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In the Laboratory

Analysis of Gold Ores by Fire Assay W

Kristy M. Blyth, David N. Phillips,* and Wilhelm van Bronswijk
Department of Applied Chemistry, Curtin University of Technology, P.O. Box U1987, Perth, Western Australia 6845;

A number of techniques have evolved over the years to so-called “gangue” of the ore to form a molten sodium boro-
analyze gold in gold-bearing ores. Aqua regia digestion fol- silicate glass called a “slag”.
lowed by solvent extraction and flame atomic absorption spec- The gold descends through the lower-viscosity slag and
trometry (FAAS) is used extensively as an assay method for is collected in the molten lead at the bottom of the crucible.
gold ores (1–5). However there has been at least one report The molten mass is poured into a mold and allowed to so-
of low assays with this method, where some of the gold was lidify. After the lead button is freed from the slag with a ham-
not extracted from the ore (6). Tewari and Gupta (7) de- mer, the lead is removed from the precious metals by a process
scribed a dissolution procedure for gold in geological samples known as cupelling. The lead is absorbed into a bone-ash
using an oxidative–complexation regime with potassium per- cupel leaving a small bead known as a prill. If a silver assay is
manganate and hydrochloric acid. After filtration, the required, the prill is first treated with concentrated nitric acid,
[AuCl4]− is treated with an excess of tin(II) chloride and the weight loss quantifying the silver content. The gold is
mercury(II) chloride to coprecipitate the gold in a mercury then dissolved in aqua regia and determined by FAAS.
amalgam, which is then dissolved in aqua regia and the gold
determined by FAAS. Hoang et al. (8), in a close examina- Types of Ore
tion of the work of Tewari and Gupta (7), reported a modi- There are many gold-bearing ores in Earth’s crust, rang-
fication of the method that produced significantly improved ing from acidic (high in silica) to basic (high in limestone)
gold recoveries by removing pitfalls arising from the gold– and from reducing (high in sulfides) to oxidizing (high in
mercury amalgam and aqua regia digestion stages. However, iron and manganese). The fire-assay technique thus gains in-
fire assay is the oldest method and remains the most reliable creased diversity since the percentages of the flux components
for the determination of gold in gold-bearing ores (9–12). It need to be varied for each type of ore. For example, a higher
is to this day the industry standard method and is also used proportion of sodium carbonate is used for acidic ores, while
for the analysis of silver- and platinum-group metals. With more borax is utilized for basic ores. Other interesting redox
the increase in the price of gold and the working of low-grade chemistry arises from the analysis of sulfide ores. The reduc-
ore deposits throughout the world, many samples reach the ing power of the sulfide ore eliminates the need for flour in
laboratory that have levels of gold in the 5–15 g ton᎑1 range. the flux, and the excess sulfide is overcome by the addition
At Curtin University of Technology we have developed a labo- of an oxidizing agent such as potassium nitrate.
ratory exercise for the analysis of gold in gold-bearing ores Some other fascinating chemistry in the fire-assay tech-
using the fire-assay technique. nique is associated with a process known as inquarting. It is
the separation or “parting” of silver from the gold in the prill,
Background where the separation is quantitative when the prill contains
25% gold and 75% silver. If necessary, sufficient silver, in
Experimental Overview the form of silver nitrate, must be added to the flux to achieve
The fire-assay exercise is carried out by students enrolled such quantification.
in our three-year undergraduate Applied Chemistry degree
course. It forms part of the third-year inorganic chemistry Experiment
laboratory program that is applied in nature and from which
other exercises have been previously reported (13, 14). There The students are given a standard-analyzed sample of
are major benefits that may be derived by incorporating a gold ore assaying 49 ppm. It is a sulfide ore but, by design,
fire-assay exercise in such a course. This method of analysis this information is not given to the students. We do not re-
not only provides students with an introduction to the tech- quire the students to sample their own ore, as the principles
nique of fire assay, but also covers some very interesting acid- of sampling and associate statistics are dealt with as previ-
base and redox chemistry. ously described (13). Each student uses the same flux for-
The assay fusion involves firing the gold ore with a flux mulation and mass of silver nitrate to ensure uniformity of
mixture at 1150 ⬚C. The flux mixture contains lead(II) ox- results throughout the class. The only variables are the masses
ide and flour, which may be considered to be the redox re- of flour or nitre1 that we assign to each student that, by de-
agents. The other components are silica, sodium carbonate, sign, leads to a range of gold analysis data from the total class
and borax, which are the acid–base reagents. The flour, a cohort.2
cheap source of carbon, reduces the lead(II) oxide to form Two laboratory periods, total of 8 hours, are devoted to
molten lead at that temperature: the exercise. In the first week, the students carry out the as-
say fusion and the separation of the lead button from the
PbO + C → Pb + CO slag. The cupelling, the preparation of the working standards
from a 1000 ppm gold standard, and the FAAS determina-
The silica, sodium carbonate, and borax combine with the tion of gold are carried out in the second week.

