Usage: Although substitute and replace have the same meaning, the structures they are used in are different. You replace A with B, while you substitute B for A.
a person or thing serving in place of another: [countable] The coach sent in a substitute when his star player was injured. [uncountable] For most of us there is simply no substitute for hard work.
A substitute is something that you have or use instead of something else. She is seeking a substitute for the very person whose departure made her cry.
substitute (third-person singular simple present substitutes, present participle substituting, simple past and past participle substituted) (transitive) To use in place of something else, with the same function.
A substitute is something or someone that you use instead of something or someone else. If you substitute one thing for another, you use it instead of the other thing.
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Usage: Although substitute and replace have the same meaning, the structures they are used in are different. You replace A with B, while you substitute B for A.