Samples Containing Iridium

General Information

Iridium (Ir) is the fourth of the six platinum group metals (PGMs –Ru, Os, Rh, Ir, Pd and Pt) to be addressed in this series. Iridium’s chemistry is similar to that of rhodium. Iridium’s presence in the earth’s crust is very low at ~ 10-6 g /kg. Ir in the earth’s crust along with Rh and Pt are of geochemical interest as indicators of meteorite impacts. Ir deposits are associated with Pt, and it is also found alloyed with Os osmiridium (syserkite) and iridiosmium (nevyanskite). Most of the world’s Ir comes from South Africa where ~ 75% of the world’s ~3 metric tons/year production occurs. Ir alloyed with Pt is used industrially to make electrodes, crucibles, electrical contacts, etc., as these alloys can withstand long periods of high current and temperature. For example, crucibles made from Pt/Ir alloys can withstand prolonged temperatures of 2000 ºC which is required for growing single crystal oxides. In the spectroscopy analytical laboratory Ir is alloyed with Pt to make inert corrosion resistant nebulizer capillaries. An alloy of 75% Pt and 25% Ir is not soluble in laboratory mineral acids including freshly prepared aqua regia. Interestingly, the old international meter bar is made of a Pt/Ir alloy.

Some Ir Chemistry – A Brief Summary

  • Name – Iridium comes from the Greek work iris (rainbow).
  • Oxidation States – 0, +1, +2, +3, +4, +5, +6
  • The most stable oxidation states are +3 and +4
  • Inorganic Ventures Ir CRMs are all in the +4 oxidation state.
  • CRMs manufactured by Inorganic Ventures that are in HCl contain Ir as the Ir(Cl)6-2 complex ion.
  • Reactions – The fixed alkali hydroxides or carbonates precipitate from boiling solutions of IrClor IrCl4 as dark blue Ir(OH)4, insoluble in all acids except HCl.  Potassium nitrite, added to hot solutions of iridium salts, gives first a yellow color and finally a yellow precipitate insoluble in H2O or acids. H2S reduces Ir+4 to Ir+3 and then precipitates Ir2S(brown) which is soluble in alkali sulfides. Sulfurous acid precipitates Irº (black) from hot solutions. Potassium and ammonium chloride form respectively the dark-colored, slightly soluble K2IrCl6 and (NH4)2IrCl6. Metallic Zn precipitates Irº from hot solutions. Formic acid effects the same result. (From: Qualitative Chemical Analysis by R.K. McAlpine and B.A. Soule, D. Van Norstrand Company, 1933.)
  • Metals – Freshly precipitated Ir° is soluble in aqua regia. Unfortunately, the ignited metal is insoluble in all acids. Pt/Ir alloys up to 10% Ir can be dissolved in aqua regia, however, very slowly. For higher Ir contents the metal is mixed with NaCl and heated to 800 ºC and Cl2 gas is passed over the mixture forming the double chloride salt which dissolves in water. If the Pt and Ir are alloyed (the Pb is added) with at least 10 times its weight with Pb and dissolved in HNO3 the Pb and Pt dissolve leaving insoluble Ir.
  • Oxides – Two oxides of Ir, which have been well identified, are Ir2O3 and IrO2.  These oxides are not soluble in acids.  See ref (1) below for methods.

The Handling and Use of Ir CRMs- A Summary

Location:  Group 9, Period 6
Atomic Weight:  192.22
Coordination Number:  6
Chemical Form in Solution:  IrCl6-2

Storage & Handling:  Keep tightly sealed when not in use. Store and use at 20 ± 4°C. Do not pipet from container. Do not return portions removed for pipetting to container.

Chemical Compatibility:  Soluble in HCl, HNO3, H2SO4, and HF aqueous matrices. May cause AgCl precipitation when mixed with Ag+. Stable with all other metals.

Stability:  2-100 ppb levels. 2-100 ppb levels stable for months in 1% HNO3 / LDPE container. 1-10,000 ppm solutions chemically stable for years in 10% HCl / LDPE container.

Ir Containing Samples (Preparation & Solution):  Metal (elevated temperature with aqua regia or HCl / Cl2 {gas} ); Ores (HF / H2SO4digestion followed by aqua regia digestion); Platinum scrap (aqua regia digestion).

Atomic Spectroscopic Information:  (red text indicates severe at similar concs.)

Technique / LineEstimated D.L.*OrderTypeInterferences

ICP-OES 224.268 nm

0.03 µg/mL



Cu, Nb, Hf

ICP-OES 212.681 nm

0.03 µg/mL



Ta, Yb, Au, V

ICP-OES 205.222 nm

0.06 µg/mL




ICP-MS 191 amu

2 ppt




*ICP-OES D.L.'s are given as radial / axial view

Sample Preparation Methods for the Platinum Group Metals and Gold Compatible with AAS, ICP-OES and ICP-MS Measurement

An excellent review paper (Balcerzak, 2002) that discusses sample preparation methods for the platinum group metals and gold (Au) is readily available1, and this review compares the following commonly used methods for these metals:

  1. Fire assay
  2. Wet chemical acid digestion
  3. Oxidizing fusion
  4. Chlorination

The reader is encouraged to consult this paper for detailed information on these sample preparation methods.

For general information on sampling and sub-sampling see:

1 Balcerzak, M. , ANALYTICAL SCIENCES, Vol. 18, July 2002, pp 737 -750 (PDF)