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We had a chemistry test and one of the questions was this:
What is the pH of $1,4^{-8} M$ $HCl$ in water?


This is such a small amount of acid that you need to take into concideration the self ionization of water. So the way our chemistry teacher did it on the test was something similar to the first answer on this site: https://www.quora.com/What-is-the-pH-of-10-6-M-HCl-aq

They find the total $[H_3O^+]$ in the solution by adding the $1,0*10^{-7}M$ $H_3O$ from self ionization of water and get:
$1,14*10^{-7}M$.
Then they just find the pH:
$-\log(1,14*10^{-7}M)$
This is $6,943$ which becomes a pH of $6,9$

I did this and got right on the test, but something didn't sit right with me:
If $[H_3O^+]$ was $1,14*10^{-7}M$ and $[OH^-]$ was $1,0*10^{-7}$ (from self ionization of water), then $1,0*10^{-14}M^2≠[H_3O]*[OH^-]$ and the solution is not in equilibrium. So I came up with another way to calculate the pH:

I also first find $[H_3O^+]$ to be $1,14*10^{-7}M$ but then I think that $x$ amounts of $H_3O^+$ and $OH^-$ has to react so the solution is in equilibrium, so I set up an equation:
$1,0*10^{-14}M^2=(1,14*10^{-7}M-x)*(1,0*10^{-7}M-x)$
When I solve for $x$ I find that $6,755*10^{-9}$ mole has reacted per liter. Then I take away that from the original $[H_3O^+]$ and get that the current $[H_3O^+]$ is $1,07245*10^{-7}M$. Then I just find the pH of the solution:
$-\log(1,07245*10^{-7}M)$
This is $6,9696$ which becomes a pH of $7,0$

A pH of $7,0$! Not $6,9$! And the teacher deducted points for $7,0$! I got $6,9$ on the test and full marks so I'm not that mad anyway, but I'm curious what is the most right answer. I also discussed it with my teacher and I think he somewhat understood my problem, but not my solution.

Edit:
I see that my question was a little unclear. I would like to know which answer is most right and if my thought process is correct.

Tuskies
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    The simple calculation for strong acids pH = - log c neglects water autodissociation and is justified only for c >> 10^-7 mol/L. – Poutnik Apr 16 '23 at 16:42
  • I never understood why they keep teaching people 'approximate' methods for pH calculation, which only seems to generate confusion and a lot of playing with sketchy assumptions. Nowadays one can solve exact systems numerically using open-source software, so there is really no need to approximate anything (except the activity vs concentration story). And for a solution of a single strong acid in water, even the exact system is analytical, so... Maybe they should teach students how to build the exact system first, and then show how it can be simplified in special cases. – user6376297 Apr 16 '23 at 16:52
  • See for instance https://chemistry.stackexchange.com/a/97840/41751 . The equation that the user derived is valid for any concentration of HCl, you only solve it as a 2nd degree one, without making any assumptions or simplifications. And remember to replace $1$ with the actual $[HCl]_0$. – user6376297 Apr 16 '23 at 16:55
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    I believe using approximations and "doing stuff in your head" is the only way to get a proper grasp on the more complex topics and learning about chemistry. There are already too many people using computers without actually knowing what they do. But this is actually not the place to discuss this. However, this question does show that critical thinking is not lost when using approximations. – Martin - マーチン Apr 16 '23 at 17:12
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    Knowing what approximations you can use in the given situation is actually a sign you have a good qualitative understanding of the system (what is important, what is not). This is one reason such calculations are still taught as exercize – Greg Apr 16 '23 at 17:39
  • @user6376297 thx for the link! I'm not totally satisfied with it, but it did help me a little. – Tuskies Apr 16 '23 at 17:52
  • The famous example is for weak acids the equation pH = 0.5(pKa - log c), which is derived applying 2 approximations and the user must know what are they and if he/she can afford to use the equation (which is valid at conditions c >> [H+] >> [OH] ) – Poutnik Apr 16 '23 at 18:07
  • Expression formatting reference: Basics/CH+Math expressions/Upright vs italic/Math tutorial // MathJax is preferred not to be used in CH SE question titles for indexing and question list displaying reasons. – Poutnik Apr 16 '23 at 18:40
  • It is a pity this discussion is closed. Because I have redone all the calculation, and I have found $\ce{[H+] = 1.21·10^{-7}}$ and $\ce{pH = 6.917}$. It is impossible to develop all the calculations under the small space available in the comment : Sorry ! – Maurice Apr 16 '23 at 20:15
  • @Maurice Q&A sites are not meant for discussions, this is not a forum. Only questions, answers and temporary comments for clarification. If you still feel chatty, well, there are separate chat rooms, but without decent MathJax support. If your approach is substantially different from the answers in the linked duplicate questions, then do feel free to post your answer to the original question. – andselisk Apr 16 '23 at 20:25
  • @Martin-マーチン : you are absolutely right, there are a lot of people who just apply maths to chemistry and miss the meaning / field knowledge. On the other hand, when I studied chemistry, these approximate equations were taught to me as something to just learn by heart and apply, without understanding them. It was only much later in my career that I finally understood that a chemical system can be mapped to a system of equations. That was my point: tell people how that's done, and then explain how the original system can be simplified. IMO that's better than the other way around. – user6376297 Apr 17 '23 at 10:50
  • @Greg : indeed, 'knowing' is the operative word here. If you just learn things by heart, it does not help you understand anything. But I disagree on the 'qualitative' bit of your comment. The topic here is all and only about quantitative matters. In fact, even reducing the exact system to the approximate one requires making assumptions about the relative magnitude of terms in sums, so again quantitative. Purely qualitatively we could only say that adding an acid to water will always lower its pH. But here they are asking the user what the actual pH is, so... – user6376297 Apr 17 '23 at 10:55
  • @user6376297 I guess everyones experience is different, but in my education these approximations were explained from high school and up. We can argue day and nigh about how you define “qualitative” in this situation. My point is that knowing that there is a 2-5-10 orders of magnitude difference between two components is part of the understanding of chemistry, and estimating error is a useful and not very difficult to learn skill. – Greg Apr 17 '23 at 12:41
  • @Greg : I get your point, and there is actually no need to argue. The stubborn fact we cannot ignore is that countless people keep stumbling on the use of these approximate equations, meaning they are not so well understood or obvious to people, in real life / practice. There is probably some stats in SE regarding how often such questions pop up and are immediately closed because they are duplicated. I think the OP here got a nice answer and will eventually get value from it, but that went necessarily via explaining the origin of the exact system and its simplification, again as per my point. – user6376297 Apr 17 '23 at 15:30
  • In fact, this is something that happens very often in my line of work, where people are bothered by the 'more complicated' version of a theory, so they learn the 'simplified' version, which only works within a set of well-defined assumptions. Inevitably, they end up forgetting that the assumptions ever existed, and apply the same theory to all cases, including many where the assumptions do not hold (I have a very recent case in mind). So, simplified equations + assumptions = good if used well; simplified equations taken for granted for all cases = recipe for disaster. – user6376297 Apr 17 '23 at 15:35

