The reason that guacamole turns brown is because it oxidizes. Acid in the lemon juice slows down this process.
Besides the acidity in the lemon juice, which tristan mentions, the ascorbic acid (vitamin C) found in large quantities in lime and lemon juice also slows oxidation/browning of the guacamole. Another effective method is to place plastic wrap down directly touching the guacamole to cut off the oxygen supply. I have found this to be of help when storing guacamole in the fridge over a day or two.
The acid and antioxidants in citrus juices prevent oxidation by creating an acidic layer which absorbs the oxygen before it can be incorporated into the chemical processes within an avocado, which prevents the brown discoloration typical of oxidation.
Preventing oxidation of the avocado is the same reason that keeping the avocado pit in a bowl of guacamole will help delay it from turning brown.
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