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MH SET 2018: 28 January, Paper III, Chemical Sciences

  • Date: 28 January 2018
  • Paper code: JAN33318
  • Series: A
  • Language: Bilingual
  • 32 pages
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Test Booklet Code & Serial No.
                                                                                                                    A
                                                       Paper-III
                                                   CHEMICAL SCIENCE
Signature and Name of Invigilator                                                                Seat No.
1. (Signature) .........................................                                                  (In figures as in Admit Card)
      (Name) ................................................                    Seat No. ..............................................................
2. (Signature) .........................................                                                   (In words)

      (Name) ................................................                      OMR Sheet No.

JAN - 33318                                                                                         (To be filled by the Candidate)
Time Allowed : 2½ Hours]                                                                            [Maximum Marks : 150
Number of Pages in this Booklet : 32                                                   Number of Questions in this Booklet : 75
                     Instructions for the Candidates
1.        Write your Seat No. and OMR Sheet No. in the space provided            1.
          on the top of this page.
2.        This paper consists of 75 objective type questions. Each question
          will carry two marks. All questions of Paper-III will be compulsory,   2.
          covering entire syllabus (including all electives, without options).
3.        At the commencement of examination, the question booklet
          will be given to the student. In the first 5 minutes, you are
          requested to open the booklet and compulsorily examine it as           3.
          follows :
          (i)      To have access to the Question Booklet, tear off the
                   paper seal on the edge of this cover page. Do not accept
                                                                                         (i)
                   a booklet without sticker-seal or open booklet.
          (ii)     Tally the number of pages and number of questions
                   in the booklet with the information printed on the                    (ii)
                   cover page. Faulty booklets due to missing pages/
                   questions or questions repeated or not in serial
                   o rder or any other discre pancy should not be
                   accepted and correct booklet should be obtained
                   from the invigilator within the period of 5 minutes.
                   Afterwards, neither the Question Booklet will be
                   replaced nor any extra time will be given. The same
                   may please be noted.
          (iii)    After this verification is over, the OMR Sheet Number
                   should be entered on this Test Booklet.                               (iii)
4.        Each question has four alternative responses marked (A), (B),
          (C) and (D). You have to darken the circle as indicated below on
          the correct response against each item.                                4.                       (A), (B), (C)   (D)
          Example : where (C) is the correct response.

                             A        B                 D
                                                                                                    (C)
5.        Your responses to the items are to be indicated in the OMR
          Sheet given inside the Booklet only. If you mark at any place                                   A        B              D
          other than in the circle in the OMR Sheet, it will not be evaluated.
                                                                                 5.
6.        Read instructions given inside carefully.
7.        Rough Work is to be done at the end of this booklet.
8.        If you write your Name, Seat Number, Phone Number or put               6.
          any mark on any part of the OMR Sheet, except for the space            7.
          allotted for the relevant entries, which may disclose your             8.
          identity, or use abusive language or employ any other unfair
          means, you will render yourself liable to disqualification.
9.        You have to return original OMR Sheet to the invigilator at the
          end of the examination compulsorily and must not carry it with         9.
          you outside the Examination Hall. You are, however, allowed
          to carry the Test Booklet and duplicate copy of OMR Sheet on
          conclusion of examination.
10.       Use only Blue/Black Ball point pen.                                    10.
11.       Use of any calculator or log table, etc., is prohibited.               11.
12.       There is no negative marking for incorrect answers.                    12.
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JAN - 33318/III—A




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JAN - 33318/III—A
                                 Chemical Science
                                          Paper III
Time Allowed : 2½ Hours]                           [Maximum Marks : 150
Note : This paper contains seventy five (75) multiple choice questions, each
       question carrying Two (2) marks. Attempt All questions.

