Sciencemadness Discussion Board - Easy sulfite ion in a pinch...

Easy sulfite ion in a pinch...

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teodor - 24-2-2026 at 01:05

Quote: Originally posted by semiconductive

Equilibrium equations (2) and (3), talk about diatomic gas molecules dissolved in water.
They aren't clear exactly what state the gas is in, and because there are electron transfers I assume you will treat these equilibriums as a chemical reaction and not just a dissolution process:

H₃O + 2e⁻ ⇌ H₂ + 2·H₂O #(2)
1/2·O₂ + H₂O + 2e⁻ ⇌ 2·OH⁻ #(3)

If I assume the gas is the reactant, and the ions are the product, then I will get a specific constant that tells how hard it is for a diatomic gas to turn into ions:

KH₂(aq) = [ H₃⁺ ]² · [2e⁻] / ( [ H₂ ] · [H₂O] )
KH₂(aq) = [ H₃⁺ ]² / ( [ H₂ ] )

Nee, they talk how water itself keep the balance between it's element. It's not about solubility of diatomic gases. I think it will be nice to attach here some works on classical theory of O2 solubility in H2O. It would be interesting to compare the results. I can do this later.

"Argon has approximately the same solubility in water as oxygen and is 2.5 times more soluble in water than nitrogen." (wikipedia) - there is no explanation for this even in the frame of a general ionization theory which is bigger and includes more instruments than just that band theory.

BTW, there is a nice line of gass solubility in water which you can use to test applicability of any theory of choice:

H2 < N2 < CO < O2 < CH4 < Ar < NO < C2H6 < C2H4 < Propan < COS < N2O < CO2 < C2H2 < Cl2 < H2S < SO2 < HCl < NH3

As for SO2 ionization, according to https://pmc.ncbi.nlm.nih.gov/articles/PMC6658418/
we have this equilibrium:

1) SO2 + H2O <-> H+ + HSO3(-)
2) HSO3(-) <-> H+ + SO3(2-)
3) 2HSO3(-) <-> S2O5(2-) + H2O

Despite the fact that in pure water the rate constants of 2) and 3) is quite low this (as usual) could be shifted by presence of other substances.

But what is different from seeing the process on atomic-interaction vs thermodinamics level is that for the later SO2 + H2O <-> H+ + HSO3- would be not visible if the recombination time is quite fast. Generally all those recombined ions are not distinguishable from unionized SO2 molecule. So, the number of ionized molecules doesn't represent the actual ionization level we can see experimentally which is also the resultat of interactions during the movement. And the model of dispersed molecules randomly mixed is not the actual liquid water structure which is basically 3d frame of hydrogen bonded H2O with corridors filled with monomeric H2O (see for example different works of Henry Frank and Mariorie Evans who studied liquid water structures and distributions of ions in it).

But again, it is the case of Pure water. For SO2 I would start to see how the clathrate structure becomes possible with lowering of temperature: https://doi.org/10.1021/jp037019j
Obviously, it doesn't appear by jump and there are some intermediate interactions which leads to it.
(Clathrate is a structure of "caged" gas molecules. It could be no interaction between those molecules and solvent molecules, only interaction between solvent molecules which creates a "net" holding gas).

And generally, as the works of Frank & Evans suggest, many dissolved substances in water form "iceberg" of water molecules which surround some dissolved molecules and this "iceberg" has an ice crystalline structure in micro form.

I assume I provided enough illustrations why there is not possible to apply a single theory for answering the question of gas solubility.

[Edited on 24-2-2026 by teodor]

P.S. The equilibrium 1)-3) is not quite right for the understanding of the solution mechanism of SO2 in H2O.
According to spectroscopic study of water by Simon & Waldmann (ZAAC publication in 1956) there are 4 detectable equilibriums:

Here O2S...OH2 is some hydrated form of SO2.

[Edited on 24-2-2026 by teodor]

semiconductive - 25-2-2026 at 11:32

Quote:

Do you have the conditions of infinite dilution in water in your experiment? pKa is solvent-dependent. When we talk about absolute acids, I don't want to have any formic acid on my skin.

