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The main limitation with XE is the maximum amount of user data, several optional Oracle components available in other editions are not included with XE, see the license documentation for details.
The instance can handle as many concurrent sessions as the host OS (and the schema design) can support. Physical memory and process or other resource limits on the host will usually come into play first, and the XE total memory limit of 1GiB for the instance may also be a factor limiting total user sessions.