The Constitution gives the Vice President two, and only two, official duties. The first is to preside over the U.S. Senate as President of the Senate. The other is to assume the office of President if the elected President dies or resigns. The Constitution also creates the position of President Pro Tempore of the Senate, to be elected by the senators, to preside over the Senate in the absence of the Vice President of the United States. The President Pro Tem is one of the elected senators.
So, according to the Presidential Succession Act of 1792, when there was no Vice President, either because the Vice President had died or resigned or moved up to the Presidency, the President Pro Tem was next in line to be President. He was also the presiding officer of the Senate, since there was no Vice President to serve as President of the Senate. In other words, the President Pro Tem was filling both of the official duties given by the Constitution to the Vice President of the United States. In these situations, this person was referred to as the Acting Vice President, and even addressed as Mr. Vice President in certain social settings.
One of the most common presidential trivia questions is a trick question asking who was the first president. The trick is that the person asking the question will say that George Washington is not the correct answer, and will claim the President of the Congress of the Confederation at the time the Constitution was ratified is the "correct" answer. This is, of course, completely incorrect since the President of the Congress was more like the Speaker of the House of Representatives today, merely a presiding officer.
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