I don't want it on my skin, either even mildly dilute. It doesn't hurt much worse than an ant bite (when it hurts at all), but I'd rather have dilute sulfuric.

Because strength isn't everything -- an acid's ability to penetrate through skin oils and get into skin contact counts for about half of the damage an acid can do to skin.

------

In my experiments, I start from dilute solutions and work my way up to concentrated.

My reason for approaching chemistry this way is identical to semiconductor engineering.

The basic equations are most correct and fully studied for pure substances AKA -- like intrinsic semiconductors.

Standard conditions for ions is also on the dilute side: 25 [°C] and 1 [Molar].

There are corrections that can be applied successively to band theory in order to model semiconductors in more complicated situations.

I expect a similar math approach is possible (even if it hasn't been done yet) in chemistry.

Since I already know semiconductor equations, I can (hopefully) apply them to chemistry without having to 'start completely over' from scratch.

Quote:

Formic acid can react with alcohol to form ester, citric acid is not. So, I assume their strength in non-aqueous conditions are reverted.

hmmm...
Strength (i've been taught) is determined by the relative bond energy of the acid 'molecule' to a particular hydrogen vs. the magnitude of polarization of the solvent.

In many of my experiments with formic acid and alcohol, at boiling 100 [°C] and above temperatures, the combination did not appear (to me) form significant amount of esters.

I expect esters of simple alcohols to be non-ionic and generally non-conductive.

Conductivity I can measure with an ohm meter. The conductivity of experiments I've done -- generally stay at a constant level that appears to be a variable of temperature and nothing else. ( Unless I allow the solution to evaporate ).

The only exception to this that I've encountered is with 1,2,3-ppol and citric acid. It polymerizes. ( My experience is limited, granted. )

Weak bond = strong acid (because hydrogen gets free, easily. )
Strong bond = weak acid ...

In polyprotic acids, I expect the weakest bond will usually break first regardless of solvent. So, I'm not sure what to think about your assumption. Could there be a catalyst involved?

semiconductive - 25-2-2026 at 13:01

Quote:

Yes: Equation (#2, #3) aren't about a dissolution of hydrogen or oxygen from atmosphere into solution.

Rather: The equations are about the atom count-preserving transformation between water plus diatomic H₂ or O₂ and ions in solution.

However, the context of the paper implies that both H₂ and O₂ (diatomic gas molecules) are in intimate contact with a solvent, water. If the author is ignoring the solvation of these molecules in equations #2 and #3, then am I (at least) justified in claiming they are in the gasseous state ?

That is to say, gasses found under the surface of a solvent rather than outside the liquid all-together ?

Quote:

As for SO2 ionization, according to https://pmc.ncbi.nlm.nih.gov/articles/PMC6658418/
we have this equilibrium:

1) SO2 + H2O <-> H+ + HSO3(-)
2) HSO3(-) <-> H+ + SO3(2-)
3) 2HSO3(-) <-> S2O5(2-) + H2O

Despite the fact that in pure water the rate constants of 2) and 3) is quite low this (as usual) could be shifted by presence of other substances.

For right now, let's begin assuming a pure solvent so I can at least work some simple math out and hopefully design an experiment capable of testing the theory (a little bit).

In the Russian article, the only substances being considered were ions, radicals, and pure water. Therefore, only Hydrogen and Oxygen and combinations thereof, are present as substances.

The logical progression with SO₂ in water, will be to consider small quantities first and develop stronger concentration math, later.

Quote:

But what is different from seeing the process on atomic-interaction vs thermodynamics level is that for the later SO2 + H2O <-> H+ + HSO3- would be not visible if the recombination time is quite fast. Generally all those recombined ions are not distinguishable from unionized SO2 molecule.

I don't quite follow.
Aren't the equilibrium constants for the time averaged (long term) case ?
eg: The number Kxxx is for how many are distinguishable over a long period of time?

Right now, in the Russian article, I'm only dealing with the equilibrium equations.

Quote:

So, the number of ionized molecules doesn't represent the actual ionization level we can see experimentally which is also the result of interactions during the movement. And the model of dispersed molecules randomly mixed is not the actual liquid water structure which is basically 3d frame of hydrogen bonded H2O with corridors filled with monomeric H2O (see for example different works of Henry Frank and Mariorie Evans who studied liquid water structures and distributions of ions in it).

