Restoring Alkalinity to the Ocean

Im a BM wrote:So, let's talk about the thermodynamics of adding acid to water and see if there is a difference between pure water and sea water in the response.

Some of the vocabulary involved:

atomic radius, ionic radius, hydrated radius, charge density, and enthalpy of hydrogen bond formation.

Im a BM wrote: Even in concentrated form, sulfuric acid is virtually 100% dissociated into separate hydrogen ions and sulfate ions.

Im a BM wrote:It contains very little water to hydrate the ions.

Im a BM wrote: Compared to other elements, hydrogen has a very small atomic radius.

Im a BM wrote: When the water molecules line up around a hydrogen ion added to solution, the formation of hydrogen bonds releases energy.

Im a BM wrote: If that acid is added to sea water, many water molecules initially present have already formed a hydrated radius around an ion (sodium, chloride, bicarbonate, etc.) and have already released the energy from the enthalpy of hydrogen bond formation.

Im a BM wrote: POP QUIZ for those who are already experts in thermodynamics.

Two one liter flasks at the same temperature, one with pure water and one with sea water.

Will one of them heat up more than the other when a drop of concentrated acid is added?

Im a BM wrote:
1970. My seventh grade science teacher did a demonstration that went awry.

He wanted to show us why they say, "add acid to water. don't add water to acid."

He had a flask about 2/3 full of pure water.

He had an eyedropper with concentrated sulfuric acid.

He asked for a volunteer to come hold the flask while he added a drop of acid.

The student volunteer got spooked when it instantaneously heated up and he dropped the flask.

Im a BM wrote:
So, let's talk about the thermodynamics of adding acid to water and see if there is a difference between pure water and sea water in the response.

Im a BM wrote:
Some of the vocabulary involved:

atomic radius, ionic radius, hydrated radius, charge density, and enthalpy of hydrogen bond formation.

Im a BM wrote:
Even in concentrated form, sulfuric acid is virtually 100% dissociated into separate hydrogen ions and sulfate ions.

It contains very little water to hydrate the ions.

Im a BM wrote:
Water molecules will line up their dipoles to form a hydrated radius around an ion in solution, held close to each other by hydrogen bonds.

Im a BM wrote:
Compared to other elements, hydrogen has a very small atomic radius.

Im a BM wrote:
The ionic radius is the distance between the nucleus and the most distant associated electron in the ionized form of the atom.

Im a BM wrote:
In the case of many cations, the ionic radius is smaller than the atomic radius, because they lost the electron(s) in the outermost shell to become ions.

Im a BM wrote:
The ionic radius of sodium is smaller than the ionic radius of potassium, because potassium has a lot more electrons than sodium, filling up more of the more distant outer shells.

Im a BM wrote:
Both sodium and potassium ions have the same charge (+1). Because the sodium ionic radius is so much smaller than the potassium ionic radius, sodium ions have much higher charge density than potassium.

Im a BM wrote:
As a consequence of the higher charge density, sodium actually lines up water molecules into a hydrated radius that is LARGER than the hydrated radius of potassium.

Im a BM wrote:
Hydrogen ions have the smallest ionic radius of all.

Im a BM wrote:
There are no electrons at all to occupy the outermost, or even the innermost, shell.
A proton is smaller than a hydrogen atom, yes.
[quote]Im a BM wrote:
Hydrogen ions have very high charge density and create a large, hydrogen-bonded hydrated radius in water.

Im a BM wrote:
When the water molecules line up around a hydrogen ion added to solution, the formation of hydrogen bonds releases energy.

Im a BM wrote:
If concentrated acid is added to pure water, none of the water molecules initially present are part of the hydrated radius of any ion. Except for extremely tiny concentration of H+ and OH-

If that acid is added to sea water, many water molecules initially present have already formed a hydrated radius around an ion (sodium, chloride, bicarbonate, etc.) and have already released the energy from the enthalpy of hydrogen bond formation.

Im a BM wrote:
POP QUIZ for those who are already experts in thermodynamics.

Two one liter flasks at the same temperature, one with pure water and one with sea water.

Will one of them heat up more than the other when a drop of concentrated acid is added?

What will happen to the surface tension, boiling point, and vapor pressure of the solutions - will they increase or decrease after adding acid?

Yeah, I'm inviting a stupid word game to expose the ignorance of our "resident experts in science" regarding thermodynamics.

Im a BM wrote: We can eliminate the confounding variable of anything that can be construed as an "exponential effect" by referring directly to the concentration of hydrogen ion, rather than pH.