1780 Journal of Chemical Education • Vol. 81 No. 12 December 2004 •

In the Laboratory

Table 1. Gold Assay as a Function Typical Student Data for the Exercise
of Flour and Nitre Mass Representative results obtained by students over a five-
Mass of Flour/g Mass of Nitre/g Gold Assay (ppm) year period are shown in Table 1. The data show that addi-
1 0 31 tion of 4 g of nitre to the flux mixture leads to the accurate
2 0 31 result for this ore. The oxidizing capacity of this mass of nitre
3 0 29
leaves sufficient sulfide ore to reduce the appropriate quan-
tity of lead(II) oxide to form the correct size lead button.
4 0 31
5 0 33 Report
0 1 32 In their final reports, students use the class averages re-
0 2 35 ported on the posters for each addition of flour or nitre. They
0 3 43 may then conclude that a sulfide ore is being utilized and
0 4 49 how the quantity of flour or nitre is affecting the size of the
0 5 47 lead button and thus the accuracy of the gold assay.
NOTE: Gold in the sample assay is 49 ppm. All values are ± 10% RSD. Postlaboratory Questions
As part of the report, we also require that postlabora-
tory questions be completed to ensure the student achieves
the maximum benefit from the exercise.
Equipment and Chemicals • What problems can you envisage with the sampling
of gold-bearing ores?
The only equipment necessary to carry out the fusion
and cupelling is a 1200 ⬚C kiln and a 1000 ⬚C muffle fur- • What ore types may cause problems in the fire assay
nace. The gold ores, flux, crucibles, and cupels are commer- technique and how are they overcome?
cially available and not expensive (15). Crucibles (U.S. $1) • Briefly discuss other methods for the analysis of gold
may be reused, cupels are U.S. $0.20 each, thus the com- in gold-bearing ores.
bined cost of the consumables of flux, gold ore, silver nitrate
and gold standard approximate to U.S. $1.50 per student.
Hazards This experiment achieves many goals. The students work
with a real sample, a gold-bearing ore. Fire-assay technique
Proper attention and caution should be applied when is a very worthwhile quantitative analytical technique to in-
handling the concentrated acids. Nitric acid is a strong oxi- troduce to students. It covers interesting theory including
dizing agent, avoid contact with organic and combustible acid–base and redox chemistry and other concepts such as
materials. It is corrosive to the eyes and skin and can cause inquarting and cupelling. Pooling the class data allows the
severe burns. Avoid inhaling the vapor. Hydrochloric acid is students to write a substantial report describing the role of
corrosive to the eyes and skin and will cause irritation to the each component in the assay mixture and identify the type
skin. Avoid inhaling the vapor. Eye protection should be used of ore being analyzed.
at all times. A face mask and heat-resistant gloves should be
used when handling the crucibles in the kiln and mechani- WSupplemental
cally removing the glass from the lead button. The kiln and Material
muffle furnace should be placed in a fumehood so that any Instructions for students and notes for the instructor are
toxic vapors are taken away. Acetylene used in the FAAS is available in this issue of JCE Online.
highly flammable. The protective glass should always be in
place in front of the burner to prevent contact with the flame.
The MSDS sheets must be consulted for each chemical prior Notes
to its handling. 1. Nitre is another name for potassium nitrate.
2. An oxidizing or acidic ore could be substituted for the sul-
Results and Discussion fide ore used in our exercise, where only the mass of flour would
Prelaboratory Questions be used as the class variable since there is no reason to add nitre.
A series of questions are required to be completed prior
to the commencement of the laboratory to ensure the stu- Literature Cited
dents are well prepared for the exercise. 1. Strong, M. B.; Murray-Smith, R. Talanta 1974, 21, 1253.
• Outline the fire-assay process, paying particular detail 2. Gowing, C. J. B.; Potts, P. J. The Analyst 1991, 116, 773.
to the purpose of each step. 3. Beevers, J. R. Econ. Geol. 1967, 62, 426.
4. Das, B. C.; Siefken, T. C. Proceedings 12th Royal Australian
• Define inquarting and discuss its purpose.
Chemical Institute Analytical Division Conference; Perth, Aus-
• Explain the roles of the concentrated acids in the dis- tralia, 1993; Disc 6, Paper 44.
solution of the prill. 5. Rivoldini, A; Haile, T. Atom. Spectrosc. 1989, 10, 89. • Vol. 81 No. 12 December 2004 • Journal of Chemical Education 1781

In the Laboratory

6. Hall, G. E. M.; Valve, J. E.; Welland, F. F. J. Geochem. Explor. 11. Bugbee, E. E. A Textbook of Fire Assaying, 3rd ed.; Wiley: New
1989, 34, 157. York, 1948.
7. Tewari, R. K.; Gupta, J. R. Atom. Spectrosc. 1995, 16, 90. 12. Van Loon, J. C. Pure Appl. Chem. 1977, 49, 1495.
8. Hoang, T. A.; Mullings, L. R.; Phillips, D. N.; Sills, I. D. Atom. 13. Dunn, J. G.; Phillips, D. N.; Van Bronswijk, W. J. Chem. Educ.
Spectrosc. 1998, 19, 10. 1997, 74, 1188–1190.
9. Fulton, C. H.; Sharwood, W. J. A Manual of Fire Assaying; 14. Dunn, J. G.; Phillips, D. N.; Van Bronswijk, W. J. Chem. Educ.
McGraw-Hill Book Company Inc.: New York, 1929. 1997, 74, 1186–1187.
10. Shepard, O. C.; Dietrich, F. W. Fire Assaying; McGraw-Hill 15. Mathews Industrial Products, Osborne Park, Western Austra-
Book Company Inc.: New York, 1940. lia. (accessed Sep 2004).

1782 Journal of Chemical Education • Vol. 81 No. 12 December 2004 •