Right now, my semiconductor training leads me to believe that there will be groupings of water molecules that depend on the previous history of electrostatic disturbances.

Random, to me, means "can not be predicted". Saying "3d" corridors with hydrogen bonding, and not giving a formula that predicts it -- is identical (to me) to the idea "random". So, I'm a bit lost.

I merely think: There is some history of events that leads to a particular configuration of water molecules in groupings of various sizes.

teodor - 25-2-2026 at 14:37

Quote: Originally posted by semiconductive

Aren't the equilibrium constants for the time averaged (long term) case ?
eg: The number Kxxx is for how many are distinguishable over a long period of time?

If it is a constant which is determined experimentally - yes.
If it is a constant which predicted by local molecular/atomic interactions - probably no. Because, my opinion is that getting probability of ionization of a single molecule based on its structure, orbitals, levels etc doesn't predict the actual balance of ions in solution. At least for me it is not obvious that we can get the behaviour of any macro processes from properties of a micro process. I see a big logical gap, I would say - a missing axiom of micro process scalability to make a macro impact. As I said, there are laws of a single man behaviour and there are laws of a crowd behaviour. Those things that determine the behaviour of a crowd is not visible when we study a single man behaviour, like every man has 0.001% impact and you don't see how if you study example of a single man.

Another example is social insects. You unable to predict a behaviour of a bee swarm studying only few bees.

Your believe is that you can decompose any chemical property to a finite number of some well-modelled finite cases. It is possible, may be, I don't now, but in any case, there is no obligation from Nature.

And semiconductor devices are specially designed devices with intention to get some desired properties and amplify some micro effects to macro levels. And the chemical solution is just a chemical solution without anything like that.

Chemists can build 30 theories for the same process and select one which they can prove experimentally. But I don't know cases when they go from other side - build everything from a single theory.

It's strange if you would think about that. But all chemical processes are driven by entropy changes. Not by single-molecular impact.

[Edited on 25-2-2026 by teodor]

semiconductive - 25-2-2026 at 17:58

Quote:

But again, it is the case of Pure water. For SO2 I would start to see how the clathrate structure becomes possible with lowering of temperature: https://doi.org/10.1021/jp037019j
Obviously, it doesn't appear by jump and there are some intermediate interactions which leads to it.
(Clathrate is a structure of "caged" gas molecules. It could be no interaction between those molecules and solvent molecules, only interaction between solvent molecules which creates a "net" holding gas).

And generally, as the works of Frank & Evans suggest, many dissolved substances in water form "iceberg" of water molecules which surround some dissolved molecules and this "iceberg" has an ice crystalline structure in micro form.

I made a login at ACS, agreed to be an associate (non-profit), and then paid to access the article for 48 hours. Ouch. I can buy a few more articles, but not a lot at these prices for so little information. Hopefully, we can learn a bit from this article.

Reading through the first part of the article, I appreciate (very much) that they describe how the measurements were made and exactly what equipment was used.
( I'd love an FTIR or germanium prism myself, but can't afford it. This makes the article price seem worth it! )

I notice in the Zhang and Ewing's article, that they do a phase diagram (figure 2.)
This is potentially very useful for what I'm trying to do.

If I had just data points, (like in earlier posts), I would try to fit them to an equation.

Notably, Z,E say that they are fitting data to the Clausius-Clayperion equation for extrapolation. If this is the same Clausius as the Calusius in the Mossotti-Clausius equation, then I know this Clausius is a bit sloppy and uses a mildly bad approximation for ionization ... which still hasn't been fixed even in NIST reference data.

But, glossing over that for now...

Equation (3) is Henry's constant solvation as molecules of SO₂.

No clarification is given as to what form the 'solvation' is in ; so I immediately wonder if this includes or dis-cludes "Clathrate" situations ?

