The determination of plathum, palladium and rhodium in autocatalyst.

An
exploration of sample preparation techniques for the rapid sequential multi-
elementai ICP-MS analysis

br
Mark Payette

Submitted to tbe Department of Cbemishy and Biochcmisty

in partial fiifilment of the requirements for the degree
or Master of Science in Chemistry

Laurentian University
Sudbury, Ont.
lune, 1997

O Mark Payeîte, June, 1997

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 The project was to d m l o p a f
a and irisxpaisive mabod to eil'ièctively d e t h e
the concentration of platinum, pailadiwn and rbodium in new and used crushed automob'ie
catalytic converters. INCO Ltd., Sudbury Division, Copper Clift: Chrimio. is the iargest
North American autocatalyst r e q d a . The prias paid for the used cataiyst units depend
on the content of the platinum group eiements (PGEs). The buyer's r e a h are compand
with the sdlers results (Ledoux Co.) and if necessary, the resuits obtawd by a referee
laboratory. Enoneous r d t s can becorne a t n w l y costly for the company and therefore
the detennination of platinun, palladium, and rhodium concentration in autocatalyst is of

PreKmly INCO Ltd., Sudbury h i s i o n uses a nickel d d e preconcentration of

the PGEs followed by tellurium coprecipitation. Oace the telluriurn coprecipitate is
dissolved, the samples are thm anaiyzed on both en inductively couple plrisma optical
emission spectrometer (ICP-OES) and an atomic absorption spectrometer (AAS). The
results reported are f?om duplicated aoaiysis which are monitored by the use of sample of
a Certified Reference MaterÎal (NIST 2556 and 2557).

Fue assay preconcentration is a very effective method of removing the PGEs h m

the interferhg mat* that may affect the ICP-OES and AAS r d t s . Unfortunately, tthis
technique requires a dedicated analyst about 38 man hours to perform a single analysis
fiom stm to finish. Thaefore other fmer, and e q d y precise and accurate methods are
king explored. Sincc the ma& of dissolved autocatdyst affects the ICPSES and AAS
results, it was decideci to try the inductively coupleci plasma mass spectrometcy (IB-MS).
With this instrument, ma& affects are minimized and possie interferences can be
prediaed prior to sample anaiysis. This instrument aiso offirs the possibüity of paforming
a fm semiquantitative d y s i s on the sample which wül S o m the d y s t of possible
interferences. Since mat* interferences are no longer of great SiBaificance, samp1e
preparation techniques other than f ~ e a s s have
~ y bem învestigated in this snidy, including
acid dissolution, microwaveasisteddigestion and alkali fùsion.
 Of the three methods listed above, aikali fusion wu the only method that muid
effectively dissolve the supponiag autocatalyst matrix. As a r d t , the extraction of
platinum, palladium, and rhodium was IarBJy incteased (-100 % for aii PGEs) as
cornparrd to the d y t i c a i results nom both &d dissolution and microwaveassisted
digestion. On the other b d , acid dissolution and microwaveassisted digestion were able
to effectively extract platinum and pailaâiwn (> 98%) but d d wt be used to extract
rhodium (- gû?!). It is belîeved that rhodium f o m an undissolvaô1e oxide with the d d
dissolution and microwave-assisted digestion sample preparation techniques thus affecting
the analytical detemination of the spscies. Using a correction fiutor for the rhodnim
element could e m e the use of the acîd dissolution and rnicrowaveassisted digestion
techniques thus providing for a much cleaner dissolved sample for ICP-MSandysis.
 Acknowledgments

There have been a host of individuals who have been essential to the completion of
this research project and to each ofyou 1am t d y tlilinknil for your patience, kindness and
helpfilness.

To begin with I wouid like to thank Inco Limiteci for pamitting me to use th&
facilities for my research. Without such support many snidents would not have the
opportunity to do graduate research degnes. 1 speak for al1 those students who in some
way have been touched by the kindness of Iaco Limited and other companies like Inco
Ltd..

