Just thought I'd post this here for the benefit of anyone else getting started on 2Talk...
I've been having a play around with the free 2Talk account prior to porting our landline to them. I installed Zoiper on my phone and registered my account with no problems.
When I dialled a number and got the voice prompt to "Please enter your password, followed by the hash key", it wouldn't accept the PIN number that was set for my account. It took me far too long to realise that I needed to change the PIN away from its initial value in the online control panel before things started working - there was no prompting I noticed saying that this was necessary.
I hope that saves someone else a few minutes of frustration...