Section A

Question 1 ( 1.0 marks) Solution:

What is the coordination number in a rock-salt type structure?

In rock-salt, every Na+ ion is surrounded by 6 Cl ions and each Cl ion is surrounded by 6 Na+ ions. Thus, the coordination number of each type of ion in rock salt is 6.

Question 2 ( 1.0 marks)

State Raoults law for a binary solution containing volatile components.

Solution:

Raoults law states that for a solution of volatile liquids, the partial vapour pressure of each component in the solution is directly proportional to its mole fraction.

Question 3 ( 1.0 marks)

What is meant by order of a reaction being zero?

Solution:

For a zero-order reaction, the sum of the powers to which the concentration terms are raised is zero. Thus, the reaction is independent of concentration.

Question 4 ( 1.0 marks)

Write the IUPAC name of the following compound:

Solution:

The IUPAC name of the given compound is 3, 3-dimethyl-butanoic acid.

Question 5 ( 1.0 marks) Solution:

Mention one commercial use of N, N-Dimethyl aniline (DMA).

DMA is used as a promoter in the curing of polyesters and vinyl ester resins. It is also used for the preparation of several organic compounds.

Section B
Question 6 ( 2.0 marks)
State as a mathematical formula the de Broglie relationship for moving particles. What experimental evidence is available for this concept? OR Specify the ranges of values for quantum numbers ml and ms for an electron in an atom when the n quantum number value for it is 2. What is the significance of these values for the orbitals?

Solution:

According to De Broglie relationship for moving particles,

Where, is the wavelength of the wave associated with mass m moving with velocity v This concept was experimentally verified by Nickel Crystal with the help of the diffraction pattern of electrons. OR When Principal Quantum number, n = 2, l = 0, 1 When l = 0,

This signifies that the electron is present in the s sub-shell, and can have two orientations. When l = 1,

This signifies that the electron is present in the p sub-shell, which has 3 orbitals. Electrons in each orbital can have two orientations.

Question 7 ( 2.0 marks) Solution:

When can an endothermic process be spontaneous? Give an example of such a process.

Endothermic reactions can be made spontaneous by increasing the entropy of the system. For example

It is an endothermic reaction, but spontaneous.

Question 8 ( 2.0 marks)

Write balanced chemical equations for the following reactions:

(i)

(ii)

Solution:
(i)

(ii)

Question 9 ( 2.0 marks)

Explain any one of the following statements: (i) The transition metals are well known for the formation of interstitial compounds. (ii) The largest number of oxidation states are exhibited by manganese in the first series of transition elements.

Solution:

(i) Small atoms like hydrogen, carbon, boron and nitrogen occupy the interstitial sites in the lattices of transition metals. This gives rise to their interstitial compounds. This is mainly due to the vacant d orbital in transition metals and variable oxidation states. (ii) In each group of transition metals, oxidation states increase with increase in atomic number, reach a maximum in the middle, and then, start decreasing. The increase in oxidation states is due to the increase in the number of valence electrons with the increase in atomic number. As manganese lies in the middle, it has the maximum number of valence electrons. Hence, it shows maximum oxidation states.

Question 10 ( 2.0 marks) Solution:

Draw the three-dimensional representations of (R) - and (S) - butan- 2- ol.

Question 11 ( 2.0 marks)

Write chemical reaction equations to illustrate the following reactions: (i) Williamson synthesis of ethers (ii) ReimerTiemann reaction

Solution:

(i) Williamson synthesis of ethers: It is used for preparing both symmetrical and unsymmetrical ethers. It involves the treatment of alkyl halide with sodium alkoxide or sodium phenoxide to give ether and a sodium salt of halide.

(ii) ReimerTiemann reaction:

It involves the reaction between phenol and chloroform in the presence of an aqueous alkali at 333 K 343 K to give salicylaldehyde.

If the reaction is carried out with carbon tetrachloride, salicylic acid is produced.

Question 12 ( 2.0 marks) Solution:

Distinguish between addition polymers and condensation polymers and give one example of each class.

Addition polymer (i) It is formed when the monomer units are repeatedly added to form long chains. No elimination of any by-product takes place. (i)

Condensation polymer It is formed when two or more monomer units react together. Elimination of simple compounds like H2O, ROH takes place. For example: Nylon (6, 6) is a condensation polymer obtained from hexamethylene diamine and adipic acid.

(ii)

(ii) (iii)

(iii) For example: Polythene is addition polymer of ethylene.

Section C
Question 13 ( 3.0 marks)
Answer the following in the light of MO theory:

(a) Which has a higher bond order, C2 or

(b) Which species is not likely to exist, Li2 or Be2? OR (a) Compare the structural shapes of the following species:

SF6 and SF4 (b) What type of intermolecular forces exists between Cl2 and CBr4 present in a mutual solution?

Solution:
(a) In C2, Number of electrons = 12

Electronic configuration =

Now, bond order =

In

Number of electrons = 12+ 2 = 14

Electronic configuration =

Therefore, C22- has the higher bond order. (b) For Li2: Number of electrons = 6

Electronic configuration =

For Be2: Number of electrons = 8 Electronic configuration =

Therefore, Be2 is unstable and is not likely to exist. OR (a) SF6 molecule has perfect octahedral geometry, while SF4 has distorted trigonal bipyramidal geometry.

