We show that the thermal annealing of thiol-capped PbS colloidal quantum dots provides a means of narrowing the nanoparticle size distribution, increasing the size of the quantum dots and facilitating their coalescence preferentially along the 100 crystallographic axes. We exploit these phenomena to tune the photoluminescence emission of an ensemble of dots and to narrow the optical linewidth to values that compare with those reported at room temperature for single PbS quantum dots. We probe the influence of annealing on the electronic properties of the quantum dots by temperature dependent studies of the photoluminescence and magneto-photoluminescence.