1.   The correct statement for atomic absorption spectroscopy (AAS) from the
     following :
     (A) Non-metals are determined by direct methods
     (B) Beer’s law is not obeyed over wide concentration range
     (C) Separate lamp for each element to be determined is required
     (D) Al, Ti, W, Mo and Si can be detected by AAS
2.   The capacity to undergo exchange reaction by the hydrated metal ions of the
     same size in ion exchange chromatography follows the order :
     (A) Al3+ > Ca2+ > Th4+ > Na+
     (B) Th4+ > Al3+ > Ca2+ > Na+
     (C)   Na+ > Ca2+ > Al3+ > Th4+
     (D) Ca2+ > Al3+ > Th4+ > Na+
3.   The thermal methods (I) and their parameters (II) are given below :
           I                                            II
     (a) TG                                       (e)    T
     (b) DTG                                      (f)   dm/dt
     (c) DTA                                      (g)   dH/dt
     (d) DSC                                      (h) Mass
     The correct match is :
     (A) (a)-(e), (b)-(f), (c)-(g), (d)-(h)
     (B) (a)-(f), (b)-(g), (c)-(h), (d)-(e)
     (C) (a)-(h), (b)-(f), (c)-(e), (d)-(g)
     (D) (a)-(g), (b)-(e), (c)-(f), (d)-(h)

                                              3                            [P.T.O.
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4.   The intervalence band in Mixed-valent compounds usually occurs in the ..........

     region.

     (A) Ultra-violet                        (B) Visible

     (C) Near infrared                       (D) Far infrared

5.   In the base-catalysed substitution of Cl– by OH– in [Co(NH3)5Cl]2+ under

     strongly basic conditions, the first step in the mechanism is :

     (A) Conversion of an ammine to amido ligand

     (B) Substitution of Cl– by OH–

     (C) Dissociation of Cl– to give 5-coordinate intermediate

     (D) Assocaition of OH– to give 7 coordinate intermediate

6.   To satisfy the 18 electron rule the value of n in the complex [Rh( 5—C5h5)(CO)n]

     should be :

     (A) 2                                   (B) 3

     (C) 1                                   (D) 4

7.   The correct order of Nephelauxetic parameter ( ) of the ligands is :

     (A) CN > NCS > en > NH3       H2O

     (B) H2O > NH3 > en > NCS > CN

     (C) en    CN > NCS > NH3 > H2O

     (D) H2O > NH3 > NCS > CN > en

8.   Jahn-Teller distortion will be exhibited by :

     (A) [Mn(H2O)6]2+                        (B) [Cr(H2O)6]3+

     (C) [Ni(H2O)6]2+                        (D) [Cu(H2O)6]2+

                                         4
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9.   Rieske protein is a [2Fe-2S] cluster wherein :
     (A) One Fe atom is coordinated to two terminal imidazole ligands and the other
         Fe atom is coordinated to two terminal cystine ligands
     (B) Both Fe atoms are coordianted to two terminal imidazole groups each
     (C) Both Fe atoms are coordianted to two terminal cystine groups each
     (D) Both Fe atoms are coordianted to one terminal imidazole and one cystine
         each
10. [Ni(dipyridyl)3]SO4 records three transitions in electronic spectra at 12,650 cm –1,
    19,200 cm–1 and 26,000 cm–1. The 10 Dq of the complex is :
     (A) 12650 cm–1                             (B) 15180 cm–1
     (C) 10120 cm–1                             (D) 26000 cm–1
11. In which of the following organometallic complexes, the carbon based ligands
     is both    and     bonded.
     (A) [Fe( 5-C5H5)2]                         (B) [PtCl3( 2-C2H4)]–
     (C) [Co(CO)5NH3]2+                 (D) [Al(CH3)3]
12. The EPR spectra of [Mn(H2O)6]2+ (55Mn=I=5/2) with zero field splitting show
     five set of lines. Each set further consist of ........... ...hyperfine lines (At. No.
     Mn = 25)
     (A) 5                                      (B) 6
     (C) 30                                     (D) 1
13. In the Wacker catalystic cycle if methanol is used in place of water as nucleophile
     the product will be :
     (A) Ethanol                                (B) Methyl vinyl ether
     (C) Acetaldehyde                           (D) Acetone
14. ‘A’ type of ground Mülliken symbol in complex having oh symmetry is :
     (A) t2g3 eg2                               (B) t2g1 eg0
     (C) t2g3 eg1                               (D) t2g6 eg3