So, rather than say "pH 7", say 0.0000001 molar H+. Sea water, with pH about 8+, becomes 0.00000001 molar H+. And now there is no parameter that can be construed as "exponential".

Im a BM wrote: Because "Mr Chemistry Genius" needed to be given the "correct answer" to refute the apparently false claim that pure water shows greater pH change than sea water when a drop of acid is added.

Im a BM wrote: Because the term ocean "acidification" is the significant depletion of carbonate ion alkalinity, at least by 30%, due to carbon dioxide inputs that form carbonic acid.

IBdaMann wrote:

sealover wrote:If I take a liter of pure water and add just one drop of concentrated acid, I will see a huge drop in pH.

So, Mr. Chemistry Genius, the correct answer is that if you were to get your hands on some magical acid whose pH is 0.0, and you were to add one single drop to one liter/litre of pure water (pH 7.0) and one single drop to one liter/litre of sea water (pH 8.4), the impact of a drop of the acid would be more pronounced on the sea water than on the pure water.

Do the math.

sealover wrote: Remember, this thread is about restoring "alkalinity" to the sea.

That's like restoring white to snow. It's already there. Just go out and claim victory!

sealover wrote:Alkalinity is another word for acid neutralizing capacity.

Great circular definition ... and acidity is another word for alkaline neutralizing capacity.

Acidity is the ability to provide a hydrogen ion. Alkalinity is the ability to accept a hydrogen ion.

sealover wrote:The alkalinity of pure water arises entirely from hydroxide ions.

Do you see what I mean? Only a scientifically illiterate moron would refer to the alkalinity of pure water. Next, you'll be talking about the temperature of deep space.

sealover wrote:The overwhelming majority of the alkalinity in sea water arises from bicarbonate and carbonate ions.

Let's not forget hydroxide, silicates and phosphates. They're people too.

sealover wrote:A 30% depletion of the ocean's alkalinity has resulted in only a small decrease in pH.

That's just one number so I can see how you could so easily pull that out of your arsewhole. I think it explains the stink quite nicely.

sealover wrote:On the other hand, it has caused a HUGE change to the bioavailability of carbonate ion.

The "bioavailability"? Don't you mean the "ecolobiquity"? ... or maybe the "presenvironance"?

Im a BM wrote:
[quote]IBdaMann wrote:So, Mr. Chemistry Genius, the correct answer is that if you were to get your hands on some magical acid whose pH is 0.0, and you were to add one single drop to one liter/litre of pure water (pH 7.0) and one single drop to one liter/litre of sea water (pH 8.4), the impact of a drop of the acid would be more pronounced on the sea water than on the pure water.

IBdaMann wrote:

Im a BM wrote:It is much more revealing of human psychology than water chemistry how someone could create an absurd, convoluted word game to claim that sea water changes more than pure water when a drop of acid is added.

Well put. This is exactly what you've been doing. You screwed up on the chemistry that you have been claiming is your area of expertise. It was a rookie error and instead of thanking me for correcting you, you began delving ever deeper into word games in order to make your confusion appear to be may fault.

Chemistry 101: As a solution moves away from 7, e.g. from pure water to sea water, the effect is exponential. I suspect that the reason you did not know this is that [b]you are a totally dishonest, uneducated, scientifically illiterate moron who slept through high school, but I was genuinely polite and cordial when I pointed this out. You were so fearful of your charade being blown that you became apoplectic and went on the offensive. You didn't notice that it was already too late. You didn't notice that everyone on this site was already aware that you are a charlatan, a pretender. You didn't notice that all you had to do was to say "thank you, you are correct." You didn't notice that you simply allowed your poor wording (of the question) confuse you and that you could have just rewritten your question to reflect that as a solution moves away from 7, the effect is exponential.

Instead, you first denied that it was exponential, revealing your mathematical incompetence. Then you became desperate and began making longer, more numerous and more incoherent attempts to confuse readers into thinking that I was somehow just wrong, and that I am somehow being ridiculous by claiming that as a solution moves away from 7[/b], the effect grows exponentially.

How is that working out for you? Have you considered going back to school? Would you like me to teach you chemistry? Just ask nicely and we might be able to work something out.

Oh, remind me again, why do I owe you an apology?

Im a BM wrote:There is no chemical parameter, "exponential" or otherwise, that changes more in sea water than in pure water when a drop of acid is added.

Great word games! This is to what it has come. Your statement doesn't even make any sense. You are a babbling idiot. Please continue.