SO₂(g) ⇌ SO₂(aq) # (3) H , Henry's constant

Moving on, (4) is the standard Ionisation/disassociation constant which is parallel to what was going on in the Rusian (Shimkevich) paper for O₂ and H₂. Only, in the present paper, they are kind enough to say (aq), which Shimkevich didn't bother to do in the Russian paper. Still, it's not balanced in the way Draconic needles me to do. I think they mean:

SO₂(aq) + 2·H₂O ⇌ H₃O⁺ + HSO₃⁻ # (4) K, first ionization constant.

Notably, they next do the exact same kind of constant calculation (5) as in the Russian Shimkevich paper for (2),(3), eg: by putting the gas in the denominator as a "reactant", ignoring the water and then putting ions in the numerator as a "product".

eg: Z,E, imply:
---------------------------
[ HSO₃⁻ ] [ H₃O⁺ ] / [ SO₂(aq) ] = K

Since n of [ HSO₃⁻ ] = n of [ H₃O⁺ ] in this reaction, therefore:

[ HSO₃⁻ ]² / [ SO₂(aq) ] = K
[ HSO₃⁻ ] / √( [ SO₂(aq) ] ) = √( K )
---------------------------

But, now I see Z,E include inside of equation (5) Henry's constant for atmospheric dissolution. It's underneath the same radical even though the left side of the equation talks about aqueous (?clatharite?) sulfur dioxide and not atmospheric.

[ HSO₃⁻ ] / [ SO₂(aq) ] = √( K/HpSO₂ ) # (5)

I'm not sure what they've done.

'H' is a variable name for Henry's constant and also hydrogen,
'pSO₂' is a variable name for millimeters of mercury of sulfur dioxide.

So I'm guessing that HpSO₂ = [ H · pSO₂ ], a "molar" concentration amount that they just didn't put inside brackets.

But, if that's the case then why isn't the concentration on the left side of the equals, in the denominator, under a square root sign? ( I answer myself below. )

The symbolic equivalence ( algebraic equivalence of #5) looks .... wrong?

I read on a little bit, and they talk about an assumption they are making on activity constants being unity. However, this is only true at the 'dilute' stage and not when concentrations get very high. I'd like to start with weak concentrations for in that case it's safe to assume Molar = Molal .... But, the paper has already mentioned that the chart they are using saturated liquid solutions of water and SO₂.

So, I'm flummoxed. I'm not sure if saturated = dilute.

This kind of teaching disconnect happens a lot when I read chemistry papers, and I don't get it. What have I just paid for?

I'll try to work it out numerically:

vvvvvvvvvvvvvvvvvvvvvvvvvvvvvvvvvvvvvvvvvvvvvv
The example he gave was:
t=-10 [°C]
H = 5.0 [ mol/(kg·bar) ]
K = 0.030 [ mol/Kg ]
pSO₂ = 0.900 [ bar ]

I can compute: H·pSO₂ = 4.5 [ mol/Kg ]

( And I am bothered by the fact that he doesn't say [ mol/Liter ]. It's been 20+ years, but still I didn't think we were supposed to put down Kg unless it was a molal measurement. Maybe I'm out of date... )

Next: in the paper, he says his example gives 0.93% solvated gas.
So, let's see if I can calculate that. Digits after a _ are not significant, but are included for rounding purposes.

[ HSO₃⁻ ]² = K · [ SO₂(aq) ]
[ HSO₃⁻ ] = √( 0.030 "[mol/Kg]" · 4.5 "[mol/Kg]" )
[ HSO₃⁻ ] = 0.36_74 "[ mol/Kg ]"

Therefore, I get a ratio of [ HSO₃⁻ ]/[ SO₂(aq) ] = 0.36_74 [mol/Kg] / 4.5 [mol/Kg] = 8.1_64 %

He says 'this ratio' is 0.08, which would be 8%
But, that would give 100%-8% = 92%
100% - 8.1_64% = 91.8_36%
OK. it's not quite 93%, but that's just round-off nitpicking.

Equation (5) right side is √( K/ [ SO₂(aq)] ) = √( 0.030 / 4.5 ) ≈ 8.1_64%

I know:
1/√(2) = √(2)/2
So, I know that √(K)/√( [ SO₂(aq)] ) = √(K)·√( [ SO₂(aq)] )/[ SO₂(aq)]

But that means eq #5 is equivalent to saying:
[ HSO₃⁻ ] = √(K · [ SO₂(aq)] ) ... which is correct by an earlier manipulation.