1 would also like to thank Zbig Waszczylo for his guidance and profound
knowledge of chemistry, Dave Maskery for bis insight and impeccable memory, Phil
Gougeon for his extra tirne, Carmen for his ICP analysis, Dennis and John for their insight,
and al1 those who have directly or indirectly s i e d my grad studies. There are also many
other individuais h m hco Ltd.Central Process Technology Laboratory that L would like
to thank. For those aot listed here, and you know who you are, 1 am very much indebted
to you and 1thank you from the bottom of my heart.

Lastly I would like to thPnk Dr. J. Bo&, Dr. N. BeIzüe, and Dr. F. Smith for
accepting me as a graduate student, and aiso ali Laurentian Chemistry Faculty for allowing
me to pursue my cûeam.

Mark Payette
Acknowledgments

Table of contents

Table of Figures

Table of Tables

Chapter 1 Introdudion
1.1 The history, occurrence and importance of platinum group
elements

1.2 Autocatalyst composition and chmcterization

1.3 Two-way and three-way catalytic systems

1.4 Analytical methods for the determination of the PGE

1.4.1 The fire Assay pre-concentration method

1.4.2 Acid dissolution techniques on used autocatalyst

1 -4.3 The microwave assisted dissolution technique and

autocatalyst samples

i .4.4 The alkaline fusion techaique for used autocatalyst

1.5 Analytical methods for PGE determinationin catalytic

converters

1.5.1 Introduction

1-5.2 Spectrophotorneük (Colorimetric) methods

1.5-3 GravUnetrîc analysis

1.5.4 X-Ray fluorescence @RF) spectroscopy

 1.5.5 Neutron activation anaiysis (NU) 20

1 -5.6 Atomic absorption spectroscopy (AU) 22

1.5.7 Emission speztroscopy (ICP-OES) 24

1.5.8 Inductively coupled plasma mass spectroscopy (ICP-MS) 25

1.6 Purpose and scope of this project 27

Chapter 2 Experîmental Procedures for Autocatalyst Quantification

2.1 Sample pre-treatment

2.1.1 Sample preparation

2.1.2 Sarnple calcination

2.1.3 Sample weighing

2.2 Test Method #1 :Acid dissolution method prior to ICP-MSanalysis

2.3 Test Method #2 :Microwave-assisteci dissolution

2.4 Test Method #3 :Zirconium fusion of autocatalyst samples

2.5 Final sarnple preparation step prior to ICP-MS utilizing isotope dilution
and interna1 standard techniques

2.6 ICP-MSanalysis (Optional Parameters)

2.7 instrumental caiibration and interkence removal

2.8 Selection of intemal standard

2.9 Isotope preparation

Chapter 3 Results and Discussion

3.1 Assessrnent o f ma& interferences

3.2 Test Method #1 :Acid dissolution of autocatalyst ssmpls

3.2.1 Introduction
3.2.2 Autocatalyst type affects on acid dissoiution

3.2.4 The effect ofleaching time in open beaker digestions

3.2.5 Studying the various acid cornbitions

3.3 Test Method $2 :Microwave-assisteddigestion of

autocatdyst samples

3.3.1 Introduction

3.3.2 Effect ofvarying the microwave digestion time

3.3.3 Effect of the addition of HF to the microwave samples

3.4 Test Method #3 : Sodium peroxide fusion of samples

3 -4.1 Introduction

3 -4.2 Problems arising from alkali ma& composition

3 -4.3 Problems due to interna1 standard selection

3 -4.4 Sample drying prior to dissolution

3 -4.5 Effects of sample Ne and qumtity offlux

3.4.6 Automated fluxing

3.5 Sample fision rmlts and discussion

3 .S. 1 Test rnethod #3A :Discussion of remlts ftom mass match4

internai standards.

vii
3 .S.2 Test method 3B: Discussion on nailts &om isotope diiution
internai standards

Chapter 4 Conclusion

References

Appendut A Detailed üst of methods and their steps

Appendix B Asset Fies for ICP-MS analysis

Appendk C Seaii-quantitative analysis r d t s of Autocatalyst

 Table of Figures

Figure 1.1 Dia- of the two types ofautomobile catalytic converters.

