Promotion of PostgreSQL standby and application reconnection
To be truly highly available you will need some logic built into the application to handle this.  You can do this sort of thing with pg_pool, but what if pg_pool breaks?

I think there are many ways you could work this one, but the way I would do it would be:

Master DB (lets call it A), and two slaves (lets call them B and C).  B pulls changes from A and C pulls changes from B in a cascading replication setup.  This means if A fails and is a gonner promote B, no need to change C as its already a slave of B, when A is back you make it a slave of C and so on.

You will need to make changes to your application so that it has some intelligence in it regarding the state of the database.  This would be typically done by having a layer that manages the connections, and it runs a test query (like "SELECT current_timestamp") if the query passes all is fine and it gives the connection to your application to use.  Each application will need to know a list of servers to use in which order so the one that writes will use A first then B.  So in the event the primary fails it tries the secondary (and potentially the third and so on), until it gets one where the test query works.

With this in place if C fails its only read only, the applications will just fail over to B or A and start using C if you get it back.  If B fails, same deal though you might want to do something with C pointing it to A.  If A fails then the system will go read only (but will still work for all read queries).  There will then need to be some human intervention to say "yep A is gone", promote B (which will only take seconds), when B is promoted the writers will go though the connection layer, it will test A and fail test B and pass to the application will get a connection to B which is now a master so writes will be allowed.

I appreciate that this is still not a full HA solution (as there is still a manual step, but its a very simple and quick one), but I think we are going to have to wait for PostgreSQL 9.5 for that.

As I say I dont think there is one dead cert right answer to this, but this is how I would have done it.

Hope it helps