pH Meter Calibration

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So what meters are recommend? (I am leaning toward the milwaukee - Model MW101)

From the discussion
Hach PocketPro+ $110 (best place to buy? Looks like direct)
Replacement pH probe is $67

In the first post here I describe calibration and stability checks which, if passed, indicate that the meter is suitable for brewing provided, of course, that it has good reliability.

This new Hach unit and a Hanna pHEp meter are the only ones on which I have done cal and stability checks. Based on my findings on the Hach, at least two other people on here have bought them and done the stability checks. This unit looks good - so far. But we don't know how robust the thing is, how long the electrode is expected to last... I showed it to the brewer at Gordon Biersch yesterday and he went off and ordered one on the spot. He'll certainly beat it up in his normal use of it and has promised to let me know how it does for him. If he is happy with it at the end of year then my recommendation for it will go from tentative to definite.

I have also done stability checks on the Hanna pHEp. It is quite stable but you can't calibrate it because it decides for itself when to accept the calibration reading and it does so too soon. This can be worked around quite simply by subtracting the average cal check (4 and 7 pH) error to all subsequent readings but I don't recommend this meter simply because people who are using a pH meter for the first time get confused enough about having to do cals as it is.


Thoughts on the below
Milwaukee MW101 pH Meter w/Battery $80 (2 point) - BNC pH Probe Style
RESOLUTION 0.01 pH
ACCURACY (@25°C) ±0.02 pH
http://www.bulkreefsupply.com/catalog/product/view/id/709/

I have not done stability or calibration checks on the MW101 nor have I seen anyone else publish data. I have never had one in my hands. What is disturbing about this meter is that it gets an average review score of 2.5. Half of the reviews are 5 stars and the other half 0 stars. It seems that you either get a meter you like or a complete piece of junk with the chances being about 50/50. Another 'problem' is that these meters are analog. The advantages to digital are well known (though some stubbornly refuse to accept them) and as I have set them out so many times before, I won't do it again. I put problem in quotes because you can very well use an analog meter with manual TC (provided you are in the 50% that get a working meter). People did it for years. There is an MW102 which is the digital version. I have no stability or cal check data on it either and don't know anything about its reliability.


(You can get 2 Wire pH Lab Probes from HongKong for < $20 that work great 3 months and fine so far with this on my Marine Tank)
- http://www.ebay.com/itm/251124829815?ssPageName=STRK:MEWAX:IT&_trksid=p3984.m1438.l2649

This is just an electrode - you still need a meter (and a temperature probe unless you want to do TC manually). The electrode is, of course, where the rubber meets the road. This one doesn't have a particularly good spec.

& Here at the top 2 that get good reviews on the Marine Side ...

I can't comment on any of these. I look for laboratory grade instruments as in mash pH measurement you really want to be as accurate as possible. When I see a laboratory grade instrument maker's label (Hach) on a $125 meter I get excited and hope wells, as they say, eternal. But I'm also a cynical SOB. If the Hach turns out to have shortcomings comparable to those I know about in other inexpensive meters I'll throw it on the heap with them.
 
I have not done stability or calibration checks on the MW101 nor have I seen anyone else publish data. I have never had one in my hands. What is disturbing about this meter is that it gets an average review score of 2.5. Half of the reviews are 5 stars and the other half 0 stars. It seems that you either get a meter you like or a complete piece of junk with the chances being about 50/50. Another 'problem' is that these meters are analog. The advantages to digital are well known (though some stubbornly refuse to accept them) and as I have set them out so many times before, I won't do it again. I put problem in quotes because you can very well use an analog meter with manual TC (provided you are in the 50% that get a working meter). People did it for years. There is an MW102 which is the digital version. I have no stability or cal check data on it either and don't know anything about its reliability.

Where did you find reviews on the ME101 ?
or the ME102 ?

Amazon?
 
Several people have reported unfavorable comments on their experiences with the MW101 here and there are others at Amazon. OTOH some people have praised the 101 to the sky here even arguing that the fact of no ATC represents an advantage as it lets the manufacturer spend more on the 'important' parts of the meter. As I said, I have seen little on the MW102 so I don't know if they solved their QC problems in this model or not.
 
You sold me on the Hach even though it is backordered till 2-12-14
$110+17.00 shipping from Ames Iowa -
Pocket Pro+ pH Tester with Replaceable Sensor - 9532000

Replacement $67.00 pH sensor, replacement - 9532001


Is Hach direct the only place to order from for this item?
 
