Metal nanoparticles coated with an organic monolayer, so-called monolayer protected clusters (MPCs), can show quantised charging at room temperature due to their sub-attofarad capacitance arising from the core size and the nature of the protecting monolayer. In this tutorial review, we examine the factors affecting the energetics of MPC charging. In the first section, the underlying physics of quantised charging is outlined and we give an overview of the various methods that can be used to measure single electron transfer to nanoparticles. In the subsequent sections, we discuss how electrochemical measurements can be used to give information on the quantised charging of freely diffusing and films of immobilised MPCs. The predictions of models used to determine MPC capacitance are compared with experimental data from the literature.