Birla Institute of Technology & Science, Pilani, Rajasthan 333031 COMPREHENSIVE EXAMINATION II Semester, 2011-2012 Course Title: Chemistry

Laboratory Course Number: CHEM F110 Date: 11.05.2012 Make up (CLOSED BOOK) Time: 60 minutes Max. Marks: 60
Note:

Q.1 Conductance of three liquids I,J and K (each occupying volume of 50 ml) was measured as cI, cJ and cK respectively, using same conductivity cell. Chemical analysis proved that I was triply distilled water, J was 0.1 N hydrochloric acid and K was 0.1 N acetic acid. 1 ml of 0.1 N NaOH was added to each of these and the conductance was measured again. What can you comment about the conductometric observations of these liquids? (A) |cI-cJ| increases and |cJ-cK| decreases on addition of the base. (B) |cI-cJ| decreases and |cJ-cK| increases on addition of the base. (C) |cI-cJ| as well as |cJ-cK| decrease on addition of the base. (D) |cI-cJ| as well as |cJ-cK| increase on addition of the base. Q. 2 In a conductometric titration of acetic acid against potassium hydroxide, the rate of increase in conductance before the endpoint is less than the one after the endpoint. The dominant factor responsible for this is.... (A) K+ ions are bulkier than H+ ions (B) CH3COO- ions are bulkier than OH- ions (C) Water molecules are created before endpoint thereby reducing the (D) Conductivity of OH- ions is always greater than that of H+ ions Q.3 In a conductivity cell, the two metal plates of dimensions I x J cm2 are held parallel to each other at a distance K cm. Which of the following alterations will keep the conductivity measurements using the cell unaltered? (A) I is doubled, J is halved and K is increased to 1.5 times the original (B) I is halved, J is doubled and K is halved (C) I is doubled, K is doubled and J kept unaltered (D) I, J and K are all doubled Q. 4 CH3COOH (aq) + C2H5OH (aq) = CH3COOC2H5 (aq) + H2O (l), for this reaction, y ml z (N) NaOH is required for the neutralization of the mixture containing 4 ml 4(N) HCl, pure ethanol and 1 ml glacial acetic acid. x ml z (N) NaOH is required for the neutralization of 4 ml 4(N) HCl. If density of glacial acetic acid is b gml-1, then the amount of ethanol is consumed in the esterification is as follows (MW of glacial acetic acid is 60): (A) z(y x)/1000 mol (B) z(x-y)/1000 mol (C) [b/60 z(y-x)/1000] mol (D) [b/60 z(x-y)/1000] mol Q. 5 Which is the rate determining step in the following mechanism of esterification: (A)

There are three pages with 30 questions on the first two pages, and the third page is the answer sheet. Match the Code A or B on all pages of your question paper with the code on your answer sheet. Indicate the most appropriate answer by entering A, B, C or D in the box provided in the answer sheet. Do not overwrite. Do not do rough work on the answer sheet. Do not use pencil. Each correct answer will be awarded two marks. One mark will be deducted for every two wrong answers. Useful data (At. Wt.: Na = 23, K = 39, Ca = 40, Cu = 63)

(B)

(C) 1

(D)

Q. 6 The activation energy for esterification of propionic acid with ethanol and 1-butanol are 52.6 and 47.3 kJmol-1, respectively. For the same increment of temperature in esterification of propionic acid with ethanol and 1-butanol, separately, the relative change of rate of forward reaction (A) will be faster with ethanol than that of propanol (B) will be slower with ethanol than that of propanol (C) will be initially faster with ethanol but at a certain temperature the rate will be slower than that of propanol (D) rate of the reactions in both cases will remain unaffected with temperature. Q.7 Total calcium and magnesium ions content in water is at least 0.05 mmol/L. What volume of the EDTA solution with a concentration of 10 mmol/L should be added when 50 mL of a water sample is titrated? (A) 2.50 mL (B) 0.25 mL (C) 0.025 mL (D) 25 mL Q. 8 At the end point in the complexometric titration of a standard solution of EDTA, the blue colour is due to (A) EDTA (B) Eriochrome Black T (C) Calcium ions (D) Magnesium ions Q. 9 In determination of total hardness of water with EDTA, the reaction at end point is (wherein H 2Y2- is disodium salt of EDTA) (A) Mg+2 + HIn2- MgIn- + H+ (B) MgIn- + H+ Mg+2 + HIn2+2 + 2(C ) Mg + H + MgY MgIn + H2Y2 (D) Ca+2 + H2Y2- CaY2-+ 2H+ Q.10 During the acid-base titration of acetic acid using NaOH, which statement is true regarding oxalic acid? (A) Oxalic acid helps to identify the end point during the acetic acid- NaOH titration (B) Oxalic acid is a primary standard (C) Oxalic acid takes part in the titration reaction of acetic acid with NaoH (D) Oxalic acid gives pink color with phenolphthalein so it is used during the titration where phenolphthalein is used as an indicator. Q. 11 The pH at the equivalence point is more than 7 for the titration of (A) Strong acid-Weak Base (B) Strong Acid- Strong Base (C) Weak Acid-Strong Base (D) Weak Acid-Weak Base Q. 12 Calculate the pH of the buffer solution made from 0.20M HC 2H3O2 and 0.50M C2H3O2- that has acid dissociation constant for HC2H3O2 of 1.8 X 10-5. (A) 5.1 (B) 4.3 (C) 2.7 (D) 4.7 Q. 13 A first order reaction is half-completed in 45 minutes. How long does it take for 99.9% of the reaction to be completed? (a) 300 mins (b) 576 mins (c) 460mins (d) 448 mins Q. 14 For a first order reaction which equation is correct? (X = conc of the reactant at time t, X0 = initial conc of the reactant; k = rate constant of the reaction) (A) ln[X] = ln[X0] + kt (B) ln[X0] = ln[X] kt (C) ln[X] = ln[X0] kt (D) ln[X] = ln[X0] k/t 2

