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Well if you are gonna study Chinese from Pinyin, trying on the combination directly is better but probably will lead you to a NOT STANDARD one, which actually is easier to a local Chinese to follow and understand.
You have probably already seen this but I'll share just incase. I too have decided to start with pinyin. I was told this table is alot of help. Constants on the left, vowels at the top, syllables in the table. I am still trying to figure out the best way of using the table. It may be a helpful tool when learning to pronounce words.
As I experienced, the second strategy will be better, because the initials has effect on finals in pronunciation. For example qī and chī. In pronunciation the two 'ī" very different.
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