# NaHCO₃ + HNO₃ → NaNO₃ + H₂O + CO₂ … but something weird happens to me in practice

I put 98% white fuming nitric acid and then I pour some sodium bicarbonate expecting $\ce{NaNO3}$ being formed, I'm not really using much water because it will make evaporation takes ages, even so $\ce{NaHCO3}$ should give $\ce{NaNO3}$ when in contact with $\ce{HNO3}$ and it seems so, $\ce{CO2}$ is formed very quickly so I suppose the reaction is happening... and I can see those white crystals (as the solution is over-saturated of $\ce{NaNO3}$) I shake, shake and shake, and pour more Sodium bicarbonate tills $\ce{HNO3}$ gets a pH around 7 (usually a bit less like 5 or 2) when I notice that it doesn't want to react anymore, however, I try to add mol per mol.

I know there's some unreacted $\ce{HNO3}$ but it should decompose into $\ce{H2O} + \ce{NO2}$ so I put it to start drying in a hot plate, and then the solution becomes yellow (decomposing) it's suddenly brown... and then my "supposed" $\ce{NaNO3}$ is yellowish/pink... and I wonder that seems like a $\ce{NaNO3} + \ce{NaNO2}$ mix but it makes no much sense, I tried with $\ce{NaOH}$ instead $\ce{NaHCO3}$ and it's the same ending color; it's not working... what did I do wrong? how to do it properly?

• Both nitric acid and bicarbonat may contains slight inpurities. Yellowish-brown color is usual for iron (III) cation, – permeakra Sep 4 '13 at 5:29

Let's look at the equation first:

$$\ce{NaHCO3 + HNO3 \to NaNO3 + H2O + CO2}$$

In other words, when added in equal parts, you'd ideally expect the bicarbonate anion to be protonated by the nitric acid, forming weaker carbonic acid (which will dissociate into water and carbon dioxide under temperature or even agitation), and the remaining ions will pair up into sodium nitrate (soda niter) solution in water.

However, nitric acid is tricky, and doesn't like to act "ideally". First, you already know that nitric acid decomposes into nitrogen dioxide and water; this happens whether you want it to or not. Highly exothermic reactions (most nitric acid reactions, including this one, are so) ramp up this inevitable side reaction with the extra heat. This will reduce your yield, but I'd expect it to go the other way than you apparently did; 1:1 mixtures of acid and bicarbonate will inevitably leave unreacted bicarbonate in the solution (not acid) along with some dissolved nitrogen dioxide (aka nitrite hydrate, $\ce{H2NO3}$).

In addition, "pure" WFNA is defined as anywhere north of 98% nitric acid, so pretty much any quantity of nitric acid you could get is likely to have impurities. So, I think your first mistake was to keep adding sodium bicarbonate; if you mixed a mass of "pure" (>98%) WFNA (even if you made it from scratch) with equivalent molar weight of sodium bicarb, you'll have a small excess of bicarb due to impurities in the nitric acid (pre-existing and created), but the solution will still read acidic (because of dissolved $\ce{CO2}$ and $\ce{NO2}$) after you've added more bicarb than will dissolve in the solution.

Now, heating the equilibrium solution to obtain the dry solid salts will remove the water from the dissolved nitrogen dioxide, and it will start acting like the nitrite ion it is, reacting with any unreacted bicarbonate to form yellow sodium nitrite, water and more $\ce{CO2}$. This sounds like exactly what happened to you, resulting in a more yellowish solid than the pure white soda niter you were expecting.

If you're not careful with the heat while evaporating off the water, parts of the reaction, namely the precipitating solid collecting on the bottom of the flask, can be superheated beyond boiling, and reach the temperature at which both of the niter salts will decompose into sodium oxide and more oxides of nitrogen. This is typically accomplished only at temperatures in excess of those capable with the average benchtop rig, but it becomes more thermodynamically favorable in the presence of excess sodium (which you have in the sodium bicarbonate). I'm not saying this happened - it's more likely that the nitric acid decomposed more than you might have wanted - but it's a theoretical possibility.

• it makes sense... I will try to reduce the temperature and add excess of nitric acid instead trying to neutralize each other. and so hoping $\ce{CO2}$ will just leave as gas. – Felishia Sep 3 '13 at 23:58