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Consider an acidic solution with Hydrogen ion concentration, $\ce{[H+]}$ of $10^{-5}\:\mathrm{M}$. Since $\:\mathrm{pH} = -\log \ce{[H+]}$ the $\:\mathrm{pH}$ of solution is $5$. Suppose we dilute solution 10 times with water. Now, $\ce{[H+]}$ is $10^-6\:\mathrm{M}$ and $\:\mathrm{pH}$ is $6$. Further dilution should increase $\:\mathrm{pH}$ from $6$ to $7$ and then from $7$ to $8$ and so on. Can this go in for ever? Does this not imply that an acidic solution can be made basic/alkaline simply by adding water? But that doesn't happen? What prevents it?

Is there anyone already found answer for this problem or it is just an unsolved basic problem of Chemistry?

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2 Answers 2

up vote 10 down vote accepted

Water undergoes autoionization, i.e., it reacts as follows:

$$ \ce{H2O + H2O <=> H3O+ + OH-} $$

The equilibrium constant for this reaction at standard conditions is $K_w = [\ce{H3O+}][\ce{OH-}] \approx 1.0 \cdot 10^{-14}$. In pure water, $[\ce{H3O+}] = [\ce{OH-}]$, hence $[\ce{H3O+}] = \sqrt{K_w} \approx 1.0 \cdot 10^{-7}\ \textrm{M}$.

Suppose we dilute a solution with some initial concentration of $[\ce{H3O+}]_i = \frac{n_i}{V_i}$, where $n_i$ is the initial number of moles of $\ce{H3O+}$ and $V_i$ is the initial volume. If I now add a volume $\Delta V$ of pure water (which would contain $(1.0 \cdot 10^{-7}) \cdot \Delta V$ moles of $\ce{H3O+}$) the resulting final concentration can be crudely approximated as:

$$ [\ce{H3O+}]_f \approx \frac{n_i + (1.0 \cdot 10^{-7}) \cdot \Delta V}{V_i + \Delta V} $$

We can see what value this expression approaches as we make the solution more and more dilute by taking the limit as $\Delta V \to \infty$:

$$ \lim_{\Delta V \to \infty} \frac{n_i + (1.0 \cdot 10^{-7}) \cdot \Delta V}{V_i + \Delta V} = 1.0 \cdot 10^{-7} $$

Therefore, $[\ce{H3O+}]$ tends towards $1.0 \cdot 10^{-7}$ with further dilution, so $pH$ will approach a value of $7.0$.

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You forget that pure water already contains $\ce{H_3O^{+}}$ ($\ce{Kw}=\ce{[H_3O+][OH^{-}]}=14$,). If you have an acidic solution, you will be able to reach the neutral point ($\ce{pH} = 7$) after enough dilution, but it will never be alkaline. You can see this as similar to a limit or infinite sum $\lim_{x\rightarrow \infty } \frac{x}{x+1}=1$, but when you look at finite $x$ it will never actually be 1.

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