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The 5% rule applies to when you use the ICE table. If K is less than 10^-3, then you can assume that X is so small that it will not make a difference. For example if you have K=X^2/(0.3-X), then you can change it to X^2/0.3 because the X in the denominator becomes negligible. The 5% rule is if you find that X is less than 5% of the initial concentration, then the approximation is valid.
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