Comparing electronic pH measurement with that obtained by Bench Photometer

Is there any way to determine the pKa change (and thus a correction factor) for the phenol red method used by the Hanna photometer?

Only by measuring it somehow, unless you can find published data for seawater, and that is fairly unlikely.
 
Well, I hate to be a bugger here, but spectrophotometric methods do actually exist for phenol red both in freshwater (~0 ionic strength, 10 < T < 30 C, P = 1atm) (Yao and Byrne, 2001) and sea water (33 < S < 37 ppt, 0 < T < 30 C, P = 1 atm) (Robert-Baldo et al., 1985).

However, pK1 of phenol red is a bit low if you're trying to measure high-pH, warm, saline water like would be coming out of a reef tank (or the warm, surface ocean), though it works. It's definitely useful for colder, lower pH sea water. The pKa of m-cresol purple makes it much better suited for most seawater pH measurments.

The available calibrations also express pH on the Free scale. That works fine in solutions of low ionic strength (freshwater) since Free-scale pH and NIST-scale pH (aquarists use the NIST scale) are pretty much the same. In sea water Free pH values are a bit lower than NIST values due to ion pairing effects (~0.03 units--e.g., 8.198 on NIST scale = 8.169 on Free scale). With a set composition of major ions in sea water one can usually convert with reasonable confidence. However, since artificial sea water we use is bound to vary from NSW at least a little in major ion composition at a given salinity, adding 0.03 units to Free pH may not be a solid conversion to go to NIST pH.

In any event, pK1 @ 20.0 C is 7.564 +/- 0.002, @ 25.1 C is 7.495 +/- 0.006, @ 30.1 is 7.451 +/- 0.006, all @ 35 ppt, 1 atm. There's a small salinity dependence too.

In any event, pK1 can be well estimated over a range of temperatures and within a modest range of salinities using and equation of the form,

pK1 = A/T - B + C*log(T)

and the experimental data give us (including a salinity correction)

pK1 = (4834.00/T) - 84.31 + 30.7580*log(T) + 0.004(35-S)

where T is temp. in Kelvins and S is salinity in ppt (Robert-Baldo et al., 1985).

Absorbances are measured @ 433 nm, 588 nm, and 700 nm. The 433 and 588 nm provide a ratio for max absorbance of the yellow and red forms of the dye and 700 nm is used to correct for baseline shifts in the spectrometer. pH is then calculated as,

pH = pK1 + log ((R-e1)/(e2-R*e3))

where R is the absorbance ratio of 433/588 nm, e1 = 0.0038, e2 = 2.6155, and e3 = 0.1234.

Clearly you'd want to do all of that with a spreadsheet so you can just plug in temp, salinity, and absorbance values in have it spit out pH for you.

BUT, and of course it's a big but, that only works if you have a decent spectrophotometer and can measure at those wavelengths.

The pK1 at 0 ionic strength @ 20 C is 8.071, @ 25 C is 8.032, and @ 30 C is 8.000. Due to the much lower ionic strength, the indicator is going to behave differently and have different absorbances at any given pH, even after taking ionic strength into account.

Suffice it to say that, without a spectrophotometer and working within the ranges for the behavior for phenol red is known (either freshwater, = very low ionic strength, OR sea water at salinity ~33-37) at a stable, known temperature, it becomes a very difficult proposition to try to extrapolate a reliable correction factor from freshwater absorbance values to seawater values.

The best options are either 1) a pH meter with decent combination electrode, or a decent spec., and I'd recommend m-cresol purple for spectrophotometric pH (pKa of m-cresol purple is ~8.20 @ 25 C, 1 atm, 35 ppt on NIST pH scale--the mean pH of sea water).

Hope that makes sense of why a simple correction factor here just isn't prudent (or likely to work) and why a pH meter probably is the best option in this case :)

cj
 
Thanks for your input :)

The more I read/research this subject, the more I come to the conclusion that the Hanna photometers are not such great instruments, at least not for people wishing to test sea water. Out of 39 advertised tests (ranging from aluminum to zinc, it appears that this instrument can only test accurately for ammonia, phosphate and nitrite in sea water...

Absorbances are measured @ 433 nm, 588 nm, and 700 nm. The 433 and 588 nm provide a ratio for max absorbance of the yellow and red forms of the dye and 700 nm is used to correct for baseline shifts in the spectrometer

The Hanna instrument only reads at one wavelength, 525nm, and it would thus not be possible to use your formula to calculate a "corrected" pH. It also gives a direct pH read-out, calibrated for the phenol red die, so it would be fruitless to use another die, such as the m-cresol purple previously mentioned.

Pity - I would have liked to use it every week or two as a check on the electronic pH meter, as it's quite a hassle to remove it's probe from the system for calibration (it's mounted in the sump return pipe, and necessitates stopping the return pump and unscrewing the probe before it can be calibrated...)
 
<a href=showthread.php?s=&postid=14175287#post14175287 target=_blank>Originally posted</a> by New Reefer
Thanks for your input :)

The more I read/research this subject, the more I come to the conclusion that the Hanna photometers are not such great instruments, at least not for people wishing to test sea water. Out of 39 advertised tests (ranging from aluminum to zinc, it appears that this instrument can only test accurately for ammonia, phosphate and nitrite in sea water...



The Hanna instrument only reads at one wavelength, 525nm, and it would thus not be possible to use your formula to calculate a "corrected" pH. It also gives a direct pH read-out, calibrated for the phenol red die, so it would be fruitless to use another die, such as the m-cresol purple previously mentioned.

