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 2014/2015 : SEMESTER 2 ACADEMIC SESSION 2014/2015 : SEMESTER 2 SCES2250 : SPEKTROSKOPI MOLEKUL & INTERPRETASI MOLECULAR SPECTROSCOPY & INTERPRETATION Jun 2015 June 2015 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. Questions should be answered according to the instructions given in each section. (Kertas soalan ini mengandungi 4 soalan dalam 7 halaman yang dicetak) (This question paper consists of 4 questions on 7 printed pages)

2 Jawab TIGA (3) soalan dalam bahagian ini. Answer THREE (3) questions in this section. BAHAGIAN A (67 MARKAH) SECTION A (67 MARKS) 1. (a) Bincangkan dua faktor yang akan memberi kesan kepada lebar garisan spektra. Discuss two factors that will affect the width of spectral lines. Jarak gelombang radiasi yang diserap semasa peralihan spektroskopi tertentu adalah 400 nm. Ungkapkan radiasi ini dalam sebutan frekuensi dan nombor gelombang. Hitungkan perubahan tenaga untuk peralihan dalam kj/mol. The wavelength of the radiation absorbed during a particular spectroscopic transition is 400 nm. Express this radiation in term of its frequency and wavenumber. Calculate the energy change during the transition in kj/mole. Interferometer ialah komponen yang terpenting pada sebuah spektrometer Fourier Transform. Gunakan gambarajah yang sesuai untuk menghuraikan bagaimana komponen ini berfungsi dan menghasilkan corak gangguan daripada cahaya monokromatik. Interferometer is the most important component of a Fourier Transform spectrometer. Use appropriate diagram(s) to describe how this component functions and produces an interference pattern from a monochromatic light. (8 markah/marks) 2. (a) Jelaskan perbezaan keamatan garisan spektra dalam spektrum putaran apabila nombor kuantum putaran J meningkat. Explain the variation in the intensity of spectral lines in a rotational spectrum as the rotational quantum number J increases. Nombor gelombang bagi peralihan untuk spektrum putaran tulen 12 CO disenaraikan dalam Jadual 1. Wavenumber of the transitions for pure rotational spectrum of 12 CO are tabulated in Table 1. 2/7

3 Jadual 1 Table 1 Peralihan/ Transition Nombor gelombang/ Wavenumber, cm -1 J = 0 J = J = 1 J = J = 2 J = J = 3 J = J = 4 J = J = 5 J = J = 6 J = (i) (ii) (iii) Kirakan pemalar putaran, B (cm -1 ), dengan menggunakan peralihan J = 0 J = 1. Calculate the rotational constant, B (cm -1 ), from J = 0 J = 1 transition. Kirakan momen inersia, I, dan panjang ikatan, r (dalam nm), untuk molekul 12 CO. Calculate the moment of inertia, I, and the bond length, r (in nm), for the 12 CO molecule. Pemalar putaran dan panjang ikatan yang ditentukan daripada peralihan J = 6 J = 7 adalah berbeza daripada yang ditentukan daripada J = 0 J = 1. Terangkan mengapa. The rotational constant and bond length determined from J = 6 J = 7 transition are different from those determined from J = 0 J = 1 transition. Explain why. (12 markah/marks) 3/7

4 Berikan peraturan pilihan bagi peralihan fundamental untuk getaran anharmonik. Terangkan mengapa peralihan dari keadaan kuantum getaran dengan nombor kuantum getaran v > 0 tidak diperhatikan untuk molekul pada suhu bilik? Give the selection rule for the fundamental transition of anharmonic oscillator. Explain why the transitions from vibrational quantum state with vibrational quantum number v > 0 is not observed for molecules at room temperature? (8 markah/marks) (d) Takrifkan bahagian-p dan bahagian-r bagi peralihan getaran-putaran. Lakarkan spektrum getaran-putaran bagi molekul dwiatom heteronuklear. Labelkan bahagian-p dan bahagian-r, peralihan R(1), dan peralihan P(1). Define P-branch and R-branch in vibration-rotation transitions. Sketch a vibrational-rotational spectrum for a heteronuclear diatomic molecule. Label the R and P branches, R(1) transition, and P(1) transition. (7 markah/marks) (e) Jelaskan mengapa pendarfluor berlaku pada panjang gelombang yang lebih panjang daripada penyerapan. Explain why fluorescence occurs at longer wavelength than absorption. (4 markah/marks) Jawab DUA (2) soalan daripada soalan 3(a), 3 dan 3 berikut. Answer TWO (2) questions from the following questions 3(a), 3 and (a) Pertimbangkan molekul linear N 2 O dengan sambungan N N O. N 2 O mempunyai berapa mod getarani? Berikan mod getaran untuk N 2 O dan tentukan mod getaran yang mana adalah aktif Inframerah. Consider the N 2 O linear molecule with connectivity N N O. How many vibrational modes does N 2 O possess? Give the vibrational modes for N 2 O and determine which of the vibrational modes are Infrared active. (5 markah/marks) Tentukan simbol sebutan atom yang mungkin kepada konfigurasi elektron 2s 1 2p 1. Determine the possible atomic term symbols for an electron configuration of 2s 1 2p 1. (5 markah/marks) 4/7