The fimt (top picture) is the pellet type catalytic converter while
the second (bottom pichue) is the monolithic type cataiytic
converter.

Figure 1.2 Flow-Chart illustrating the recychg pathway of new and used
catalytic convertas.

Figure 3.1 The effect of eutocatalyst type on the extracfion of PGEs in new
and spent catalyst ushg an aqua regia dissolution to sample dryneu.

Figure 3.2 The percent extraction of PGEs in aushed autocatalyst (NET 2557)
and using aqua regi'a over a 4 hour period.

Figure 3.3 PGE recoveries from a variety of acid combinations in open-beaker

digestions of MST 2557 (Honeycomb).

Figure 3.4 Calcination r d t s from LECO and water analysis of NIST 2557
(honeycomb) autocatalyst.

Figure 3.5 Calcination nsults from LECO and water analysis of NIST 2556
(Pellet) autocatalyst.

Figure 3.6 Effea ofvarying sample weight on PGE extraction on dned

autocataiyst samples(2 Hours @ 500°C) (NIST 2556 Pellet)

Figure 3.7 Effect ofvarying sample weight on PGE d o n on dried

autocatalyst sarnples(2 H o m @ 5ûû°C) (NIST 2556 Honeycomb)

Figure 3.8 E f f i of varyiag flux weight on PGE d o n on dried autocatalyst 80

samples(2 Hours @ 50°C) (NiST 2556 Peliet)

Figure 3.9 Effect of varying flux weight on PGE d o n on dried autocatalyst 81

samples(2 Hours @ 500°C) (NIST2557 Honeycomb)
 Table of Tables

Table 1.1 Platinun metals and their neighbors in the periodic table
Table 1.2 Pirysical properties of the platiaum group elements.

Table 1.3 The typical content of autocatalyst Cm Mg).

Table 1.4 Matrix composition (non-certified results) as reported by National

Institute of Standards and Technology În Gaithersbug, MD (1993)

Table 2.1 Operathg conditions for the microwave digestion of a

-O. 1O gm catalyst ample.

Table 2.2 Operational parameters used on ICP-MSfor the anaiysis of

sodium peroxide fiision samples

Table 2.3 Spectral removal of possible Merences fiom Cu, Y, Sr,

and Pb.

Table 2.4 Relative abundance of natural isotopes used in this project.

Table 3.1 The percent extraction of PGEs in crushed autocatalyst (NET 2557)
and using aqua regia over a 4 hour period.

Table 3.2 Efféct of varying the microwave digestion time on SRM 2556 (Pellet)
and SRM 2557 (honeycomb) while digesting with aqua regia and HF.
Table 3.3 Effect of adding HF to the microwave digestionfor samples of
SRM 2556 (pellet) and SRM 2557 (honeycomb)

Table 3 -4 Perceni difference for MST 2556 somples dissohred using

microwave dissolutionand not treated with HF,

Table 3.5 Percent Werence for NIST 2556 samples disrolved using
microwave dissolutiontreated with HF.
Table 3.6 Percent differeuce for MST 2557 samples dissolvecl
using microwave dissolution and not a a e d with HF.

Table 3.7 Percent Werence for MST 2557 saxnples dissolved

ushg microwave dissolution treated with HF.

Table 3.8 Repeatability ofmicrowave resutts for MST 2556 and 2557 samples
wiîhout HF.

Table 3.9 Repeatability of microwave redts for MST 2556 and 2557 samples
with HF.

Table 3.10 Cornparison of ICP-MSnsults validating the addition of 2 mL of

concentrated HCl to the aspirated sample to help improve the
accufacy ofPGE determination and remove the bias.

Table 3.1 1 Percent merence of ICP-MSresults using Ntheniurnand thallium

intemal standards.

Table 3.12 Precision of ICP-MSresults using nithenium and thallium intemal

standards.

