Question for Apera Users: Time to Finalize pH Reading

DanF

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Mar 17, 2019
594
Chandler, AZ
Pool Size
12500
Surface
Plaster
Chlorine
Salt Water Generator
SWG Type
CircuPool RJ-45 Plus
I find that I need to wait quite some time before my pH reading stabilizes using my Apera PH60. The smiley face, which should indicate that the reading is stable, comes on shortly after immersion in the sample, but then oscillates off/on while the pH reading continues to rise. For example, the reading starts off at 7.2 but climbs to 7.6 by the end of the 8 minute power-up time. If I power the unit on, it continues to rise slightly thereafter.

I'm not concerned over a reading of 7.6 vs 7.7; just wondering of other folks see the same behavior when using the Apera to test pH. I believe I read here that water temperature and pH are correlated, so perhaps the pH rises after the sample is drawn, until the Apera's temperature matches the sample temperature? As a test I took the unit out of the kitchen cabinet where I store it, left it in the KCl soaking solution and powered it up. There was practically no variation in pH (maybe .02) during the entire 8 minutes.

@mgtfp - I recall you posting similar results. Am I on the right track here?
 
How are you storing this probe between uses? Most pH probes (commercial grade that I have used in lab work) need to be stored in a saturated KCl solution (not DI water) or else you will change the concentration of the internal electrolyte and/or damage the thin glass permeable membrane that allows for ion transfer.

Are you calibrating the probe before use? How is the probe reacting to calibration solutions?
 
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Hi Matt. I store the probe 24/7 in a 3 molar KCl solution sold by Apera. Prior to testing I swirl the tip in distilled water and wipe with a tissue. After testing I again swirl in distilled water prior to storing in the KCl solution.

I don't calibrate before every test, but about once per month (12-15) tests. Upon placing the probe in the 7.0 calibration solution, the probe responds much like I described above when I tested the KCl solution. IOW, the meter quickly displays the pH value.

I'm not a chemist, but I'm starting to think the probe's behavior when testing pool water is due to the temperature delta between the pool water and the probe. Once the two equalize the probe reaches a more constant value. Perhaps I should bring the pool water sample inside, let it warm up for 8-10 minutes, then test.
 
What I noticed with the PH60, is that the temperature reading takes a while to stabilise. I have a thermometer permanently in the pool, and when sticking the PH60 into the pool it can take a couple of minutes until the PH60 shows the same temperature as my pool thermometer, particularly in winter when the PH60 is being stored at room temperature, but the pool sits at only 45-50°F. While the temperature is still adjusting, the pH reading keeps changing. My interpretation is that this is the temperature compensation of the PH60, the meter takes the current temperature reading to do the temperature compensation, and only once the PH60 temperature reading matches the actual water temperature, the temperature compensation will result in the properly compensated pH reading. During that whole time, the smiley face usually keeps showing, because the PH60 doesn't "know" that it's temperature still hasn't reached the pool temperature.

Mind you, this effect is very small, we are talking about changes in the second digit once the temperature reading is in the ball park. For a quick "yes, the pH is the the sevens" test, you don't have to wait very long. If you are using your pool for water chemistry experiments, then you should wait a bit longer (I can for example determine whether my CYA has properly dissolved by testing the pH and comparing it with the expected pH change calculated with Chem Geek's spreadsheet). My experience is, that once the PH60 temperature is within 0.5°C of the actual water temperature, the pH reading is rock stable. But that's all more of academic interest. In summer, I just dip the meter into the pool, and within about 20-30 seconds I usually get a reading that's accurate enough. In winter, I wait a bit longer, until the temperature reading is not too far off. But in winter I test my water not that often anyway, everything's pretty stable then.

The other effect is what JN already mentioned about proper storage, and that's probably more what's behind your observations. I always store my PH60 in KCl storage solution. Before I started doing that, it used to take a bit longer until the smiley face stabilized each time.

