Inorganic Reaction Mechanism - Question Bank
Inorganic Reaction Mechanism
Sem - II (2023)
Question Bank
1. For [M(OH2)6]2+ (M = 1st transition series metal), the Id path for ligand substitution reaction operates
for the late members like [Fe(OH2)6]2+, while the Ia path operates for the early members like
[V(OH2)6]2+. Explain. (3)
2. [Cr(OH2)6]3+ reacts through the Ia path while [Cr(NH3)5(OH2)]3+ reacts through the Id path. Explain.
(3)
3. [M(OH2)6]3+ (M = Fe, Cr) react through the Ia path while their hydrolyzed forms [M(OH)(OH2)5]2+
react through the Id path. Explain. (3)
4. How can you determine ΔV‡? Comment on the sign of ΔV‡ for the dissociative and associative
activation of the outer exchange process of metal ions. (2+2)
5. For the solvent exchange process, ΔV‡ is positive for [Mn(DMF)6]2+ while it is negative for
[Mn(OH2)6]2+. Explain. (3)
6. Explain the following water exchange rate sequence for the bivalent metal ions of 1st transition series:
Cu2+ > Cr2+ > Mn2+ ≈ Zn2+ > Fe2+ > Co2+ > Ni2+ > V2+ (4)
7. Explain the following ligand exchange (by using *CN-*) rate sequence:
[Ni(CN)4]2- > [Pd(CN)4]2- > [Pt(CN)4]2- (4)
8. Explain the unusually high outer exchange rate of [Co(OH2)6]3+. (4)
9. Explain the outer exchange rate sequence for:
[Al(OH2)6]3+ > [Sc(OH2)6]3+ > [Ti(OH2)6]3+ > [V(OH2)6]3+ > [Fe(OH2)6]3+ (3)
10. Perfect D-mechanism is likely to operate for the highly anionic complexes like anion of
Inorganic Reaction Mechanism - Question Bank
[Co(CN)5(OH2)]2-, aquation of [Fe(CN)5L]2-, aquation of [Cr(NCS)6]3-, etc. Explain. (3)
11. Explain the following CN- exchange rate order:
[Mn(CN)6]3- > [Cr(CN)6]3- > [Fe(CN)6]3-/4- (4)
12. [M(bipy)3]3+ is more stable than [M(en)3]3+ (M = Co, Cr) but [M(bipy)3]3+ reacts much faster than
[M(en)3]3+ in acid catalyzed dissociation. Explain. (4)
13. Compared to the trivalent transition metals, the outer exchange rate of lanthanides (Ln3+) are
relatively faster.
14. How can you determine ΔS‡ by using the Eyring equation? How can you interpret the mechanism of
solvent exchange reaction by using the ΔS‡ parameter? (2+2)
15. ΔS‡ is positive for aquation of [Co(NH3)5L]3+ while it is negative for aquation of [Cr(NH3)5L]3+ (L =
neutral ligand like DMSO, urea, etc.). Explain. (4)
16. ΔS‡ is positive for aquation of [Co(NH3)5L]3+ (L = neutral ligand) while it is negative for
[M(NH3)5X]2+ (X = anionic ligand). Explain. (4)
17. Explain the following ligand exchange rate order:
[Pt(CN)4]2- > [PtI4]2- > [PtBr4]2- > [PtCl4]2- (4)
18. Derive the rate law of ligand substitution reaction in terms of Eigen-Wilkins mechanism. How can you
determine the rate constant (k1, k-1) and Keq (pre-equilibrium constant) for:
[S-M-X] + Y → [S-M-Y] + X (Charges not shown) (4)
19. [S-M-OH] + Y → [S-M-Y] + H2O (Charges not shown)
How can you distinguish the Id and Ia mechanisms of the above ligand substitution reaction by
considering the Eigen-Wilkins mechanism? (4)
20. Explain the linear free energy relationship (LFER) for the acid hydrolysis reaction of the
Inorganic Reaction Mechanism - Question Bank
Co(III)-complexes:
[Co(NH3)5X]2+ + H2O → [Co(NH3)5OH2]3+ + X- (4)
21. Explain the steric effect in the aquation rates of
trans-[CoCl(N-N)2]2+ where N–N denote the ethylene diamine ligand having different substitutions.