Q. 15. An increase of temperature from 500 K to 510 K increases the number of bimolecular collision by about. (A) 10% (B) 1% (C) 50% (D) 100% Q. 16 Given the following compounds: A) succinic acid B) citric acid C) tartaric acid D) glucose. Which of the following statements is incorrect: (A) A is a dicarboxylic acid which condenses with acidified resorcinol followed by NaOH addition to give green fluorescence (B) B is a dicarboxylic acid which gives white ppt with cold CaCl2 solution (C) C is a dicarboxylic acid which gives silver mirror with Tollen's reagent (D) D is a sugar which gives a solid osazone product with 2,4-DNP Q. 17 Given two statements: 1. Fructose contains aldehydic functional group 2. Fructose gives +ve tollen's test. Choose the correct statement: (A) 1 is true, 2 is true (B) ) 1 is true, 2 is false (C) ) 1 is false, 2 is false (D) ) 1 is false, 2 is true Q. 18 Statement 1: Aldehydes give negative Tollen's test. Statement 2: Ketones give negative test with 2,4-DNP. Choose the correct option for the two statements: (A) 1 is correct, 2 is incorrect (B) 1 is correct, 2 is correct (C) 1 is incorrect, 2 is incorrrect (D) 1 is incorrect, 2 is correct Q. 19 The equivalent weight of sodium thiosulfate pentahydrate is (A) 124.08 (B) 157.91 (C) 248.17 (D) 78.95 Q. 20 25 mL of household bleach [Ca(OCl)Cl] solution was mixed with 30 mL of 0.50 M KI and 10 mL of 4N acetic acid. In the titration of the liberated iodine, 48 mL of 0.25 N Na2S2O3 was used to reach the end point. The molarity of the household bleach solution is (A) 0.48 M (B) 0.96 M (C) 0.24 M (D) 0.024 M Q. 21 Which of the following statement in incorrect? (A) In iodometric titration analyte is reducing species (B) Iodometric titration is an indirect titration (C) In iodometry there are two reactions (D) In iodometric titration, KI is added to the reaction mixture to increase the solubility of iodine Q. 22 [Cu(C2O4)2]2- exist in (A) Monomeric (B) dimeric (C) Polymeric (D) amorphous form

Q. 23 FTIR of K2[Cu(C2O4)2].2H2O might give idea about (A) C-O bond strength (B) d-d transition energy of Cu(II) (C) Copper to oxalate charge transfer energy (D) oxalate to copper charge transfer energy Q. 24 One mmole of CuSO4.5H2O reacted completely with potassium oxalate to result in 0.283 gm of recrystallized K2[Cu(C2O4)2].2H2O. Under this reaction condition, the % yield of product will be (A) 100 (B) 80 (C) 60 (D) 50 Q. 25 Synthesis of dibenzolactone is an example of ................................... reaction! (A) Friedel-craft (B) Claisen-Schmidt condensation (C) Michael addtion (D) Bechmann rearrangement Q. 26 The rate of self aldol condensation of acetone is ..................w.r.t the rate of aldol condensation reaction with benzaldehdye. (A) faster (B) slower (C) equal in rate (D) initially slower then faster Q. 27 Among the carbonyls given, which will form dibenzalacetone type product faster with acetone? (A) p-OMe-Benzaldehyde (B) benzaldehyde (C) p-NO2-Benzaldehyde (D) o-Me-Benzaldehyde
Q. 28 Activation of a TLC plate is:

(A) removing of water/moisture (B) removing of adsorbed substance (C) removing of moisture and adsorbed impurity (D) to stabilize the silica gel Q. 29 An example of stationary phase in normal phase chromatography: (A) calcium phosphate (B) cellulose powder (C) long chain aliphatic acid (D) aluminium sulphate

Q. 30 To run a normal TLC plate, a chemist:

(A) places it in a jar with solvent among iodine crystals (B) places it in an oven to dry it (C) places it under a UV lamp (D) places it

4. (d)

=448 mins 5.(C) ln[X] = ln[X0] kt 6. (b) Here, we know frequency A of a bimolecular reaction

A=

RT S R e Nh

A1 T1 500 = = 0.99 A2 T2 510 Increase in the number of collision = 1 0.99 = 0.01 = 1%

So, AT and we can write