^^^^^^^^^^^^^^^^^^^^^^^^^^^^

So, this is a 0.36 [mol/kg] ions solution. That's not a factor of ten less than a 1 molar solution, which is standard conditions.

If he means this is a saturated solution of ions because of how much gas will dissolve, then I think it will not be horribly wrong if he substitutes molal values for molar values. At least, it's not a concentrated solution of ions.

But: 4.5 [moles/kg] of SO₂ in solution is a rather concentrated amount of gas.
It makes me nervous to mix molal and molar units ...

[Edited on 26-2-2026 by semiconductive]

semiconductive - 25-2-2026 at 21:51

Re-reading your last post, I have two questions:

1) At what temperature do you believe clathrate structure first begins to exist?
2) Do you expect clathrate SO₂ to be surrounded by a vacuum space that is equivalent in density to SO₂ as an atmospheric gas ?
eg: 1 molecule of SO₂ at gas density, surrounded by many water molecules at water density.... such that the gas molecule displaces 22.4 Liter divide by Avagadro's number and a factor of pressure to give a tiny unit of molecular space....

AKA: What determines the average density a clathrate unit has for each molecule of SO₂ vs. just pure water with no SO₂ ?

Next: From the article, an ionization strength distinction is made that really makes me wonder about the molar/molal issues. I'm clearly missing some detail.

See: J. Phys. Chem. A, Vol. 108, No. 10, 2004 p. 1683

Quote:

However conditions considered in the uptake by the water
component of ice or snow by trace amounts of atmospheric SO₂,
where pSO₂ is typically 10⁻⁶ bar, 20-30 the calculated ratio is 80.
In these cases the dissolved sulfur oxides are essentially all
(99%) HSO₃⁻.

For, if we are in a 'dilute' scenario, then one molecule of gas could not affect another one (often) because they are so far apart in water/ice, that they seldom interact directly.

But the fact that he is claiming an ionization rate difference that depends on the travel distance between SO₂ molecules -- and this makes it hard for me to picture what mechanism is causing ionization or suppressing it.

How does the ice/water know how much SO₂ is trapped in cages especially in the colder cases where solid ice doesn't move ?

I'm also thinking:
If clathrate structure implies a different 'state' than free gas, then there will be an enthalpy of formation difference. eg: Just as there is an enthalpy of formation difference between ice and liquid water. Clathrate ice is a stressed structure. I suppose it can't be identical to a de-gassed ice structure.

[Edited on 26-2-2026 by semiconductive]

teodor - 26-2-2026 at 01:37

Of course you know that you can download almost any article for free or at a very small monthly payment (depending on the number of downloads per day) from shadow libraries like SciHub, Anna's Arcvhive or NexusSTC. There is a general agreement even between scientists affiliated by universities that the official publishers don't have in mind to support individual researchers, mostly the same as chemical companies don't plan to support amateur chemists. Sometimes we do tricky ways to get chemicals, the same is true about books & articles.

Thank you for very detailed response. I will look into it.

[Edited on 26-2-2026 by teodor]

bnull - 26-2-2026 at 03:29

Quote:

There is a general agreement even between scientists affiliated by universities that the official publishers don't have in mind to support individual researchers, mostly the same as chemical companies don't plan to support amateur chemists. Sometimes we do tricky ways to get chemicals, the same is true about books & articles.

My former teachers didn't care about the origin of the references. To be frank, they even shared links or the articles and books themselves, many times with a "University of [Elsewhere]" watermark. The libraries were already paying too much for useless journals. $ 42,00 to read a paper that resulted from research funded by government grants in a public university was a bit to much.

[Edited on 26-2-2026 by bnull]

teodor - 26-2-2026 at 03:59

May be it can be useful, because those shadow libraries often change their domains, the up-to-day access info is here: https://open-slum.pages.dev/
Sometimes you also have to use TOR browser due to local provider/country restrictions.

And it is true, bnull. I also wanted to pay for articles in the past but one scientist from some famous and old university in Germany said that even their staff is using SciHub because the university is unable to pay for everything they need.

