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The Liverpool Scotland constituency had a very large number of residents who had moved there from Ireland, fleeing the Great Hunger caused by potato blight. At the time, all of Ireland was part of the United Kingdom, so they were just moving to a different part of the state. The Great Hunger became a rallying point for Irish Nationalism, accounting for the election of an Irish Nationalist Member of Parliament.
Note that T. P. O'Connor was the MP for the whole of the Irish Nationalist period. Liverpool is still a notably Irish-influenced city.
The "Liverpool Scotland" name comes from Scotland Road, part of a turnpike route to Scotland, which lay at the centre of the constituency.