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In 1764 he married Helen Duff, the daughter of his cousin, the first Earl of Fife. Duff was promoted to rear-admiral of the blue on 31 March 1775, and in April was sent out as commander-in-chief at Newfoundland. His posting was brief, in 1776 he became rear-admiral of the white and in September 1777 he was appointed to the command of the Mediterranean, with the 60-gun HMS Panther as his flagship.
His portrait was painted by Sir Joshua Reynolds for Greenwich Hospital. Increasingly ill with gout during his later years, he died at Queensferry on 6 June 1787, his death being attributed to an attack of gout in the stomach. He had a number of children by his marriage to Helen Duff:
Jean (b. 1765, married 1791 James Clerk of Bonnington)
A son (b.1766, dsp)
Robert William (b.1767, grandfather of Robert Duff)
A child (b. 1775, d. young)
Adam (1775–1840)
James Alexander Duff (1777–1800)