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Oil and water separate because water is a polar compound and oil is a non polar compound. Or, water has a positive charge on one side of the compound and a negative charge on the other side. It mixes with compounds with charges on one side. Oil does not have any electric charges. It only mixes with a compound that has no electric charges.
Oil separates from water for two reasons. First of all, it is electrically repelled from water because the lipid molecules that comprise oil are electronically well balanced whereas water is highly polar. The result is that no part of the lipid is attracted to either electric pole of the water molecule. Despite this, oil and water can be combined via agitation (such as mixing a vinaigrette). However, oil is less dense than water and will eventually float to the top of the oil/water mixture.

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