Jawab soalan mengikut arahan yang diberikan dalam setiap bahagian. Questions should be answered according to the instructions given in each section.

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1 UNIVERSITI MALAYA UNIVERSITY OF MALAYA PEPERIKSAAN IJAZAH SARJANA MUDA SAINS EXAMINATION FOR THE DEGREE OF BACHELOR OF SCIENCE PEPERIKSAAN IJAZAH SARJANA MUDA SAINS DENGAN PENDIDIKAN EXAMINATION FOR THE DEGREE OF BACHELOR OF SCIENCE WITH EDUCATION SESI AKADEMIK 2014/2015 : SEMESTER 1 ACADEMIC SESSION 2014/2015 : SEMESTER 1 SCES2230 : KIMIA FIZIK II PHYSICAL CHEMISTRY II Disember 2014/Januari 2015 December 2014/January 2015 MASA : 2 jam TIME : 2 hours ARAHAN KEPADA CALON : INSTRUCTIONS TO CANDIDATES : Kertas soalan ini mengandungi Bahagian A, B dan C. This paper consists of Section A, B and C. 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 11 soalan dalam 9 halaman yang dicetak) (This question paper consists of 11 questions on 9 printed pages)

2 BAHAGIAN A (25 MARKAH) SECTION A (25 MARKS) Jawab mana-mana EMPAT soalan dari (1-6) dalam Bahagian A. Setiap soalan mempunyai markah yang sama. Answer any FOUR from questions (1-6) in Section A. Each question has equal mark. 1. Persamaan asas berhubungan dengan fungsi keadaan temodinamik bagi sistem tertutup diberikan seperti berikut: The fundamental equations relating the thermodynamics state functions in a close system is given as du = TdS pdv dh = TdS + Vdp da = SdT pdv dg = SdT + Vdp Terbitkan hubungan Maxwell. Ungkapkan persamaan ini bagi sistem tertutup di mana pertukaran jirim tidak dibenarkan. Derive the Maxwell relationship. Express these equations for a close system where mass exchange is not allowed. 2. Bagi sistem terpencil, berikan syarat bagi perubahan berbalik dan spontan. Bagaimana syarat-syarat ini diubah untuk sistem yang berada pada tekanan dan suhu tetap. For an isolated system, give the conditions for a spontaneous and reversible change. How are these conditions modified for a system at constant pressure (p) and temperature (T)? 3. Terangkan skima Ehrenfest yang mengklasifikasikan perubahan fasa kepada tertib pertama dan kedua. Berikan contoh sketsa jika perlu. Describe the Ehrenfest scheme for the classification of phase transition into the first and second order. Give sketched examples if necessary. 4. Berikan persamaan Clayeyron. Air mendidih pada 100 C pada tekanan biasa 1 atm. Apakah tekanaan yang perlu dikenakan untuk menurukan suhu didih kepada 97 C? Maklumat berikut mungkin berguna. Haba pengewapan air ialah 40.7 kj mol 1, ketumpatan air pada 100 C ialah 0.96 g ml -1 dan ketumpatan wap ialah 0.6 gl -1. Diberikan juga 1 L atm = 100 J. Give the Clapeyron equation. Water boils at 100 C under normal 1 atm pressure. What is the pressure needed to be applied to decrease the boiling temperature to 97 C? The following information may be useful. The heat of vaporization of water is 40.7 kj mol 1, density of water at 100 C is 0.96 g ml -1 and density of steam is 0.6 gl -1. Given also 1 L atm = 100 J. 2/9

3 5. Kira perubahaan tenaga bebas Gibb ( G) bagi pemampatan isoterma dari 1 atm ke 100 atm pada 25 C untuk 30 g air yang berketumpatan g cm -3 pada suhu yang sama. Nyatakan andaian anda. Calculate the change in the Gibb s free energy ( G) for an isothermal compression from 1 atm to 100 atm at 25 C of 30 g water whose density is g cm -3 at the same temperature. State your assumption. 6. Bagi gas unggul tenaga bebas molar ialah G = G + RTln p p 0. Bagi gas nyata, persamaan ini diubah mengguna konsep fugasiti. Berikan persamaan yang mendefinasikan fugasiti dan tulis semula persamaan tenaga bebas di atas dalam sebutan fugasiti. Kira pekali fugasiti bagi gas pada 100 atm dan 500 K, anggap faktor kemampatannya ialah For an ideal gas the molar free energy is G = G + RTln p p 0. For a real gas, this equation is modified using the concept of fugacity. Give the defining equation of fugacity and re-write the free energy expression above in term of fugacity. Calculate the fugacity coefficient of a gas at 100 atm and 500 K, assuming its compressibility is Z = 1 + B RT p dan/ and B = Lmol 1. Diberikan juga R = L atm K 1 mol 1 Given also R = L atm K 1 mol 1 3/9