Pity - I would have liked to use it every week or two as a check on the electronic pH meter, as it's quite a hassle to remove it's probe from the system for calibration (it's mounted in the sump return pipe, and necessitates stopping the return pump and unscrewing the probe before it can be calibrated...)

I have not looked at the Hanna meter specifically but I would think you could also test adquately for nitrate, iron, copper and silica. Typicaly good photometer ammonia tests require digestion
 
Thanks for posting that data, Chris. :)

So going back to the original post, it does seem to work out well that the pKa for this specific dye is off by ~0.5 pH units between freshwater and seawater, and the photometer came out off by a similar (or possibly larger) amount and in the expected direction.

It's always nice when the theory and the practice correspond. :D
 
<a href=showthread.php?s=&postid=14175534#post14175534 target=_blank>Originally posted</a> by therealfatman
I have not looked at the Hanna meter specifically but I would think you could also test adquately for nitrate, iron, copper and silica. Typicaly good photometer ammonia tests require digestion

The Hanna manual states the following possible interferences for the above-mentioned tests:

Nitrate - chloride above 100 PPM (so I guess the 19500 odd PPM chloride in full-strength sea water would be a bit much... or would this be "neutralized" by the sodium part of the salt?). I have done a few nitrate tests using this instrument on my tank water, and the result is always shown as 0.0 mg/l. Now I know that my water is pretty low in nitrate, with Tropic Marin, Hagen and Sera hobby-type test kits giving "0" readings, but I doubt if it is actually below 0.0 PPM, so I'm assuming that something is causing some interference...

Iron low range - it states: "sample pH should be between 3 and 4 to avoid developed color to fade or turbidity formation".

Copper low range - it states: "for samples overcoming buffering capacity of reagent (around pH 6.8), pH should be adjusted between 6 and 8".

Silica - the mentioned interference substances are normally at much lower concentrations in sea water (e.g. phosphate above 60mg/l), so if our water is close to NSW this test should be possible
:)

I would love to be able to test for iron and copper - could anyone knowledgeable please explain how I should go about changing the pH as per the above, especially how to drop it to between 3 and 4 without causing any other interference.upset of the test - do I just add some strong acid???
 
Nitrate - chloride above 100 PPM (so I guess the 19500 odd PPM chloride in full-strength sea water would be a bit much... or would this be "neutralized" by the sodium part of the salt?

No, that sounds like a show stopper. :D

What is the detection limit claimed for copper and iron? Probably higher than you'd see in a reef tank, especially iron.
 
<a href=showthread.php?s=&postid=14176695#post14176695 target=_blank>Originally posted</a> by Randy Holmes-Farley

What is the detection limit claimed for copper and iron? Probably higher than you'd see in a reef tank, especially iron.

Hi Randy,

For the copper it's 0 - 1000 micro grams per liter for the copper low-range test, with a resolution of 1ug/l and an accuracy of ±10ug/l ±5% of reading,

and for the iron it's 0 - 400ug/l, with a resolution of 1ug/l and an accuracy of ±10ug/l ±8% of reading.

The stated interference limits for the iron test is:
Cadmium - above 4.0mg/l; Chromium3+ - above 0.25mg/l; Cobalt - above0.05mg/l; copper - above 0.6mg/l, Manganese - above 50.0mg/l; Molybdenum - above 4.0mg/l; Nickel - above 1.0mg/l and Nitrite ion - above 0.8mg/l

For the copper test they only state that the following will cause interference, but they don't give any concentration values for these: Silver; Cyanide.

Oh, as an aside - this instrument also has a function to quantitatively measure the water's color, in a range from 0 to 500 PCU (Platinum Cobalt Units...). I am playing around with this to see if it has any significant value to us hobbyists (I'm thinking here of measuring actual clarity improvement and/or reduction of "yellowness" of the tank water when using ozone, as a possible use...)
 
The amount of iron I recommend to dose is about 2 ug/L, so I don't think that test is useful at +/- 10 ug/L.

Last time I checked with a high end machine (an $80,000 ICP-AES), my tank had 13 ug/L copper. So I also do not think that +/- 10 ug/L is very useful either.
 
<a href=showthread.php?s=&postid=14175534#post14175534 target=_blank>Originally posted</a> by therealfatman
Typicaly good photometer ammonia tests require digestion

On this subject: The Hanna instrument's test procedure for this parameter requires a "digestion" time of 3.5 minutes before the actual reading is taken. I did my first ammonia test last night, and it did not work. After adding the required amount of reagents the water turned a milky white with (what I presume to be) calcium and magnesium precipitate.

An hour or so on Google confirmed this being a problem when testing sea water with the Nessler method. Various articles recommend that one should pre-treat the sample with a "Mineral Stabilizer" to keep these elements in solution, but the Hanna manual did not say a word about this...

Can anyone please recommend what "Mineral Stabilizer" I should use - keep in mind that I will probably have to order / buy this from a chemical supplier, if it is not a commonly available product.
 
Re: Re: ph meter

Re: Re: ph meter

<a href=showthread.php?s=&postid=14169932#post14169932 target=_blank>Originally posted</a> by New Reefer
Umm, no, I don't think you have this quite right... the photometer shines a light through a glass cuvet (small bottle...)

Oops. Should have read carefully, (did not quite realize one instrument was photometric). That said, any photometric pH error should still be standardizable and reliable. I'd still guess is that the spectrophotometric filter/detector combo is not quite right, or insufficiently accurate relative to the pH meter.
 
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