SCES2250 : SPEKTROSKOPI MOLEKUL & INTERPRETASI MOLECULAR SPECTROSCOPY INTERPRETATION

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1 UNIVERSITI MALAYA UNIVERSITY OF MALAYA PEPERIKSAAN IJAZAH SARJANA MUDA SAINS EXAMINATION FOR THE DEGREE OF BACHELOR OF SCIENCE SESI AKADEMIK 2009/2010 : SEMESTER 1 ACADEMIC SESSION 2009/2010 : SEMESTER 1 SCES2250 : SPEKTROSKOPI MOLEKUL & INTERPRETASI MOLECULAR SPECTROSCOPY INTERPRETATION November 2009 November 2009 MASA : 2 jam TIME : 2 hours ARAHAN KEPADA CALON : INSTRUCTIONS TO CANDIDATES : Kertas soalan ini mengandungi Bahagian A dan B. This paper consists of Section A and B. Jawab soalan mengikut arahan yang diberikan dalam setiap bahagian. Answer the questions according to the instructions given in each section. (Kertas soalan ini mengandungi 6 soalan dalam 9 halaman yang dicetak) (This question paper consists of 6 questions on 9 printed pages)

2 SCES2250/02 BAHAGIAN A (67 MARKAH) SECTION A (67 MARKS) Jawab soalan (1) dan pilih dan pilih antara soalan (2) atau (3). Answer questions (1) and choose between question (2) and (3). 1. (a) Bincangkan faktor yang mempengaruhi keamatan garisan spektrum bagi suatu peralihan. Discuss the factors that affect spectral line intensity of a transition. (9 markah/ marks) (b) Gambarajah di atas menunjukkan susunan biasa sebuah spektrometer serapan. Dengan menjelaskan fungsi setiap bahagiannya, perihal bagaimana spektrometer ini berfungsi. The figure above is a typical arrangement of an absorption spectrometer. By explaining the functions of the different parts of the spectrometer, describe how the spectrometer works. (15 markah/ marks)

3 SCES2250/03 (c) Jelaskan bagaimana kesan Doppler menyebabkan berlakunya pelebaran heterogenus bagi suatu peralihan spektroskopi. Explain how Doppler Effect causes heterogeneous broadening of a spectroscopic transition. (10 markah/ marks) 2. (a) Jarak ikatan bagi molekul CN + adalah nm. Kirakan frekuensi dalam unit cm -1 bagi garisan putaran tulin (pemutar tegar) di dalam spektrum CN + yang sejajar dengan perubahan nombor kuantum putaran seperti berikut: 0 1, 1 2, 2 3, 3 4. The bond length of the CN + molecule is nm. Calculate the frequencies in cm -1 for the pure rotational lines (rigid rotator) in the spectrum of CN + corresponding to the following changes in the rotational quantum numbers: 0 1, 1 2, 2 3, 3 4. (12 markah/ marks) (b) Sekiranya frekuensi getaran ω e bagi CN dan CN + adalah 2069 cm -1 dan 1580 cm -1, kirakan pemalar daya bagi CN dan CN + dan berikan komen anda tentang jawapan yang diperolehi. If the bond vibrational frequencies ω e for CN and CN + are 2069 cm -1 and 1580 cm -1 respectively, calculate the force constants of CN and CN + and comment on the values obtained. (6 markah/ marks) (c) Diberi bahawa D, pemalar herotan, adalah. Kirakan D dan frekuensi di dalam unit cm -1 untuk garisan putaran tulin (pemutar tidak tegar) di dalam spektrum CN + yang sejajar dengan perubahan nombor kuantum putaran seperti berikut: 0 1, 1 2, 2 3, 3 4. Given that D, the distortion constant is, calculate D and the frequencies in cm -1 for the pure rotational lines (non-rigid rotator) in the spectrum of CN + corresponding to the following changes in the rotational quantum numbers: 0 1, 1 2, 2 3, 3 4. (10 markah/ marks) (d) Lakarkan spektrum CN untuk kedua-dua pemutar tegar dan pemutar tidak tegar. Sketch both the rigid and non-rigid pure rotational spectra of CN. (5 markah/ marks)

4 SCES2250/04 3. (a) Tenaga paras tenaga bagi suatu getaran tak-harmonik diberi oleh: Tenaga keupayaan Morse diberi oleh dan ia akan menghasilkan persamaan di atas sekiranya dan. Jika diberi bahawa r e, D e, ω e dan ω e x e masing-masing adalah nm, cm -1, cm -1 dan cm -1 untuk suatu molekul AB, plotkan [V(r)-D e ] melawan r. Tunjukkan di dalam lengkungan yang terhasil, dengan nilainya sekali, 10 paras tenaga getaran yang pertama. The vibrational energy levels of an anharmonic vibration is given by: The Morse potential, given by generates the equation above if and. Given that r e, D e, ω e and ω e x e are nm, cm -1, cm -1 and cm -1 respectively for an AB molecule, plot [V(r)-D e ] against r. Indicate in the curve, with values, the first 10 energy levels. (20 markah/ marks) (b) Dengan menganggap bahawa getaran molekul AB ini menghasilkan sebuah spektrum, kirakan frekuensi untuk fundamental, overtone pertama dan overtone kedua. Tunjukkan peralihan ini di dalam plot anda. Assuming that the vibration of this AB molecule exhibits a spectrum, calculate the fundamental, first overtone and second overtone frequencies. Indicate the transitions on your plot. (7 markah/ marks)

