Chili powder and cayenne pepper are two different things. Cayenne pepper is pure ground dried chillies. Chili powder is a blend of spices, of which cayenne happens to be but one. The other ingredients include cumin, garlic powder, oregano and paprika. But it's roughly one part cayenne to seven parts other things (depending on the recipe, and I've got one for you below).
That means cayenne is 8 times hotter than chili powder, and if your recipe calls for two tablespoons of chili powder and you use two tablespoons of cayenne pepper instead — well, let's just say that you probably won't make that mistake twice.
Fortunately, you don't have to make that mistake even once. Just remember chili powder is a spice blend. Cayenne pepper is pure ground cayenne pepper.
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