# KFT 232 Physical Chemistry II [Kimia Fizik II]

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1 UNIVERSITI SAINS MALAYSIA Second Semester Examination 2010/2011 Academic Session April/May 2011 KFT 232 hysical Chemistry II [Kimia Fizik II] Duration: 3 hours [Masa : 3 jam] lease check that this examination paper consists of THIRTEEN pages of printed material before you begin the examination. Instructions: Answer any FIVE (5) questions with at least ONE question from art B. Answer each question on a new page. You may answer either in Bahasa Malaysia or in English. If a candidate answers more than five questions, only the answers to the first five questions in the answer sheet will be graded. In the event of any discrepancies, the English version shall be used. Appendix: Fundamental constants in physical chemistry. 2/-

2 ART A Answer not more than FOUR questions (a) The molar heat capacity of one mole of an ideal gas is given by C = a + bt + ct 2 where a, b and c are constants. The gas was heated from 300 to 500 K at constant pressure. Calculate w, q, U and H as a function of a, b and c for this process. If the process is an isochoric reversible process, calculate U, q and w. (10 marks) According to Joule-Thomson experiment, show that H T C JT where µ JT is the Joule-Thomson coefficient. Calculate H if 1.0 mol of CO 2 gas was compressed from 0 to 100 atm at 300 K, given that µ JT / K atm -1 = x 10-3, and, C / J K -1 mol -1 = x 10-3 T x 10-7 T 2. (10 marks) 2. (a) For the chemical reaction, N 2 + 3H 2 2NH 3, the enthalpy and the free energy changes are and kj mol -1, respectively, at 298 K. Calculate the free energy change at 500 K and show whether the reaction is spontaneous at this temperature by using Gibbs-Helmholtz equation. (8 marks) Derive the following equations: H U S S V T 2 A G T T V (12 marks) 3/-

3 3. (a) What are the values of the entropy change for the reversible cooling of 1.0 mol of O 2 (g) from 298 K to O 2 (l) at K? Given that -3- vap H = 6.82 kj mol -1 at K and C = (7/2) R (8 marks) For the liquid gas phase equilibrium, derive the Clausius-Clapeyron equation shown below, dln Δ vaph 2 dt RT Calculate the heat of vaporization and the vapour pressure of propene at 225 K from the following experimental data for the propene vapour pressure at different temperatures. TK Torr (12 marks) 4. (a) Consider a Carnot engine, represented in the figure below, operating between 500 and 0 C using 1 mol of an ideal monatomic gas. If V 1 = 0.01 m 3 and V 2 = 0.1 m 3, calculate: V 3 and V 4. q, w, and U for each step. (iii) q, w and U for the overall process, and, (iv) the efficiency of the engine. (10 marks) 4/-

4 -4- At 30 C and 1 atm, the molar volume of a solution mixture consisting of benzene and cyclohexane is expressed by the following equation: V X 2.64 X 2 m B B where V m is the average molar volume of solution (cm 3 mol -1 ) and X B is the mole fraction of benzene. Determine: The partial molar volumes of benzene and cyclohexane when the mixture contains 0.6 mole fraction of benzene. The volume of solution consisting of 5 mol of pure liquid benzene and 3 mol of pure liquid cyclohexane. (10 marks) 5. (a) Ethanol and methanol form a very nearly ideal solution. The vapour pressure of methanol is 88.7 Torr and that of ethanol is 44.5 Torr at 20 C. (iii) Calculate the mole fraction of methanol and ethanol in a solution obtained by mixing 100 g of each. Calculate the partial pressure and the total vapour pressure. Calculate the mole fraction of methanol in the vapour. (10 marks) The fugacity for a van der Waals gas is given by ln f nrt nb ln V nb V nb 2an RTV At what pressure is the standard state of argon if a = atm dm 6 mol -2 and b = dm 3 mol -1? (10 marks) 5/-

5 -5- ART B Answer at least ONE question. 6 (a) The solubility, S, for the sparingly soluble salt, [Co(NH 3 ) 6 ] 3+ [Fe(CN) 6 ] 3- in the presence of various concentrations of KNO 3, m, was obtained at 25 o C. S x 10 5 /mol kg m x 10 4 /mol kg Calculate the solubility product of the salt and the mean ionic activity coefficients of the [Co(NH 3 ) 6 ] 3+ and [Fe(CN) 6 ] 3- ions at each concentration. Compare these mean ionic activity coefficients with the values calculated by using the Debye-Hückel limiting law. Given: Debye-Hückel constant, A = kg ½ mol -½ (12 marks) The rates of ionic reactions in solution are proportional to the concentrations of activated complexes. Derive an equation relating the logarithm of the rate constant to the ionic strength and the charge numbers, Z A and Z B, of the ions, A and B, respectively. 7. (a) Consider the following cell with transference at 25 o C: (8 marks) (iii) Derive an expression for the emf of this cell with transference. Calculate the emf of this cell at 25 o C, if the transference number of Na + ion is 0.40 for NaCl solutions and the mean ionic activity coefficients for 0.1 m and m NaCl solutions are 0.60 and 1.0, respectively. Calculate the emf of this cell without transference. (12 marks) 6/-

