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ChemBuddy — The buffer capacity provides the following:

$$\ce{HA <=> H+ + A-}$$

Total concentration of the buffer $c_\mathrm{buf}$ is given by

$$c_\mathrm{buf} = [\ce{HA}] + [\ce{A-}]\tag{19.3}$$

From dissociation constant definition we have

$$[\ce{HA}] = \frac{[\ce{H+}][\ce{A-}]}{K_\mathrm a}\tag{19.4}$$

But shouldn't

$$c_\mathrm{buf} = [\ce{HA}] + [\ce{A-}] + [\ce{H+}]?\tag{1}$$

The total concentration at equilibrium is

$$c(1 - \alpha) + 2c\alpha = c(1 + \alpha)\neq c,\tag{2}$$

hence the initial concentration of buffer is different from that at equilibrium.

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  • $\begingroup$ you asked a question, then you replied correctly. The quantity of matter is conserved. $\endgroup$ Commented Sep 4, 2015 at 18:55
  • $\begingroup$ I don't understand. Does that mean they have given wrong equation? I have proved that its different in the last line. $\endgroup$
    – Aditya Dev
    Commented Sep 4, 2015 at 19:15
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    $\begingroup$ At the equilibrium, [HA]=c(1−α) and [A-]=cα. The quantity of matter of the specie A is conserved. So, the total amount of all species having A is c. So, c=[HA]+[A-]=c(1−α)+cα $\endgroup$ Commented Sep 4, 2015 at 21:23
  • $\begingroup$ Using the given definition of total concentration of buffer makes sense because that value does not change when the acid dissociates. Your proposed definition would make everything very complicated. $\endgroup$
    – Karsten
    Commented Jun 9, 2021 at 15:35

1 Answer 1

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Initially in the solution the following equilibria exist

$$\ce{HA <=> H+ +A-}$$
and
$$\ce{H2O <=> H+ +OH-}$$

Let initial concentration of $\ce{HA}$ be $a_1$ and that of $\ce{A-}$ be $a_2$. Now to a litre of this buffer solution, let's say you have added $\mathrm dn$ moles of strong acid to it. The acid dissociation constant of $\ce{HA}$ be $K_a$ and the ionic product of water, $K_w$. By adding acid, you have disturbed the equilibrium, and from Le Chatelier's principle, both the reactions go backwards.

$$\ce{HA <<=> H+ + A- }\tag{1} \label{eqn:1}$$
$K_{eq}=K_a$ $$\ce{H2O <<=> H+ +OH-} \tag{2} \label{eqn:2}$$
$K_{eq}=K_w$

Let the new equilibrium concentrations of $\ce{HA},~\ce{A-},~\ce{H+},~\ce{OH-}$ be $a_1+\mathrm dx,~a_2-\mathrm dx,~\frac{K_a\cdot a_1}{a_2}+\mathrm dn-\mathrm dx-\mathrm dy,~\frac{K_w\cdot a_2}{K_a.a_1} - \mathrm dy$ respectively.

At equilibrium, for $\ref{eqn:1}$,

$$K_a = \frac{(\frac{K_a\cdot a_1}{a_2} +\mathrm dn-\mathrm dx-\mathrm dy)\cdot (a_2 - \mathrm dx)}{a_1+\mathrm dx} \tag{3} \label{eqn:3}$$

and for $\ref{eqn:2}$,

$$K_w = (\frac{K_a\cdot a_1}{a_2}+\mathrm dn-\mathrm dx-\mathrm dy)\cdot (\frac{K_w\cdot a_2}{K_a.a_1}-\mathrm dy) \tag{4} \label{eqn:4}$$

Dividing $\ref{eqn:3}$ by $\ref{eqn:4}$, we get

$$(K_a)\cdot (\frac{K_w\cdot a_2}{K_a\cdot a_1}-\mathrm dy)=(K_w)\cdot (\frac{a_2-\mathrm dx}{a_1+\mathrm dx})\\ K_w\cdot a_2+\frac{K_w\cdot a_2}{a_1}\cdot \mathrm dx-K_aa_1\mathrm dy-K_a\mathrm dx\mathrm dy=K_wa_2-K_w\mathrm dx$$

Neglecting the term $K_a\mathrm dx\mathrm dy$, we get

$$dx= \frac{K_a\cdot {a_1}^2}{K_w(a_1+a_2)}\cdot \mathrm dy$$

and also from $\ref{eqn:3}$

$$K_a\cdot (a_1+\mathrm dx)=(\frac{K_a\cdot a_1}{a_2}+\mathrm dn-\mathrm dx-\mathrm dy)\cdot (a_2-\mathrm dx)$$

Which on simplifying and neglecting terms of the type $\mathrm da\cdot \mathrm db$ will give,

$$\mathrm dn= (\frac{{K_a}^2\cdot {a_1}^2}{K_w\cdot {a_2}^2}+\frac{K_a\cdot {a_1}^2}{K_w\cdot (a_1+a_2)}+1)\cdot \mathrm dy \tag{5} \label{eqn:5}$$

By definition,

$\beta = \frac{\mathrm dn}{\mathrm{dpH}}$ and $\mathrm{pH}=-\log_{10} {[\ce{H+}]}$.