I highly recommend using KCl storage solution. I am at the end of the third pool season with my Apera, and it's still going strong. Calibration remains rock stable over months. A bottle of storage solution costs me about 10 bucks, and it lasts a long time, as you can reuse it as long as you don't contaminate it. I always rinse my PH60 first with tap water and then with distilled water (I keep some in a little container with a lid that I use just for swirling my PH60 in after it's been pre-cleaned under the tap. Then I dry it with a clean tissue and put it back into the storage cap filled with KCl solution. From time to time it needs a top up, and sometimes I start from scratch again and give the cap a proper clean. Seems to be working.
 
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Mine ‘stabilizes’ after a couple of minutes. If left until it times off, it might rise a few more hundredths. I just leave it in the pool while I do my other tests and then take the reading. If it has timed off, I turn it on and take the reading. If yours continues to rise tenths over last few minutes, sounds like something is wrong with it.
 
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Just saw that you replied in the meantime to JN.

I would let the water sample warm up. You want to know what the pH is at the pool's temperature, so you should let the PH60 adjust to the water temperature, not the other way round.

pH changing with temperature is a real effect, but the pH-meter needs to know the actual water temperature for a proper reading.

You can also take a larger water sample inside, e.g. in an empty ice cream tub, if you prefer to test inside and you are dealing with large temperature differences. But even with just a small reagent tube sample the effect shouldn't be of too much concern as long as you are only interested in a one digit accuracy. You might see some drifting while the meter first adjusts to the sample temperature, and then they both together adjust to room temperature (which will then actually result in a real pH change, do you shouldn't wait that long).

To get the same precision as a phenol red test, the temperature only has to be in the ball park, the remaining fluctuations in the second digit are of not much practical importance.
 
If yours continues to rise tenths over last few minutes, sounds like something is wrong with it.
Agree. Once the meter's temperature reading doesn't change anymore, the pH reading should be stable. But the initial temperature difference is large, the PH60 takes a couple of minutes to show the right temperature, much longer than my pool thermometer.

But again, it depends on the accuracy you're after.
 
I store the probe 24/7 in a 3 molar KCl solution sold by Apera. Prior to testing I swirl the tip in distilled water and wipe with a tissue. After testing I again swirl in distilled water prior to storing in the KCl solution.
Sounds pretty much like what I am doing. I am only using a different brand of 3molar KCl, the original Apera stuff is quite expensive here in Aus, and I tend to think that 3M KCl is 3M KCl, no matter the brand name.

EDIT: I rinse with tap water before testing, not with distilled. After that I rinse it with massive amounts of pool water anyway, I am not concerned about contaminating my test sample with tap water.

I only rinse with distilled water before putting it into storage solution, that's where I want to minimise contamination.
 
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I would suggest doing as others say - put the probe in the pool and take a reading as soon as the smiley face comes on. These are temperature compensated probes for a reason - so you don’t have worry about temperature equalization. The probes are designed to handle a difference in temp between the internal electrolyte and the sample water. And yes, pH does change with temperature.

Another issue is cyanuric acid. Without getting into details, pH probes measure the voltage difference across a membrane when charged ionic species are separated by a distance (aka, the definition of electric field or voltage). The assumption is that the main species that accumulate at the sample water surface is hydrogen ions. Thus, the detected voltage is related to pH. However, in pool water, there is still an appreciable amount of charged cyanurate ions in solution and those can affect the accumulation of charge at the glass membrane surface. So the slow drift in pH with time can be related to cyanurate “poisoning”. This is why stable ORP readings can be very difficult to achieve in a high CYA water sample - the available oxidizer (HOCl) is low and the cyanurate ions can accumulate and poison the membrane surface.

I would also not go through the cleaning ritual - simply remove the probe from the KCl storage solution, swirl it in the pool then take a reading. Afterwards, rinse the probe briefly under clean tap water and store it right back in the KCl. Absolutely DO NOT touch the glass bulb with paper towel, air bursts or anything like that. Pull, measure, rinse, store. Everything else is unnecessary and will only potentially shorten the life of probe.
 
