Hi Scottie,
To the best of my understanding (I developed electrodes, not the electronics, but I heard quite a lot from the guys who did the electronics), a shift in the two ground potentials can cause the A/D converter, because it's not isolated, to measure against the wrong ground. Ideally the reference electrode should form the "ground" for the A/D converter, but in a system where the pH input isn't isolated the ground and the reference electrode are often connected over a shunt resistor. In such a system, the real "ground" for the A/D converter is a wierd mix out of the reference electrode potential and the ground from the main supply (or battery if it's a bettery-driven meter). What happens then is that the "external" ground influences the "internal" ground over the shunt resistor and the signals shift. This is quite easy to imagine when you consider that the actual measuring circuit is a low-voltage high impedance circuit which is just begging to be corrupted.
The problem is basically a ground-loop where you end up shifting small currents through the reference electrode, thus changing the reference electrode potential. Because of the very small currents involved in pH measurements, it doesn't take much to have a big effect on the pH reading. Also, even passing small currents through the reference electrode will greatly shorten the lifetime of the reference electrode (The silver chloride will end up all being oxidised or reduced depending on which direction the current is flowing - a properly functioning reference electrode needs both metallic and reduced silver in immediate vicinity of the lead-off wire). Both problems will be solved by isolating the meter with an optically isolated RS232 connection.
It's truly an electronics problem. A properly isolated pH meter will not suffer from this problem (But they're expensinve of course). Simply sticking an RS232 optocoupler between the instrument and the computer usually does the job.
Shane.
PS
Do I understand that you are performing pH measurements in non-aqueous solutions? If so, make sure you're using the correct electrode for the job. Non-aqueous measurements are extremely difficult, and only the correct combination of electrode and meter will give correct results. This has a lot to do with the very high impedance of the solution which in turn greatly increases the impedance of the liquid junction of the reference electrode (Which a non-isolated, standard pH meter simply cannot handle). You then end up with a double high-impedance circuit. To get anything close to good readings (which is hard at the best of times in non-aqueous), you need a good meter AND a good electrode. I've published on this matter before. A sleeve-type reference electrode is really the only choice for non-aqueous measurements. Do a search for "Solvotrode" to see what an optimised non-aqueous pH-electrode looks like.
<\rant>Message Edited by shoneill on 03-01-2005 09:22 AM
Using LV 6.1 and 8.2.1 on W2k (SP4) and WXP (SP2)