On differentiating this, we get

$$\mathrm{dpH} = \frac{-1}{[\ce{H+}]}\cdot \frac{1}{\log_e10}\cdot \mathrm d[\ce{H+}]$$

Substituting this in the definition of buffer capacity,

$$\beta = \frac{-\log_e10\cdot [\ce{H+}]\cdot \mathrm dn}{\mathrm d[\ce{H+}]} \tag{6} \label{eqn:6}$$

Here,

$$\mathrm d[\ce{H+}] = \mathrm dx+\mathrm dy-\mathrm dn = -\frac{{K_a}^2\cdot {a_1}^2}{{a_2^2}\cdot K_w}\cdot \mathrm dy$$

Substituting this expression of $\mathrm d[\ce{H+}]$ and $\mathrm dn$ from $\ref{eqn:5}$ in $\ref{eqn:6}$, we get,

$$\beta = \log_e10\cdot [\ce{H+}]\cdot \frac{(\frac{{K_a}^2\cdot {a_1}^2}{{a_2}^2\cdot K_w}+\frac{K_a\cdot {a_1^2}}{K_w\cdot (a_1 + a_2)} +1)}{\frac{{K_a}^2\cdot {a_1}^2}{{a_2}^2\cdot K_w}}\\ \beta = \log_e(10)[\ce{H+}](1 + \frac{K_w}{{[\ce{H+}]}^2} + \frac{{a_2}^2}{(a_1+a_2)\cdot K_a})\\ \beta = \log_e10( [\ce{H+}] + \frac{K_w}{[\ce{H+}]} + \frac{{a_2}^2\cdot [\ce{H+}]}{(a_1+a_2)\cdot K_a})$$

Substituting $[\ce{H+}]= \frac{K_a\cdot a_1}{a_2}$ in the third term, we get

$$\beta = \log_e10( [\ce{H+}] + \frac{K_w}{[\ce{H+}]} + \frac{a_1\cdot a_2}{(a_1+a_2)})$$

Multiplying numerator and denominator of the third term with $K_a$,

$$\beta = \log_e10( [\ce{H+}] + \frac{K_w}{[\ce{H+}]} + \frac{K_a\cdot a_1\cdot a_2}{K_a\cdot (a_1+a_2)})$$

Taking $a_2$ common from the denominator and cancelling the $a_2$ in the numerator and substitute $\frac{k_a\cdot a_1}{a_2}=[\ce{H+}]$ and multiplying numerator and denominator with $[\ce{H+}]+K_a$, we get

$$\beta = \log_e10([\ce{H+}] + \frac{K_w}{[\ce{H+}]} + \frac{(\frac{K_a\cdot a_1}{a_2})\cdot (K_aa_1+K_aa_2)}{{([\ce{H+}]+{K_a})}^2}$$

Taking $K_a$ out from the numerator and substituting $[\ce{H+}]=\frac{K_a\cdot a_1}{a_2}$, we get

$$\beta= \log_e10([\ce{H+}]+[\ce{OH-}]+ \frac{[\ce{H+}]K_a(a_1+a_2)}{([\ce{H+}]+K_a)^2})$$

So, in your expression, of course, $C_{\text{buf}}=a_1+a_2=[\ce{HA}]+[\ce{A-}]$ and not $[\ce{HA}]+[\ce{A-}]+[\ce{H+}]$

$$\beta= \log_e10([\ce{H+}]+[\ce{OH-}]+ \frac{[\ce{H+}]K_aC_{\text{buf}}}{([\ce{H+}]+K_a)^2})$$

You will get the same result if a small amount of base is added.

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    $\begingroup$ You should read Which symbols are written in roman (upright) font and which are italicized?. I have corrected it for now. And it is better to use $$...$$ (block mode) over $... $ (single line mode) when writing long block of equations. $\endgroup$ Commented Jun 10, 2021 at 4:35
  • $\begingroup$ @NisargBhavsar Thanks for the edit and I'll definitely look into it $\endgroup$
    – Adithya
    Commented Jun 10, 2021 at 6:34
  • $\begingroup$ Time flies. I asked this question like 5 years ago and I don't even understand what I even asked right now. $\endgroup$
    – Aditya Dev
    Commented Jun 17, 2021 at 0:17

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