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Yes, more often than not petrol stations in the rural areas are represented by national chains like Tesco's, Jet, Morrisons, and locals like Go. Most of them will have a cash point also.
There are also lots of self-service petrol stations where the pay point is next to the pump and an attendant is not required at all.
Tip: Get a Tesco Loyalty card before leaving and you'll accrue bonus points as your trip progresses.