Im a BM wrote:There is NO CHEMICAL PARAMETER that "changes exponentially" in sea water when a drop of acid is added.

Im a BM wrote:Nor does a troll ever admit they were wrong about anything.

Im a BM wrote:Nor do the insults and anti scientific claims ever stop.

IBdaMann wrote:

Im a BM wrote:There is NO CHEMICAL PARAMETER that "changes exponentially" in sea water when a drop of acid is added.

The exponential change occurs as you move away from 7.0 ... I believe I have stated this many times. You know that the inverse is a logarithm.

Im a BM wrote:Nor does a troll ever admit they were wrong about anything.

?

Im a BM wrote:Nor do the insults and anti scientific claims ever stop.

The claim here is a mathematical one. I claim that the inverse of a logarithmic function is an exponential function ... but you claim otherwise, yes?

Im a BM wrote:Okay, let's do the math.

Im a BM wrote:Let's assume that "7.0" refers to pH 7.0.

Im a BM wrote:We add one drop of acid to pure water, which starts at pH 7.0

Im a BM wrote: It moves away from pH 7.0 when the pH drops by a lot.

Im a BM wrote: We add one drop of acid to sea water, which starts at pH about 8.3.

It moves TOWARD pH 7.0 when the drop of acid is added. Very slightly.

Im a BM wrote: So, the "exponential change" only appears to occur with pure water, not sea water.

Im a BM wrote:But the slow, steady decline in pH gets SLOWER as it approaches pH 6.35

pH 6.35 has a special place in sea water chemistry. It is the first pKa of carbonic acid.

H2CO3 = H+ + HCO3- dissociation constant (ka)= 4.5 x 10 to the minus 7.

pKa = 6.35 (negative logarithm of dissociation constant)

When pH = 6.35, the concentration of carbonic acid and bicarbonate ion are equal. This is where sea water has its maximum buffering capacity. But you can hardly call it sea water after you have titrated it down to pH 6.35

But as you add more drops of acid near pH 6.35, that is where you see the smallest change in pH per drop added.

The other dissociation constant related to carbonic acid is for the very weak acidity of the bicarbonate ion.

HCO3- = H+ + CO3(2-) dissociation constant Ka2 = 4.7 x 10 to the minus 11.
pKa2 = 10.33

If we add sodium hydroxide to sea water, it will move pH AWAY from 7 as it goes up from about 8.3.

But if we keep adding more and more base, the rate of pH rise will slow as it approaches pH 10.33. Sea water has the second most buffering capacity at pH 10.33. But it really isn't sea water at that point.

So, the greatest "exponential effect" occurs when adding acid to pure water, as the pH moves rapidly below 7, where "the exponential change occurs as you move away from 7.0."

Im a BM wrote:
Before getting into the thermodynamics of heat produced during formation of hydrogen bonds, I'll clarify a few points.

Im a BM wrote:
Charge density of an ion is the charge per volume or charge per surface area.

Usually reported as coulombs per cubic meter.

Im a BM wrote:
Sodium ion has much higher charge density than potassium ion.

Im a BM wrote:
Water molecules approaching the surface of a sodium ion encounter a much stronger electric field, compared to potassium, to line up their dipoles and form hydrogen bonds.

Im a BM wrote:
The hydration of sodium ion creates a hydrated radius that is actually larger than the hydrated radius of potassium ions.

The hydrated radius is the distance from the nucleus to the furthest water molecule tightly alligned around the ion by hydrogen bonds.

Im a BM wrote:
This slippery sheath of strongly bound water molecules increases the effective size of the ion.

Im a BM wrote:
Hydrated potassium ions can fit into spaces where hydrated sodium ions are too large to enter, such as the interlayers of illite clays.

Im a BM wrote:
A bare hydrogen ion has 2 times ten to the TENTH power as much charge density as a sodium ion. Water molecules get close to a VERY strong electric field when they hydrate a hydrogen ion.

Im a BM wrote:
Anyone who knows how to look up the definition of terms can see that "hydrated radius" is a very real thing,

Im a BM wrote:
and that reporting charge density as volts alone is "unit error".

Im a BM wrote:
We can eliminate the confounding variable of anything that can be construed as an "exponential effect" by referring directly to the concentration of hydrogen ion, rather than pH.

Im a BM wrote:
So, rather than say "pH 7", say 0.0000001 molar H+. Sea water, with pH about 8+, becomes 0.00000001 molar H+. And now there is no parameter that can be construed as "exponential".

Im a BM wrote:
Add a drop of strong acid to a 0.0000001 molar H+ versus a 0.00000001 molar H+ solution, and eliminate any potential "exponential effect" complicating the interpretation of what happens.