[Edited on 26-2-2026 by teodor]

semiconductive - 26-2-2026 at 11:40

Further thoughts that occurred to me after sleeping on the article.

Autoionization of water ( or ice ) generates [ H₃O⁺ ] , and it is possible according to the Rusian (Shimkevich) paper that radicals of uncharged [ H₃O ] are also produced by statistical breaking of bonds without transferring charge.

For very dilute acids, the autoionization value of water -- at least the [ H₃O⁺ ] ion if not the [ OH⁻ ] ion -- can not be neglected in mass action law calculations unless the ionized concentration of the acid is far greater than the pH value of distilled (degassed) water. In the present article, the authors ( Zhang and Ewing ) have neglected common ion effects in both their first example calculations without stating why.

I worked out the pH change of distilled water in an earlier post, and it is temperature dependent.
https://www.sciencemadness.org/whisper/viewthread.php?tid=16...

I have no reason to believe that ionization constants (on a molal basis) will be much different for ice than for liquid water. eg: Because the same mass action laws are used for solid semiconductors as are used for liquid solutions.

There will be a small intercept change that will depend on the enthalpy of formation of ice -- or clathrate ice; but this will not affect the order of magnitude of the curve fit much (if at all).

Therefore, since ( 1/(273.15-10) ≈ 0.0038):

At -10 [°C], pH + pOH ≈ 15.4 # From my graph in earlier post

Now, the article we've been reading is about acid ionization.
This means SO₂ generates [ H₃O⁺ ] ions in addition to [ SO₃⁻ ] ions.

It is permissible to neglect the common ion pH effects when the concentration of the acid ion is much larger than the pH value. (It is not necessary to neglect the effect, for the calculation can always be done with the effect included.); BUT -- In the present example, the acid ion concentration needs to be much greater than: 1.413 [ μmol / L ] to justify neglecting the common ion effect. Therefore: As long as acid ion concentration is above 14[ μmol / L ] , the math may ignore common ion effects with only a minor loss in accuracy of the results.

However, the quote I just pulled from the paper says the total gas concentration pSO₂ is typically 10⁻⁶ [ bar ].
Therefore the Henry's constant *total* gas concentration is 10⁻⁶ [bar] · 5 [ mol/(kg·bar) ] = 50 [ μmol / kg ]

Now: If only 8% of this solvated gas ionized (to match the stronger concentration's ionization rate), the ion level would be 4 [ μmol / kg ] of ions. Which is substantially less than 14[ μmol / L ].

It's not safe, even assuming the ionization rate of a more concentrated SO₂ solution to neglect common ion effects. Zhang and Ewing do not justify why they are avoiding computing common ion effects in the mass action law.

The authors decided to take a 'shortcut' that is hard to notice might be 'wrong' and made a surprising claim about dilute acids. It would save a lot of time if they had just done the full computation including common ion effects.

Teodor, have you verified the calculations in the article you referred me to?

Does the common ion effect with a pH+pOH ≈ 15.4 still support the author's conclusion that 99% of the SO₂ dissolved at 50 [ μmol / kg ] is ionized?

I mean, you can get the articles for free (or not) at your discretion.
Which means you can check them , too, in order to justify me publishing permanently publicly free chemistry information based on them.

( I'd rather spend my time actually making progress and sharing it with the community as a whole; rather than forcing people to read mis-information. )

[Edited on 27-2-2026 by semiconductive]

teodor - 27-2-2026 at 01:09

I didn't check the math, but in my opinion presence of an error doesn't make the work worthless. Sometimes new articles and discoveries are appearing as fixing previous errors. I am not here for fixing errors in articles if I don't understand why we need this math for experiments. There are many obstacles for doing anything you try to do well, and the error in some article could be not the main reason of failure especially if you understand the problem. But if you see an error and other don't it could be you don't understand the problem, so I agree it will be nice to be on the same page as authours. But, as a general attitude, I think the wise position is to accept the possibility of errors, because errors are quite usual things. We should concentrate ourselves only on the errors which have impact on what we try to get.