1 Answers1

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If no usable equation is ready, you can always use in acido-basic calculations the scenario below. It is less straight-forward than some ready to use (often simplified) equations, but it is generally valid ( putting aside the Pandora's box of activities).

You start with 3 types of equations

  • The law of charge conservation - total charge has to be zero
    $$[\ce{H+}] = [\ce{OH-}] + [\ce{A-}] \label{1}\tag{1}$$

  • The law of mass conservation - in a specific form of conservation of total molar amount/concentration of particular forms of given substance:
    $$c(\ce{HA}) = [\ce{HA}] + [\ce{A-}] \label{2}\tag{2}$$

  • The equations for all present acido-basic equilibrii
    $$K_\mathrm{w} = [\ce{H+}][\ce{OH-}]=\pu{e-14} \label{3}\tag{3}$$
    $$K_\mathrm{a} = \frac{[\ce{H+}][\ce{A^-}]}{[\ce{HA}]} \label{4}\tag{4}$$

Generally, we get a set of N equations for N variable and one often has to apply justified simplifications.


But in our case, things go smoothy to the simple solution:

We have welcome simplification, as we can assume there is not HA present for strong acids as $K_\mathrm{a}$ in \eqref{4} is effectively infinite and therefore
$$c(\ce{HA}) = [\ce{A-}]\label{2a}\tag{2a}$$

After substitution of \eqref{2a} and \eqref{3} to \eqref{1}, we get:

$$[\ce{H+}] = \frac{K_\mathrm{w}}{[\ce{H+}]} + c(\ce{HA}) \label{5}\tag{5}$$

$$[\ce{H+}]^2 - c(\ce{HA}){[\ce{H+}]} - K_\mathrm{w} = 0 \label{6}\tag{6}$$

$$[\ce{H+}] = \frac{c(\ce{HA}) \pm \sqrt{(c(\ce{HA}))^2 + 4K_\mathrm{w}}}{2} \label{7}\tag{7}$$

We accept only the plus sign variant, the other root is negative.

$$[\ce{H+}] = \frac{c(\ce{HA}) + \sqrt{(c(\ce{HA}))^2 + 4K_\mathrm{w}}}{2} \label{8}\tag{8}$$

$$\mathrm{pH} = -\log{[\ce{H+}]}\label{9}\tag{9}$$

If it neglect water auto-dissociation and pronounce $K_\ce{w} = 0$ then the equation \eqref{8} reduces itself to simple:

$$[\ce{H+}] = c(\ce{HA})\label{10}\tag{10}$$

Poutnik
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