An example device includes a processor to connect to an electrode disposed within a microfluidic volume and to connect a second electrode that includes a surface of silver metal disposed within the microfluidic volume. The processor is to apply an electrical potential between the electrode and the second electrode when the microfluidic volume contains a fluid that contains chloride ions to form a layer of silver chloride on the surface of the second electrode. The processor is further to cease application of the electrical potential and operate the second electrode as a reference electrode in a measurement process performed within the microfluidic volume.