Im a BM wrote:
So, an imaginary equation of

Magnitude of effect = delta (solution)/delta (pH) gets changed to

Magnitude of effect = delta (solution)/delta (H+)

At least now the ratio can have comparable units for meaningful comparison, but the equation is still meaningless without specifying what "solution" means.

Supposedly, there is some "solution" parameter that shows a change that is more than the change to hydrogen ion concentration on a linear scale.


This magic solution parameter changes much more in sea water than it does in pure water when acid is added, but the name of that parameter is a secret.

Im a BM wrote:
Could it be carbonic acid concentration or carbonate ion concentration?

Im a BM wrote:
That would be worth discussing.

Of course, this happens when we add the "magical acid with pH 0.0", which apparently does not really exist?

Im a BM wrote:
Because "Mr Chemistry Genius" needed to be given the "correct answer" to refute the apparently false claim that pure water shows greater pH change than sea water when a drop of acid is added. (original text available on page 1)

Here come the absurd word games!

Even the basic term "alkalinity" is just a word game.

And that's the only word game I want to play right now.

Because the term ocean "acidification" is the significant depletion of carbonate ion alkalinity, at least by 30%, due to carbon dioxide inputs that form carbonic acid.

Im a BM wrote:
It is easy to mix up a non-magical acid which has pH 0.0, or even less than zero. 1 molar hydrochloric acid, for example, has pH 0.

Im a BM wrote:
But an acid we refer to as "who" would be magical indeed.

Im a BM wrote:
Yes, the "impact"... on the sea water. Obviously this refers to some kind of exponential change that occurs to the acid or something.

Im a BM wrote:
And that is the "correct answer" to refute the obviously incorrect claim that pure water shows a big change in pH upon addition of acid.

Im a BM wrote:
I guess I owe somebody an apology for my failure to understand buffering.

Im a BM wrote:

IBdaMann wrote:

Im a BM wrote:It is much more revealing of human psychology than water chemistry how someone could create an absurd, convoluted word game to claim that sea water changes more than pure water when a drop of acid is added.

Well put. This is exactly what you've been doing. You screwed up on the chemistry that you have been claiming is your area of expertise. It was a rookie error and instead of thanking me for correcting you, you began delving ever deeper into word games in order to make your confusion appear to be may fault.

Chemistry 101: As a solution moves away from 7, e.g. from pure water to sea water, the effect is exponential. I suspect that the reason you did not know this is that [b]you are a totally dishonest, uneducated, scientifically illiterate moron who slept through high school, but I was genuinely polite and cordial when I pointed this out. You were so fearful of your charade being blown that you became apoplectic and went on the offensive. You didn't notice that it was already too late. You didn't notice that everyone on this site was already aware that you are a charlatan, a pretender. You didn't notice that all you had to do was to say "thank you, you are correct." You didn't notice that you simply allowed your poor wording (of the question) confuse you and that you could have just rewritten your question to reflect that as a solution moves away from 7, the effect is exponential.

Instead, you first denied that it was exponential, revealing your mathematical incompetence. Then you became desperate and began making longer, more numerous and more incoherent attempts to confuse readers into thinking that I was somehow just wrong, and that I am somehow being ridiculous by claiming that as a solution moves away from 7[/b], the effect grows exponentially.

How is that working out for you? Have you considered going back to school? Would you like me to teach you chemistry? Just ask nicely and we might be able to work something out.

Oh, remind me again, why do I owe you an apology?

Im a BM wrote:There is no chemical parameter, "exponential" or otherwise, that changes more in sea water than in pure water when a drop of acid is added.

Great word games! This is to what it has come. Your statement doesn't even make any sense. You are a babbling idiot. Please continue.

For a solution to change "from pure water to sea water", there is no "exponential effect" - just an irrelevant pivot from the point that pure water is less buffered against pH change than sea water.

Im a BM wrote:
There is NO CHEMICAL PARAMETER that "changes exponentially" in sea water when a drop of acid is added.

Im a BM wrote:
Nor does an acid have to be "magical" to have pH = 0.

Im a BM wrote:
Nor does a troll ever admit they were wrong about anything.

Im a BM wrote:
Nor do the insults and anti scientific claims ever stop.

Im a BM wrote:
Okay, let's do the math.

The "exponential change occurs as you move away from 7.0"

Let's assume that "7.0" refers to pH 7.0.

We add one drop of acid to pure water, which starts at pH 7.0

It moves away from pH 7.0 when the pH drops by a lot.

