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Why not start with wikipedia
http://en.wikipedia.org/wiki/Proto-I...pean_phonology
Because PIE was not written, linguists must rely on the evidence of its earliest attested descendants, such as Hittite, Sanskrit, Ancient Greek, and Latin in order to reconstruct its phonology.
The reconstruction of abstract units of PIE phonological systems (i.e. segments, or phonemes in traditional phonology) is much less controversial than their phonetical interpretation. This especially pertains to the phonetic interpretation of PIE vowels, laryngeals and voiced stops
http://en.wikipedia.org/wiki/Centum-Satem_isogloss
The centum group includes Italic, Celtic, Germanic, Hellenic and Tocharian. This group merged PIE dorso-palatals and dorso-velars but retain the labio-velars as a distinct set.[2] Tocharian largely reflects a situation where all three PIE dorsal series as well as all voicing/aspiration distinctions (originally constituting nine separate consonants) have merged into a single phoneme /k/. This has led some writers to suggest that Tocharian does not fit the Centum-Satem model.[3] However, some PIE labiovelars are in fact represented by a labiovelar-like element or by a non-original sequence /ku/. Along with other evidence, this suggests that labiovelars were distinct in Proto-Tocharian and only later merged with velars (as happened independently in Old Irish and to some extent in some other languages), making Tocharian a clearly Centum language.[4]
The satem languages (which have the sibilant where the centum equivalents have the velar) include Baltic, Slavic (or Slavonian), Armenian and Indo-Iranian. This group lose the labial element of the PIE labiovelars and thus merge them with the dorso-velars while the dorso-palatals remain distinct.[5] Balto-Slavic is largely satem but evidences centum development in some words, suggesting that "Satemization" was incomplete. There is residual evidence of various sorts in satem languages of a former distinction between velar and labiovelar consonants, indicating the earlier centum state.[citation needed]
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