12/28/21, 11:27 AM Trace Analysis Guide

Trace Analysis Guide

Trace Analysis Guide: Part 11 By Paul Gaines, Ph.D.

Overview
A liquid that is atomized using a nebulizer is the most reliable and convenient form of sample introduction
to the inductively coupled plasma. If your sample is a liquid or soluble in a liquid then the sample
preparation is relatively simple. If the sample is not soluble in a solvent then sample preparation techniques
such as acid digestion, ashing, or fusion are required. The solvent used exclusively for the preparation
techniques to be discussed in this section is water.

Acid digestions have the advantage of retaining 'volatile' analytes (reflux condenser is needed for some
trace elements) and the disadvantage of being tedious when large sample sizes are required. They are ideal
if the sample size is < 1 gram. The acid that this guide will focus upon is nitric acid (HNO3). Nitric acid is
popular because of its chemical compatibility, oxidizing ability, availability, purity, and low cost.

Nitric Acid Digestions

Nitric acid* is used primarily in the preparation of inorganic sample types.++ It is a very useful component in
the destruction of organics but cannot by itself completely decompose organic matrices.

*All reference to HNO3 will mean 69% 'concentrated' nitric acid unless specified otherwise.

++The conventional meaning of inorganic is intended along with the presence of low molecular weight water

soluble organic cmpds. and organometallic cmpds. containing relatively small molecular weight organic
components.

The following is a summary of some common inorganic dissolutions using nitric acid:

Dilute 10 - 15 % aqueous dilution - Alkaline earth oxides, lanthanide oxides, actinide oxides, Sc2O3,
Y2O3, La2O3.
1:1 HNO3 + H2O - V2O5, Mn oxides, CuO, CdO, Hg oxides Tl oxides, Pb oxides, Bi oxides, Cu0, Zn0, Cd0,
Hg0, Pb0.
Concentrated (69%) HNO3 - Mn0, Fe0 (hot), Co0, Ag0, Pd0 (hot), Se0, As0, Bi0, Re0.
1:3 HNO3 + HCl - Pt0, Au0, steel, Fe/Ni alloys, Cu alloys, Cr/Ni steel.
1:1:1 HNO3 + HF + H2O - The metal and oxides of Ti, Zr, Hf, Nb, W, Sn, Al, Si, Ge, Sb, Te, As, Se, Mo and
numerous alloys and oxide mixtures containing one or more of these elements.

https://www.inorganicventures.com/trace-analysis-guide/acid-digestions-of-inorganic-samples 1/3
12/28/21, 11:27 AM Trace Analysis Guide

The only major group of elements not listed above are the alkaline earths, of which are all water soluble.

TIP: Our Interactive Periodic Table lists sample preparation techniques for over 70 elements of interest.

In the examples listed above nitric acid is acting:

as a strong acid where inorganic oxides are brought into solution...

     (1)  CaO + 2H3O+  ⇀  Ca+2 + 3H2O 

as an oxidizing agent / acid combo where zero valence inorganic metals and nonmetals are oxidized
and brought into solution...

     (2)  Feo + 3H3O+ + 3HNO3 (conc.)  ⇀  Fe+3 + 3NO2↑ (brown) + 6H2O

OR

     (3)  3Cu0 + 6H3O+ + 2HNO3 (dilute)  ⇀  2NO↑ (clear) + 3Cu+2 + 10H2O 

In addition, nitric acid does not form any insoluble compounds with the metals and non-metals listed. The
same cannot be said for sulfuric, hydrochloric, hydrofluoric, phosphoric, or perchloric acids.

Facts About Nitric Acid

The highest valence of nitrogen is +5. This is the valence of nitrogen in nitric acid. All three N-O bonds
are sp2 hybrid and the NO3- molecule is planar and symmetrical.

The oxidizing ability of nitric acid decreases (reduction potential decreases) as the concentration
decreases. Below 2M, the oxidizing ability is nearly eliminated.
Nitric acid undergoes both one and three electron changes. As illustrated above with reaction (2) the
one electron change is observed when concentrated. In comparison, the 3 electron change is observed
when dilute in reaction (3). The presence of brown fumes is indicative of reactions going by 1 electron.

     (4)  H3O+ + HNO3 + e-1  ⇀  NO2↑ (brown) + 2H2O : Concentrated

     (5)  3H3O+ + HNO3 + 3e-1  ⇀  NO↑ (clear) + 5H2O : Dilute
Nitrate is generally considered to be a 'poor ligand' in that it's coordination ability is not enough to keep
hydrolysis from occurring. This statement may be contradicted in certain inorganic text books.
The most common 'good ligands' used in combination with nitric acid are HCl, HF, and tartaric acid (for
Sb). If nitric acid was a better ligand, these additional acids would not be needed.
https://www.inorganicventures.com/trace-analysis-guide/acid-digestions-of-inorganic-samples 2/3
12/28/21, 11:27 AM Trace Analysis Guide

Concentrations of HNO3 between 65% and 69% are known as 'concentrated'; concentrations greater
than 69.2% are known as 'fuming nitric acid'.
100% nitric acid is light and heat sensitive and boils at 84 °C. 'Concentrated' nitric acid boils as an
azeotrope (with water at 69.2% HNO3) at a temperature of 121.8 °C. The distilled HNO3 (trace metals
grade) should be at the 69.2% concentration level.
Check with your manufacturer of doubly distilled nitric acid to determine if the container in which it is
packaged is nitric acid leached prior to use. In the case of Teflon containers, the container material is
generally assumed to be pure.
PTFE and PFA Teflon can be heated with concentrated nitric acid, even at high pressures or with
combinations such as nitric + HCl, nitric + HF, and nitric + H2O2.
Nitric acid is not a strong enough oxidizing agent by itself to convert organic molecules to CO2 and H2O
(completely oxidize).

Further Reading
Part 12: Acid Digestions of Organic Samples
Trace Analysis Guide: Table of Contents
More Guides and Papers

https://www.inorganicventures.com/trace-analysis-guide/acid-digestions-of-inorganic-samples 3/3