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If we take 50 ml of two different liquids and mix them they will not always add up to 100 ml. The mixture will be 100 ml only when the chosen liquids don't mix with each other at all, somewhat as in case of oil and water mix.

Alcohol does mix well with the water and therefore the final mixture will have a volume less than 100 ml. At molecular level this happens because molecules of alcohol can fit well between water molecules (compared to molecules of oil between water), thus occupying less overall space, resulting in a smaller volume.

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