trans-[CoCl2(N–N)2]+ + H2O → trans-[CoCl(OH2)(N–N)2]2+
22. Explain the aquation rate orders for the Cl- complexes of Co(III) and Cr(III):
(replacement of Cl- ligand by H2O)
[CoCl(NH3)5]2+ < [CoCl(MeNH2)5]2+
[CrCl(NH3)5]2+ > [CrCl(Me2NH)5]2+ (4)
23. [CoCl(en)2(L)]2+ + H2O → [Co(OH)(en)2(L)]2+ + Cl-
In the above aquation reaction (L = π-donor ligand), the cis complex reacts faster than the trans complex
(i.e., kcis ≫ ktrans). The cis complex leads to 100% retention of configuration while the trans complex
leads to isomerisation. Explain. (4)
24. [CoCl(en)2(L)]2+ + H2O → [Co(OH)(en)2(L)]2+ + Cl-
In the above aquation reaction (L = strong π-acceptor ligand), the trans complex reacts faster than the
cis complex (i.e., ktrans > kcis). In both the cis and trans isomers, there is a 100% retention of
configuration. Explain. (4)
25. The acid catalyzed aquation of [M(CO3)(NH3)4]+ (M = Co, Rh, Ir) in the following reaction occurs
almost at the same rates though the lability order is:
Co(III) > Rh(III) > Ir(III). Explain. (4)
26. [Co(NH3)5(OH2)]3+ + NO2-/H+ → [Co(NH3)5(ONO)]2+ (fast) → [Co(NH3)5(NO2)]2+ (slow)
Explain the above relative rate of the two steps. (4)
27. Give the D–CB mechanism of base hydrolysis of [Co(NH3)5Cl]2+ and explain the origin of rate
enhancement:
[Co(NH3)5Cl]2+ + OH- → [Co(NH3)5OH]2+ + Cl- (4)
Inorganic Reaction Mechanism - Question Bank
28. Derive the rate law for base D–CB mechanism of base hydrolysis of [Co(NH3)5X]2+ (X = Cl, N3, NCS,
etc.)
[Co(NH3)5X]2+ + OH- → [Co(NH3)5OH]2+ + X- (4)
29. Base hydrolysis of [CoCl2(PPh3)2]+, [CoCl(en)2]+ and [CoCl(bpy)2]+ is much slower than that of
[Co(NH3)5Cl]2+. Explain. (4)
30. (i) [Co(NH3)5Cl]2+ + Y- → [Co(NH3)5Y]2+ + Cl- (in DMSO)
(ii) [Co(NH3)5Cl]+ + Y- → [Co(NH3)5Y]2+ + Cl- (in presence of small amount of base, B)
Y- = N3-, SCN-, NO2-, etc.
The reaction (ii) is much faster than reaction (i). Explain. (4)
31. Explain the relative rates of base hydrolysis of [Co(NH3)5X]2+ and [Cr(NH3)5X]2+ (X = Cl, N3, NCS,
etc.)
[M(NH3)5X]2+ + OH- → [M(NH3)5OH]2+ + X- (4)
32. Draw the geometrical isomeric structure of [CoCl(NH3)(trien)]2+ and explain their relative rates of
base hydrolysis:
[CoCl(NH3)(trien)]2+ + OH- → [Co(OH)(NH3)(trien)]2+ + Cl- (4)
33. Draw the red and purple isomers of [Co(NH3)(trien)]2+ and explain their reactivity order in base
hydrolysis.
Explain the stereochemistry of the product.
