How do I switch master with slave and vice versa on MySQL?
If you use a DBVIP, you could remove the DBVIP from the Master and bring it up on the Slave.

EXAMPLE

Let's make up a DBVIP, like 10.1.2.30.

Put this up on the Master in the OS

ip addr addr 10.1.2.30/24 dev eth1


Replace your IP in your application with 10.1.2.30, Let the application continue to run for a while, making sure the DBVIP is being used by the application.

Here is something aggressive:


service httpd stop on all Apache Servers
service mysql stop on the Master
ip addr del 10.1.2.30/24 dev eth1 on the Master
ip addr add 10.1.2.30/24 dev eth1 on the Slave
service httpd start on all Apache Servers
SHOW PROCESSLIST; on the Slave to make sure there are incoming DB Connections


If you see DB Connections coming in from the Apache Servers, CONGRATULATIONS you have manually performed a failover.

UPDATE 2012-09-19 14:28 EDT

If you cannot use a DBVIP, you must do more work instead

STEP 01) Activate Binary Logging on the Slave

Add this to /etc/my.cnf on the Slave

[mysqld]
log-bin=mysql-bin


STEP02) service mysql restart on the Slave

Binary Logging should be enabled in the Slave

STEP03) Run the CHANGE MASTER TO command on the Master using the Slave as its Master


Use mysql-bin.000001 as the Master_Log_File
Use the following number as the Master_Log_Pos

107 for MySQL 5.5
106 for MySQL 5.1
98 for MySQL 5.0



STEP04) Run START SLAVE; on the Master

At this point


the Master is the Slave's Slave
the Slave is the Master Slave


This configuration is better known as 


Master/Master
Circular Replication


STEP05) service httpd stop on all Apache Servers

STEP06) Change the IP address in the App to Connect to the Slave 

STEP07) service httpd start on all Apache Servers

STEP08) SHOW PROCESSLIST; on the Slave to make sure there are incoming DB Connections

If you see DB Connections coming in from the Apache Servers, CONGRATULATIONS you have manually performed a failover without MySQL Downtime. The only downtime there is comes from the Window of time STEP05 - STEP07.