4 7. Berikut ialah penguraian N 2 O 5, The decomposition of N 2 O 5, BAHAGIAN B (25 MARKAH) SECTION B (25 MARKS) 2N 2 O 5 = 4NO 2 + O 2 telah dikaji bagi pengiraan kepekatan gas oksigen pada fungsi masa dan ( ) N 2 O 5 didapati bahawa, d[o ] 2 = s -1 dt [ ]pada kemalaran T dan P, tindak balas tersebut lengkap ke arah kanan. Apakah nilai separuh hayat tindak balas dalam keadaan tersebut? is studied by measuring the concentration of oxygen as a function of time, and is found ( ) N 2 O 5 d[o ] 2 that = s -1 dt [ ] at constant T and P, the reaction goes completely to the right. What is the half life of the reaction under these conditions? (5 markah/ marks) 8. Hidrolisis sebatian CH 3 (CH 2 ) 6 CH 2 -Cl dalam larutan mengandungi 80% etanol berlaku mengikut tertib tindak balas pertama. Nilai-nilai pemalar tindak balas dicatatkan seperti berikut, The hydrolysis of CH 3 (CH 2 ) 6 CH 2 -Cl in 80% ethanol follows the first order rate equation. The values of the specific reaction rate constants are as follows T, o C k, s (a) Lakar log k melawan 1/T Plot log k against 1/T (b) (c) Kira tenaga pengatifannya. Calculate the activation energy. Tentukan faktor pra-eksponen. Determine the pre-exponential factor. (10 markah/ marks) 4/9

5 9. Eksperimen alur molekul mengambarkan tindak balas berikut, A molecular beam experiments show that the reaction Cs + Br 2 - CsBr + Br berlaku melalui mekanisma harpoon dengan keratan rentas tindak balas adalah 150 Å 2. Terangkan kenyataan ini terutamanya pada maksud mekanisma harpoon dan keratan rentas tindak balas. Diberi bahawa tenaga pengionan bagi Cs ialah 3.9 ev, afiniti elektron bagi Br 2 ialah 1.8 ev dan pemalar faraday C mol -1, buktikan bahawa mekanisma lompatan setara dengan nilai keratan rentas tindak balas. proceeds via a harpoon mechanism with a reaction cross section of 150 Å 2. Explain this statement especially the meaning of the terms harpoon mechanism and reaction crosssection. Given that the ionization energy of Cs is 3.9 ev, the electron affinity of Br 2 is 1.8 ev and faraday constant is C mol -1, confirm that the an electron jump mechanism is consistent with the reaction cross section. (10 markah/ marks) 5/9

6 BAHAGIAN C : KIMIA KUANTUM (50 MARKAH) SECTION C : QUANTUM CHEMISTRY (50 MARKS) Jawab DUA (2) soalan dalam Bahagian ini. Answer TWO (2) questions in this Section. 10. (a) Tuliskan nota pendek daripada dua topik yang berikut: Write short note on two of the following topics: (i) (iii) (iv) Kesan fotoelektrik Photoelectric effects Prinsip ketidakpastian Heisenberg Heisenberg uncertainty principle Pengkuantuman ruang Space quantization Operator Hamiltonan bagi atom helium Hamiltonian operator for helium atom (10 markah/ marks) (b) Tunjukkan yang mana fungsi berikut adalah eigenfungsi bagi operator d dx : Show that which of the following functions are eigenfunctions of the operator d dx : (i) exp (ikx), cos (kx), (iii) exp (-kx 2 ), dimana k adalah suatu pemalar. where k is a constant. (4 markah/ marks) (c) Bagi sesuatu zarah yang berjisim m dihadkan bergerak dalam satu peti berdimensi-satu, For a particle of mass m confined to move in a one-dimensional box, (i) Terbitkan satu ungkapan bagi operator Hermiltonan bagi zarah ini, diberi tenaga potensialnya adalah sifar di dalam peti. Derive an expression for the Hamiltonian operator for the particle, given that the potential energy of the particle is zero in the box. 6/9