6 -6- The emf of the cell t H 2 (g, 1atm) HCl (aq, m) AgCl(s) Ag(s) measured between 0 and 90 o C is as follow: E/V = x 10-4 T x 10-6 T 2 where T is the temperature in o C. Write the cell reaction and calculate G, H and S for the cell reaction at 50 o C. (8 marks) 7/-

7 -7- AENDIX UNIVERSITI SAINS MALAYSIA School of Chemical Sciences General data and fundamental constants Quantity Symbol Value ower of ten Units Speed of light c m s -1 Elementary charge e C Faraday constant F=N A e C mol -1 Boltzmann constant k J K -1 Gas constant R=N A k J K -1 mol L bar K -1 mol L atm K -1 mol LTorr K -1 mol -1 lanck constant h J s ħ = h/2п J s Avogadro constant N A mol -1 Standard acceleration of free fall g m s RT/F Conversion factors Useful relation Unit relations 1 ev x J Energy 1 J = 1 kg m 2 s kj mol -1 = V at 25 o C = 1 A V s cm -1 Force 1 N = 1 kg m s -2 1 cal 1 atm J ka ressure 1 a = 1 N m -2 = 1 kg m -1 s -2 = 1 J m Torr 1 cm x J Charge 1 C = 1 A s 1 Å 1 L atm m J otential difference 1 V = 1 J C -1 = 1 kg m 2 s -3 A -1 Atomic Weights Al C Fe Sb Cs Kr K Ar Cl b Ag As Cr Li Na Ba Co Mg S Be Cu Mn Sn Bi F Hg W B Au Ne Xe Br He Ni Zn Cd H N Ca I O /-

8 -8- TERJEMAHAN Arahan: Jawab LIMA (5) soalan sahaja dengan sekurang-kurangnya SATU soalan daripada Bahagian B. Jawab setiap soalan pada muka surat yang baru. Anda dibenarkan menjawab soalan ini sama ada dalam Bahasa Malaysia atau Bahasa Inggeris. Jika calon menjawab lebih daripada lima soalan, hanya lima soalan pertama mengikut susunan dalam skrip jawapan akan diberi markah. Sekiranya terdapat sebarang percanggahan pada soalan peperiksaan, versi Bahasa Inggeris hendaklah diguna pakai. Lampiran: emalar asas dalam kimia fizik. 9/-

10 (a) Apakah nilai perubahan entropi untuk penyejukan berbalik bagi 1.0 mol O 2 (g) daripada 298 K kepada O 2 (C) pada K? Diberi : wap H = 6.82 kj mol -1 pada K dan C = (7/2) R (8 markah) Bagi keseimbangan fasa gas-cecair, terbitkan persaman Clausius- Clapeyron yang ditunjukkan berikut: dln dt ΔwapH 2 RT Kirakan haba pengwapan dan tekanan wap propena pada 225 K daripada data eksperimen yang berikut untuk tekanan wap propena pada suhu yang berbeza: TK Torr (12 markah) 4. (a) ertimbangkan satu enjin Carnot yang beroperasi antara 500 dan 0 C dengan menggunakan 1 mol gas unggul monatom. Jika V 1 = 0.01 m 3 dan V 2 = 0.1 m 3, kirakan V 3 dan V 4 q, w, dan U untuk setiap langkah (iii) q, w dan U untuk proses keseluruhan dan (iv) kecekapan enjin. (10 markah) 11/-

11 -11- ada 30 C dan 1 atm, isipadu molar bagi campuran larutan mengandungi benzene dan sikloheksana diungkapkan dengan persamaan yang berikut: V m X B 2.64 X 2 B dengan V m ialah isipadu molar purata bagi larutan (cm 3 mol -1 ) dan X B ialah pecahan mol benzena. Tentukan: Isipadu molar separa benzena dan sikloheksana apabila campuran mengandungi 0.6 pecahan mol benzena Isipadu larutan mengandungi 5 mol cecair benzena tulen dan 3 mol cecair sikloheksana tulen. (10 markah) 5. (a) Etanol dan metanol membentukkan larutan yang amat menghampiri unggul. Tekanan wap metanol ialah 88.7 Torr dan yang bagi etanol ialah 44.5 Torr pada 20 C. (iii) Kirakan pecahan mol metanol dan etanol di dalam satu larutan yang diperoleh dengan mencampurkan 100 g setiap satu. Kirakan tekanan pecahan dan tekanan wap total. Kirakan pecahan mol metanol di dalam wap. (10 markah) Fugasiti bagi satu gas van der Waals diberi dengan ln f nrt nb ln V nb V nb 2an RTV ada apakah tekanan adalah keadaan piawai bagi argon jika a = atm dm 6 mol -2 dan b = dm 3 mol -1? (10 markah) 12/-

13 -13- Emf sel t H 2 (g, 1atm) HCl (ak, m) AgCl(p) Ag(p) yang telah disukat di antara 0 dan 90 o C ialah seperti berikut: E/V = x 10-4 T x 10-6 T 2 T ialah suhu dalam o C. Tulislah tindak balas sel keseluruhan dan kirakan G, H and S bagi tindak balas sel pada 50 o C. (8 markah) -ooooooo- 14/-

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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

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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

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