I assume that by 'pH Stabilizer' you mean something like the product sold under the name '5.2'. People us it in the belief that it will do what it says it will do on the label but it won't for reasons that I have gone into so many times before here that I won't repeat it again.

If you mean buffers in the broader sense people use them to do things like calibrate pH meters, hold the pH of solutions in the region where a desired reaction proceeds most effectively etc.
 
No, I think they now have distributors as I have seen others selling their gear. I'd try a search on the meter and see what pops up.

Not much luck besides direct, and the price is better direct so far.
 
You sold me on the Hach even though it is backordered till 2-12-14
$110+17.00 shipping from Ames Iowa -
Pocket Pro+ pH Tester with Replaceable Sensor - 9532000

Replacement $67.00 pH sensor, replacement - 9532001


Is Hach direct the only place to order from for this item?

$110? Wow. It didn't take long for retailers to stick it to Canadians with the very recent currency exchange rate change. For Canada the price is $123 plus $19 shipping.
 
I'm going to purchase a Hach Pocket Pro+, but I'm confused about the way to store the electrode. I couldn't find any storage solution on the Hach website, and so I called the company. A tech support person told me that storage solution is not required for this meter, and that the electrode only needed tap water for storage to prevent drying. The user manual also has nothing in it about storing the electrode. Does this make any sense?
 
No, not that they wouldn't put anything about it in the manual at least but I have never seen anything like this. You are not the only one puzzled. I've called them. Other people who have bought the unit have called them and the story is all pretty much the same. Store it dry or put a couple of drops of water in the cap to keep the humidity up (the cap is tightly sealed with an O - ring). So that's what I do - just put in a couple of drops of water, not enough to cover the bulb by any means, just enough to keep it humid inside the cap.
 
Just bought the MW102. It has ATC and is spec'd up to 70 deg C (that's not a typo). For the first time I have a pH meter in my hands that I could, in theory, measure mash pH w/out cooling samples. I know you've stated not to do this as 'it shortens the life of the probe'. And I never have with all my previous meters. But. It is very seductive to not have to cool each sample. Adding phosphoric acid in increments can be very tedious. If I didn't have to cool, I wouldn't even sample. I'd just float a small strainer in the mash and drop in the probe, removing the whole show, of course, to add acid and stir. Think of the time savings. Oooooh.

So. Based on my understanding from this thread, I should heat cal solutions up to a representative mash temp and calibrate at that temp. Assuming I do this, I don't have to offset .35, like a room temp reading. Correct? Or would it make sense to just calibrate at room temp, and observe whatever offset I get at mash temp (which would be the .35 plus whatever error is being introduced by the meter so far from it's cal point(s) temps), and just math that in every time? At this point, I have ask the deadly question: how much is the probe life shortened. These devices have come a long way since I started using them in the early 90's. Perhaps the probes have as well? After all, it's spec'd to 70 deg C. Will I be the only guinea pig here?
 
Just bought the MW102. It has ATC and is spec'd up to 70 deg C (that's not a typo). For the first time I have a pH meter in my hands that I could, in theory, measure mash pH w/out cooling samples. I know you've stated not to do this as 'it shortens the life of the probe'.
Yes, you could, and yes, it does.

First thing I hope you will do is run the stability check on your new meter. The MW101 has gotten a bad rep mostly for reliability and we hope that the newer design solves the problems.

So. Based on my understanding from this thread, I should heat cal solutions up to a representative mash temp and calibrate at that temp.
While doing the stability check you could heat the buffer and record pH error (the difference between a reported reading and the pH of the buffer - don't forget that buffer pH changes with temperature and you need the actual buffer pH to get the actual error). Now plot the error vs. temperature difference re the calibration temperature i.e. the measurement temperature minus the calibration temperature. The slope of a linear fit to the error vs temperature difference is (pHi - 7)/Tc. Multiplying the slope by Tc, the calibration temperature (in Kelvins) gives the difference between pHi and 7 and so you can estimate pHi for your meter. If it is close to 7 then you may be able to get away without calibrating at near mash temperature. If the line fitting etc. looks overwhelming just looking at the error data will give you an idea. If heating the buffer 20°C results in a pH error of, for example, 0.2 then pHi is too far from 7 and you should cal. at mash temp.



Assuming I do this, I don't have to offset .35, like a room temp reading. Correct?

No, you wouldn't unless you want to compare your pH values to what everyone else is doing. To refer your measured pH to room temperature you would multiply the difference between room temperature and the temp. at which the reading was made (°C) by 0.0055. It would actually be better if you made a series of measurements on a cooling sample in order to determine what the slope for your mashes actually is.


