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Just something as simple as the character for "one" has the On readings "ichi"
and "itsu." So how would I know which one to use if I saw this as part of a
compound?
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2012-07-22T19:49:52.840
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readings
How to know which On reading to use?
Unless someone knows something that I don't, you just have to learn it for
each word. Sometimes a word's pronunciation has evolved so that 9 times out of
10 it's pronounced one way, and that 10th time its the other. For example,
it's a pretty safe bet that the On-yomi for `一` in a compound is `いち` or `いっ`
(depending on the sound following it), but every now and then you'll find it
read `いつ` (as in `単{たん}一{いつ}` which is so hard for me to remember).
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2012-07-22T21:34:48.123
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There really is no trick to learning how to read the ON reading, it just comes
down to practice. The best way is to start at the beginning with 1 nensei
workbooks and work your way through to college.

Practice and stay positive, and get into as many real conversations as you
can. You will catch on a lot quicker in actual use than from a book. You will
hear " ** _baka_** " a number of times a day, and then when you read 馬鹿 you
will remember that it is not pronounced " ** _uma-shika_** ".
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2012-07-23T00:00:44.163
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Just to add color, there are [some
kanji](http://ja.wikipedia.org/wiki/%E9%9F%B3%E8%AA%AD%E3%81%BF#.E5.A4.9A.E9.9F.B3.E5.AD.97),
where the reading depends on the semantics. However, I doubt this is common
enough to really be useful for learning to read kanji.

Otherwise, I agree with @silvermaple that the best way probably is to memorize
the most common on'yomi, and then memorize the most common exceptions. There
are also kanji like 重 (ちょう and じゅう), where both readings are common, so you
pretty much have to memorize all the common combinations.
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