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We were trying to dissolve a piece of metallic lead in concentrated nitric acid until we found out that concentrated nitric acid is not a suitable media, as long as it produces a layer of lead oxide which is harder to dissolve.

We tried then with nitric acid 1:4 in water and could notice a little advance in the digestion but it still looks like it is going to take a long time...

Does anyone have struggled with this before?

Edit: It dissolved overnight. Sorry for being that impatient and thank you for all the help.

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    $\begingroup$ Powder it, maybe? $\endgroup$ Commented Mar 9, 2022 at 23:44
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    $\begingroup$ How about hot nitric acid? $\endgroup$
    – Mithoron
    Commented Mar 10, 2022 at 0:26
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    $\begingroup$ Do you have an ultrasonic bath? $\endgroup$
    – Waylander
    Commented Mar 10, 2022 at 7:08
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    $\begingroup$ For your future reference look up en.wikipedia.org/wiki/Lead(II)_nitrate. In the Chemical Properties and Reactions section they show the solubility of lead nitrate in nitric acid solutions, which decreases strongly with acid concentration. It's due to the common ion effect, which is significant because the concentration of nitrate ions from your 1:4 diluted nitric acid solution is comparable with that of the saturated water solution of the lead salt. $\endgroup$ Commented Mar 10, 2022 at 13:44
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    $\begingroup$ You are right, thank you. I should have done some search first before just attempting to get it into solution by brute force. $\endgroup$
    – Cris
    Commented Mar 10, 2022 at 13:55

1 Answer 1

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Some ideas are given by Bell[1]. The author recommends:

Experiments in this laboratory have shown that mixtures of fluoroboric acid, hydrogen peroxide, and ethylenediaminetetraacetic acid (EDTA) rapidly dissolve lead alloys at room temperature. The addition of EDTA is necessary to prevent the formation of insoluble salts during the dissolution step.

Understanding, and optimizing, nitric acid

Nitric acid performs relatively poorly because the lead nitrate (not any oxide) produced by the reaction has more limited solubility in nitric acid solution than in plain water. This is due to the common ion effect, and also at high concentration to nitric acid being a poorer solvating agent for ions than plain water (as distinct from its power as a reactant).

It follows that to maximize the solubility the acid should indeed be diluted with water. Using lead nitrate solubility data from Ferris[2] and the stoichiometry of the reaction between lead and nitric acid, the salt solubility is limited by the acid if the initial acid (before it reacts) is 21-23 weight% $\ce{HNO3}$ or more, depending slightly on whether the acid is reduced to $\ce{NO}$ or $\ce{NO2}$. With a more dilute acid, including the 1:4 diluted mixture that was actually used, saturation is avoided and the reaction proceeds until either the metal or the acid is exhausted.

References

1. Harry F. Bell (1973). "Rapid dissolution technique for lead alloys". Anal. Chem., 45, 13, 2296–2297. https://pubs.acs.org/doi/10.1021/ac60335a027.

2. L. M. Ferris (1960). "Lead nitrate-nitric acid-water system". J. Chem. Eng. Data, 5(3), 242. https://pubs.acs.org/doi/10.1021/ac60335a027.

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