Or would it make sense to just calibrate at room temp, and observe whatever offset I get at mash temp (which would be the .35 plus whatever error is being introduced by the meter so far from it's cal point(s) temps), and just math that in every time?
If you cal at room temp and pHi is close to 7 then you can just take the reading as it is. If pHi not close to 7 then you can figure out what the correction is from (pHi - 7)*delta_T/T_cal (all T's in Kelvins). In other words you can correct the corrections.

At this point, I have ask the deadly question: how much is the probe life shortened. These devices have come a long way since I started using them in the early 90's. Perhaps the probes have as well? After all, it's spec'd to 70 deg C. Will I be the only guinea pig here?

Can't help you there. Is the spec for the ATC or for the electrode? If it is for the ATC I don't understand as the ATC algorithm just pushes numbers and I can't understand why 70 would be a limit. I can understand how the electrode might have a temperature limit, however.
 
I was bored on Sunday, so I performed the stability tests to see how the MW-101 performs in this respect. I guess its OK.

One added thing I note is that when in the 7.00 solution, the pH response creeps lower over time. With the 4.00 solution, the response creeps up. I'm not sure why that occurs.

MW101-7response_zps51a15821.jpg


MW101-4response_zps1a115ff4.jpg
 
Martin,

What volume of solution did you use? It seems that stability is dependent on temperature - and delineated by the 3.5 hour mark. The deltas aren't horrible, but the drift from 7.01 downward seems disturbing. Did you have ATC on?

I have the MW100 and need to do a longer stability test. I think we have the same probe, I just have manual calibration and no ATC.
 
"disturbed" is strong language... but the tolerance is supposed to be within 0.01 on that meter, but no spec on over time. Mine is supposed to be within 0.02... yet has the same probe as the MW101 but no ATC function. I am wondering if the drift is mechanical (probe) or related to the algorithm.

Yeah more than good enough for brewing, better than expected for a sub $100 meter.
 
I'll will be performing the stability test on my new (unused, as yet) MW102, per AJ's recommendation. I just can't yet, because I want fresh buffer solutions (mine are 8 years old), I didn't buy any with the meter, and I want to save the little buffer solution packets that came with the meter for emergency use. As soon as I get back to LHBS to buy some, I'll test this meter and add to the data collection.
 
Those look pretty good. The reason why they may be going in different directions is that the 7 reading depends on how you have set the offset and the 4 reading depends on offset and gain.

You might get slightly better (and slightly better would be really good) results if you waited longer before moving from 7 buffer to 4 and staying in the 4 buffer longer before finalizing the gain adjustment. Clearly this cannot be half an hour each but up to 10 minutes may be a fair investment of your time.
 
... but the tolerance is supposed to be within 0.01 on that meter, but no spec on over time.

I have seen lots of meters specified with phrases like "Precision 0.01; Accuracy ±0.01". There is no question in my mind as to what the precision part means but only in one case have I seen a manufacturer say what the accuracy spec means. If you have a instrument with precision 0.01 and you calibrate it with 4.00 buffer and, at the end of calibration, take a reading and it is anything other than 3.99. 4.00 or 4.01 (which allow for toggling of the LSB in the A/D) then it is clearly unstable. If you wait long enough in the 4 buffer, however, eventually the reading will wander off. So time is clearly part of the picture. So is the distribution of errors. Is the spec'ed number the median error magnitude, the median error magnitude or the rms error? Over how long a period of time?

AFAIK there is no ASTM X-yyy-Z practice "Procedure for measuring and reporting pH meter error of electronic instruments" but here's what I think it should say: pH error is the rms difference between the calculated pH of a NIST traceable buffer and the ATC compensated instrument reading where the buffers are held in a constant temperature water bath for both calibration and error measurement. Measurements are to be taken once per minute for the first 10 minutes and once every five minutes thereafter in the first hour and once every 10 minutes subsequently. A minimum of 25 reading must be processed.
..

Yeah more than good enough for brewing, better than expected for a sub $100 meter.

Keep in mind that the 'accuracy' as specified here is the accuracy of the meter/electrode combination. That error has to be rss'ed with the buffer error and the temperature error. The goal would be to have the meter/electrode part better than 0.02 pH so that the rss of this with the other two error sources would be about 0.03 - 0.04.
 
