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

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1 UNIVERSITY OF MALAYA UNIVERSITI MALAYA EXAMINATION FOR THE DEGREE OF BACHELOR OF SCIENCE PEPERIKSAAN IJAZAH SARJANA MUDA SAINS EXAMINATION FOR THE DEGREE OF BACHELOR OF SCIENCE WITH EDUCATION PEPERIKSAAN IJAZAH SARJANA MUDA SAINS DENGAN PENDIDIKAN ACADEMIC SESSION 2012/2013 : SEMESTER 1 SESI AKADEMIK 2012/2013 : SEMESTER 1 SCES2230 : PHYSICAL CHEMISTRY II KIMIA FIZIK II January 2013 Januari 2013 TIME : 2 hours MASA : 2 jam INSTRUCTIONS TO CANDIDATES : ARAHAN KEPADA CALON : This paper consists of Section A, B and C. Kertas soalan ini mengandungi Bahagian A, B dan C. Questions should be answered according to the instructions given in each section. Jawab soalan mengikut arahan yang diberikan dalam setiap bahagian. (This question paper consists of 8 questions on 11 printed pages) (Kertas soalan ini mengandungi 8 soalan dalam 11 halaman yang dicetak)

2 SCES2230/02 Answer ALL question in this section. Jawab SEMUA soalan dalam bahagian ini. 1. Define, Takrifkan, SECTION A (25 MARKS) BAHAGIAN A (25 MARKAH) (a) Collision diameter (d). Diameter perlanggaran (d). (b) Collision cross section A eff. Keratan rentas perlanggaran A eff. (4 marks/markah) 2. The decomposition of N 2 O 5, Penguraian sebatian N 2 O 5 adalah, 2N 2 O 5 = 4NO 2 + O 2 is studied by measuring the concentration of oxygen as a function of time, and is found that d[o 2] = ( s -1 )[ N 2 O 5 ] at constant T and P, the reaction goes dt completely to the right. What is the half life of the reaction under these conditions? dimana kajian dilakukan dengan mengukur kepekatan oksigen pada fungsi masa, didapati bahawa d[o 2] = ( s -1 )[ N 2 O 5 ] pada keadaan malar T dan dt P, tindakbalas mengarah ke kanan sepenuhnya. Apakah separa-hayat tindakbalas didalam keadaan tersebut? (5 marks/markah)

3 SCES2230/03 3. Chloroform reacts according to the following equation in the presence of sodium methoxide in methanol solution. Klorofom bertindakbalas mengikut persamaan tindakbalas berikut dengan kehadiran natrium metoksida didalam larutan metanol. CHCl 3 + OMe - CCl MeOH (fast) (pantas) - CCl 3 CCl 2 + Cl - (slow) (perlahan) and CCl 2 products (fast) dan CCl 2 hasil (pantas) An experiment was done to measure the order of the slow step with respect to CCl 3 - and to determine the amount of Cl - produced in time, t at 57.9 o C by titration with 0.01 N AgNO 3, volume (V), ml being required. The following results were obtained. Kajian makmal telah dijalankan bagi menentukan tertib bagi peringkat perlahan merujuk kepada CCl 3 - dan menentukan banyaknya Cl - dikeluarkan pada masa, t pada suhu 57.9 o C secara pentitratan dengan 0.01 N AgNO 3, isipadu (V), ml yang diperlukan. Keputusan berikut telah diperolehi. t / min V / ml (a) Plot ln(v - V) vs t. Lakar ln(v - V) lawan t. (b) Determine the rate constant of the slow step reaction. Tentukan pemalar kadar bagi tindakbalas peringkat perlahan. (8 marks/markah)

4 SCES2230/04 4. 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 Hidrolisis sebatian CH 3 (CH 2 ) 6 CH 2 -Cl dalam larutan mengandungi 80% etanol berlaku mengikut tertib tindakbalas pertama. Nilai-nilai pemalar tindakbalas dicatatkan seperti berikut, T, o C k, s (a) Plot log k against 1/T Lakar log k melawan 1/T (b) (c) Calculate the activation energy. Kira tenaga pengaktifannya. Determine the pre-exponential factor. Tentukan faktor pra-eksponen. (8 marks/markah)

