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Hg-Ir (Mercury-Iridium)

Article  in  Journal of Phase Equilibria · July 2003

DOI: 10.1361/105497103770330442

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Hg-Ir (Mercury-Iridium)
C. Guminski
Experimental information about the Hg-Ir system is
sparse but it is sufficient to sketch an assessed phase dia-
gram. [Moffatt] presented the low-temperature part of the
diagram at constrained pressure. In this evaluation we pre-
sent the phase relationships at 0.101 MPa in Fig. 1. Since
the melting point of Hg (−38.8290 °C) [ITS-1990] is not
measurably shifted by the presence of Ir, it may be con-
cluded that the solids are almost completely immiscible.
Virtually pure (Ir) is in equilibrium with virtually pure liq-
uid Hg up to the boiling point of Hg (356.623 °C) and
gaseous Hg is in equilibrium with almost pure Ir up to the
melting point of Ir (2447 °C) [Massalski2]. [Moffatt]’s ver-
sion of the diagram is similar to that shown in Fig. 1, except
that the liquid, instead of the gas, is present above the boil-
ing point of Hg. Hg may maintain as liquid up to its critical
point (1492 °C and 151 MPa) [1992Gum].
[1956Str] attempted to determine a solubility of Ir in
liquid Hg at room temperature by chemical analysis of fil-
trate of the saturated amalgam; its content in Hg was below
the analytical detection limit of 0.001 at.% Ir. [1973Jan]
performed similar experiments at 500 °C at a sensitivity
level of 10−5 at.% Ir, and also, no Ir was found in the filtrate
as a result of spectrophotometric analysis. [1989Gum] pre-
dicted the solubility at 25 °C based on a regular solution
model (1 × 10−26 at.% Ir) and the cellular model of
Fig. 1 Hg-Ir assessed phase diagram at 0.101 MPa
Journal of Phase Equilibria Vol. 24 No. 4 2003
Phase Diagram Evaluations: Section II
Miedema et al. [1983Nie] (2 × 10−9 at.% Ir). While the
predictions are disparate, both indicate values far below
detectability. Experimental corroboration comes from
[1964Rhy] who found no attack on Ir by liquid Hg after the
equilibration for 168 h at 550 °C and from [1987Kou], who
observed no detectable solubility of Ir in Hg during elec-
troanalytical measurements at room temperature.
No interaction between the metals was observed in x-ray
diffraction (XRD) studies of [1973Jan1] and [1981Sut], in
the corrosion investigations by [1964Rhy], thermogravim-
etry by [1995Fer, 2002Fer], scanning electron microscopy
[1995Fer, 1998Nol, 2002Fer], atomic force microscopy
[1998Nol], energy dispersive x-ray microanalysis [1995Fer,
2002Fer], x-ray photoelectronic spectroscopy of amalgam-
ated Ir as well as Ir-Pt surfaces by [1999Fer], nor in elec-
troanalytical experiments of Hg redox processes on Ir elec-
trodes by [1981Sut], [1986Kou], [1987Kou], [1998Nol],
[1999Fer], and [1999Fer]. The effect of incomplete removal
(∼95% efficiency) of electrodeposited Hg from Ir surface
observed by [2003Mil] seems to be rather related to an
interaction of Hg with Ir oxide than to any Hg-Ir interaction
with formation of an intermetallic compound or a concen-
trated solid solution of Hg in Ir. In an attempt to determine
Hg solubility in solid Ir, [1973Jan2] equilibrated Ir powder
with Hg in a quartz ampoule at 800 °C for 350 h. The lattice
373
 Section II: Phase Diagram Evaluations

Table 1 Crystal Structure and Lattice Parameter Data

Composition, Pearson Space Strukturbericht Lattice Parameters Temperature,

Phase at.% Ir Symbol Group Designation Prototype a, nm b, nm °C References

␣Hg 0 hR1 R3m A10 ␣Hg 0.3005 ␣ ⳱ 70.53° −48 [Massalski2]

␤Hg 0 tI2 I4/mmm … ␤Hg 0.3995 0.2825 −196 [Massalski2]
Ir 100 cF4 Fm3m A1 Cu 0.38392 … 25 [Massalski2]
Ir (a) 100 0.3837 … 800 [1973Jan2]
Ir (b) ∼100 0.3836 … 800 [1973Jan2]
(a) Before equilibration with Hg
(b) After equilibration with Hg

