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The Secretary of State negotiates treaties but they must be approved by the President and ratified by the Senate.
The president can negotiate treaties, but they must be ratified by the senate to go into effect. He can appoint ambassadors, and they also must be approved by the senate.
The executive branch negotiates treaties. The Senate must approve those treaties. The answer can be found in Article II Section 2 of the US Constitution. It reads: "He shall have Power, by and with the Advice and Consent of the Senate, to make treaties, provided two thirds of the Senators present concur" (He is referring to the President.)
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The President has the duty of negotiating and signing treaties with the advice of the Senate. He also appoints the Secretary of State and the department of State reports to him. He may hold summit meetings with other heads of state and iron out conflicts with other nations. He has the power to order military strikes which can sometimes makes other countries want to negotiate.