If your employer proposes monitoring software, make sure you know exactly what is being monitored and the purpose. Monitoring is invasive and should not take place just for the sake of it; there should be a good business reason.
Make sure that there is a written policy and that it covers the circumstances in which data collected from monitoring can be used.
In particular, make sure you know what is and is not acceptable for you to be doing at work. Your employer should set out whether accessing private emails is acceptable and when, such as during lunch breaks or whether you are allowed to use your wok account to send/receive personal correspondence.
Read more here.