                                            5                                      [P.T.O.
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15. Which of the following pairs of coordination complexes do not undergo inner
    sphere electron transfer reaction ?
    (A) [Co(NH3)5NO3]2+/[V(OH2)6]2+
    (B) [Co(NH3)5I]2+/[V(OH2)6]2+
    (C) [Co(en)3]3+/[V(OH2)6]2+
    (D) [Co(NH3)5Br]2+/[V(OH2)6]2+
16. The dn electron configuration of the first row transition metal ions that show
    ‘high-spin’—‘low-spin’ transition are :
    (A) d4 and d5                             (B) d5 and d6
    (C) d4, d5, d6 and d7                     (D) d4, d5 and d6
17. The measurement of the intensity of the scattered light as a function of the
    concentration of the dispersed phase form is the principle of :
    (A) Colorimetry                           (B) Turbidimetry
    (C) Nephelometry                          (D) Phosphorimetry
18. Racemization of octahedral complexes containing three bidentate rings by the
    Ray-Dutt twist mechanism forms intermediates of .............. point group.
    (A) D3h                                   (B) C 2v
    (C) C 3v                                  (D) D 2h
19. The 31P{OH} NMR spectra of HPO(OH)2 and H2PO(OH) (I = 3p, 1H = 1/2) shows
    respectively :
    (A) doublet and triplet                   (B) triplet and triplet
    (C) triplet and doublet                   (D) doublet and doublet
20. The following statement is incorrect with respect to 57Fe Mössbauer spectra
    of FeCl3.6H2O and FeCl2.4H2O :
    (A) Both the compounds show doublet with equal quadrupole splitting
    (B) Both are compounds show doublet with unequal quadrupole splitting
    (C) Both the compounds are high spin complexes of Fe(II) and Fe(III)
         respectively
    (D) Valence contribution is present in FeCl2.4H2O while lattice contribution
         is present in FeCl3.6H2O

                                          6
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21. Which of the following pairs of elements have (n 2) f 7 (n 1) d 1 ns2 electronic
    configuration ?

    (A) Sm, Cm                                (B) Gd, Cm

    (C) Eu, Cm                                (D) Er, Cm

22. Which of the following statements with respect to ‘trans effect’ is true ?

    (A) Ammonia > Chloride                    (B) Water > Chloride

    (C) Pyridine > Chloride                   (D)   Chloride > Ammonia

23. In the layered structure of CdI2, Cd2+ occupies ........... octahedral sites.

          1                                         1
    (A)                                       (B)
          2                                         3

          1
    (C)                                       (D) 1
          4

24. A dimeric Ruthenium (IV) complex [K4(Cl5Ru—O—RuCl5] is diamagnetic at

    room temperature (26°C) althrough there are two unpaired electrons per Ru(IV)

    ion, the magnetic behaviour can be best explained by :


    (A) Antiferromagnetic coupling            (B) Ferromagnetic coupling


    (C) Ferrimagnetic coupling                (D) Antiferrimagnetic coupling

25. Tetragonal distorted complexes will be exhibited by :

    (A) Low spin Fe2+                         (B) High spin Cr2+

    (C) High spin Mn2+                        (D) Ni2+

                                          7                                   [P.T.O.
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26. The major products P and Q formed in the following reaction sequence

    are :




    (A)




    (B)




    (C)




    (D)




                                   8
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27. The following reaction is an example of :




              Benzophenone + Isobutene     h




    (A) Norrish type I reaction           (B) Norrish type II reaction

    (C) Borton reaction                   (D) Paterno-Buchi reaction

28. The major product formed in the following reaction is :




    (A)                                   (B)




    (C)                                   (D)




                                      9                                  [P.T.O.
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29. Major product formed in the following reaction is :




    (A)                                     (B)




    (C)                                     (D)



30. Find out the correct structure of L-Ribose if the structure of D-Ribose is :




    (A)                                     (B)




    (C)                                     (D)



                                       10
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31. Major product formed in the following reaction is :




    (A)                                    (B)




    (C)                                    (D)




32. The major product formed in the following reaction is :




    (A)                                    (B)




    (C)                                    (D)




                                      11                                 [P.T.O.
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33. Structure of the ‘tagged’ amino acid formed in the following reaction is :




     (A)                                      (B)




    (C)                                 (D)




                                       12
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35. Major product formed in the following reaction is :




    (A)                                    (B)




    (C)                                    (D)




36. The major product formed in the following reaction is :




    (A)                                    (B)




    (C)                                    (D)




                                      14
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37. The correct match of natural products in Column-I with class in Column-II

    is :