Quote: Originally posted by semiconductive

( I'd rather spend my time actually making progress and sharing it with the community as a whole; rather than forcing people to read mis-information. )

Nice, but I don't understand what is the subject of your current research. And, as I know from my experience, that means 60-65% of people also can't, so there is no big community here. It will be nice to explain it in 2-3 sentences. The topic of getting "free SO3(2-) ions" I believe is closed, does it?

P.S. So, 10^-7 vs 10^-2 (mol/kg) - the difference between H2O self ionization and SO2 ionization in water. Common ion effect reduces the water self ionization further. It's not water affects ionization of SO2, it is SO2 affects self-ionization of water because everything is calculated relative to water here. That means the common-ion effect is a part of SO2 ionization constant, because it is ionization IN WATER. Why do you expect to see the water self-ionization equation included in the article?

And water radicals don't have any macro effect. At all. They are not a part of any equation because their impact on the process is below any achievable purity of the experiment if anything beyond local micro-conditions is considered. I would say, include interaction with the glass walls first.

Quote: Originally posted by semiconductive

(Saul Patai, "The chemistry of carboxylic acids and esters".

As for ester preparation see e.g. Vogel III,97 (1st edition): n-Butyl Formate, ethyl formate, n-Propyl Formate. Pay attention to water-free chemicals requirement.

[Edited on 27-2-2026 by teodor]

semiconductive - 27-2-2026 at 13:55

Quote:

No, it's not closed.

But, I need to be able to make measurements with equipment I have and not equipment that is impossible for me to buy. I can build an FTIR optical scanner, but to do so -- I would need some math problems solved that I can't solve myself; and I would need my 3D printer to work. ( See my other threads and comments on the Planck Distribution, and on refurbishing a ball mill to make glass dust. )

I haven't said the article you linked me is useless. The FTIR data in it, although suspect in a few ways because of electronics issues like an epoxy tipped thermistor rather than a glass DO-35 package used in the temperature regulation loop -- the graphs are actually very useful to those who can see it (legally).
But:

Note:
I have already shown that the Lorenz-Lorentz equation, from 1879, 1878, is slightly wrong.
This is the 'best' equation known for detecting density of ions to date with the equipment I have at home.

However: The Lorentz equation at any temperature other than 25 [°C] fits data worse than a linear electronic model based on undergraduate electronics taught to me in ~1990. That means the chemical community as a whole has had over 100 years to correct a minor math mistake that Lorentz and Lorenz made, and did not do it even though my non-chemistry teacher, Dr. Aziz Inan, taught me the math to model it correctly way back in ~1990.

It's now 2026.

In the article you've just given me, did you notice the mention of Clausius and Lorentz, and the fact that they are fitting the data to these equations ? The article is 2004.

I have a lot of reason to suspect repetitions of errors that I've already tried to correct in this thread in the very article just linked.

I can't buid and FTIR, but I can build a refractometer.
I will share my results with this community.

In industry, I have taken the semiconductor equations and applied them to transistors using my oscilloscope and non-linear capacitance measurements. I did it because the equations in the electronic industry were wrong in the same way that the Lorenz Lorentz equation is in most chemistry articles today. When I called up a company (IXYS semiconductor), and pointed out an error in the data sheet -- and asked for the correct data, I was given a response very like the one you just gave me in the previous post.

At which point I began to cite for the man on the phone the internal characteristics of the IXYS IGBT transistor and tell him exactly the gain of his transistor which is a "trade secret". Normally, this kind of display of knowledge gets a hate response -- but on this particular call, it was the engineer who designed the transistor who was talking to me and he was shocked. His response was to ask me "how did you figure that out, it's impossible to tell from the outside." And my response was, "no it's not -- I've been trying to tell you how it's done for 15 minutes and you don't listen."

People in industry treat each other as idiots, when people seldom are, and strangely have low tolerance for anyone intelligent.

Einstein himself would probably be booed and banned from talking on a physics forum, today, if he were alive and people didn't actually know who was posting.

It's not a big community here. AI's are more than 60% of people reading my posts.
I bet they will understand (figure out) what I've said and summarize it correctly before trained chemists will. I do write too much, but the information I'm trying to convey is in the text I've written.

