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II Semester 2018-19

CHEM F111 General Chemistry Date of upload: 12 Feb 2019 Date of test: 19 Feb 2019
Pool of Assignment 2 (based on Lec. No’s 08-12 & self-study topic Thermochemistry of handout)

1. The ground state term of carbon atom with configuration 1s22s22p2 is 3P. What levels arise from this
term? Identify the ground state with reasoning. (J =2, 1, 0. Ground state: 3P0)
2. For the excited state configuration 1s1 2s1, write the total wave function of the lowest and highest energy
states.
3. Work out the ground state term symbol for 3d2 and how many states belong to the lowest level? (3F2
and 5 states).
4. Fraunhoffer observed two distinct spectral lines at around 589 nm (D lines) in the solar spectrum.
Account for the spectral lines in detail through proper energy level diagram.
5. State which of the following are transitions allowed / forbidden and why? A) 2s → 1s, B) 3P2 → 1F2
C) 5d → 2s, D) 3F4 → 3D3? (Only D is allowed and remaining three (A, B & C) are forbidden)
6. Solution to Schrodinger wave equation for Hydrogenic atom gives the spin of the electron. Justify for or
against this statement and briefly state how spin was discovered?
7. Write the Schrodinger equation for the molecular hydrogen cation considering the Born Oppenheimer
approximation.
8. Predict bond angles (H-N-H) in ammonia (NH3) based on the Valence Bond Theory. Compare the VB
predicted bond angle with the experimentally observed bond angle for this molecule. Indicate the
improvement made in this VBT approach address this problem. (90⁰ and 107⁰ respectively)
9. Prove that any two hybridized (sp3) wavefunctions of carbon in a methane molecule are orthogonal to
each other, given that each atomic orbital is normalized to 1.
10. Write total valence bond wavefunction for the σ-bond of nitrogen molecule. (Ψ (σ-bond) = [ψ2pzA(1)
ψ2pzB(2)+ ψ2pzA(2) ψ2pzB(1)][α(1)β(2)-α(2)β(1)]
11. Find the normalization constant and write the normalized wavefunction for the antibonding molecular
𝟏
orbital of hydrogen molecule. (N = 1/(2(1-S))1/2 ; ψABMO = [𝟐(𝟏−𝑺)]𝟏/𝟐 (ψ1s(A)- ψ1s(B)))
12. Draw MO diagram and MO electronic configuration with parity of molecular orbitals for O2. Indicate
whether it is paramagnetic or diamagnetic. (Paramagnetic)
13. Draw MO diagram of CO molecule. Write the MO electronic configuration. Calculate bond order.
Indicate HOMO and LUMO in CO molecule. (Bond order = 3; HOMO is 3σ and LUMO is 2π)
14. Two moles of an ideal gas is compressed from 3 bar pressure to 6 bar pressure isothermally and
reversibly at 300 K. Calculate (i) w and (ii) H in the process (in kJ). (w = 3.46 kJ & H = 0)
15. Two moles of an ideal gas initially at 1000 kbar pressure is suddenly expanded against a constant
external pressure of 100 kbar until the internal pressure of the gas becomes equal to the external
pressure. If the initial and final temperatures are 300 K, then calculate w in the process (in kJ). Given
that, R = 8.314 LbarK-1 mol-1. (w = - 4.49 kJ).
16. Fifteen grams of zinc is treated with hydrochloric acid in a container open to the atmosphere at 25 oC.
Calculate w (in J) in the process. Assume that any gas is produced in the reaction behaves like an ideal
gas. Given that, atomic weight of Zn is 65.38 g mol-1. (w = - 567.38J).
17. (i) Standard enthalpy of vaporization of water at 100 oC is 40.66 kJ mol-1. Calculate the standard internal
energy of vaporization of water at 100 oC; (ii) The standard reaction enthalpies, rHo of the following
two reactions are known:
Fe2O3(s) + 3CO(g)  2Fe(s) + 3CO2(g), rH1o = -26.8 kJ mol-1
FeO(s) + CO(g)  Fe(s) + CO2(g), rH2o = -16.5 kJ mol-1
Calculate rHo of the reaction: Fe2O3(s) + CO(g)  2FeO(s) + CO2(g). (rHo = 6.2kJ mol-1)
18. The standard enthalpy of combustion of C6H6(l) at 25 oC is -3268 kJ mol-1, calculate the standard
enthalpy of combustion of C6H6(l) at 100 oC. Given that, standard heat capacities in the temperature
range 25 oC to 100 oC, CPo (C6H6, l) = 136.1 JK-1 mol-1, CPo (CO2, g) = 37.11 JK-1 mol-1, CPo (H2O, l) =
75.291 JK-1 mol-1and CPo (O2, g) = 29.355 JK-1 mol-1. (Ho = -3261 kJmol-1)

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