There are several questions here, let me try and address each one...
Since this appears to be an internet application with federated servers, using the implied HTTP Protocol makes a lot of sense. This could be done via Form POSTs, GET, or even REST-ful submission of some custom data structure. In the end, the exact approach to use will need to come down to the size and complexity of the information being communicated. Many architectures employ these approaches and often combine them with encrypted, signed, and/or encoded payloads for security. One short-fall to consider with these approaches is that they will require you to clearly communicate all request / response message formats, field ranges, and variations since these mechanisms are not really self-describing. On the other hand, these patterns use very common protocols, are easily understood, easy to implemented, and are typically lean on-the-wire.
In constrast, architectures with very complex structures often chose to use WSDL-based web services. Also driven by common standards, these tend to be self-describing, inherently versionable, although they can take more time and energy to implement. There are a lot of advantanges to web services which are driven by many WS-* standards which may be worth investigating further in your case.
As for the reservation process... many similar architectures will employ an orchestration model such as the following:
- Find open booking spaces
- Make a reservation for a booking space. This places an expiring lock on a space while the requestor fills in all required booking information. This mitigates against race conditions that could lead to multiple bookings for the same space
- Once all required booking information is received and validated the booking is confirmed and permamently locked from use by other requestors
As for the SQL-style DB comment, I can't really say given the amount of information supplied. With that said, my instincts tell me a SQL-style DB is completely reasonable for this problem set. I have databases with many pedabytes and have very high SLA's. You implied a need for high availability and SQL-based databases have a few decades of proven support behind them in this area.
Hope this helps.