5 SCES2250/05 (c) Perolehi simbol sebutan bagi pasangan elektron tidak setara di bawah: Determine the terms symbols for the pairs of non-equivalent electrons below: (i) (ii) pp ps Jadual Pemalar Table of constants Pemalar Planck (Planck s constant) h 6.63 x J s Kelajuan cahaya (Speed of light) c 3 x 10 8 m s -1 JAR (RAM) C; N 12g mol -1 ; 14g mol -1 (6 markah/ marks)

6 SCES2250/06 Data yang berguna: Useful data: Nisbah magnetogirik: Magnetogyric ratio: BAHAGIAN B (33 MARKAH) SECTION B (33 MARKS) ( 1 H) = x 10 7 rad T 1 s 1 ; ( 13 C) = x 10 7 rad T 1 s 1 ; ( 2 H) = x 10 7 rad T 1 s 1 Jawab soalan 4 dan pilih antara soalan 5 atau 6. Answer question 4 and choose either question 5 or (a) Eksperimen NMR melibatkan dua proses: pengujaan dan pengenduran. Dengan bantuan gambarajah aras tenaga bagi sistem nukleus spin I = ½, jelaskan dua proses ini. Tunjukkan kesandaran masa bagi pengenduran spin kekisi dan pengenduran spin spin. Lakarkan kesandaran masa bagi isyarat NMR dan tunjukkan maklumat yang terkandung dalamnya. The NMR experiment involves two processes: excitation and relaxation. With the aid of the energy level diagram for a spin I = ½ nuclear system, show these processes. Show the time dependence of spin lattice relaxation and of spin spin relaxation. Sketch the time dependence of the NMR signal and indicate the information it contains. (b) Terangkan kebaikan medan magnet tinggi dalam NMR. Explain the advantages of high magnetic field in NMR.

7 SCES2250/07 (c) Spektrum proton NMR bagi alkohol etil (CH 3 CH 2 OH) dalam larutan CDCl 3 adalah seperti di atas. The proton NMR spectrum of ethyl alcohol (CH 3 CH 2 OH) in CDCl 3 solution is shown above. (i) (ii) Dengan menggunakan simbol dan bagi komponen spin proton dalam medan magnet, tunjukkan bagaimana setiap garis triplet pada 1.2 adalah dihasilkan oleh komponen spin proton yang mengkupel dengan kumpulan proton pada 1.2. Using and for the spin components of the proton in a magnetic field, show how each line in the triplet at 1.2 is associated with the spin components of the protons which couple with the group at 1.2. Isyarat pada 2.42 adalah lebih lebar daripada garis yang lain dalam spektrum dan juga tidak menunjukkan pengkupelan spin-spin dengan kumpulan proton yang lain. Terangkan bagaimana lebaran garis tersebut berlaku dan terangkan mengenai ketiadaan pengkupelan spin spin dengan kumpulan proton yang lain. The signal at 2.42 is broader than other lines in the spectrum and does not show spin spin coupling to the other groups of protons. Explain how the line broadening occurs and the absence of spin spin coupling to the other groups of protons. (20 markah/ marks)

8 SCES2250/08 5. Ditunjukkan di bawah adalah spektrum NMR proton 270 MHz bagi metilena klorida (CH 2 Cl 2 ) dalam larutan CDCl 3. Spektrum tersebut terdiri daripada satu garis. Shown below is the 270 MHz proton NMR spectrum of methylene chloride (CH 2 Cl 2 ) in CDCl 3 solution. The spectrum consists of a single line. (i) Terangkan mengapa pengkupelan spin spin antara dua proton tidak diperhatikan. Explain why the spin spin coupling between the two protons is not observed. (ii) Kedua-dua nukleus klorin, 35 Cl and 37 Cl, mempunyai spin I = 3/2. Terangkan mengapa spektrum tersebut tidak menunjukkan pengkupelan spin spin antara proton dan nukleus klorin. The chlorine nuclei, 35 Cl and 37 Cl, both have spin I = 3/2. Explain why the spectrum does not show spin spin coupling between the protons and the chlorine nuclei. (13 markah/ marks)

9 SCES2250/09 6. Ditunjukkan di bawah adalah spektrum 13 C NMR yang proton-dekupel bagi etil benzena (10 % mol dalam larutan CDCl 3 (D = 2 H)). Shown below is the proton decoupled 13 C NMR spectrum of ethyl benzene (10 % mole in CDCl 3 solution (D = 2 H)). (i) Garis pada dan mewakili setiap dua karbon (karbon orto dan meta). Semua garis yang lain dalam spektrum mewakili satu karbon. Terangkan mengapa keamatan garis dalam spektrum berbeza (atau tidak berkadaran dengan bilangan nukleus). The lines at and represent two carbons each (ortho and meta carbons). All the other lines in the spectrum represent one carbon each. Explain why the intensities of the lines vary in the spectrum (or are not proportional to the number of nuclei). (ii) Garis-garis triplet pada 77 adalah berkaitan dengan pelarut ( 13 C 2 HCl 3 ). Terangkan mengapa keamatan triplet pelarut adalah sangat rendah walaupun kepekatan pelarut sangat tinggi. The triplet of lines at 77 belong to the solvent ( 13 C 2 HCl 3 ). Explain why the intensity of the solvent triplet is very low in spite of the high solvent concentration. TAMAT END (13 markah/ marks)

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