Do the size of the system need to be that much larger for 95C compare to 100C ? In my understanding the post talk about methods that do not involve pressure. On top of that if you want more heat you may simply use a liquid switch higher boiling temp.
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Yes because at 100C you can use phase change to transport water, which means you've built a primitive heat pipe.
At 95C H transport is slow so heat will accumulate until it reaches 100. But then you have boiling and, w/out good seals water loss.