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Topic: Few questions in acidity  (Read 3409 times)

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Offline knight820

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Few questions in acidity
« on: September 19, 2013, 05:07:32 AM »
1)What is the effect on acidity of solution when V2O5 is added to molten AlCl3?
It seems no common ion effect on it, but I have no idea on what reaction will occur on it.

2)What is the order of lewis acid strength of these compounds towards N(CH3)
BF3,B(C2H5)3,B(OC2H5)3,BBr3

Thank you!

Offline magician4

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Re: Few questions in acidity
« Reply #1 on: September 21, 2013, 06:05:46 AM »
ref. 1): "acidity" is not well defined in non-aqueous "solutions" ( i.e. V2O5 in molten Al2Cl6 as "solvent")
.. so I don't see how something not defined might be influenced here
(furthermore, it is quite difficult to have a melt of Al2Cl6, as it usually sublimes before it melts)

ref. what happens, two potential reactions come to mind:

- V2O5 being a strong oxidizer, it might well produce some chlorine initially at elevated temperatures, for example:
V(+V) + 2 Cl-  ::equil:: V(+III) + Cl2
V2O5 + 4 Cl-  :lequil: 2 VO2- + 2 Cl2 + O2-
(amongst other redox-processes)
the oxygen-dianions stepwise will transform Al2Cl6 to Al2O3 + 6 Cl-

- this chlorine, however, might transform V2O5 to VOCl3 , which is voilatile under these conditions (b.p. 127 °C )
6 Cl2 + 2 V2O5  :rarrow: 4 VOCl3  :spinup: + 3 O2

the oxygens produced thereby in turn might re-oxidize the V(+III), so my total process expectation would be
2 Al2Cl6 + 2 V2O5  :rarrow: 4 VOCl3 :spinup: + 2 Al2O3

... but I wouldn't bet the ranch on that


ref order of lewis acid strength:
take a look at what kind of inductive effects the different substituents are known to have
the less electron density remains at the boron, the more strong a  lewis-acid it will become

regards

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Offline knight820

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Re: Few questions in acidity
« Reply #2 on: September 23, 2013, 09:15:32 AM »
For the second question, don't the steric effect taken place?
I know BBr3 is stronger acid than BF3 due to pi-interaction,
but how about BBr3 and B(C2H5)3?

Thanks!

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