The way we use our master-slave db, is to use the master for all "active usage", and the slave for all reporting (where it doesn't matter if the data is still "catching up" slightly). Depending on your needs, you could have -all- data manipulation occur on the master, and -all- data reading occur on the slave. This especially helps when you have blocking inserts or updates. (Note: Also consider the "insert delayed" MySQL syntax where possible, which helps avoid blocking too.)
As far as the PHP support for this, all you really need is to keep clean handling for multiple (two) database connections, and use the master (read/write) or slave (ONLY READ) db connection as desired.