The sharpness of chilli powder is felt when the concentrated capsaicin is locally released into the saliva of the mouth. Actually, this compound has no flavour or odour but acts directly on the pain receptors in the mouth and throat causing the eyes to water and the nose to run, and even leads to perspiration on the skin. The extreme case of such event is called chemical burn that can last for several minutes. It is advised, therefore, that contact of capsaicin with sensitive skins of eyes and nose should be avoided; and hand should be thoroughly washed before using in the toilet. Capsaicin is a crystalline compound in the monoclinic class. It is slightly soluble in water, but is readily soluble in oil and other organic solvents. So when oil is added to the chilli powder, the capsaicin gets dissolved and distributed in the oil and coats a larger area of the mouth. Thus the hotness appears reduced on addition of oil.
Source: thehindu.com