Tutorial 4- Answers
1)
Bond order= 0.5[electrons in bonding molecular orbital – electrons in antibonding molecular
orbital]
BO = 0.5[3-2] = 0.5
Since it contain unpaired electrons, it is paramagnetic in nature.
2)
o22+ >o2+ > o2> o2-
3) Hybridisation of Co in ground state: 3d7 4s2
Hybridisation of Co3+ in excited state: 3d6 4s0. Since it is high spin complex
Hence, Co3+: t42g eg2
CFSE = Number of electrons in t2g×(− 0.4)Δo + Number of electrons in eg×(0.6)Δo
⇒CFSE = 4×(− 0.4)Δo + 2×(0.6)Δo
⇒CFSE = − 1.6 Δo + 1.2 Δo = − 0.4 Δo
4) High spin d4 configuration
⇒ t2g eg
∴ CFSE=3× (–0.4) + 1×0.6Δ0
= –1.2+0.6Δ0
= –0.6Δ0
5) We know that,
Crystal field stabilization energy= (− 0.4x+0.6y)Δ0 + zP
Where x= number of electrons occupying t2g orbital
y= number of electrons occupying eg orbital
z= number of pairs of electrons
For low spin d6 complex electronic configuration = t2g6e0g
∴ x=6, y=0, z=3
Hence crystal field stabilization energy (− 0.4×6+0×0.6)Δ0+3P
= − 12/5 Δ0 + 3P
6) For a molecule to be aromatic in nature,
● First, it must be cyclic.
● Second, every atom in the ring must be conjugated.
● Third, the molecule must have [4n+2] pi electrons (we’ll explain in depth what that means,
below)
● Fourth, the molecule must be flat
Though it obeys 4n+2 pi electrons, it is not flat in nature, thus the system is not aromatic in
nature.
7)
A B C D
A is cyclic, planar, conjugated and obeys 4n + 2 pi electrons, thus it is aromatic
B is not cyclic, hence it is non aromatic
C is not planar, not conjugated nor it obeys 4n + 2 pi electrons, so it is non aromatic.
D is cyclic, planar, conjugated and obeys 4n + 2 pi electrons, thus it is aromatic.
8)
9) C
10) A
11) C
12)
13)
14)
15)
[CoF6]3- = Co3+ = (d)6 = t2g4eg2
[Fe (CN)6]4- = Fe2+ = (d)6 = t2g6eg0
[Cu (NH3)6]2+ = Cu2+ = (d)9 = t2g6eg3
16) Answer: b) iii > iv >I > ii
Explanation: The rate of electrophilic substitution depends on the nature of the substituent
already present in the benzene ring.
If the substituent is o/p directing (activating groups) then the rate of substitution increases. If it is
meta directing (deactivating groups) then the rate of substitution decreases.
In the given question, activating groups are -NHCOCH3 and isopropyl groups. The NHCOCH3 is
more activating than the isopropyl group as it shows +M effect (l.p donation from N-atom to the
ring through resonance increases electron density) making further substitution easy. On the other
hand isopropyl just stabilizes by +I effect. +M effect is stronger than +I effect. As a result (iii) is
more reactive than (iv).
ii) is least reactive towards electrophilic substitution because -NO2 is a deactivating group. Nitro
group reduces the electron density in the benzene ring due to its strong–I effect making further
substitution difficult, so the rate decreases.
Thus the correct order is iii> iv > i >ii
17.)
18.)
19.) a -6, b-4, c -6, d-6, e -5
20.) Correct Answer– (d.) –0.6 Δ0
CFSE = 3 ( –0.4)Δ0 + 0.6Δ0
= –1.2Δ0 + 0.6Δ0 = –0.6Δ0
21.) Correct Answer– (c.) d4 to d7 co-ordination entities are more stable for the strong field as
compared to weak field cases.
22.) Answer. Fe is in +2 oxidation state, and therefore the configuration will be 3d6.
Since the ligand is a strong field ligand, the excitation energy is greater than the pairing energy.
Therefore, the configuration is t2g6 eg0.
CFSE= 6 × (– 0.4Δ0) = – 2.4 Δ0.
23).a). A – Chlorobenzene B - Phenol
b) Dow’s process
c) HCl, 623 K and 300 atm
24) a
25)
Electron-donating groups can increase the electrophilic substitution reaction rate.
26) d
NHCOCH3 is ortho-para directing.
27) b
28) d
29) CFSE =6 x (-0.4 Δ0) +3(0.6 Δ0) = -2.4 Δ0 + 1.8 Δ0= -0.6 Δ0= 0.6x12500= -7500cm-1
30) To calculate the crystal field splitting energy (Δ₀) of the [Ti(NCS)₆]³⁻ complex,
we can use the formula:
Δ₀ = hc / λ
Given: h = 6.626 × 10⁻³⁴ J·s (Planck's constant) c = 3.0 × 10⁸ m/s (speed of light) λ = 544
nm = 544 × 10⁻⁹ m (wavelength) NA = 6.02 × 10²³ ions/mol (Avogadro's number)
First, let's calculate the energy (E) associated with the absorption event using the equation:
E = hc / λ
E = (6.626 × 10⁻³⁴ J·s) * (3.0 × 10⁸ m/s) / (544 × 10⁻⁹ m)
E = 3.65 × 10⁻¹⁹ J
Now, let's convert the energy to kJ/mol:
E (J/mol) = (3.65 × 10⁻¹⁹ J) * (NA / 1000)
E (J/mol) = (3.65 × 10⁻¹⁹ J) * (6.02 × 10²³ ions/mol / 1000)
E (J/mol) = 2.19 × 10⁵ J/mol
Finally, let's convert the energy to kJ/mol:
E (kJ/mol) = 2.19 × 10⁵ J/mol / 1000
E (kJ/mol) = 219 kJ/mol
Therefore, the crystal field splitting energy (Δ₀) of the [Ti(NCS)₆]³⁻ complex is 219 kJ/mol.
31)
Co(II) in the octahedral complex has d7 high spin configuration. Thus the
CFSE would be 0.8∆ o.
Thus ∆ o = 18000cm-1/0.8 = 22500cm-1.
∆ t=4/9 x ∆ o.
∆ t = 12000 cm-1.
CFSE for Co(II) in tetrahedral is 1.2∆ t .
Therefore CFSE = 1.2 x 10000 cm-1
CFSE = 12000 cm-1.
32) The following are the explanations given:
1. Aromatic - only 1 of S's lone pairs counts as π electrons, so there are 6 π
electrons, n=1.
2. Not aromatic - not fully conjugated, top C is sp3 hybridized.
3. Not aromatic - top C is sp2 hybridized, but there are 4 π electrons, n=½.
4. Aromatic - N is using its 1 p orbital for the electrons in the double bond, so its
lone pair of electrons are not π electrons, there are 6 π electrons, n=1.
5. Aromatic - there are 6 π electrons, n=1 because the N assumes sp2 hybridization.