5 Namakan kawasan pada spektrum elektromagnet yang terlibat dalam spektroskopi elektronik. Jelaskan mengapa sebahagian besar daripada kompleks logam peralihan adalah sebatian berwarna. Name the region in electromagnetic spectrum that is involved in the electronic spectroscopy. Explain why most of the transition metal complexes are coloured compounds. (5 markah/marks) [JAR 12 C, 12.0 g mol -1 ; JAR 16 O, 16.0 g mol -1 ; pemalar Planck, 6.63 x J s; kelajuan cahaya, 3.0 x 10 8 m s -1 ; pemalar Avogadro, 6.02 x mol -1 ] [RAM 12 C, 12.0 g mol -1 ; RAM 16 O, 16.0 g mol -1 ; Planck s constant, 6.63 x J s; speed of light, 3.0 x 10 8 m s -1 ; Avogadro constant, 6.02 x mol -1 ] 5/7

6 BAHAGIAN B (33 MARKAH) SECTION B (33 MARKS) Jawab semua soalan. Answer all questions. 4. (a) Tenaga bagi proton dalam satu medan magnet B o ialah E=- m I B 0, dimana adalah nisbah magnetogiriknya. Tunjukkan frekuensi resonan bagi proton, L, diberi oleh The energy of the proton in a magnetic field B 0 is given by E= - m I B 0, where is its magnetogyric ratio. Show that the resonance frequency of proton, L, is given by L = B 0 / 2. (3 markah/marks) Diberi bagi nukleus 13 C adalah bernilai x 10 7 rad T 1 s 1, apakah frekuensi resonan bagi nukleus ini dalam sesuatu 100 MHz spektrometer NMR? ( = x 10 8 rad T 1 s 1 bagi proton) Given for 13 C nucleus is x 10 7 rad T 1 s 1, what is the resonance frequency of this nucleus in a 100 MHz NMR spectrometer? ( = x 10 8 rad T 1 s 1 for proton) (3 markah/marks) Spektrum 100 MHz 1 H NMR (B o = 2.35 T) bagi asid asetik mengandungi dua garisan, satu pada δ=2 bagi proton CH 3, dan satu pada δ=11 bagi proton COOH. Hitungkan perbezaan medan magnet tempatan yang dialami oleh dua jenis proton ini. Gunakan jawapan anda untuk menerangkan mengapa medan magnet yang digunakan dalam eksperimen NMR semestinya adalah stabil dan seragam. The 100 MHz 1 H NMR spectrum (B o = 2.35 T) of acetic acid contains two lines, one at δ=2 for the CH 3 protons and the other at δ=11 for the COOH proton. Calculate the difference in the local magnetic field experienced by these two types of protons. Use your answer to explain why the magnetic field used in NMR experiments must be stable and homogeneous. (8 markah/marks) 6/7

7 (d) Terangkan mengapa anjakan kimia bagi proton dalam gelangan aromatik biasanya adalah besar, manakala nilainya adalah sangat kecil bagi proton yang bertempat di atas dan di bawah gelangan. Anda dikehendaki melakarkan satu gambarajah untuk menerangkan jawapan anda. Explain why the chemical shift observed for protons in the aromatic ring is usually large, but the value is very small for protons situated above and below the ring. You are required to draw a diagram to illustrate your answer. (e) Bagi molekul yang mengandungi dua proton yang wujud dalam persekitarann kimia yang berbeza (merupakan satu sistem spin AX), For molecule containing two protons in different chemical environments (an AX spin system), (i) (ii) Berikan empat keadaan spin bagi molekul ini. Give the four spin states of the molecule. Tenaga bagi setiap keadaan spin diberi oleh The energy for each of these spin states is given by E (m A, m X ) = - h ν A m A - h ν X m X + m A m X h J. Tentukan tenaga bagi semua keadaan spin yang diberi dalam (i). Determine the energy for all the spin states given in (i). (iii) (iv) (v) Lukiskan satu gambarajah paras tenaga untuk menerangkan keputusan yang didapati dalam (ii). Draw an energy levels diagram to explain the results obtained in (ii) Tunjukkan peralihan yang dibenarkan. Indicate the allowed transitions. Ramalkan spektrum proton NMR bagi molekul ini. Predict the proton NMR spectrum of this molecule. (9 markah/marks) (f) Berikan dua kelebihan menggunakan medan magnet yang tinggi dalam spektroskopi NMR. Give two advantages of using a high magnetic field in NMR spectroscopy. (4 markah/marks) TAMAT END 7/7

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