           Column-I                                 Column-II

    (P) Cholesterol                         (i)     Polysaccharide

    (Q) Cellulose                           (ii) Steroid

    (R) Quinine                             (iii) Vitamin

                                            (iv) Alkaloid

    (A) (P)—(iii), (Q)—(i), (R)—(iv)

    (B) (P)—(ii), (Q)—(iv), (R)—(i)

    (C) (P)—(ii), (Q)—(i), (R)—(iv)

    (D) (P)—(i), (Q)—(iii), (R)—(iv)

38. Amongst the following the rate of cis-trans isomerisation is expected to be

    highest in :


    (A)                                       (B)




    (C)                                       (D)




                                       15                                   [P.T.O.
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39. The major product formed in the following reaction is :




    (A)                                    (B)




    (C)                                    (D)




40. T h e pr ot on decou pl ed 13C NMR spectrum of HF2C—CH2Cl will show :


    (A) C1 as singlet and C2 as singlet


    (B) C1 as triplet and C2 as triplet


    (C) C1 as triplet and C2 as singlet


    (D) C1 as doublet and C2 as singlet

                                      16
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41. The correct structure of a compound that exhibits the following 1H-NMR spectral
    data is :
     3.8(S, 3H), 3.9 (S, 3H) 6.82 (dd, J = 8 and 2 H2, 1H), 7.06 (t, J = 8 H2, 1H),
    7.15 (dd, J = 8 and 2 H2, 1H)



    (A)                                      (B)




    (C)                                      (D)




42. Major product formed in the following reaction is :




    (A)                                      (B)
                                                   3




    (C)                                      (D)




                                        17                                  [P.T.O.
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43. Major product formed in the following reaction is :




    (A)                                    (B)




    (C)                                    (D)




                                      18
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44. Major product formed in the following reaction is :




    (A)                                    (B)




    (C)                                    (D)




45. Major product formed in the following reaction is :




    (A) P =           ; Q =                (B) P =          ; Q =




    (C) P = Q =                            (D) P = Q =


                                      19                             [P.T.O.
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46. The major product formed in the following reaction is :




    (A)                                    (B)




    (C)                                    (D)




47. Major product formed in the following reaction is :




    (A)                                    (B)




    (C)                                    (D)



                                      20
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48. Major product formed in the following reaction is :




    (A)




    (B)




    (C)




    (D)




                                      21                             [P.T.O.
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49. Major product formed in the following reaction is :




(A)                                  (B)




(C)                                  (D)




                                      22
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50. The major product P and Q formed in the following reactions are :




    (A)




    (B)




    (C)




    (D)




                                     23                                 [P.T.O.
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51. One of the most widely used functions for the van der Waals potential is the

     Lennard-Jones expressed as :

                             A ik   Cik                                            A ik   Cik
     (A) ELJ                   6     12               (B)       ELJ                 12
                 nonbonded   rik    rik                                nonbonded   rik    rik6
                 pairs                                                 pairs


                             A ik   Cik                                            A ik   Cik
     (C) ELJ                                          (D)       ELJ                  6
                 nonbonded
                              12
                             rik      6
                                    rik                                nonbonded    rik   rik12
                 pairs                                                 pairs


52. Coeffi ci en t of t h er m al ex pan si on ( ) is given by :

           1    V                                                 1    V
     (A)                                              (B)
           V    T P                                               V    T P

           1     V                                                1     V
     (C)                                              (D)
           V2    T P                                              V2    T P

53. The distribution function for identical indistinguishable particles can be

                                                 gj
     represented by the equation N j        (    )/ kT
                                                                , which of the following statements
                                           e j              a

     is correct ?

