While most forbidden substances are בטל בששים, nullifiable as one in sixty (or some other ratio), there is an extra stringency attached to chometz that it is forbidden even במשהו, the smallest amount, and cannot be nullified. Whatever chometz represents—haughtiness, desire, other bad middos, however you want it—is something so contrary to the essence of a Jew and holiness that it becomes absolutely intolerable even by the smallest amount.
The Rebbe once quoted Chazal that chometz is assur b'mashehu and explained: Thinking that one is mashehu (something) makes him "chometzdik" and hence restrained (the word assur means both restrained and forbidden) from attaching himself to kedusha. As it says regarding haughtiness that Hashem says, "He and I cannot both dwell together."
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