In this paper, a new correlation is developed to predict liquid/liquid separation dynamics with a focus on a water/oil mixture. The correlation employs a force balance on the droplets to predict the rising velocity of the oil phase. The effect of droplet coalescence on the droplet's rising velocity is investigated, and the new correlation predicts the coalescence rate based on the oil/water volume fraction, as well as the initial droplet diameter. To develop the correlation for droplet coalescence, a series of new numerical simulations of a batch oil/water separation process were conducted. An equivalent experiment was conducted, the results of which agree well with the numerical predictions (relative error of 13.39%). The new correlation can predict the rate of separation with a relative error of 6.35% compared to numerical predictions.