The measurement electrode’s purpose is to generate the voltage used to measure the solution’s pH. This voltage appears across the thickness of the glass, placing the silver wire on one side of the voltage and the liquid solution on the other. The reference electrode’s purpose is to provide the stable, zero-voltage connection to the liquid solution so that a complete circuit can be made to measure the glass electrode’s voltage. While the reference electrode’s connection to the test liquid may only be a few kilo-ohms, the glass electrode’s resistance may range from ten to nine hundred mega-ohms, depending on electrode design! Being that any current in this circuit must travel through both electrodes’ resistances (and the resistance presented by the test liquid itself), these resistances are in series with each other and therefore add to make an even greater total.
An ordinary analog or even digital voltmeter has much too low of an internal resistance to measure voltage in such a high-resistance circuit. The equivalent circuit diagram of a typical pH probe circuit illustrates the problem: