The electromotive force (emf) of a cell is its terminal voltage when no current is flowing through it. The terminal voltage of a cell is the potential difference between its electrodes. A voltmeter cannot be used to measure the emf of a cell because a voltmeter draws some current from the cell. To measure a cell’s emf a potentiometer is used since in a potentiometer measurement no current is flowing. It employs a null method of measuring potential difference, so that when a balance is reached and the reading is being taken, no current is drawn from the source to be measured.
This video explains how to measure the internal resistance of a given primary cell using potentiometer.