So what meters are recommend? (I am leaning toward the milwaukee - Model MW101)

From the discussion
Hach PocketPro+ $110 (best place to buy? Looks like direct)
Replacement pH probe is $67

Thoughts on the below
Milwaukee MW101 pH Meter w/Battery $80 (2 point) - BNC pH Probe Style
RESOLUTION 0.01 pH
ACCURACY (@25°C) ±0.02 pH
http://www.bulkreefsupply.com/catalog/product/view/id/709/

(You can get 2 Wire pH Lab Probes from HongKong for < $20 that work great 3 months and fine so far with this on my Marine Tank)
- http://www.ebay.com/itm/251124829815?ssPageName=STRK:MEWAX:IT&_trksid=p3984.m1438.l2649

& Here at the top 2 that get good reviews on the Marine Side

American Marine Pinpoint pH Monitor $99 (2 Point Calibration / .01 resolution / Accuracy ?)
(just needs a 4.0 cal packet added)
BNC Replaceable Probe Style (You can get Lab Probes from HongKong for $20 that work great)
http://www.marinedepot.com/American...ine_Pinpoint_Monitors-AM1111-FITEMOID-vi.html

and this one is $37.00
Hanna Instruments Checker pH Pen (2 Point Calibration / Accuracy ±0.2 pH )
http://www.marinedepot.com/Hanna_In...ums-Hanna_Instruments-HN1135-FITEMOID-vi.html
Another one to add to your list is the Omega PHH-7011. It seems to have all of the specs of the Hach PocketPro+, but comes in at $99, includes a carrying case, and replacement electrodes are only $39.

I have not seen anyone test this meter yet.
 
Very cool thread guys; interesting reading. I'd been wanting a pH meter for a long time now, but after reading Palmer and Kaminski's Water book, I really learned how much i needed one (that book should be sold in a package deal that comes with a good pH meter). Anyway, I went on Amazon and I just bought the Hanna pHEp meter. I liked a lot of the features that I read about it, but unfortunately, didn't realize that bit about user acceptance of calibration. Oh well, thankfully I knew a thing or two about calibrating and using pH meters from my chemistry background, which was helpful because the in-box calibration instructions weren't too clear. I just did my calibration few hours ago. I did a two-point calibration with the 4.01 and 7.01 pH buffer solutions, and I knew to add a "rinse bath" of DI between steps and an additional check solution for stability. My first try at calibrating it, the meter did exactly what ajdelange warned about and it accepted the cal too quickly. I knew that it shouldn't have done that when it wasn't stable, so I erased the cal, rinsed the electrode with more DI, and did the cal again. The second time went a lot better, I got the electrode a bit deeper into the solutions and made sure they were stirred. Both buffers then took about 20-30 seconds for the pH reading to stabilize before it was accepted into the cal. After the cal, I checked a few of the reference solutions I had with very promising results, so now I believe i have a good calibration in there. These instruments are not black boxes, so you do have to be careful. I think it should be a good meter, and i'll keep you posted on how it preforms.

Another question I had though is that, sadly, the kit i got did not come with electrode storage solution. It came with packets of calibration buffers and an "electrode cleaning solution", but not any storage solution. There was a little sponge in the electrode compartment, but it was actually rather dry and hard. I'll probably pick up some storage solution at some time, but what should i do now? I think i have some KCl, so would it be wise to mix up a saturated KCl solution and use a few drops of that in my sponge for now, or should I wait with a dry-ish electrode until I get the actual recommended solution? Either way, i don't want to hurt my electrode, so i'm concerned.

Edit: back with some data. I tested a few more solutions i found laying around in my garage. I found an old bottle of 0.10M acetic acid and some Nitric acid. I tested the pH of the acetic acid without diluting it. My calculations said that 0.10 M acetic acid should have a pH of 2.8 and I measured a pH of 2.6 at 17.1 C. The nitric acid I found was 60% concentration, so I diluted 10 mL of it with 120 mL of DI to make a 1M solution. By definition, a one M solution of a strong acid should have a pH of 0.0, and I measured a pH of 0.3 @ 19.1 C for the diluted nitric. Granted, this was some quick kitchen chemistry and i could have easily been off by +/- 2 mL of acid or water, so I would hope most of the error came from volumetric measurement or chemical age/dilution. Next time I go into my lab, i'll do some better testing of it. As it is, how's that degree of error WRT mash pH measurement?
 
