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Many Russian interrogatives start with к-:

кто? кому? куда? кем? как? который? где? (<кде?) когда?

On the other hand, some interrogatives start with ч-. They seems to be case variants of "что?":

что? чему? чем? чего? о чём?

I suppose that all these interrogatives came from Proto-Indo-European "q-", which also gave English wh- (as in what, who, when, which,...).

Yet I wonder why кто ("who") and "что"("what") got different initial consonant? Can it be explained solely by dissimilation?

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    Nice question. Чей, however, is not a form of что. – Quassnoi May 23 '13 at 13:17
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Кто ("who") and "что"("what") have different initial consonants due to the so-called Slavic first palatalization which happened rather early, in the Proto=Slavic times.

Кто < Pr-Sl. *kъ-to

Что < Pr-Sl. *čь-to

During this palatalisation *k changed *k > *kʲ > *č before front vowels. *ь being a front vowel, *čь is the result of *ki undergoing the Slavic first palatalization, this *ki is a cognate of Greek ti ("what") and Latin quid ("what").

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