of solvent due to osmosis is called osmotic pressure () of the solution. Yes, the osmotic pressure of a solution is colligative property. The osmotic pressure is expressed as.
=
n RT V

Where, = osmotic pressure n = number of moles of solute V = volume of solution T = temperature From the equation, it is clear that osmotic pressure depends upon the number of moles of solute n irrespective of the nature of the solute. Hence, osmotic pressure is a colligative property. (b) Given, Kb = 0.512 k kg mol-1 w2 = 15.00 g w1 = 250.0 g M2 = 58.44 g Using the formula,
Tb =
1000 Kb w2 w1 M2 1000 0.512 15.00 250.0 58.44
7.680 = 0.52 14.600

Now, Tb = To + Tb = 373 + 0.53 = 373.53 K Ans29. (a)

(i) Propanal (CH3CH2CHO) can be distinguished from propanone (CH3COCH3) by iodoform test. Being a methyl ketone, propanone on treatment whith I2/NaOH undergoes iodoform reaction to give a yellow ppt. of iodoform CH3COCH3 + 3NaOI Propanone CHI3 + CH3COONa + 2NaOH

Iodoform

Propanal on the other hand does not give this test.

NaOI CH3CH2CHO No yellow ppt. of

Propanal

Iodoform

(ii) Benzaldehyde (C6H5CHO) and acetophenone (C6H5COCH3) can be distinguished by iodoform test. Acetophenone, being a methyl ketone on treatment with I2/NaOH undergoes iodoform reaction to give a yellow ppt. of iodoform. On the other hand, benzaldehyde does not give this test. C6H5COCH3 + 3NaOI Acetophenone

C6H5COONa + CHI3 Iodoform

+ 2NaOH

NaOI C6H5CHO No yellow ppt of iodoform

Benzaldehyde (b) (i)

(i)K Cr O / H SO (ii) CH3CH2CH2CH2OH CH3CH2CH2COOH

2 2 7 2 4

(ii) Dil.H2SO4

Butanol (iii)

Butanoic acid

OR (i) Cannizaro reaction In this reaction, the aldehydes which do not have an hydrogen atom, undergo self oxidation and reduction

(disproportionation) reaction on treatment with a concentrated alkali. Example:

(ii) Decarboxylation The decarboxylation reaction can be carried out either by using soda lime or by electrolysis Using soda lime Sodium salts of carboxylic acids when heated with soda lime (NaOH + CaO) in the ratio 3:1 undergoes decarboxylation reaction to yield alkanes.
NaOH CaO R COONa R H + Na2CO3 Heat

(Alkane) Electrolytic decarboxylation Electrolysis of aqueous solutions of sodium of potassium salts of carboxylic acids give alkanes having twice the number of carbon atoms present in the alkyl group of acid. This is known as Kolbes decarboxylation.
+ 2RCOONa 2RCOO + 2Na + H2O 2OH + 2H

At Anode: H2 2H+ + 2e-

(b) (i)

(ii)

(iii) C6H5CONH2 C6H5COOH Benzoic acid Ans30. (a)

H3 O+ heat

(i) As we move down the group 17, the size of the atom increases from fluorine to chlorine. The larger difference in the size of N and Cl results in the weakness of strength of N Cl bond. On the other hand, the difference in size of N and F is small; consequently the N F bond is quite strong. As a result, NF3 is an exothermic compound. (ii) Due to the small size of F atom, the three lone pair of electrons on each F atom F F molecule repels the bond pair. As a result, F F is most reactive of all the four common halogens. (b)
2SO2 + CO2 + 2H2O (i) C + 2H2SO4

Sulphur dioxide (ii) P4 + 3NaOH + 3H2O PH3 + 3NaH2PR2 Phosphine (iii) Cl2 + 3F2 2ClF3
,CO2

(excess)

Chlorine trifluoride OR

(a) (i) In a period, the electro negativity decreases in the order Cl > S > P. As a result, the loss of H+ ions decreases. Thus, the acidic strength of the hydrides decreases in the following order: HCl > H2S > PH3 (ii) The tendency to form pentahalides decreases down the group 15 due to inert pair effect i.e., in Bi the s-electrons remain inert and do not take part in bonding. (b) (i) P4 + 10SO2Cl2 4PCl5 + 10SO2 (ii) 2XeF2 + 2H2O 2Xe + 4HF + O2 (iii) I2 + 10HNO3 2HIO3 + 10NO2 + 4H2O (conc).