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 2 ACADEMIC SESSION 2009/2010 : SEMESTER 2 SCES2250 : SPEKTROSKOPI MOLEKUL & INTERPRETASI MOLECULAR SPECTROSCOPY & INTERPRETATION April/Mei 2010 April/May 2010 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 5 soalan dalam 8 halaman yang dicetak) (This question paper consists of 5 questions on 8 printed pages)

2 SCES2250/02 BAHAGIAN A (60 MARKAH) SECTION A (60 MARKS) Jawab dua (2) soalan sahaja. Jawab soalan (1) dan pilih satu soalan antara soalan (2) atau (3). Answer two (2) questions only. Answer question (1) and choose between questions (2) or (3). 1. [30 markah/ marks] a) Tuliskan nota pendek mengenai dua (2) topik di bawah: Write short notes on two (2) of the topics below i) Faktor-faktor yang mempengaruhi pelebaran garisan spectra Factors that influence the broadening of spectral lines ii) Deskripsi penuh spektrometer serapan dua alur Full description of a double beam absorption spectrometer iii) Profil keamatan bagi spektrum putaran CO The intensity profile of CO rotational spectrum (18 markah/ marks) b) Bincangkan Transformasi Fourier dan kegunaannya dalam bidang spektroskopi Discuss Fourier Transformation and its use in spectroscopy. (12 markah/ marks)

3 SCES2250/ [30 markah/ marks] Soalan 2 adalah berasaskan spektrum pancaran gas Cl 2 di bawah: Question 2 is based on the emission spectrum of Cl 2 gas depicted below: E ex = cm 1... r Cl Cl v Spektrum di atas (kiri) yang direpresentasi oleh lengkungan keupayaan getarannya (kanan) menunjukkan spektrum pancaran untuk gas Cl 2 yag telah diuja pada cm - 1. Spektrum ini menunjukkan siri puncak dan setiap puncak merupakan pancaran pendafluor pada keadaan tenaga getaran dengan nombor kuantum v (=0,1,2...). The spectrum above (left), represented by its vibrational potential curve (right) shows the emission spectrum of gaseous Cl 2 excited at cm 1. The spectrum shows a sequence of peaks, and each peak corresponds to the fluorescence at the vibrational state with the quantum number v (= 0, 1, 2,...) a) Dapatkan anggaran tenaga paras-paras tenaga getaran v (= 1, 2, 3) pada keadaan elektronik asas Cl 2 dalam unit kj mol -1. Obtain the approximate energies for the vibrational energy levels v (= 1, 2, 3) at the ground electronic state of Cl 2, in kj mol 1. (7 markah/ marks)

4 SCES2250/ 04 b) Berasaskan pengiraan dalam soalan 2(a) dan menganggap bahawa getaran Cl 2 adalah aktif IR, lakarkan spektrum getaran Cl 2 dengan mengambil kira getaran fundamental, overtone pertama dan overtone kedua. Pastikan bahawa frekuensi getaran dalam cm -1 dilabel bagi setiap puncak getaran di dalam spektrum tersebut. Based on the calculations of question 2(a) and by assuming that Cl 2 vibration is IR active, sketch the Cl 2 vibrational spectrum, taking into consideration the fundamental, first overtone and second overtone vibrations. Ensure that vibrational frequencies of each peak on the spectrum are labelled appropriately in cm-1. (8 markah/ marks) c) Adakah spektrum getaran asli bagi Cl 2 wujud? Apakah alasan anda? Does the Cl 2 pure vibrational spectrum exist? What is the reason? (3 markah/ marks) d) Cuba kirakan nilai x e (pemalar tidak harmonik) bagi molekul Cl 2. Attempt to calculate the value of x e (anharmonic constant) for the Cl 2 molecule. 3. [30 markah/ marks] (12 markah/ marks) a) Diberi bahawa jarak ikatan molekul bagi H 35 Cl adalah nm, Given the bond length of H 35 Cl is nm, i) Apakah jarak ikatan bagi D 35 Cl, H 37 Cl dan D 37 Cl? What are the bond lengths of D 35 Cl, H 37 Cl and D 37 Cl? (18 markah/ marks) (2 markah/ marks) ii) Apakah jarak antara garisan dalam spektrum putaran bagi H 35 Cl, D 35 Cl, H 37 Cl dan D 37 Cl? What are the respective spacing between rotational spectral lines in the rotational spectrum of H 35 Cl, D 35 Cl, H 37 Cl and D 37 Cl? (14 markah/ marks)

