Remember in C (and C++) a string is normally just an array of characters (this is assuming that you are not using some string class or another, e.g. MFC CString) that has the last character of the string set to theNULL character (value 0 or '\0').
So to get the value of any given character all you have to do is reference that character like so
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char string[] = "Hello World";
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char c = string[2];
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Run this code and c will contain the value of the third character in the string (remember array indexes start at 0) or 'l' which has a value of 108 (in ASCII or ANSI).
If you are using a string class then most classes have a way of determining the value of a character at a specific location within a string but I would need to know the class to be able to answer the question.