Buffer (pH of a weak acid decreases when we add NaOH Yes, really

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Discussion Overview

The discussion revolves around the behavior of the pH of a weak acid buffer solution when titrated with NaOH, specifically questioning why the pH decreases upon the initial addition of NaOH before increasing with further additions. The context includes calculations related to the titration of hydrofluoric acid (HF) with sodium hydroxide (NaOH).

Discussion Character

  • Technical explanation, Debate/contested, Mathematical reasoning

Main Points Raised

  • One participant notes that the pH of a 0.100M HF solution decreases from 2.08 to 1.888 after the addition of 1.00mL of NaOH, which seems contrary to expected behavior.
  • Another participant requests clarification on the calculations leading to the reported pH values.
  • Detailed calculations are provided for the equilibrium concentrations of HF and its dissociation products after the addition of NaOH, showing a decrease in pH with the initial addition of NaOH.
  • There is a suggestion to check the calculations for accuracy, particularly regarding the equilibrium expression and the value of x.
  • A participant mentions that their teacher also confirmed the calculations but was puzzled by the initial decrease in pH.
  • Another participant emphasizes the importance of not ignoring the variable x in the calculations and suggests verifying the results by plugging back into the equilibrium constant expression.

Areas of Agreement / Disagreement

Participants express uncertainty regarding the initial decrease in pH and whether the calculations are correct. There is no consensus on the explanation for the observed behavior of the buffer solution.

Contextual Notes

Participants highlight potential issues with assumptions in the calculations, particularly regarding the significance of the variable x in the equilibrium expressions. The discussion does not resolve these mathematical uncertainties.

daivinhtran
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Buffer (pH of a weak acid decreases when we add NaOH! Yes, really..

This is not homework, but just something that I find not following general rule. Just wondering why.
So
We have the titration of 20.0 mL of .100M HF with .100M NaOH

With 0mLof NaOH, the pH=2.08 (by calculating)

But with 1.00mL of NaOH, the pH is 1.888 (by calculating)

BUT then with 2.00ml of NaOH, the pH increases to 2.213
After that, it keeps increasing and follow the rule

given the Ka= 6.8e-4

Can someone explain it?
 
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Show how you got this result.
 
Borek said:
Show how you got this result.

For V of NaOH=0mL

The equilibrium equation is
HF <=> H+ + F-
.1M
-x +x +x
.1 x x

(x^2)/.1 = Ka = 6.8e-4
x= .008246 = [H+]
pH = 2.083745544

With V of Naoh=1mL

HF + OH- <=> F- + H20
(.02)(.1) (.001)(.1)
.002mol .0001mol
-.001mol -.001mol +.001mol
= .0019mol 0 .0001mol

=> [HF]=.0019mol/(.021L) = .090476 M
[F-]= .0001mol/(.021L) = .00476M

Equilibrium equation:
HF <=> H+ + F-
.090476 M .00476M
-x +x +x
.090476 M x .00476M

.00476x/.09476 = 6.8e-4
[H+] = 1.86847 = x
pH= 1.868472988
 
Last edited:
daivinhtran said:
.090476 M .00476M
-x +x +x
.090476 M x .00476M

Check the last line again.
 
Borek said:
Check the last line again.

Yes, I did, sir.

My teacher also checked it but she had no clue why it's like that..

SHe also did the same calculation and get the same pH.
 
Borek said:
Check the last line again.

we're probably not supposed to ignore the x in this one, right?
 
Don't guess, try. The compare numbers you get with the numbers you got earlier.

Simple check is always to plug concentrations you get into Ka and seeing if the calculated value agrees with the given one.
 

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