Ligand field theory and CuCl2 colors

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Discussion Overview

The discussion revolves around the color change observed in copper (II) chloride when it transitions from an anhydrous form to a hydrated dihydrate form. Participants explore the implications of ligand field theory on the color change, particularly focusing on the d orbital splitting and the expected wavelengths of light absorbed and reflected by the compounds.

Discussion Character

  • Exploratory
  • Technical explanation
  • Debate/contested

Main Points Raised

  • One participant states that according to ligand field theory, water is a stronger field ligand than chloride, suggesting that the dihydrate should exhibit larger d orbital splitting and thus absorb longer wavelengths.
  • Another participant challenges this reasoning, asserting that larger d orbital splitting corresponds to a higher energy difference, which would imply absorption of shorter wavelengths.
  • It is noted that the color observed is complementary to the color absorbed, which is a critical aspect of the discussion.
  • A participant introduces the possibility of charge-transfer transitions affecting the observed color, indicating that these transitions may have higher oscillator strength compared to d-d transitions.
  • Another participant points out the structural differences in the hydrated complex, mentioning that the presence of two water molecules along the axis and four chlorines in the equatorial plane disrupts octahedral symmetry.
  • A participant references external sources that provide differing explanations for the color change, expressing skepticism about their accuracy and seeking clarification from a specific textbook.

Areas of Agreement / Disagreement

Participants express differing views on the relationship between d orbital splitting and the observed color change, indicating that multiple competing explanations remain unresolved. There is no consensus on the correct interpretation of the color change in copper (II) chloride.

Contextual Notes

Participants highlight the complexity of the color change, suggesting that assumptions regarding symmetry and the nature of electronic transitions may be critical to understanding the phenomenon. There are also references to external literature that may not be universally accessible, which could limit the discussion.

khanhhung2512
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Copper (ii) chloride is a light brown solid, which slowly absorbs moisture to form a blue-green dihydrate.
According to ligand field theory, water is a stronger field ligand than chloride. As a result, the dihydrate form should have a larger d orbital splitting than the anhydrous form. Thus, the color (complementary to the wavelength absorbed) of the dihydrate form should have a longer wavelength than the anhydrous form's. But why is the opposite observed here?
If my reasoning is not correct, then please tell me the reason for the color change above.
Thank you very much.
 
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Unless I am missing something, you got it wrong. Larger d orbital splitting means higher energy difference so a shorter wavelength.
 
Well, the color we see is complementary to the color absorbed.
 
There are a zillion of possible explanations.
There can be charge-transfer transitions invoved which have a much higher oscillator strength than the weak d-d transitions.
Also in the hydrated chloride there are two water molecules along the axis and four chlorines in the equatorial plane, so this complex doesn't have a symmetry octahedral symmetry.
 
khanhhung2512 said:
Well, the color we see is complementary to the color absorbed.

That's what I missed
grumpy_borek.png
 
These are two answers I found on the net http://answers.yahoo.com/question/index?qid=20110915202418AA2v9AN
While both answers seem wrong to me, one mentioned Advanced Inorganic Chemistry 6th ed (1999). p 868-869 (F. A. Cotton, G. Wilkinson, C. A. Murillo, M. Bochmann). If anyone has access to that book, please tell me what it really said.
Thanks.
PS: I only have access to the third edition of that book, so I don't know the corresponding pages.
 

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