Summary:
Article is not completely wrong.
Article contains useful data that has to be separated from errors in Lorenz-Loretnz curve fits before I can use a spectrometer and refractometer (home built) to publish curves that will reflect the measurements I can make.
I appreciate the article, but don't know how much SO₂ gas will affect refraction measurements as you haven't answered my questions regarding clathrate. I consider the $50 cost, an investment that will not pay off for probably a year or two at the rate I'm going.

I'm disabled, I'm slow, and I've made companies millions of dollars when they listen to me. You can see a patent of mine used in nearly every cellphone in the world which was stolen by over 13 U.S. companies. I have not been paid for it. No one gives a damn about talent.

This is why science is not progressing, but industry is playing games with government in order to gain both military and monetary advantages rather than improving the world as a whole. ( End of soap box. )

If you give me good data, I will give you answers to "formidable" challenges in chemistry, eventually.
I'm not unwilling to pay for it -- so long as it's within my social security disability budget.

[Edited on 28-2-2026 by semiconductive]

teodor - 28-2-2026 at 04:32

Quote: Originally posted by semiconductive

You can see a patent of mine used in nearly every cellphone in the world which was stolen by over 13 U.S. companies. I have not been paid for it. No one gives a damn about talent.

This is why science is not progressing, but industry is playing games with government in order to gain both miliatry and monetary advantages rather than improving the world as a whole. ( End of soap box. )

If you give me good data, I will give you answers to "fomiddable" challenges in chemistry, eventually.

Should I doubt about that?

I was working with many talented people and was a lead of a research branch. We had good connection with scientific work in one of the best university in the country and applied their scientific achievements in industry. Later I was a part of startup which developed new type of processor based on light effects.

Over last several year I see a constant degrading of sciencemadness.org forum in the part of inorganic and physical chemistry. Sometimes I visit a site with hope someone will publish interesting experiments in the area.

What you are saying about problems of talented people is partially true. Until some point. Because such people very often have misconception about the role they play in human society. The truth is that society as a whole doesn't have requirement in talented people. I recommend you to read the book "The Immortal Fire Within. The Life and Work of Edward Emerson Barnard" by William Sheehan. By one's man life example you can see how things really work. This is before multi-billion companies (Google etc) started to create a special "zoos" where talents inside have impression they are important for the humanity as a whole.

The truth is that your talent is your gift and your bane at the same time. And you must work against this bane. It is your duty.

To make one step against "I have not been paid for it. No one gives a damn about talent. etc (AI understand me and you don't)" I would advice to improve a communication habbit a bit. A very simple thing I am asking again and again. In 2-3 sentences please describe what you are doing and what you are trying to achieve. I will not re-read your previous posts because it will take time from reading what other great people wrote, and those people always followed this simple rule: just make clear and understandable what they are doing without requiring additional mental efforts from readers. We are solving problems so complex that economy of mental power is the necessary thing which is a habbit of all scientists and that shows that a man has experience in solving complex tasks, going on a border of his mental abilities and he just will not use this power to understand what SM user wrote in his post if that user don't make any effort to make it easy. If you read Einstein or any other great physicist you would agree about the simple and very easily understandable way how they described their work.

I asked Google AI: "what is the subject of work of a user semiconductive from sciencemadness.org forum?"

And this is the response:

"Based on the Sciencemadness.org forum, user semiconductive is an Electrical Engineer who studies chemistry as a hobby. Their work focuses on several technical areas, particularly at the intersection of electronics and chemical engineering:

Electrochemistry and Electroplating: They have experimented with plating metals (such as Nickel) in non-aqueous, organic solvents. They have also researched the electroplating of iron pyrite (a semiconductor) onto metal substrates in sulfide solvents.

Electronics Construction and Design: They are involved in designing and repairing electronic circuits, including specialized analytical equipment.

Analytical Equipment: They have worked on designing and calibrating analytical systems, such as thermocouple data acquisition systems.
Chemical Processes: They have posted regarding the solubility of NaOH in organic solvents (glycerol/methanol) and the electrochemistry of Aluminum anode oxidation.

Their forum profile indicates they study chemistry to help improve the Third World.
"

I would say not so much AI can understand.

Do you familiar with Richard Feynman's theory of electroplating?

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