I just leave it in the pool while I do my other tests and then take the reading.
Thanks. How exactly do you leave it in the pool? Do you suspend it somehow?
If yours continues to rise tenths over last few minutes, sounds like something is wrong with it.
I would agree...except that I replaced the probe about a year ago, and calibration tests are spot on. By "spot on" I mean 6.98-7.02.
I would also not go through the cleaning ritual...
Thanks Matt...but the owner's manual and usage videos specifically state to use distilled water - before and after testing. Dunno.
I would suggest doing as others say - put the probe in the pool and take a reading as soon as the smiley face comes on.
Makes sense, but if I do that my pH going forward will be significantly lower (0.4-0.5) than what I have been used to recording for water chemistry purposes (PoolMath).
Perhaps the only way to know is to calibrate the Apera with the comparator; however I have such a color issue with the drops that I find myself just guessing--which is why I got the Apera in the first place.:confused:
 

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Tap, bottled or distilled, any of them will work. When you rinse it you just give it a little shake and maybe, if you really want to, wipe the outside of the tip. The amount of rinse water you drag into the storage cap should be minimal, a few drops at most. So there’s really no way that you’d contaminate a 3M KCl solution. Also, the storage solution should be changed frequently as well, maybe once a month or so. In the lab we would rinse and refill storage solutions weekly … but our probes were being used on a constant basis all day long.

Yeah, I would recommend getting a friend to read the comparator for you so you can see the rough difference between the probe and phenol red. My concern is that you are trying to let the probe stabilize but it’s giving you a false high reading because of other issues highlighted. In reality, a probe like the Apera should give a read in under a minute, not 10 minutes.
 
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Thanks Matt...but the owner's manual and usage videos specifically state to use distilled water - before and after testing. Dunno.
I guess, the distilled water before testing that the manual is referring to might be more important when you have a small sample in a lab and you don't want to contaminate that. And you would have distilled water in a lab in abundance anyway. In my pool, I have pool water in abundance, and I'm very happy to add a few drops of left over rinse water to it.

I was a bit more cautious about contaminating my storage solution until now. But I think I will take Matt's advice on board and simplify life by just using tap water from now on. I tap it dry (only the outside, not touching the prob) anyway.

but if I do that my pH going forward will be significantly lower (0.4-0.5

That does sound a bit excessive...
 
details, pH probes measure the voltage difference across a membrane when charged ionic species are separated by a distance (aka, the definition of electric field or voltage). The assumption is that the main species that accumulate at the sample water surface is hydrogen ions. Thus, the detected voltage is related to pH. However, in pool water, there is still an appreciable amount of charged cyanurate ions in solution and those can affect the accumulation of charge at the glass membrane surface. So the slow drift in pH with time can be related to cyanurate “poisoning”. This is why stable ORP readings can be very difficult to achieve in a high CYA water sample - the available oxidizer (HOCl) is low and the cyanurate ions can accumulate and poison the membrane surface

Thanks for that explanation, Matt. I knew about CYA poisoning of ORP probes, but didn't put 1 and 1 together and apply that also to pH probes.

I do experience a slow drift of up to 0.1 to 0.2 pH-units when sticking a room temperature probe into cold pool water in winter after the smiley face popped up. Since that drift settles once the Apera temperature reading approaches the pool thermometer reading, I always attributed that to the temperature compensation having to wait until it knew which temperature to compensate for.

I ran a test today with calibration buffer solution, no CYA involved (unless my electrode has been permanently compromised by it). I cooled the buffer down to about 5°C/41°F. The solution's pH should be about 7.09 at that temperature. I then put the warm (22°C/72°F) ph-meter in and it showed 6.96, the smiley came on immediately and remained on. I kept the meter in the solution and put them both in the fridge. The temperature reading drifted slowly down while the temperature reading drifted up. Once the temperature reading got below 6°C, the pH showed the expected 7.09.

That effect is being mentioned for example here:


Here the relevant quote from above link:

ATC (automatic temperature compensation) relies on the accurate measurement of the temperature of the solutions. This can be achieved by using an electrode with a built in temperature sensor or a separate temperature sensor. Combined pH/temperature electrodes offer the advantage that only one probe is required to perform measurements. Such sensors can suffer from a sluggish response since the glass, which surrounds such sensors, has a low thermal conductivity. Alternatively, a separate temperature sensor can be used with the pH meter.
 
