Which of the following sentences is correct?
a. He's the man that sold me that clunker.A simple grammar rule-of-thumb applies here: you use who when you are talking about a person and that when you are talking about an object. Stick with that rule and you'll be safe.
b. He's the man who sold me that clunker.
That being said, the rule-of-thumb isn't hard-and-fast. The American Heritage Dictionary says,
It is entirely acceptable to write either the man that wanted to talk to you, or the man who wanted to talk to you. [emphasis added]
Even Chaucer did it, for example.
Now, that vs. which is a bit more complicated -- a more hard-and-fast a grammatical rule. That introduces essential clauses while which introduces nonessential clauses. Some examples:
Essential: I do not trust products that claim "all natural ingredients" because this phrase can mean almost anything. (We would not know which products were being discussed without the that clause.)
Non-Essential: The product claiming "all natural ingredients," which appeared in the Sunday newspaper, is on sale. (The product is already identified. Therefore, which begins a nonessential clause.)
It seems that there is no hard and fast rule concerning these words. I thought that "which" can introduce an essential clause if there is no preceding comma.
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