5 SCES2230/05 SECTION B (25 MARKS) BAHAGIAN B (25 MARKAH) Answer ONE (1) question only in this section. Jawab SATU (1) soalan sahaja dalam bahagian ini. 5. (a) Starting with H = U + PV, derive C P = VT ( ) for a system of fixed amount whereby is the cubic expansion coefficient. Bermula dengan H = U + PV, terbitkan C P = VT ( beramaun tetap di mana ialah pekali pengembangan kubik. ) untuk sistem (4 marks/markah) (b) Find an expression for ( ) for a gas obeying the van der Waals equation of state. Evaluate the derivative for argon with a molar volume of m 3 mol -1 and a = Pa m 3 mol -2. Cari ungkapan untuk ( ) bagi gas yang mematuhi persamaan keadaan van der Waals. Nilaikan terbitan untuk argon berisipadu molar m 3 mol -1 dan a = Pa m 3 mol -2. (7 marks/markah) (c) Show the effect of increased pressure on the melting point of water at 1 atm by a rough plot of G with T. Translate the same plot in terms of P with T. The vapor pressure of n-propanol is 1.94 kpa at 293 K and kpa at 343 K. What is the enthalpy of vaporization. Tunjukkan kesan peningkatan tekanan ke atas takat lebur air pada 1 atm dengan membuat plot kasar G lawan T. Terjemahkan plot yang sama dalam sebutan P lawan T. Tekanan wap n-propanol ialah 1.94 kpa pada 293 K dan kpa pada 343 K. Apakah entalpi pengwapannya. (8 marks/markah)

6 SCES2230/06 (d) Explain what is meant by the term partial molar volume. At 25 o C and 1 atm, a solution of g of H 2 O and g of CH 3 OH has a volume of cm 3. In this solution, V = cm 3 mol -1. Find V. Terangkan apa yang dimaksudkan dengan sebutan isipadu molar separa. Pada 25 o C dan 1 atm, satu larutan g H 2 O dan g CH 3 OH mempunyai isipadu cm 3. Dalam larutan ini V = cm 3 mol -1. Cari V. (6 marks/markah) 6. (a) Calculate ΔG for the isothermal compression of 30.0 g of water from 1.0 atm to atm at 25 o C; neglect the variation of V with P and the density of water is g cm -3 at the same temperature. Hitung ΔG untuk kemampatan isoterma 30.0 g air dari 1.0 atm ke atm pada 25 o C; abaikan variasi V dengan P dan ketumpatan air ialah g cm -3 pada suhu sama. (5 marks/markah) (b) The vapor pressure of water at 25 o C is torr. Calculate the average value of ΔH m of vaporization of water over the temperature range 25 o C to 100 o C. Tekanan wap air pada 25 o C ialah torr. Hitung nilai purata ΔH m pengwapan air bagi julat dari 25 o C ke 100 o C. (5 marks/markah) (c) What is fugacity. Illustrate your explanation of the standard state of the real gas by means of appropriate graphs. Calculate the fugacity of 100 atm of Ar gas at 600 K assuming its compressibility is represented by Z = 1 +. For Ar, B = L mol -1. Apa itu fugasiti. Jelaskan penerangan anda tentang keadaan piawai gas sejati dengan mengunakan geraf yang sesuai. Hitung fugasiti 100 atm gas Ar pada 600 K dengan mengandaikan kemampatannya diwakili oleh Z = 1 +. Untuk Ar, B = L mol -1. (8 marks/markah)

7 SCES2230/07 (d) Derive the expression for the entropy change of an isothermal pressure change of an ideal gas and calculate S for the expansion of 2 mols neon (assumed ideal) from 10 to 40 L at 325 K. Terbitkan ungkapan untuk perubahan entropi bagi perubahan tekanan isoterma untuk gas unggul dan hitungkan S untuk pengembangan 2 mol neon (dianggap unggul) dari 10 ke 40 L pada 325 K. (7 marks/markah)