Im a BM wrote:
We add one drop of acid to sea water, which starts at pH about 8.3.

Im a BM wrote:
It moves TOWARD pH 7.0 when the drop of acid is added. Very slightly.

Im a BM wrote:
So, the "exponential change" only appears to occur with pure water, not sea water.

Im a BM wrote:
Now, if we measure a titration curve

Im a BM wrote:
while we perform the alkalinity test on sea water, we will see a slow but steady shift TOWARD pH 7 as we continue to add more and more drops of acid.

Im a BM wrote:
It reaches pH 7 and we continue the titration.

Im a BM wrote:
Now it is declining AWAY from pH 7. Maybe this is where the "exponential effect" kicks in.

Im a BM wrote:
But the slow, steady decline in pH gets SLOWER as it approaches pH 6.35

Im a BM wrote:
pH 6.35 has a special place in sea water chemistry. It is the first pKa of carbonic acid.
[quote]Im a BM wrote:
H2CO3 = H+ + HCO3- dissociation constant (ka)= 4.5 x 10 to the minus 7.

pKa = 6.35 (negative logarithm of dissociation constant)

When pH = 6.35, the concentration of carbonic acid and bicarbonate ion are equal.

Im a BM wrote:
This is where sea water has its maximum buffering capacity. But you can hardly call it sea water after you have titrated it down to pH 6.35

Im a BM wrote:
But as you add more drops of acid near pH 6.35, that is where you see the smallest change in pH per drop added.

The other dissociation constant related to carbonic acid is for the very weak acidity of the bicarbonate ion.

Im a BM wrote:
HCO3- = H+ + CO3(2-) dissociation constant Ka2 = 4.7 x 10 to the minus 11.
pKa2 = 10.33

If we add sodium hydroxide to sea water, it will move pH AWAY from 7 as it goes up from about 8.3.

But if we keep adding more and more base, the rate of pH rise will slow as it approaches pH 10.33. Sea water has the second most buffering capacity at pH 10.33. But it really isn't sea water at that point.

Im a BM wrote:
So, the greatest "exponential effect" occurs when adding acid to pure water, as the pH moves rapidly below 7, where "the exponential change occurs as you move away from 7.0."

IBdaMann wrote:

sealover wrote:If I take a liter of pure water and add just one drop of concentrated acid, I will see a huge drop in pH.

So, Mr. Chemistry Genius, the correct answer is that if you were to get your hands on some magical acid whose pH is 0.0, and you were to add one single drop to one liter/litre of pure water (pH 7.0) and one single drop to one liter/litre of sea water (pH 8.4), the impact of a drop of the acid would be more pronounced on the sea water than on the pure water.

Do the math.

sealover wrote: Remember, this thread is about restoring "alkalinity" to the sea.

That's like restoring white to snow. It's already there. Just go out and claim victory!

sealover wrote:Alkalinity is another word for acid neutralizing capacity.

Great circular definition ... and acidity is another word for alkaline neutralizing capacity.

Acidity is the ability to provide a hydrogen ion. Alkalinity is the ability to accept a hydrogen ion.

sealover wrote:The alkalinity of pure water arises entirely from hydroxide ions.

Do you see what I mean? Only a scientifically illiterate moron would refer to the alkalinity of pure water. Next, you'll be talking about the temperature of deep space.

sealover wrote:The overwhelming majority of the alkalinity in sea water arises from bicarbonate and carbonate ions.

Let's not forget hydroxide, silicates and phosphates. They're people too.

sealover wrote:A 30% depletion of the ocean's alkalinity has resulted in only a small decrease in pH.

That's just one number so I can see how you could so easily pull that out of your arsewhole. I think it explains the stink quite nicely.

sealover wrote:On the other hand, it has caused a HUGE change to the bioavailability of carbonate ion.

The "bioavailability"? Don't you mean the "ecolobiquity"? ... or maybe the "presenvironance"?

Im a BM wrote:
So, Mr. Chemistry Genius, the correct answer is that if you were to get your hands on some magical acid whose pH is 0.0, and you were to add one single drop to one liter/litre of pure water (pH 7.0) and one single drop to one liter/litre of sea water (pH 8.4), the impact of a drop of the acid would be more pronounced on the sea water than on the pure water.

Do the math.

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In addition to getting the basic concept of pH buffering BACKWARDS, this also displays laughable ignorance about the pH scale.

Someone with only a very superficial understanding about pH might assume that an acid would have to be "magical" to have pH = 0.0