(b) Cl2 and CBr4 are both non-polar molecules. These molecules have no permanent dipoles. Hence, dispersion forces are the only forces that operate between these molecules.

Question 14 ( 3.0 marks)

(a) Name an element with which silicon can be doped to give an n-type semiconductor. (b) Which type of crystals exhibits piezoelectricity?

Solution:

(a) When Si is doped with group-15 elements, i.e., phosphorus, arsenic, etc., n-type semi-conductor is formed. (b) Piezoelectricity is exhibited by the crystals which produce voltage when pressure or stress is applied. Example Rochelle salt, Barium titanate

Question 15 ( 3.0 marks)

The vapour pressure of water is 12.3 kPa at 300 K. Calculate the vapour pressure of a one molal solution of a non-volatile non-ionic solute in water.

Solution:

The molality of the solution is 1. Therefore, 1 mol of solute is present in 1000 g of water.

Hence, number of moles of water in 1000 g = = 55.55 Total number of moles in the solution = 1 + 55.55 = 56.55

Mole fraction of H2O = Now, according to Raoults law,

Question 16 ( 3.0 marks)

Using the values of fH and rS, given herein, calculate the standard molar Gibbs energy of formation, (fG) for CS2 (l).

Given:

Solution:

H = 89.70 kJ mol1 = 89.70 103 J mol1

T = 298 K Standard molar Gibbs energy of formation, G

= 89.70 103 J mol1 298 K 151.34 J K1 mol1 = 89.70 103 45.10 103 J mol1 = 44.6 103 J mol1

Question 17 ( 3.0 marks)

The rates of most reactions double when their temperature is raised from 298 K to 308 K. Calculate activation energy of such a reaction. (R = 8.314 J mol1 K1, log 2 = 0.3010)

Solution:

Where, k1, k2 are rate constants Ea is activation energy R is universal gas constant = 8.314 J mol1 K1 T1 = 298 K, T2 = 308 K On substituting the above values, we get

 Ea = 52897.77 = 52.9 103 J 53 kJ

Question 18 ( 3.0 marks)

State what is observed when (i) the electrodes connected to a battery are dipped into a sol. (ii) an electrolyte solution is added to a sol. (iii) an emulsion is subjected to high-speed centrifugation.

Solution:

(i) When the electrodes connected to a battery are dipped in a solution, the ions produced by the dissociation of the electrolyte move towards the oppositely charged electrodes. The cations move towards the negatively charged electrode while the anions move towards the positively charged electrode. (ii) The addition of an electrolyte causes a colloidal solution to coagulate. (iii) On high-speed centrifugation, an emulsion decomposes into its constituent liquids.

Question 19 ( 3.0 marks)

Answer the following questions: (i) Which element in the first series of transition elements does not exhibit variable oxidation states and why? (ii) What happens when a solution of copper (II) sulphate is saturated with ammonia? (iii) Why do actinoids, in general, exhibit a greater range of oxidation states than lanthanoids?

Solution:

(i) Scandium, with the atomic number 21, does not show variable oxidation states. After losing three electrons, all the orbitals in scandium are fully filled. Thus, scandium exhibits only +3 oxidation state. (ii) In the presence of ammonia, copper (II) sulphate splits into two sets having slightly different energies. Thus, dd transition occurs and it acquires blue colour. In this reaction, [Cu(NH3)4]2+ is produced. (iii) Actinoids exhibit greater range of oxidation states than lanthanoids. This is because 5f, 6d and 7s sub-shells in actinoids are of comparable energies.

Question 20 ( 3.0 marks)

(i) Linkage isomerism

(a) Illustrate the following with an example each.

(ii) Coordination isomerism

(b) Why is

paramagnetic? (Ni = 28)

Solution:
(a) (i) Linkage isomerism results when there are two ways in which a ligand can get attached to the central atom. For example, NO2 group can bind to a metal, either through a nitrogen atom or an oxygen atom, as indicated:

(ii) Coordination isomerism is shown by the compounds in which the cation and the anion are complexes.

For example, (b) In [NiCl4]2, the oxidation state of nickel is +2. Thus, Ni has 8 electrons in the 3d orbital and no electron in the 4s orbital. Chlorine, being a weak-field ligand, forms sp3 hybridisation. As there are 2 unpaired electrons in the 3d orbital of Ni, the complex is paramagnetic.

Question 21 ( 3.0 marks)

Write the nuclear reactions for the following radioactive changes:

(i)

undergoes -decay

(ii)

undergoes -decay

(iii)

undergoes K-decay

(You can put X for the symbol which is not correctly known)

Solution:
(i)

(ii)

(iii)

Question 22 ( 3.0 marks) Solution:

Explain the mechanism of nucleophilic addition to a carbonyl group and give one example of such addition reactions.

The nucleophilic addition to a carbonyl groups proceeds via the following mechanism.

