Some representative problems Chemical bonding &First Law of Thermodynamics;

Write down the unnormalized valence bond wavefunctions (with spin part) for the  bond and any one of the two 
bonds in P2 molecule (denote two phosphorus atoms as A and B and two electrons as 1 and 2). Neglect hybridization in
P atoms and assume that only three p-orbitals of each of the P atoms are involved).

Ψ1( bond) = Ψ3pz,A(1)Ψ3pz,B(2) + Ψ3pz,A(2)Ψ3pz,B(1) )[(1)(2) - (2)(1)]

Ψ2( bond) = Ψ3px,A(1)Ψ3px,B(2) + Ψ3px,A(2)Ψ3px,B(1) )[(1)(2) - (2)(1)]
OR

Ψ3( bond) = Ψ3py,A(1)Ψ3py,B(2) + Ψ3py,A(2)Ψ3py,B(1) )[(1)(2) - (2)(1)

1.Write the VB spatial wave functions for the bonds in H2O2 using the basis H1s and O2p.

__________
2.Write VB wave functions for BF3 molecule using the sp2 hybrid orbitals h on B and three F2p orbitals.

___________
_
3.Show that the sp2 hybrid orbitals h2 and h3 are mutually orthogonal. Given:
 ___________

4.Find the normalization constant and write the normalized wavefunction for the antibonding molecular
orbital of hydrogen molecule.
Wavefunction for antibonding MO ψABMO = N(ψ1s(A)- ψ1s(B))

Given that

N2(1+1-2S) = 1, N = 1/(2(1-S))1/2 ; ψABMO = (ψ1s(A)- ψ1s(B))

5. 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.
h1 = s+px+py+pz
h2 = s-px-py+pz
h3 = s-px+py-pz
h4 = s+px-py-pz

You need to prove similarly for other pair of hybridized orbitals.

Given that , and

6.Which of the molecules N2, NO, O2, C2, F2, and CN would you expect to be stabilized by (a) the addition
of an electron to form AB−, (b) the removal of an electron to form AB+?
7. Write wavefunction of antibonding molecular orbital for a heteronuclear diatomic molecule XY. The
contribution of atomic orbitals towards the corresponding bonding molecular orbitals Ψ X is 80% and Ψy
is 20%.

ΨBMO= Cx ΨX + Cy Ψy
CX2 = 80% = 0.80 and Cx =0.89
CY2 = 20% = 0.20 and CY = 0.44
ΨBMO= 0.89 ΨX + 0.44 Ψy
ΨABMO= 0.44 ΨX – 0.89 Ψy

8. Draw MO diagram of CO molecule. Write the MO electronic configuration. Calculate bond order.
Indicate HOMO and LUMO in CO molecule.

1σ22σ21π43σ2
Bond order = 3 ; HOMO is 3σ and LUMO is 2π
9.Sketch the molecular orbital energy level diagram for BrCl and deduce its ground-state electron
configurations.
Is BrCl likely to have a shorter bond length than BrCl-?

10.Arrange the species O2+, O2, O2−, O22− in order of increasing bond length.

11. In theory, a diatomic molecule can be formed from one atom of hydrogen and one atom of helium,
giving HeH. The ionization energies of hydrogen and helium are 1312 kJ mol -1 and 2372 kJ mol-1
respectively.
(i) Draw an energy level diagram for the molecular orbitals in the HeH molecule.
(ii) What is the bond order in this molecule?
(iii) Are the electrons in the σ-bonding MO of this molecule likely to be found near the H atom or near
the He atom? Give reason in one or two sentences.
(iv) What charge on HeH, would produce most stable ion possible? What would be bond order in this
ion?
(i)

(ii) 0.5

(iii) They will be near He atom owing to its higher electronegativity. The
sigma bonding MO in HeH has more weightage from the He orbitals and
closer to those orbitals energetically.
(iv) HeH+, bond order is 1

12.Calculate the work done when 83.775 g of iron completely reacts with HCl to produce FeCl2 at 298.15
K in (a) a rigid closed vessel and (b) in a vessel with piston attached to it. (Atomic mass of Fe is 55.85 g)
Fe(s) + 2HCl(aq) → Fe2+ (aq) + 2Cl- (aq) + H2 (g)
(a) w = 0 (since no change in volume)
(b) w = -p(∆V) = ~ -ngRT where ng is the number of moles of
H2 gas generated, and here is equal to 1.5 moles.
Therefore, w = -3.72 kJ.
13. The temperature of 2.0 kg of water dropped from 95 oC to 40 oC when 1.25 kg of a metal piece at 25
o
C was added to water. Calculate the heat capacity of metal if heat capacity of water is 4.184 J K-1 g-1.
Since water and metal piece are from isolated system,
Heat lost by water = Heat gained by metal piece.
Let c’ be the specific heat of metal piece.
Heat gained by the metal piece, q = m c’ ∆T = (1.25 x 103 g) x (c’) x (40 – 25)deg
Heat lost by water, q = - (2.0 x 103 g) (4.184 J K-1 g-1) (-55 deg)
Therefore, c’ = (2 x 103 x 4.184 x 55) / (1.25 x 103 x 15) J K-1g-1
= 24. 55 J K-1g-1
14. A sample consisting of 2.00 mol He is expanded isothermally at 0°C from 5.0 dm 3 to 20.0 dm3 (i)
reversibly, (ii) against a constant external pressure equal to the final pressure of the gas, and (iii) freely
(against zero external pressure). For the three processes calculate q, w, and ΔU. Can you also consider
the isothermal free expansion of a perfect gas as an adiabatic process?
For all cases ∆U = 0, since the internal energy of a perfect gas depends only on temperature. (i) ∆U = ∆H = 0
W = -nRTln(Vf/Vi) = -6.29 x 103 J; q = -W = 6.29 x 103 J
(ii) ∆U = ∆H = 0; W = − pex∆V; where pex in this case can be computed from perfect gas law
pV = nRT; p = 2.22 x 105 Pa; W = -3.34 x 103 J; q = -W = 3.34 x 103 J
(iii) ∆U = ∆H = 0; W = 0 (Free expansion); q = 0
Yes. An isothermal free expansion of a perfect gas is also adiabatic.
15. The constant-pressure heat capacity of a sample of a perfect gas was found to vary with temperature
according to the expression Cp/(J K−1) = 20.17 + 0.4001(T/K). Calculate q, w, ΔU, and ΔH when the
temperature is raised from 25°C to 100°C (i) at constant pressure, (ii) at constant volume.
16.Two moles of an ideal gas at initial pressure 1000 bar and initial volume 11.3 L undergoes a sudden
expansion against a constant external pressure of 400 bar until the internal pressure of the gas becomes
equal to external pressure with no change in the temperature. Calculate w in the process (in kJ). (2M)
For an irreversible process, w= - PextV = - Pext(V2 – V1)
We have, P1V1 = n RT1. So, 1000 bar×11.3L = (2 mol)×(8.314×10-2 LbarK-1mol-1) ×T1
Or, T1 = 67957 K.
We have, P2V2 = n RT2. So, 400 bar×V2 = (2 mol)×(8.314×10-2 LbarK-1mol-1) ×(67957 K).
Or, V2 = 28.3 L.
Therefore, w = - Pext(V2 – V1) = - 400 bar (28.3 – 11.3) L = - 6800 Lbar = -6800×100J = - 680 kJ