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Should spices and herbs be added early to a chili/stew in a crockpot slow-cooker to maximize their flavors? Or do the spices/herbs cook-out over a long time, effectively disappearing, and should instead be added late in the cooking process?

Or does the timing vary by particular herb/spice? I'm thinking of items such as bay leaves, oregano, cinnamon, chili powder, clove, and such.

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As a general rule they should go in early for a couple of reasons:

Flavours don't really cook out, they get distributed within the dish. So adding spices etc. early allows the flavours to combine. If they did cook out you could just add a touch more.

Opening a slow cooker during the cooking time lets write a lot of heat out, at best extending the cooking time. Repeatedly opening it from early in the cook (worst case) would bring the temperature down too far. So you either add things at the beginning or at the end (when the food is already cooked and hot enough all the way through that it will stay at a sensible temperature). This allows final fine adjustment at the end, but you may need to be choosy about the form in which you add the heat - some things could be hard or gritty if they haven't cooked. Fresh herbs can be added just before serving as they don't need to cook and may lose some of the fresh components of their flavour.

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    A slight modification to the rule that I use: dried herbs go in early, but fresh herbs go in towards the end. The distinctively "fresh" components do tend to cook out. – Joshua Engel Jan 18 '17 at 15:43
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    @JoshuaEngel good point in at least some cases (fresh sage or rosemary may still want to go in early for example) – Chris H Jan 18 '17 at 16:05

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