Apera PH60 can be set to hold the ph and all measurements when it stabilizes for 10 seconds. I believe it can be switched on in the set up menu. I did this to mine and it really improves the performance of the meter. Also, I store my PH60 and ORP60 in Apera's storage solution and store the meters' boxes on end (like books on a bookshelf) so that the probe is always vertical in the storage solution.
 
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I just leave it in the pool while I do my other tests and then take the reading.
“Thanks. How exactly do you leave it in the pool? Do you suspend it somehow?”

Here’s my handy dandy PH meter float. Knew that packing foam would come in handy for something.
 

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I played around a little with the Nernst Equation, which is basically behind the temperature compensation of a pH-meter (an "ideal" pH-meter when taking the Nernst Equation 1:1). Here is a graph showing the results for temperatures between 41°F and 77°F:

1647856646818.png

It shows that the same raw-data (i.e. the potential difference measured by the meter in mV) gets corrected to pH-values that are about 0.05 pH-units apart. Not very much...

Then I did some testing in my pool which currently sits at about 22°C (or about 71.5°F). First I made sure that my pH-meter (while still in its cap with storage solution) also showed a temperature of pretty much 22°C. Then I put it directly into the pool without prior rinsing so that the temperature wouldn't change and moved it a bit around so that the storage solution got flushed out. In the first 10-30 sec, the pH-value changed about 0.02 pH-units and then stayed rock stable there for minutes. Based on that, I would rule out effects like CYA-drifts (my CYA is at 80ppm, maybe slightly less after I had to drain some water after the last rain), at least on that time scale of a few minutes. And the actual potential difference measurement seems to be stable after about 10-30 sec if there are no temperature effects to be considered.

Then I rinsed the meter, put it back into the storage solution and warmed it in my hands up to about 30°C (86°F). If temperature compensation based on Nernst was the only effect, I would expect a pH of about 0.02 lower compared to the first test when putting the meter like that back into the 22°C warm pool water (some might call that cold, especially my wife...). But the instant reading was about 0.13 pH-units lower. It then took a couple of minutes for the temperature measured with the Apera to drop down and the measured pH-value to rise back to the same values as in the first test.

I suspect that the main effect is that especially the internal reference cell has to thermalize to the pool water temperature, and that the water layer directly around the measurement cell also might get affected by the initial temperature of the pH-meter. So, there is not just a temperature compensation effect with a generally constant voltage-measurement happening, but also a slow drift of the voltage-measurement because of pH-changes because of different temperatures in or around the measurement cells. While the pH was drifting during my second test, I sometimes changed the measurement mode to "mV" and actually did see the mV-value drifting as well, so it is not just an effect of a wrong temperature measurement.

On a practical scale, these effects are usually still quite small, especially during the pool season. In above example with a difference of 8°C (14.5°F), the initial measurement error of about 0.13 pH-units shrank to maybe 0.05 after one minute, which should be sufficiently accurate for pool maintenance.

In winter, the effects can be larger, as far as I remember from our last winter down under, the drift after sticking a room temperature pH-meter into cold pool water (maybe 50°F) might have been about 0.2 pH-units (maybe more, didn't pay that much attention to the initial reading).

I guess, pre-adjusting the meter temperature to the pool temperature would give the most accurate results, but that seems a bit excessive. But it could make sense to do that from time to time (maybe at a time of the year when pool and room temperature are very similar, as is currently the case in my unheated pool in early autumn) to verify that there are no additional drifts that would indicate that it's time to replace the sensor-head. But that can also be checked during the regular sensor calibration, where buffer-solution and pH-meter usually have the same temperature.
 
As an update, I noticed my probe was 13 months old. Apera recommends replacing after 12-18 months, so I purchased a new one.

I took my last reading with the old probe before installing the new probe. The old probe read 7.7 after taking about 2 1/2 minutes to stabilize. The new one read the same, but after only 20 seconds. I'm guessing the new probes just stabilize faster, and start to decline with age (don't we all)!

Thanks to all for your input.
 
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