The nitric acid I found was 60% concentration, so I diluted 10 mL of it with 120 mL of DI to make a 1M solution. By definition, a one M solution of a strong acid should have a pH of 0.0, and I measured a pH of 0.3 @ 19.1 C for the diluted nitric.
Apparently the activity coefficient for 1 M nitric acid is 0.730 so the pH of a 1 M solution would be -log(0.730*1) = 0.137
 
@ajdelange numbers for my Hach Pocket Pro+:

Time (min) pH Temp (F)
2 4.00 74.8
4 4.00 75.0
6 4.00 75.2
8 4.00 75.4
10 4.00 75.6
12 4.00 75.4
14 4.00 75.2
16 4.00 75.2
18 3.99 75.0
20 4.00 75.2
30 3.99 74.8
40 4.00 74.8
50 4.00 74.7
60 4.00 74.5
80 4.01 74.3
100 4.00 74.1
120 4.01 73.8
180 4.02 73.4
240 4.03 72.0
300 4.04 71.4
17 hours 4.08 69.1
 
No, not that they wouldn't put anything about it in the manual at least but I have never seen anything like this. You are not the only one puzzled. I've called them. Other people who have bought the unit have called them and the story is all pretty much the same. Store it dry or put a couple of drops of water in the cap to keep the humidity up (the cap is tightly sealed with an O - ring). So that's what I do - just put in a couple of drops of water, not enough to cover the bulb by any means, just enough to keep it humid inside the cap.

AJ, are you still storing your Pocket Pro+ this way, or has new information changed that?

Thanks!
 
overlooked this when I first started brewing... This is an amazing writeup
 
This new Hach unit and a Hanna pHEp meter are the only ones on which I have done cal and stability checks. Based on my findings on the Hach, at least two other people on here have bought them and done the stability checks. This unit looks good - so far. But we don't know how robust the thing is, how long the electrode is expected to last... I showed it to the brewer at Gordon Biersch yesterday and he went off and ordered one on the spot. He'll certainly beat it up in his normal use of it and has promised to let me know how it does for him. If he is happy with it at the end of year then my recommendation for it will go from tentative to definite.

AJ - Did you ever get any follow-up from this brewer on longevity for Hach Pocket Pro +.

Great write-up BTW. Mant thanks for your time and efforts to help us climb the learning curve.

Rob
 
I've decided to go with this one ($$$), it gives me Dissolved O2 also which will permit me to do much better testing with yeast propagation and fermentation experiments.
 
I was about to buy a MW102, but I've about talked myself into the MW101 *because* it has manual calibration. I think that means I can use whatever pH buffers I want to calibrate the slope -- like a saturated solution of potassium bitartrate in DI water, for a standard pH 3.55 solution. Or a 9.2 pH solution of sodium tetraborate (I'll have to look up how to mix that one again) I will still have to buy the 7.01 buffer, but that's one solution to stock instead of three.

Am I leading myself way astray here? I do that sometimes...
 
I don't want to speak for the MW102 because I don't have one but most modern meters allow you to calibrate to buffers with any pH. They contain microprocessors and it is a matter of taking two voltage and temperature readings and solving two equations for two unknowns (slope and offset). You can find the manual for the MW102 on line and I'm sure it will tell you whether you can use arbitrary buffer pH values or not. You can do that with the Hach pH +.

Of course the main question is as to why you would want to use buffers other than 4 and 7. Yes, if you could come up with a buffer pair such as 5.0 and 5.7 you would theoretically get more accurate readings than with 4 and 7 (because the 'geometric dilution of precision' is more favorable) but with 4 and 7 you can get slightly better than the ±0.02 accuracy of most commercial buffers because the GDOP is appreciably less than 0.02 so that it is the buffers that limit the accuracy. Better GDOP isn't, then, going to make any practical difference.

Can you make up a buffer to better than ± 0.02? This would be done by mixing the salts and then 'trimming' with the acid and, obviously, requires a pH meter more accurate than the one you are making up the buffers for in order to set the buffers this precisely. It also involves purchasing special grades of the salts put up for this purpose, and weighing them very precisely (having dessicated them first). Seems like a lot of trouble to go to for improbable benefit.

In going to a manual meter you also give up ATC and must, therefore, dial in the temperature readings of the solutions and buffers.
 
I would want manual calibration mainly for high pH -- for doing water treatment, both for brewing and for aquariums. High pH buffer solutions don't have a very long shelf life (or so I've heard) because they absorb atmospheric CO2. 7.01 and 4.01 are more stable.

I'll see if I can download a MW102 technical manual. The one I found online earlier looked more like a "quick start" guide and didn't really say much.
 

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