CHEMISTRY Paper 1 (Theory) Time: Three hours Maximum marks: 70 Instructions to Candidates You are allowed additional 15 minutes for only reading the question paper. You must NOT start writing during the reading time. This question paper has 11 printed pages. It is divided into four sections and has 21 questions in all. All questions are compulsory. Answer all questions. Section A has fourteen subparts. Each question carries 1 mark. While attempting Multiple Choice Questions in Section A, you are required to write only ONE option as the answer. Section B has ten questions. Each question carries 2 marks. Section C has seven questions. Each question carries 3 marks. Section D has three questions. Each question carries 5 marks. Internal choices have been provided in one question each in Sections B, C and D. The intended marks for questions are given in brackets [ ]. All working, including rough work, should be done on the same sheet as, and adjacent to the rest of the answer. Balanced equations must be given wherever possible and diagrams where they are helpful. When solving numerical problems, all essential workings must be shown. In working out problems, use the following data: Gas constant R=1·987cal deg -1mol-1=8·314JK-1mol-1 =0·0821dm3atmK-1mol-1, 1l atm =1dm3atm=101·3 J. 1 Faraday=96500 coulombs. Avogadro’s number= 6·023×10 23.
SECTION A – 14 MARKS Question 1
(A) Fill in the blanks by choosing the appropriate word(s) from those given in the brackets: [41] [ but-1-ene, but-2-ene, greater, lesser, butan-l-ol, Markonikov’s rule, Saytzeff’s rule, basic, neutral, decreases, increases, 4, 2, 6, +1, +2, +3, +4 ]
(i) 2-Chlorobutane on heating with alcoholic KOH solution gives _______ as
major product according to ________.
(ii) Greater the ________ strength of the ligand, _______ is the stability of the complex.
This paper consists of Eight printed pages. Turn over
(iii) In the complex [E(en)2 (C2O4)] NO2, the coordination number and oxidation number are _______ and _______ respectively.
(iv) The specific conductivity of the electrolyte ______ with dilution whereas its molar conductivity ________.
(B) Select and write the correct alternative from the choices given below: [71] (i) The solution of Urea boils at 100.18 oC at one atm. If K f and Kb for water are 1.86 and 0.512 K kg mol1 respectively, the above solution will freeze at:
(a) 6.54oC (b) 0.654oC
(c) 6.54oC (d) 0.654oC
(ii) The correct order of the Stiochiometries of AgCl formed when AgNO 3 in excess is added in complexes COCl3.6NH3, COCl3.5NH3, COCl3.4NH3 respectively is:
(c) 2 AgCl, 3 AgCl, 1 AgCl (d) 1 AgCl, 3 AgCl, 2 AgCl (iii) Which of the following will give carbylamine test?
(a) (C2H5)3N (b) (C2H5)2NH
(c) C2H5NH2 (d) C2H5NHCH3
(iv) Which of the following alkyl halide will undergo SN1 reaction most readily?
(a) (CH3)3CF (b) (CH3)3CCl
(c) (CH3)3CBr (d) (CH3)3CI
(v) Which of the following products are obtained in the given reaction:
(P) [A] is RCOOMg X
(Q) [A] is RCOO X (R) [B] is RCH2OH (S) [B] is RCOOH (a) Only (P) & (R) (b) Only (R) & (Q) (c) Only (S) & (P) (d) Only (Q) & (S)
(2) (vi) Assertion: Manganese show a maximum oxidation state of +5. Reason: Manganese has 5 electrons in the 3d subshell. (a) Both Assertion and Reason are true and Reason is the correct explanation of Assertion. (b) Both Assertion and Reason are true but Reason is not the correct explanation of Assertion. (c) Assertion is true but Reason is false. (d) Assertion is false but Reason is true. (vii) Assertion: The bond angle in alcohols is slightly less than the tetrahedral angle. Reason: In alcohols, the oxygen of OH group is attached to sp 3 hybridized carbon atom. (a) Both Assertion and Reason are true and Reason is the correct explanation of Assertion. (b) Both Assertion and Reason are true but Reason is not the correct explanation of Assertion. (c) Assertion is true but Reason is false. (d) Assertion is false but Reason is true.
