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Question #44251
The Question
The standard reduction potential () of 3d transition metals is dictated by the Born-Haber cycle. While the radial probability distribution (RDF) of 3d orbitals contracts across the series (increasing and ionization energies), \ce{Ni} exhibits an anomalously less negative than expected from its high ionization energy, primarily due to its exceptional hydration thermodynamics driven by high Crystal Field Stabilization Energy (CFSE).
Consider the oxidation half-cell reaction relative to the Standard Hydrogen Electrode (SHE) at :
Given the following thermodynamic data at : Enthalpy of sublimation of \ce{Ni(s)}, Sum of first and second ionization enthalpies of \ce{Ni}, Absolute enthalpy of oxidation for SHE (), Standard entropy change for the full cell reaction, Faraday's constant,
Calculate the standard hydration enthalpy () of \ce{Ni^{2+}(aq)}.
Options
- A.
-2100 kJ/mol
- B.
-2977 kJ/mol
- C.
-2092 kJ/mol
- D.
-2004 kJ/mol
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Correct Answer
Step-by-Step Solution
Explanation
How the Examiner Thinks
Exception_Exposure
Learn to identify edge cases and boundary exceptions that JEE examiners hide in math problems.
Concepts Behind This Question
Radial Probability Distribution|Electrode Potential Dependencies|E° (M²⁺/M) Anomalies
Why This Question Is Tricky
Common Mistakes
This problem tests a critical 'Hidden Variable' trap in electrochemistry and thermodynamics.
Students frequently equate the standard reduction potential directly to the absolute Born-Haber cycle sum (), forgetting two major constraints: 1) is a relative value measured against the Standard Hydrogen Electrode (SHE), meaning the absolute enthalpy of oxidation of SHE must be subtracted. 2) relates to , not , requiring the inclusion of the entropy term ().
The chemical context highlights the anomaly of Ni, where its highly contracted 3d RDF leads to a high ionization energy, but this is uniquely compensated by an exceptionally high negative hydration enthalpy, deviating from the general periodic trend.
Quick Facts About This Question
Question Information
| Subject | Chemistry |
| Chapter | Structure of Atom - Class 11 Part 1 |
| Concept | Radial Probability Distribution |
| Difficulty | 8 |
| Cognitive Load | 7 |
| Target Solve Time | 160 sec |
| Access | Free |