8 SCES2230/08 SECTION C : QUANTUM CHEMISTRY (50 MARKS) BAHAGIAN C : KIMIA KUANTUM (50 MARKAH) Answer TWO (2) questions in this section. Jawab DUA (2) soalan dalam Bahagian ini. 7. (a) Write two short notes on the following: Tuliskan dua nota pendek daripada yang berikut: (i) (ii) (iii) Wavefunction Fungsigelombang Complimentary observable Observable komplimentari Space quantization Pengkuantuman ruang (10 marks/markah) (b) Derive the quantum mechanical operators for the following: Terbitkan operator mekanik kuantum bagi yang berikut: (i) (ii) Kinetic energy of a particle moving in three dimension Tenaga kinetik bagi suatu zarah yang bergerak dalam tiga dimensi Potential energy of a harmonic oscillator Tenaga potensi bagi suatu pengayun harmonik (5 marks/markah) (c) The wavefunction for a particle of mass m confined to move in a one-dimensional box of length L is Fungsigelombang bagi suatu zarah yang berjisim m dihadkan bergerak dalam satu peti berdimensi-satu dan berkepanjangan L, ialah Ψ n = N sin, n = 1,2 (i) Determine the normalization constant N. ( sin 2 x dx = ¼ (2x sin 2x) ) Tentukan pemalar penormalan N. ( sin 2 x dx = ¼ (2x sin 2x) )

9 SCES2230/09 (ii) Where are the most likely locations of the particle in the quantum state n = 2? Dimanakah terdapat kebarangkalian yang paling besar untuk menemui zarah ini apabila zarah ini wujud dalam keadaan kuantum n = 2? (10 marks/markah) 8. (a) The wavefunction of a particle undergoing rotational motion is Fungsigelombang bagi suatu zarah yang melakukan gerakan putaran ialah Ψ = exp (-2 i ). Determine the z-component of the angular momentum of the particle. Tentukan komponen-z momentum sudut bagi zarah ini. (4 marks/markah) (b) The wavefunction describing a particular quantum state of hydrogen atom is Fungsigelombang yang menghuraikan suatu keadaan kuantum tertentu bagi atom hidrogen ialah 1 r r exp ( ) cos, 3 32 a a 2 a o o o where a o is the Bohr radius ; r and are the usual parameters in a spherical polar coordinate system. dimana a o adalah jejari Bohr; r dan adalah parameter biasa dalam sistem koordinat berkutub sfera. Show that Tunjukkan bahawa (i) (ii) the xy-plane is a nodal plane, satah-xy merupakan satu satah nodus, the maximum chances of finding the electron occurs at the z-axis ( = 0 or ), and at a distance r = 2 a o from the nucleus. Kebarangkalian yang paling besar untuk menemui elektron berlaku pada paksi-z ( = 0 atau ), dan pada satu jarak r = 2 a o daripada nukleus.

10 SCES2230/10 (iii) Draw a boundary surface diagram to illustrate the distribution of the electron in this quantum state of hydrogen atom. Lakarkan satu gambarajah permukaan sempadan untuk menunjukkan taburan elektron dalam keadaan kuantum atom hidrogen ini. (9 marks/markah) (c) Which of the following wavefunctions satisfy the Pauli principle? Explain your answer. Yang mana fungsigelombang berikut mematuhi prinsip Pauli? Terangkan jawapan anda. (i) (ii) (iii) (iv) 1s (1) 1s (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) ½ 1s (1) 2s (2) - 2s (1) 1s (2) (1) (2) + (1) (2) (5 marks/markah) Answer (d) OR (e) Jawab soalan (d) ATAU (e) (d) The wavefunction for the 1s atomic orbital of hydrogen atom is Funsigelombang bagi orbital atom 1s atom hidrogen ialah 1s = ( a 0 3 ) -1/2 exp ( -r/a 0 ), where r is the distance of the electron from the nucleus, a 0 = 52.9 pm is the Bohr radius. dimana r adalah jarak antara elektron dan nukleus, a 0 = 52.9 pm ialah jejari Bohr. Calculate the average separation between the electron and the nucleus for H atom in the ground state. Hitungkan purata perpisahan antara elektron dan nukleus bagi atom hidrogen dalam keadaan dasar.

11 SCES2230/11 Given that Diberi exp(-ax) dx =, n = 0, 1, 2, (7 marks/markah) (e) Write the Schrodinger equation for helium atom. Explain why this equation cannot be solved exactly. Name two approximation methods which can be used to determine the energy and wavefunction for helium atom. Tuliskan persamaan Schrodinger bagi atom helium. Terangkan mengapa persamaan ini tidak boleh diselesaikan dengan tepat. Berikan dua kaedah hampiran yang boleh digunakan untuk menentukan tenaga dan fungsigelombang bagi atom helium. (7 marks/markah) END TAMAT

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