     (A) a = +1 for Bose-Einstein statistics

     (B) a = –1 for Fermi-Dirac statistics

     (C) a = +1 for Fermi-Dirac statistics

     (D) a = 1/2 for Bose-Einstein statistics

54. For an isolated system :

     (A) dS = deS                                     (B) dS = diS

     (C) deS > 0                                      (D) deS < 0

                                                24
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55. If there is no net flow of electrical current, then generation of potential difference
     per unit change of pressure and generation of potential difference per unit change
     of temperature is termed as .......... respectively.
     (A) Thermoelectric power and osmotic pressure
     (B) Osmotic pressure and thermoelectric power
     (C) Streaming potential and thermoelectric power
     (D) Thermoelectric power and streaming potential
56. For any polydispersed system, which of the following statements is true ?
     (A) Number average relative molar mass is greater than mass average relative
           molar mass
     (B) Number average relative molar mass is less than mass average relative
           molar mass
     (C) Number average relative molar mass coincide with mass average relative
           molar mass
     (D) None of the above
57. A particle in a one-dimensional box of length L can be excited from n = 1
     to n = 2 state with frequency . If the box length is doubled, the frequency
     needed to achieve this transition is :
     (A)   /4                                   (B)   /2
     (C) 2                                      (D) 4
58. If operator D̂n (n times differentiate with respect to x) operates on eigenfunction
     eax, the eigenvalue would be :
     (A) n                                      (B) n
     (C)     n                                  (D) n !
59. The eigenfunctions of a rigid rotator are :
     (A) Spherical harmonics                    (B) Laguerre polynomials
     (C) Hermite polynomials                    (D) Legendre transformers

                                           25                                     [P.T.O.
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60. A ccor di n g t o H u n d’s r u l e, m ost st abl e st at e for np2 configuration is ..........
    (A) 1S 0                             (B) 3P 0
    (C) 3P 1                             (D) 3P 2
61. According to simple HMO theory, which one of the following statements about
    butadiene is true ?
    (A) It has a non-bonding MO
    (B) Exciting an electron from the HOMO to the LUMO will not change the
           bond orders
     (C) Exciting an electron from the HOMO to the LUMO will not change the
           charge densities
    (D) It is most likely to undergo electrophilic substitution at one of the two inner
        carbons
62. In the hydrogenation of C2H4 on a Ni surface both the alkene and H2 are
    adsorbed on similar active sites of the catalyst surface. Which of the following
     figures depict the reaction ?




     (A )                                             (B)




     (C)                                              (D)




                                                 26
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63. In case of heterogeneous catalysis which of the following is correct ?
    (A) At least one reactant must be physisorbed on the catalyst
    (B) At least one reactant must be chemisorbed on the catalyst
    (C) The number of active sites decrease with increase in surface area
    (D) Surface area can be determined by spectroscopic studies
64. A surface of Li metal (sample X) was suspected to be completely coated with
    a thin layer of Li2O (sample Y). When X and Y are analysed by X-ray
    photoelectron spectroscopy :
    (A) Kinetic energy of the photoelectrons from X will be higher than that
         from Y
    (B) Kinetic energy of the photoelectrons from Y will be higher than that
         from Y
    (C) Binding energy of the photoelectrons from Y will be lower than that
         from X
    (D) Kinetic energy of the photoelectrons from both X and Y will be the same
65. A reactor vessel at 1000 K contains CO2 at a pressure of 0.5 atm. Part of the
    CO2 is converted into CO by the addition of graphite. If the total pressure
    in the reactor vessel at equilibrium is 0.8 atm, the value of K P for the reaction
    of CO2 with graphite is :
    (A) 1.8                                   (B) 3.24
    (C) 0.324                                 (D) 09
66. For the equilibrium Fe(s) + H2O(g)     FeO(s) + H2(g), the number of components,
    phases and degrees of freedom are respectively :
    (A) 3, 3, 2                               (B) 3, 4, 2
    (C) 3, 3, 3                               (D) 3, 2, 1

                                         27                                    [P.T.O.
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67. Given below is the wave function of a particle :




    Which of the following is correct ?
    (A) The particle is more likely to be found near B
    (B) The particle is more likely to be found near A
    (C) The shaded area represents the energy of the particle when it travels through
          a distance dx
    (D) The shaded area represents the amplitude of the particle in an area dx
68. The de Broglie wavelength of an electron travelling with 1% speed of light
    is about :
    (mass of electron and speed of light are 9.109 × 10–31 kg and 2.998 ×
    108 ms–1 respectively) :
    (A) 243 m                                (B) 243 cm
    (C) 243 Å                                (D) 243 pm
69. Surface tension of Br2(I) water and mercury are 41.0 mNm–1, 72.0 mN/m and
    486.2 mNm–1 respectively at 25°C. These values imply that :
    (i)   Metallic bonding is weaker than covalent bonding
    (ii) Hydrogen bonding is stronger than van der Waals bonding
    (iii) Metallic bonding is stronger than hydrogen bonding
    (iv) All types of intermolecular forces are of similar strength
    (A) (iii) and (iv)                       (B) (ii) and (iii)
    (C) (i), (ii) and (iii)                  (D) (iv), (ii) only

