Wednesday, 13 May 2015

acid base - Is the Henderson–Hasselbalch equation volume independent?


Looking at this equation $\mathrm{pH} = \mathrm{p}K_\text{a} +\log\frac{[\ce{CB}]}{[\ce{A}]}$ makes me think that it is concentration independent.


What I mean is, when we look at $\frac{[\ce{CB}]}{[\ce{A}]}$, the volumes cancels out, so we are only left with the molar ratio of the conjugate acid and conjugate base. So does this mean that the pH is only dependent on the molar ratios? Obviously not, because $0.003\ \mathrm{mol/L}$ of acid $\ce{A}$ and $0.003\ \mathrm{mol/L}$ of its conjugate base is going to have a different $\mathrm{pH}$ from $0.3\ \mathrm{mol/L}$ of acid $\ce{A}$ and $0.3\ \mathrm{mol/L}$ of its conjugate base right?


What am I missing here? This is seriously confusing me. Please help, I want to use the Henderson–Hasselbalch equation to calculate the $\mathrm{pH}$ of a weak acid as it’s being titrated with a strong base, but this is making me reluctant about the results.




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