The Collector that is used for the alloy phase plays a large role in the quantitative determination of

PGEs. The most popular collectors are silver and lead or a combination of the two. In 1975, Steele
reported that 92 % of all platinum concentration determinations for the South African Ore Certification
program used lead as the collector in their fire assay (Steele et al., 1975). Lead combined with silver as a
fire assay collector has also been used for the isolation of platinum, palladium and rhodium (Beamish,
1966). Unfortunately neither of these collectors proved effective as an isolator for rhodium. Tin (Sn) has
also been used as a fire assay collector for PGE with disappointing results (Faye 1965). In 1992, Tuwati
used gold as a collector for the isolation of platinum, palladium and rhodium from autocatalyst (Tuwati,
1992). He reported a collection of 99+ % of the platinum and palladium and 99 % of the rhodium. A
disadvantage of his technique is the relative high cost of gold as a collector. In addition to the above
methods, fire-assaying procedures using nickel sulfide have been widely used (Robert, 1971). In 1987,
Date et al., also studied the use of nickel sulfide as a collector for PGE in geological samples prior to ICP-
MS analysis (Date, Davis, et Cheung, 1987). Keyworth (1982) described a detailed listing of cost, loss,
operating ranges, separational losses of PGEs while using various collectors. The nickel sulfide fire assay
pre-concentration technique for the determination of PGEs in used autocatalyst and other samples
followed by ICP-OES and AAS analysis is considered one of the most precise and accurate methods
available for PGE determinations.

The small amount of PGEs that stay in the slag during the nickel sulfide fusion step are analyzed through
a lead bead collection procedure and a final measurement is done by ICP. The results of the lead bead
analysis are then added to the nickel sulfide assay results.

Inco ltd Fire Assay (Nickel Sulfide Collection Method)

The nickel sulfide collection of the PGE was adapted from the method of Robert et al. (1971). Currently,
Inco Ltd. staff use this method for the determination of PGE in autocatalyst and other samples followed
by AA or ICP. This method was carried out as well in our present work for the comparison of accuracy
with our proposed method. The procedure involves the following steps:

1. The components of the fusion mixture (shown in Table A1) were added to a 40g clay crucible.

Table-A1 Fire assay flux for nickel sulfide collection.

Ingredient Weight (g)

Borax 60

Sodium Carbonate 30

Silica 15

Nickel 18

Sulfur Powder 9

2. A 0.1 Assay ton (2.9174g) of the autocatalyst sample was weighed out in a weighing dish, and
transferred to the loaded crucible.

3. The mixture was carefully stirred with a spatula until it was thoroughly mixed.

4. The crucible was placed in an electric furnace and heated at 980 C for 90 minutes.
5. After the fusion was complete, the crucible was removed from the furnace and the fusion melt was
quickly poured into a mold, covered with a heat resistant lid and allowed to cool down to room
temperature.

6. The nickel sulfide (-27g) button containing the PGEs was separated from the slag. The slag was saved
in the original pot and re-analyzed for any losses of PGEs in the NiS fusion step. This subsequent
analysis was carried out by a lead-collection analysis fire assay.

7. The button was transferred to a 1000 ml beaker, 600 ml of conc. HCl were added and the mixture left
overnight on a hot plate at low heat to dissolve the button. When the dissolution of the button was
complete, the beaker was removed from the heat and allowed to cool slightly.

8. 15 ml of tellurium tetrachloride (TeCl4) were added, and the mixture was boiled for 5 minutes. 40 ml
of stannous chloride (SnCl2) were added after allowing the mixture to cool slightly.

The solution was place back on the hot plate and boiled for another 10 minutes.

Note: The purpose of the addition of tellurium tetrachloride and stannous chloride was to ensure
complete removal of Pt, Pd, and Rh from solution.

9. The mixture was then filtered through a Whatman glass fibers filter grade F and the filtrate discarded.
The watch glass, beaker, and filter funnel were washed with 50 % HCl.

10. The filter containing the PGEs was transferred back into the original beaker, I2O ml of HCl and 40 ml
of HNO3 were added, and the mixture was boiled for 1 hour.

11. The solution was then filtered through a whatman glass microfiber filter paper and then the beaker
and filter holder were rinsed with 50 % HCl.