                                        28
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70. In case of radical polymerization, the kinetic chain length is given by

    expression :
                                     kp[M][I] 1/ 2
                                                       1/ 2
                                           1/2   kd
                                   2kt f
                                                 kt
    increase in the initiator concentration eventually leads to :
    (A) Higher molecular weight polymer
    (B) Low molecular weight polymer
    (C) Rate of reaction and thus the extent polymerization does not depend on
        the concentration of initiator
    (D) Fast polymerization reaction
71. Consider the following reaction in an aqueous solution :
                    I–(aq) + OCl–(aq)            IO–(aq) + Cl–(aq)
    and the following initial concentration and initial rate data for this
    reaction :

                     [I 1 ], M [OCl ], M Initial Rate, Ms 1


                        0.1      0.05                 3.05 *10 4


                        0.2      0.05                 6.10 *10 4


                        0.3      0.01                 1.83 *10 4


                        0.4      0.02                 6.12 *10 4

    Which of the following is the correct rate law for this reaction ?
    (A) Rate = k[I–]2[OCl–]                      (B) Rate = k[OCl–]
    (C) Rate = k[I–]2                            (D) Rate = k[I–][OCl–]

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72. Consider the following electrochemical cell, connected to the potential source

    (Potentiostat) with Hg as a working electrode :

              Hg/Cd2+(0.01M), Zn2+ (0.01M), HCl(1.0M)     HCl(1.0M) H2(g)|Pt

    when the potential is change towards (i) more negative direction and (ii) change

    towards the more positive direction from the equilibrium potential value, the

    following observations are expected :

    Given :

              E°(Cd2+/Cd°) = – 0.351 V,

              E°(Zn2+/Zn°) = – 0.762 V, E°(Hg2+/Hg°) = + 0.855 V

    (A) (i)    H2 evolution will start.

         (ii) O2 evolution will start.

    (B) (i)    Cd will deposit first followed by Zn.

         (ii) Hg will start oxidizing.

    (C) (i)    Zn will deposit.

         (ii) O2 evolution will be observed.

    (D) (i)    Cd will deposit.

         (ii) Hg will start oxidizing.


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73. The ideal solution made up of 5.00 mol (mole fraction = 0.606) benzene and
    3.25 mol (mole fraction = 0.394) toluene, the free energy of mixing ( Gmix)
    is equal to –13 kJ mol–1. The corresponding values for the their equimolar
    solution will be ;
    (A) Unity
    (B) ( Gmix) does not depend on mole fraction, thus equal to –13 kJ mol–1
    (C) Less negative than that of –13 kJ mol –1
    (D) More negative than that of –13 kJ mol–1
74. The ideal solution made up of 5.00 mol (mole fraction = 0.606) benzene and
    3.25 mol (mole fraction = 0.394) toluene, the change in enthalpy during mixing
    ( Hmix) would be :
    (A) zero                                  (B) 1.0 kJ mol–1
    (C) positive                              (D) negative
75. An electrochemical cell is constructed using half cell for the reduction reaction
    is given by :
               Fe(OH2)(s) + 2e      Fe(s) + 2OH–(aq); E° = –0.877 V
    It is combined with another half cell for which the cell reaction is given
    by :
                         Al3+(aq) + 3e   Al(s); E° = –1.66 V
    Activities of all the components are assumed to be unity.
    The overall reaction for the cell in the direction of spontaneous change
    is :
    (A) (Fe(OH)2(s) + Al(s)       Fe(s) + OH–(aq.) + Al3+ (aq.)
    (B) 2(Fe(OH)2(s) + 3Al(s)       2Fe(s) + 6OH–(aq.) + 3Al3+ (aq.)
    (C) 3(Fe(OH)2(s) + 2Al(s)       3Fe(s) + 6OH–(aq.) + 2Al3+ (aq.)
    (D) Fe(s) + OH–(aq.) + Al3+(aq.)       (Fe(OH)2(s) + Al(s)

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ROUGH WORK




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Source: Savitribai Phule Pune University. Question paper published by Savitribai Phule Pune University.