5 SCES2250/ 05 iii) Mengapakah terdapat perbezaan dalam jarak antara garisan bagi keempat-empat spektrum? Apakah nama kesan ini? Why are there differences in spectral line spacing for all four spectrum?what is this effect called? (2 markah/ marks) b) i) Apakah simbol sebutan bagi pasangan elektron tak sama di bawah? Deduce the term symbols for the non-equivalent electron pairs below? ss pp dd (7 markah/ marks) ii) Jelaskan secara ringkas apa yang dimaksudkan dengan fenomena pendafluor dan pendafosfor. Briefly explain the phenomena of phosphorescence and fluorescence. (5 markah/ marks)

6 SCES2250/ 06 BAHAGIAN B (40 MARKAH) SECTION B (40 MARKS) Jawab soalan 4 dan pilih mana-mana DUA soalan dari soalan 5. Answer question 4 and choose any TWO questions from question [20 markah/ marks] (a) (CH 3 ) 4 C adalah molekul tetrahedral yang mempunyai empat kumpulan metil yang setara. Bagi spektrum NMR 1 H molekul ini akan ada satu isyarat NMR untuk mewakili keempat-empat kumpulan CH 3 yang setara tersebut. Berapakah resonan yang berbeza yang terdapat pada: (CH 3 ) 4 C is a tetrahedral molecule with all four methyl groups being equivalent. In the 1 H NMR spectrum of this molecule, there would be one NMR signal for the four equivalent CH 3 groups. How many distinct resonances are there in: (i) Spektrum 1 H NMR untuk (CH 3 CH 2 ) 3 PO? The 1 H NMR spectrum of (CH 3 CH 2 ) 3 PO? (2 markah/ marks) (ii) Spektrum 1 H NMR untuk (CH 3 ) 3 SiSi(Et) 3? The 1 H NMR spectrum of (CH 3 ) 3 SiSi(Et) 3? (2 markah/ marks) (b) Skala ricih kimia pada spektrum NMR biasanya diberi dalam unit tanpa dimensi, "parts per million" (ppm), dari satu kompaun rujukan. Apakah hubungan di antara skala ricih kimia dalam Hz dan dalam skala ppm? The chemical shift scale on a NMR spectrum is typically given in dimensionless units "parts per million" (ppm) from some reference compound. What is the relationship between a chemical shift scale in Hz and a scale in ppm? (4 markah/ marks) (c) Nisbah magnetogirik untuk nukleus deuterium adalah hampir 6.5 kali lebih kecil dari nisbah untuk proton. Di dalam magnet di mana spektrum proton dapat diperhatikan pada 400 MHz, apakah anggaran frekuensi untuk sinaran frekuensi radio yang diperlukan untuk memerhatikan spektrum NMR deuterium? The magnetogyric ratio of the deuterium nucleus is approximately 6.5 times smaller than that of proton. In a magnet where a proton spectrum can be observed at about 400 MHz, what is the approximate frequency of radiofrequency radiation you would need to observe the deuterium NMR spectrum? (4 markah/ marks)

7 SCES2250/ 07 (d) Spektrum-spektrum NMR 1 H untuk propana, CH 3 CH 2 CH 3, untuk tiga spektrometer yang berbeza dengan frekuensi proton 60 MHz, 300 MHz and 600 MHz adalah seperti ditunjukkan di bawah. Bincang mengenai asas perbezaan pada spektrum-spektrum berikut. The 1 H NMR spectra of propane, CH 3 CH 2 CH 3, for three different spectrometers with proton frequencies of 60 MHz, 300 MHz and 600 MHz are shown below. Discuss the nature of the difference in the spectra. (4 markah/ marks) (e) Rajah berikut menunjukkan bahagian penting pada spektrometer NMR. The following figure shows the heart of an NMR spectrometer. i. Apakah fungsi cecair helium? What is the role of liquid helium? (1 markah/ marks) ii. Apakah fungsi cecair nitrogen? What is the role of liquid nitrogen? (1 markah/ marks) iii. Apakah yang diletakkan ke dalam bore? What is inserted inside the bore? (1 markah/ marks) iv. Magnet ini juga dibekalkan dengan dua set kumparan tambahan untuk menyesuaikan homoginasi medan magnet. Apakah nama bagi kumparan tambahan ini? The magnet is also provided with two sets of additional coils to adjust the homogeneity of the magnetic field. What are these additional coils called? (1 markah/ marks)

8 SCES2250/ [20 markah/ marks] Tuliskan nota ringkas untuk DUA di antara topik-topik berikut: Write a short note on TWO of the following topics: (a) (b) (c) (d) (e) Presesi spin Spin precession Frekuensi Larmor mempunyai tanda yang tertentu The Larmor frequency has a defined sign Relaksasi Spin-Lattice Spin-Lattice Relaxation Magnetisasi transverse dan isyarat NMR Transverse Magnetization and NMR signal Bising pada NMR NMR noise ~~~~~0000~~~~~

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