This document explains how to prevent customers from placing orders that have a total value of $0. This is useful to avoid unwanted orders, especially when you're offering free items as part of a gift with purchase promotion.
Here's how to turn on this feature:
Once you've done this, customers won't be able to complete checkout if their cart only contains items with a $0 value. Customers trying to checkout with only the free gift will see this screen and be unable to pay and checkout:
Important: This feature only works with Shopify's standard checkout. If you use a third-party checkout, this setting won't have any effect.