It seems Temperature_Ext is a QuantityType item, which sadly makes comparisons even more difficult in rules.
Here is a thread talking about it, but basically you need to change your comparison from
if (TempVol > 20 &&...
To
if (TempVol > 20|°C &&...
Edit: you might need to remove the as Number statement as well. I haven’t personally worked with QuantityType items, so not sure how it should be done best.