Example: The addition of hydrogen cyanide proceeds as follows:

Question 23 ( 3.0 marks)

Write the chemical equations for the following chemical reactions: (a) 1-Nitropropene is prepared from acetaldehyde (b) Benzonitrile is converted into acetophenone (c) A primary amine is prepared from a primary alkyl halide

Solution:
(a)

(b)

(c)

Question 24 ( 3.0 marks)

(i) Equanil (ii) Sucralose (iii) Carbon fibres

Mention one important use of each of the following:

Solution:

(i) Equanil is used in the treatment of depression & hypertension.

(ii) Sucralose is used as an artificial sweetening agent. (iii) Carbon fibres are used for preparing strong fibres such as carbon fibre-reinforced plastics.

Section D
Question 25 ( 5.0 marks)
(a) Write the formulation for the galvanic cell in which the reaction,

takes place. Identify the cathode and the anode reactions in it. (b) Write Nernst equation and calculate the emf of the following cell:

OR (a) Explain with one example each the terms weak and strong electrolytes. (b) Write the Nernst equation and calculate the emf of the following cell:

Solution:

(a) The galvanic cell is represented as

The reaction at the anode is given by

The reaction at the cathode is given by

(b) The Nernst equation for the given cell is

Here, Ecell = Ecathode Eanode = 0 (0.14) = 0.14 V

= 0.14 0.059 = 0.081 V OR (a) Strong electrolytes completely ionise when dissolved in water. For example, sodium chloride dissociates as Na+ & Cl. Weak electrolytes do not ionise completely when dissolved in water.

For example, carbonic acid dissociates as H+ & (b) The Nernst equation for the given cell is

Here,

Question 26 ( 5.0 marks)

(a) How would you account for any two of the following: (i) PbO2 is a stronger oxidising agent than SnO2 (ii) H3PO2 acts as a monobasic acid. (iii) The pKa value for HOCl is higher than that of HOClO (b) Draw the structures of the following species: (i) Peroxodisulphuric acid, H2S2O8 (ii) Xenon tetrafluoride, XeF4 OR (a) Assign reasons for any two of the following observations: (i) The lower oxidation state becomes more stable with increasing atomic number in Group 13. (ii) Hydrogen iodide is a stronger acid than hydrogen fluoride in aqueous solution. (iii) The basic character among the hydrides of Group-15 elements decreases with increasing atomic numbers. (b) Draw the structural formula for XeOF4.

Solution:
(a) (i) PbO2 is stronger oxidising agent than SnO2. This is because of the presence of poor shielding f orbitals in Pb. Thus, the effective nuclear charge on the outer shell electrons increases, and this makes PbO2 a strong oxidising agent. (ii) The structure of H3PO2 is

Though it has three hydrogen atoms, only one of these is attached to an oxygen atom. Only those hydrogen atoms are acidic which are connected to oxygen atoms; therefore, H3PO2 acts as a monobasic acid. (iii) The pKa value is determined by acidic strength. The conjugate base of HOCl is less stable than the conjugate base of HOClO. Thus, HO2Cl is a stronger acid. Also, increase in the number of oxygen atoms increases the stability of the conjugate base. (b) (i)

(ii)

OR (a) (i) The outer electronic configuration of group-13 elements is ns2 np1. On moving down the group, due to inert pair effect, there is a decrease in the tendency of the s electrons of the valence shell to participate in bond formation. This is due to the poor shielding of ns2 electrons by the intervening dorbital. Thus, the lower oxidation state becomes more stable with increasing atomic number. (ii) Hydrogen iodide is a strong acid. This is because the small size of hydrogen and the big size of iodine make the HI bond very weak. On the other hand, due to the similar sizes of H and F, the HF bond is quite strong. Thus, HI is a stronger acid than HF in aqueous solution. (iii) Among the group-15 elements, nitrogen has a small size and its density per unit volume is more. On moving down the group, the size of the central metal increases; thus, electron density decreases. As a result, the electron-donor capacity or the basic strength of group-15 hydrides decreases with increasing atomic numbers. (b)

Question 27 ( 5.0 marks)

(a) Name the three major classes of carbohydrates and give the distinctive characteristic of each class.

(b) What are nucleotides? Name two classes of nitrogen-containing bases found amongst nucleotides. OR (a) Describe the classification of lipids based on their chemical compositions. Mention the chief chemical characteristic of each class. (b) Explain the term mutarotation.

Solution:

(a) Based on their behaviour on hydrolysis, carbohydrates are classified into three major groups. (i) Monosaccharides They cannot be hydrolysed to still simpler carbohydrates. Example: Glucose (ii) Oligosaccharides They give two to ten units of monosaccharides on hydrolysis. Example: Sucrose (iii) Polysaccharides They are polymeric molecules and give large number of monosaccharide units on hydrolysis. Example: Starch (b) The monomeric units of nucleic acids are called nucleotides. It consists of three parts a phosphate group, a fivecarbon sugar and a nitrogen heterocyclic base. The nitrogen-containing bases are derivatives of two classes purine and pyrimidine. OR (a) Out of current syllabus (b) Out of current syllabus