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Question #44563
The Question
Consider the thermodynamic and spectroscopic profile of the following ligand exchange equilibrium in an aqueous medium at :
Upon heating the solution from to , the color transitions from pale pink to intense deep blue. Identify the correct set of statements regarding this transformation:
I. The forward reaction is entropically driven () due to the release of water molecules, which compensates for the endothermic enthalpy change () at higher temperatures. II. The intense deep blue color of the product is primarily attributed to an increase in the magnitude of the Crystal Field Splitting Energy (CFSE) upon replacing with . III. The d-d transitions in the blue complex are Laporte partially allowed due to p-d orbital mixing in a non-centrosymmetric geometry, leading to a higher molar extinction coefficient (). IV. The spin-only magnetic moment () increases significantly because the complex transitions from a low-spin octahedral to a high-spin tetrahedral geometry. V. The endothermicity of the forward reaction is heavily influenced by the high desolvation energy of the ions and the cleavage of six bonds.
Options
- A.
I, III, and V
- B.
I, II, and IV
- C.
II, III, and V
- D.
I, IV, and V
Check Your Answer
Correct Answer
Step-by-Step Solution
Explanation
How the Examiner Thinks
Mechanism_Trap
Don't get tricked by the process! Learn the mechanical traps used in competitive exam questions.
Concepts Behind This Question
Hydrate and Ionization Isomerism|Color and d-d Transitions|Hydrate Stability vs. Carbonyl
Why This Question Is Tricky
Common Mistakes
This question tests the 'Thermodynamic vs.
CFT' trap in coordination chemistry.
Students frequently misattribute the intense color change of transition metal complexes to an increase in ligand field strength or CFSE.
The hidden variable here is that the CFSE actually decreases due to the weaker chloride ligand and tetrahedral geometry.
The intense color arises from the relaxation of the Laporte selection rule (loss of the inversion center).
Additionally, it probes the thermodynamic intuition that ligand exchange from a higher to a lower coordination number is entropically driven but enthalpically penalized due to the hidden costs of ion desolvation and bond cleavage.
Quick Facts About This Question
Question Information
| Subject | Chemistry |
| Chapter | Coordination Compounds - Class 12 |
| Concept | Hydrate and Ionization Isomerism |
| Difficulty | 8 |
| Cognitive Load | 7 |
| Target Solve Time | 160 sec |
| Access | Free |