(C) Read the passage given below carefully and answer the questions that follow: [31] Ramesh tried his best to carry out the reaction between the pure hydrogen with pure oxygen but he failed. Mohan, a friend of Ramesh, suggested that the reaction must be carried out in the presence of Platinum catalyst. As he placed platinum in the reaction mixture, the reaction took place explosively. (i) Mention the role of catalyst in the above reaction. (ii) What is activation energy? (iii) What is the role of a promoter with respect to the rate of reaction?
SECTION B – 20 MARKS Question 2 [2] A rusted piece of iron undergoes electrochemical reactions. Write the chemical reaction taking place at: (i) the electrode that behaves as an anode (ii) the electrode that behaves as a cathode.
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Question 3 [2] What happens when (write chemical equations only): (i) Diethyl ether is treated with Phosphorous pentachloride. (ii) Ethyl alcohol is treated with Methyl magnesium bromide.
Question 4 [2] An organic compound [A] having molecular formula C6H6O gives a characteristic colour with aqueous FeCl3 solution. [A] on treatment with CO2 and NaOH at 400 K under pressure gives [B] which on acidification gives compound [C]. [C] reacts with Acetyl chloride to give [D] which is a popular pain killer. Identify the compounds [A], [B], [C] and [D].
Question 5 [2]
The rate constant for first order reaction is 60 s1. How much time will it take to 1 reduce the concentration of the reaction to th of the initial value? 10 Question 6 [2] Account for the following:
(i) Carboxylic acids are stronger acids than Phenol.
(ii) Benzaldehyde is less reactive than Propionaldehyde.
Question 7 [2] Write the IUPAC names of: (i) Linkage isomer of [Co(NH3)5 (NO2)] Cl2 (ii) Ionization isomer of [Fe(NH3)5Br] SO4
Question 8 [2] How will you convert: (i) Benzene to m-nitro benzoic acid (ii) Formaldehyde to Ethyl alcohol.
Question 9 [2] (i) Arrange the following in increasing order of their acidic strength. Benzoic acid, 4-nitrobenzoic acid, 3, 4-dinitrobenzoic acid, 4-methoxy benzoic acid. OR
(4) (ii) Identify [A], [B], [C] and [D] [2]
Question 10 [2] Can Fe3+ oxidize Br to Br2 under standard conditions? Justify your answer.
EoFe3+/Fe2+ = 0.771 V, E o Br /Br = 1.09 V
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Question 11 [2] Give a chemical test to distinguish between the following pairs of organic compounds:
(i) Phenol and Benzoic acid
(ii) Propanal and Propanone
SECTION C – 21 MARKS Question 12 [3] Identify the compounds [A], [B] and [C].
(i)
(ii)
Question 13 [3] o Vapour pressure of water at 20 C is 17.5 mm of Hg and lowering of vapour pressure of a sugar cane solution [Molecular weight of Cane Sugar = 342] is 0.061 mm of Hg. Calculate: (i) The relative lowering in vapour pressure. (ii) The vapour pressure of the solution. (iii) The mole fraction of sugar and water.