7 Tunjukkan fungsi yang berikut Show that the following function = A sin (2mE) ½ x / ], mematuhi persamaan Schrodinger di mana A adalah pemalar penormalan, dan E adalah jumlah tenaga bagi zarah ini. satisfies the Schrodinger equation where A is the normalization constant, and E is the total energy of the particle. (iii) Lukiskan satu gambarajah untuk menunjukkan taburan zarah ini dalam peti pada keadaan kuantum n = 1, 2, dan 3. Terangkan bagaimana keputusan ini boleh digunakann untuk mengilustrat Prinsip Kesepadanan. Draw a diagram to show the distribution of the particle in the box at quantum states n = 1, 2, and 3. Explain how these results can be used to illustrate the Correspondence Principle. (11 markah/ marks) 11. (a) Fungsi gelombang yang menghuraikan sesuatu keadaan kuantum tertentu bagi atom hidrogen ialah The wavefunction describing a particular quantum state of hydrogen atom is 1 r r exp ( ) cos, 3 32 a a 2 a o o dimana a o adalah jejari Bohr; r dan adalah parameter biasa dalam sistem koordinat berkutub sfera. where a o is the Bohr radius; r and are the usual parameters in a spherical polar coordinate system. Tunjukkan bahawa Show that o (i) satah-xy merupakan satu satah nodus, the xy-plane is a nodal plane, Kebarangkalian yany paling besar untuk menemui elektron berlaku pada paksi-z, dan pada satu jarak r = 2 a o daripada nukleus. the maximum chances of finding the electron occurs at the z-axis, and at a distance r = 2 a o from the nucleus. 7/9

8 (iii) Lakarkan satu gambarajah sempadan permukaan untuk menunjukkan taburan elektron dalam keadaan kuantum atom hidrogen ini. Draw a surface boundary diagram to illustrate the distribution of the electron in this quantum state of hydrogen atom. (9 markah/ marks) (b) Diberi fungsi gelombang yang menghuraikan sesuatu zarah yang memutar ialah = exp(+i ), tentukan komponen-z momentum sudut, L Z, bagi zarah ini. Given the wavefunction describing a rotating particle is = exp(+i ), determine the z-component of its angular momentum, L z. (4 markah/ marks) (c) Yang mana fungsi gelombang berikut mematuhi prinsip Pauli? Terangkan jawapan anda. Which of the following wavefunctions satisfy the Pauli principle? Explain your answer. (i) (iii) (iv) ½ 1s (1) 2s (2) - 2s (1) 1s (2) (1) (2) + (1) (2) ½ 1s (1) 2s (2) + 2s (1) 1s (2) (1) (2) + (1) (2) ½ 1s (1) 2s (2) + 2s (1) 1s (2) (1) (2) - (1) (2) 1s (1) 1s (2) (1) (2) (5 markah/ marks) Jawab soalan (d) atau (e) Answer question (d) or (e) (d) (i) Dengan menggunakan atom hidrogen sebagai contoh, bincangkan perhubungan antara nombor kuantum utama, n, nombor kuantum azimut, l, dan nombor kuantum magnet, m, dengan tenaga dan momentum sudut orbital. Using hydrogen atom as an example, explain the relation between the principal quantum number, n, azimuthal quantum number, l, and magnetic quantum number, m, with the energy and the orbital angular momentum. Tenaga dasar bagi atom hidrogen ialah ev. Apakah tenaga bagi atom hidrogen apabila elektronya telah diujah ke orbital-2s? The ground state energy of hydrogen atom is ev. What is the energy of hydrogen atom when its electron is excited to the 2s-orbital? (7 markah/ marks) 8/9

9 (e) Terbitkan operator mekanik kuantum bagi tenaga potensial untuk sesuatu pengayun harmonik. Derive the quantum mechanical operator for the potential energy of a harmonic oscillator. Terangkan secara ringkas bagaimana purata tanaga potensial bagi pengayun ini boleh ditentukan secara mekanik kuantum. Explain briefly how the average potential energy of this oscillator can be determined quantum mechanically. (7 markah/ marks) TAMAT END 9/9

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