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I was studying about the periodic table recently, and was reading a topic associated with oxides of halogens, and came across the following line

The bromine oxides, $\ce{Br2O}$, $\ce{BrO2}$, $\ce{BrO3}$ are the least stable halogen oxides (Middle row anomaly) and exist only at low temperatures. They are very powerful oxidizing agents.

So, I went to search this on Google, and found these lines

It refers to the instability of oxides of bromine as compared to relative stability of oxides of chlorine and Iodine at room temperature, the former being stable only at low temperatures.

But the line above is simply restating what the book had already told. So, is their any specific reason why this happens, or is this only due to the experimental data we have gathered?

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This is due to the transition metal contraction.

Bromine has the electron configuration $\ce{[Ar] 4s^{2} 3d^{10} 4p^{5}}. $The 3d orbital has no radial nodes and is therefore quite contracted (close to the nucleus), so there is relatively little repulsion between the 3d electrons and the 4p electrons. This makes it much harder to acheive high oxidation states of bromine (I, IV, VI for the examples you give) because the ionization energies are higher than you might expect from a simplistic approach to periodic trends.

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    $\begingroup$ Why doesn't that argument apply to iodine as well? $\endgroup$ – ron May 9 '15 at 17:56
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    $\begingroup$ @ron he is correct, it does not apply for iodine as 4d orbitals have 1 radial node, while 3d does not have them. $\endgroup$ – Rajat Jain May 9 '15 at 23:38
  • $\begingroup$ It probably applies for astatine too due to the lanthanide contraction but I'm not sure if the redox chemistry has been investigated yet. $\endgroup$ – J. LS May 10 '15 at 10:10
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    $\begingroup$ Your explanation to me seems equivalent. What is shielding other than electron-electron repulsion ? $\endgroup$ – J. LS May 10 '15 at 11:28
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    $\begingroup$ @orthocresol, If I ask this as a new question, it would be regarded as duplicate. $\endgroup$ – Nilay Ghosh Oct 30 '15 at 16:32

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