Ligand field theory and CuCl2 colors

AI Thread Summary
Copper (ii) chloride transitions from a light brown solid to a blue-green dihydrate upon moisture absorption. According to ligand field theory, water is a stronger field ligand than chloride, which should theoretically result in larger d orbital splitting and a longer wavelength for the dihydrate. However, the observed color change contradicts this expectation, leading to confusion. The discussion highlights that larger d orbital splitting correlates with higher energy differences, resulting in shorter wavelengths being absorbed, while the color seen is complementary to the absorbed color. Other factors, such as charge-transfer transitions with higher oscillator strength and the complex's lack of octahedral symmetry due to the arrangement of water and chloride ligands, may also contribute to the observed color. References to Advanced Inorganic Chemistry are made for further clarification, but access to the specific edition is limited.
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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