かわ (kawa) is the kun-yomi when used alone or as a common noun.
セン (sen) is the on-yomi in on-yomi compounds like 河川 (かせん, kasen: rivers). Note: On-yomi compounds don't use rendaku.
Rendaku (連濁): When 川 is not the first kanji in a kun-yomi compound (i.e., when it follows other kanji using Japanese readings), かわ becomes がわ (adds dakuten ゛).