12. The filtrate was placed back on the hot plate, and heated to dryness over low heat on a padded hot
plate.

13. 25 ml of conc. HCl and 5 ml of conc. HNO3 were added to the residue, and the mixture was heated
gently until the PGEs were completely dissolved.

14. The solution was transferred to a 100 ml volumetric flask and diluted to the mark with deionized
water and mixed well. The solution was then analyzed for Pt, Pd, and Rh by ARL 34000 ICP.

15. The PGEs lost to the slag in the NiS fusion step were recovered through a Pd collection, cupellation
to 100 mg Pb bead, and digestion with aqua regia. Final measurement was done by ICP-OES.

Section 2. Ledoux Acid Dissolution/Fire Assay Method

The Ledoux method is a combination of acid dissolution and fire-assay. The method layout for this thesis
originates from a fax dating to April 19, 1989. The method can use either or both AAS or ICP or DCP. The
procedure involves the following steps:

1. Four portions of the sample (100 mesh) weighing between 8 and 15 gm are transferred to a 800 ml
beakers, The samples was weighed to the nearest 0.1 mg and dried at 125 C.
2. To the pellet samples in the 800 ml beaker, 35 ml H2SO4, 35 ml H3PO4, and 50 ml of water are added
and the solution is heated to a slight boil over one hour period when decomposition should be
completed.

3. To the monolith samples in 800 ml in Teflon beakers, add 50 ml of H2O, 75 ml of HF, and 15 ml of
H2SO4. Evaporates to fumes of H2SO4. To the salts in the 800 ml glass, and respective Teflon beakers,
add about 100 ml of water, about 100 ml of HCl and 50 ml of bromine water. Boil to a minimum of 1
hour to convert rhodium to the chloride form.

4. Dilute to 400 ml, add about 5 g of sodium thiosulfate, heat to boiling, and just keep at boiling point for
2 hours.

5. Allow to settle for minimum of 3 hours. Filter and wash thoroughly with cold 1% HCl.

6. Wash precipitate back into original 800 ml beaker, pour hot dilute (1:2) aqua regia through paper, boil
and filter into reserve filtrate from the previous step.

7. Any residue small in the case of pellet, larger in the case of monoliths is treated as follows:

A) Pellets: Fume paper with HNO3 and HClO4 to dryness. Treat with aqua regia and combine with the
main solutions.

B) Monolith: Ignite in a scorifier, scarify in presence of about 25 ml of Au and cupel. Dissolve aqua regia
and check on plasma or AAS for retained Pt. Pd and /or Rh.

8. Evaporate the aqua regia solution containing the bulk of Pt, Pd, and Rh, and transfer to 200 ml
volumetric flasks. Take from each flask a 15 ml aliquot with dry pipet and check the approximate Pt, Pd,
and the exact Rh content by AAS. Clean the pipet with water, and combine with the main solution.

9. Palladium present: Transfer to separatory funnels and extract the palladium by repeated treatments
with chloroform and sodium dimethyl glyoxime solutions.

10. Evaporate the chloroform phase solutions to dryness. Add small amounts of nitric and perchloric
acids and again evaporate to dryness. Dissolve in a few ml of aqua regia, transfer to 100 ml volumetric
flasks and determine Pd by AAS or DCP. Transfer the aqueous phase (Pd removed) to 600 ml beakers.

11. Evaporate to 100 ml, add 25 ml of nitric acid, 10 ml of perchloric acid and 5 ml sulfuric acid.
Evaporate to dryness. Evaporate twice to dryness, with the intermittent addition of small amounts of
HCl. Dissolve residue in 50 ml of 3 % HCl and transfer to volumentric flasks of proper size. (Maximum for
200 g, 10 mg of Pt).

12. Prepare standards by dissolving pure Pt, to cover the range of Pt determination, in aqua regia. Add
appropriate amounts of Rh chlorine solution nitric acid-free.

13. Dilute to approximately 80 % of the volume of the flasks with 30 % HCl. Add 30 ml. 28 % stannous
chloride in 1:1 HCl. Six millimeter of the SnCl2 solution of 200 ml.

14. Compare the Pt content of the samples and standards by differential spectrometry.

15. In the absence of Pd, omit the DMG chloroform extraction, but otherwise following the procedure as
written.