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Question 14 [3] Write chemical equations to illustrate the following name reactions: (i) Perkin’s reaction (ii) Wolff Kishner Reduction reaction (iii) Clemmenson’s Reduction
Question 15 [3] Metal complexes show different colours due to d-d transitions. The complex absorbs light of specific wavelength to promote the electron from t2g to eg level. The colour of the complex is due to the transmitted light, which is complimentary of the colour absorbed. The wave number of light absorbed by different complexes of Cr ion are given below: S. No. Complex Wave number of light Energy of light absorbed (cm1) absorbed (kJ / mol) (a) [Cr A6]3 13640 163 (b) [Cr B6]3+ 17830 213 (c) [Cr C6]3+ 21680 259 (d) [Cr D6]3 26280 314 Answer the following: (i) Out of the ligands, ‘A’, ‘B’, ‘C’ and ‘D’, which ligand causes maximum crystal field splitting and why? (ii) Which of the two ‘A’ or ‘D’ will be a weak field ligand? Why? (iii) If the ligand attached to Cr3+ ion in the complexes given in the table above are water, cyanide ion, chloride ion, and ammonia (not in this order), identify the ligands in the following compounds: (a) [Cr A6]3 (b) [Cr C6]3+
Question 16 [3] (i) (a) Calculate the λ m for Cl ion from the data given below:
λ 2 1 2+ 2 m MgCl2 = 25.8.6 s cm mol and λ m Mg = 106 S cm mol 1
(b) The cell constant of a conductivity cell is 0.146 cm1. What is the conductivity of 0.01M solution of an electrolyte at 298 k, if the resistance of the cell is 1000 ohm? OR
(6) (ii) Calculate Eocell , Ecell and G for the following cell reaction at 298 K: 2Cr(s) + 3Fe2+ (0.01M) 2Cr3+ (0.1M) + 3Fe(s) (Given that Eo Cr3+/Cr = 0.74 V and Eo Fe2+/Fe = 0.44 V) Question 17 [3] Primary alkyl halide C4H9Br [A] reacts will alcoholic KOH to give compound [B], which reacts with HBr to give [C] which is an isomer of [A]. When [A] is reacted with sodium metal it gives compound [D] C8H18. Identify [A], [B], [C], [D] and write the reaction of [A] with sodium metal. Question 18 [3] The rate constant for a reaction is 1.5 107 s1 at 50oC and 4.5 107 s1 at 100oC. Calculate the Arrhenius parameter (A) and activation energy (Ea).
SECTION D – 15 MARKS Question 19 [5] (i) Give reason for the following: (a) HCOOH does not give HVZ reaction while CH3COOH does. (b) Oxidation of alcohols to get aldehyde is carried out under controlled conditions. (ii) An unknown aldehyde [A] on reacting with alkali gives a -hydroxy aldehyde, which loses water to form an unsaturated aldehyde But-2-enal. Another aldehyde [B] undergoes disproportionation reaction in the presence of conc. alkali to form products [C] and [D]. [C] is an aryl alcohol with formula C7H8O. (a) Identify [A] and [B]. (b) Write the sequence of the reaction involved. (c) Name the product when [B] reacts with Zinc amalgam and Hydrochloric acid. Question 20 [5] (i) Give reason for each of the following: (a) Among CH2Cl2 and CuCl2, which is more stable and why? (b) Transition metals show variable oxidation states. (c) Mn2+ compounds are more stable than Fe2+ towards +3 oxidation state. (Atomic Number of Mn = 25, Fe = 26)
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(ii) Give balanced and complete reactions for following:
Question 21 [5] (i) (a) Manvi was making noodles in boiling water. When he added common salt (NaCl) to boiling water, the water stopped boiling for a short while. If Manvi had added 15.0 g of NaCl to 250.0 g of water, calculate the boiling point of solution assuming that NaCl dissociated completely in water. (Kb for water = 0.512 K kg mol1; molecular mass of NaCl = 58.44 g mol1)
(b) Water vapour and liquid water are in equilibrium in a container. At room temperature, the vapour pressure of water is 25 mm of Hg. The volume is V ml.
(a) What will be the vapour pressure of water if the volume of water is reduced to V/4 ml without any change in temperature? Give a reason.
(b) Will there be a change in vapour pressure if more water (at room temperature) is added to the container? (Give reason).
OR
(ii) (a) Calculate the boiling point of urea solution when 8.0 g of it is dissolved in 250 g of water. Boiling point of pure water is 373 k.
(Kb of water = 0.52 K kg mol1 , Molecular weight of urea = 60 g/mol)
(b) A pure NaCl solution with salt concentration less than 0.91% (mass / vol.) in hypertonic solution to human blood. Is this statement true of false? Give reason.
(c) What will be the effect on the value of molality and molarity of a solution with change in temperature?
(d) An azeotrope shows positive deviation. Is the boiling point of the solution higher or lower than the boiling points of its components? Give reason.