parameter of Ir decreased after the equilibration by 0.0001
nm, which is within precision of the XRD method of the
estimation. No detectable amounts of Hg may be soluble in
Ir. [1971Ale] measured electric resistance of solid Hg satu-
rated with Ir at −40 °C and found that the solubility of Ir is
lower than the detectivity limit of 10−4 at.% Ir.
Crystal structures and lattice parameter data of pure met-
als and (Ir) are listed in Table 1.
[1983Nie] predicted limiting enthalpies of solution of
both liquid metals: 34 kJ/mol for Ir in an infinite amount of
Hg and 39 kJ/mol for Hg in an infinite amount of Ir. These
values are relatively small compared to similar values for
other high-melting transition metals and Hg.
References
1956Str: J.F. Strachan and N.L. Harris: “The Attack of Unstressed
Metals by Liquid Hg,” J. Inst. Met., 1956-57, 85, pp. 17-24.
(Experimental)
1964Rhy: D.W. Rhys and E.G. Price: “Resistance of Ir and Ru to
Liquid Metal Attack,” Met. Ind., 1964, 105, pp. 243-47. (Ex-
perimental)
1971Ale: B.N. Aleksandrov and O.I. Lomonos: “Solubility of
Metals in Solid Hg,” Zh. Fiz. Khim., 1971, 45, pp. 3003-06 (in
Russian). (Experimental)
1973Jan1: G. Jangg and T. Doertbudak: “Investigations of the
Systems of Platinum Metals and Re With Hg,” Z. Metallk.,
1973, 64, pp. 715-19 (in German). (Experimental)
1973Jan2: G. Jangg and E. Lugscheider: “The Solubility of Hg in
Various Metals,” Monatsh. Chem., 1973, 104, pp. 1269-75 (in
German). (Experimental)
1981Sut: A.A.Sutyagina, T.M. Matveeva, and T.E. Umantseva:
“Investigation of Properties of Ir Electrode Poisoned With Hg in
H2SO4 Solution,” Elektrokhimiya, 1981, 17, pp. 916-19 (in Rus-
sian). (Experimental)
1983Nie: A.K. Niessen, F.R. deBoer, R. Boom, P.F. deChatel,
W.C.M. Mattens, and A.R. Miedema: “Model Predictions for
the Enthalpy of Formation of Transition Metal Alloys,” Cal-
phad, 1983, 7, pp. 51-70. (Theory)
1986Kou: S.P. Kounaves and J. Buffle: “Deposition and Stripping
Properties of Hg on Ir Electrodes,” J. Electrochem. Soc., 1986,
133, pp. 2495-98. (Experimental)
1987Kou: S.P. Kounaves and J. Buffle: “An Ir-based Hg-Film
Electrode,” J. Electroanal. Chem., 1987, 216, pp. 53-59. (Ex-
perimental)
1989Gum: C. Guminski: “Selected Properties of Simple Amal-
gams,” J. Mater. Sci., 1989, 24, pp. 2661-76. (Review)
1992Gum: C. Guminski: “The Hg (Mercury) System,” J. Phase
Equil., 1992, 13, pp. 657-62. (Review)
1995Fer: F.L. Fertonani, A.V. Benedetti, and M. Ionashiro: “Con-
tribution to the Study of the Reaction of Hg With Pt and a Pt-Ir
Alloy,” Thermochim. Acta, 1995, 265, pp. 151-61. (Experimen-
tal)
1998Nol: M.A. Nolan and S.P. Kounaves: “Effects of Hg Elec-
trodeposition on the Surface Degradation of Microlitographi-
cally Fabricated Ir Ultramicroelectrodes,” J. Electrochem. Soc.,
1998, 453, pp. 39-48. (Experimental)
1999Fer: F.L. Fertonani, A.V. Benedetti, J. Servat, J. Portillo, and
F. Sanz: “Electrodeposited Thin Hg-films on Pt-Ir Electrodes,”
Thin Solid Films, 1999, 349, pp. 147-54. (Experimental)
2002Fer: F.L. Fertonani, E. Milare, A.V. Benedetti, and M. Iona-
shiro: “Solid State Reactions of Hg With Pure Noble Metals:
Hg-Ir System,” J. Therm. Anal. Calor., 2002, 67, pp. 403-09.
(Experimental)
2003Mil: E. Milare, E.Y. Ionashiro, Y. Maniette, A.V. Benedetti,
and F.L. Fertonani: “The Influence of Metallic Oxides Formed
by Repetitive Cyclic Voltammetry or Controlled Potential in the
Reactivity of Ir/Hg System,” to be published in Electrochim.
Acta, 2003. (Experimental)

Hg-Ir evaluation contributed by C. Guminski, Department of Chemistry, University of Warsaw, Pasteura 1, 02093 Warszawa, Poland. Literature was
searched through 2001. This work was supported by ASM International. Dr. Guminski is the Alloy Phase Diagram Program Category Editor for binary
mercury alloys.

374 Journal of Phase Equilibria Vol. 24 No. 4 2003

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