You will not face any problem with your PSU, except perhaps failure if it is very old but this is for sure powerful enough.
i3 should handle one or two VPN quite easily ;-) your CPU is already more than enough for what you describe. Then it also depends on additional services you may run.
for pfSense used as firewall, CPU will potentially limit network throughput (but you are very far from this ;D) however if you add services like HTTP proxy, blacklists via Squidguard and anti-virus, Snort and/or stuff like this, this is another story.
Then what you describe in term of computer "isolation" might not be directly related to pfSense but more to general network design where pfSense may play its own role. VLAN could be one direction.