There is no set requirement of documentation, but if they contact the original creditor and verify with them that you owe the debt and provide you with something (usually an accounting statement or bill) showing you owe it, that's usually considered "validated." If you signed up for the class but never properly withdrew, you owe the money.
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As stated, the law does not specify exactly how a collection agency is to respond to a validation request except that it must be responsive to the request. Generally, if the collection agency comes back with a (1) statement that they verified the debt with the original creditor, (2) provide the name and address of the original creditor, and (3) the amount due; that will usually be sufficient. One way to do that is provide a bill, but providing an account statement or bill is not required. One of the biggest misconceptions on the Internet (especially those debt forums) is that a collection agency must "prove" the debt to you. That is not the case under the FDCPA.
As for the underlying debt, if you failed to withdraw from classes properly, or withdrew after the deadline, the debt is owed.
Either as its first communication or within 5 days after the first communication, the collection agency must notify you of your right to dispute the debt within 30 days. If you are still within that 30-day period, you can write to them disputing the debt and they must verify the debt with the school. Guidelines for such a letter are in the AVVO Legal Guide "Disputing a Debt in response to a Debt Collection Letter."