Birla Institute of Technology & Science, Pilani, Rajasthan 333031 First Semester 2013-2014 Course Number: CHEM F111

Course Title: General Chemistry Marks: 8 Tutorial Problem Set 5 (based on Lecture No.s: 29-36 in the course hand out) Instructions to the student: The following problems should be solved as home assignment within a week of display. Any one problem will be assigned as a closed book class test in the following tutorial hour. Useful data: me = 9.11 x 10-31 kg, h = 6.626 x 10-34 Js , 1 eV = 1.602 x 10-19 J, = 1.055 x 10-34Js Q. 1 (a) Assign the structure of the compound having molecular formula C9H12S from the following 1H NMR data. (ppm) : 1.20 (doublet, 6 H, J = 6 Hz) 3.25 (septet, 1 H, J = 6 Hz) 7.25 (singlet, 5 H) [5] 13 (b) How many signals you expect in the proton decoupled C NMR of the following compounds? (i) (ii) (iii)

[3] Q. 2 (a) 32S has a nuclear spin of 3/2 and a nuclear g factor of 0.4289. Calculate the energies of the nuclear spin states in a magnetic field of 7.500T. The value of nuclear magneton is 5.051 10 [4] (b) Calculate the energy difference between the lowest and highest nuclear spin states of 15.00 T magnetic field.
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N nucleus in a [4]

Q. 3 (a) Calculate the relative population difference / for protons in a field of 0.30T at 250C. The value of = 26.752 10 and = 1.38006 10 [4] (b) The value of chemical shift of the CH3 protons in acetaldehyde (ethanal) is = 2.20 and that of the CHO proton is 9.80. What is the difference in local magnetic field between the two regions of the molecule when the applied field is 1.5T. = 1.9328 10 . [4] Q. 4 (a) Calculate the work required to compress an ideal gas of volume 1.00 dm3 at 2.00 bar isothermally to a volume of 0.667 dm3 at a constant pressure of 3.00 bar followed by another isothermal compression of 0.500 dm3 at a constant pressure of 4.00 bar. Compare the result with the work of compressing the gas isothermally and reversibly from 1.00 dm3 to 0.5 dm3. [5] (b) The value of H at 298 K and one bar for the reaction described by, 2H2 (g) + O2 (g) 2H2O (l) is -572 kJ. Calculate U for the reaction as written. [3] Q. 5 (a) Calculate fusH0 of water at -10C and one bar, given that fusH0 (0C) = 6.01kJ.mol-1, C0P (s) = 37.7J.K-1.mol-1 and C0P (l) = 75.3 J.K-1.mol-1. [4] (b) Standard enthalpies of combustion of C (s), H2 (g) and CH4 (g) are -393.5 kJ.mol-1, -285.8 kJ.mol-1 and - 890.4 kJ.mol-1 respectively at 298 K. Calculate the standard enthalpy of formation of methane, CH4 (g) [4] Page 1 of 2

Q. 6 (a) The equilibrium constant for the reaction described by 2SO2 (g) + O2 (g) 2SO3 (g) is KP = 10 at 960 K. Calculate rG and indicate in which direction the reaction will proceed spontaneously for 2SO2 (0.001 bar) + O2 (0.2 bar) 2SO3 (0.0001 bar) [5] (b) Calculate the entropy of the transition between orthorhombic sulfur, S() and monoclinic sulfur, S() where the transition enthalpy is -402 J mol-1 and the transition temperature is 369 K. Two individual entropies can also be calculated from heat capacity measurements from T = to T = 369 K and found that Sm () = Sm(,0) + 37 JK-1 mol-1 and Sm() = Sm(,0) + 38 JK-1 mol-1. Calculate the trsS and compare this with the previous one. [3] Q. 7 (a) Predict how the total pressure varies during the gas phase decomposition reaction in a constantvolume container: [2] 2 N2O5 (g) 4 NO2 (g) + O2 (g) (b) Isomerization of hydrogen iso-cyanide to hydrogen cyanide: HNC (g) HCN (g) is an example of a first-order reaction. If the rate constant at a particular temperature is 4.403 10-4 s-1, what mass of HNC remains after 1.50 hr if a 1.0 gram sample of HNC was present at the beginning of the reaction? [3] (c) For a general reaction, a A + b B products, the following initial rates are determined experimentally when reactions are set up with the initial amounts indicated in units of molarity, M. [3] [A] (M) [B] (M) Initial rate (M/s) 1.44 0.35 5.37 10-3 1.44 0.70 2.15 10-2 2.89 0.35 2.69 10-3 Assuming that the rate law can be written as, rate = k . [A]m . [B]n, determine the values of m, n, and k Q. 8 (a) The rate of a chemical reaction is found to be doubled when the temperature is raised from 25C to 35C. Determine the activation energy. [2] (b) The rate constant for the decomposition of a certain substance is 1.70 10-2 dm3 mol-1 s-1 at 24C and 2.01 10-2 dm3 mol-1 s-1 at 37C. Evaluate the Arrhenius parameter of the reaction. [4] (c) The rate constant for the reaction O (g) + O3 (g) Express this rate constant in dm3 mol-1 s-1. 2 O2 (g) is 8.0 10-15 cm3 molecule-1 s-1 at 25C. [2]

Q. 9. (a) Consider the following reaction mechanism which involves the intermediate (I): [6] A+B I I P Deduce the rate law for the reaction in two ways by (i) assuming a pre-equilibrium and (ii) considering a steady-state approximation. Comment on the results obtained in two different ways. (b) Consider a photochemical reaction A B + C. Each mole of photons absorbed causes 1.2 102 moles of A to react at 500 nm. After exposure of 200 mmol of A to the light, 1.77 mmol of B is formed. How many photons were absorbed by A? [2] *********** Page 2 of 2