Table 3.13 Percent difference of ICP-MSresults using indium and indium

intemal standards.
Table 3.14 Precision of ICP-MSm u h s ushgiridium and indaun intanal
standards.

Table 3.15 Wata concentration of previoudy dned and d y z e d a u t d f i c

samples.

Table 3.16 ICP-MSresults fiom wet and dried NIST samples

Table 3.17 Relative error involved with hand &ion ofstandard

reference materials

Table 3.18 Percent Ilifference involved with the automatic fision of

standard rderence rnatezials

Table 3.19 Repeatabiliîy associated with hand fusion of autocatalyst

Table 3.20 Repeatabüity associated with the automatic fusion of autocataiyst

Table 3.21 ICP-MSresults for Pt determination compared with nickel sulfide

fire-assay and phosphoric acidffire assay.

Table 3.22 ICP-MSresults for Pd d e t e m i d o n compand with the nickel alfide 91

fire-assay results and the phosphoric acidlfire-assay results.

Table 3.23 ICP-MSresults for Rh detemûnation compared to the nickel sulfide

fie-assay results and the phosphoric acid/fire-assay results.

Table 3.24 Percent difference of ICP-MSresults using ptlggand ~ disotopes

' ~
and indium intemai standards

Table 3.25 Precision of ICP-MSresults using and ~ d ' "isotopes and

indium internai standards.
 Chapter 1Introduction
1.1 THE HISTORY, OCCURRENCE AM)IMPORTANCE OF PLATINUM GROUP
ELEMENTS

The platinum group elanents (PGE) wasi*st of platinuni, palladium, rhodium,

iridium, osmium, and mthenium and of these metals generdy occut together in nature
(Vines, 1941). They are best known for their s p d c traits. Generally al1 PGE elements
are very rare, heavy, white to grayish-white in color, highly resistant to corrosion, and
bave high melting temperatures (Bugbee, 1981).

The first known people to recognize platinum as a separate elernent were the Re-
Columbian Indians of Enrador who worked the metai into most of their native jewelry.
The £ k treference to the metal was in a commentary by Julius Caesar Scaliger published
in 1557 after sending a sample to Spain with a letter saying that the metal wouid not melt
by fire or by any Spanish art known (MacDonald and Hunt, 1982). It was not until 1735
that the alluvial platinum h m Spanish New Granada (now Columbia) was regularly
coileaed and sent to Europe for refhing and fabrication (MacDonald and Hunt, 1982).

The next piatinum deposit to corne into production was in the Ural mountains in
Northern Russia in 1824. This platinum was to be the first water-borne grains of platinum
found to be interlaced with a gold deposits. At the the, the Ural mountains were rnined
for gold but at a later date platinum was aiso extmcted. Unfortunately, the Russian
revolution intemipted the much d e d platinwn supply. As a r d t of the Russian
revohrtion, other platinum containhg ore bodies were required to Satie the growing
demand for the PGE metals. Swn after, pktinum was found by Merensky in South A f b ,
in what is now named the Merensky r d This new deposit helped to bll the plaîinum
demand. In 1930, Canada d m joined in the -011 and rehhg of platinum. This
platinum was a byproduct of the copper-nickeI'deposits found in the Sudbury district of
Canada and it was mined and r&ed by Inco Limited and Falconbridge Limited. To this
date, oniy Canada, Russia, South Afnca and Cohnnbia refbe and seif platinum metals.

The piatinum m a s include the elements in groups 8,9, and 10 of the 2d and îd
transition periods. Their position within the paiodic table as well as th& local neighbors
can be seen in Table 1.1 (Lide, 1991). Some of the reiated physicai properties to the POE
metals are üsted in Table 1.2 (Cabri, 1981).

The industrial utüuetion of the platinum metais is continually expanding which

increases the demand for the already scarce metals (Cowley and Matthey, 1996). Thy an
mostly used in the automobile, petroieum, medical, and chemicai industries but as well
have many rninor industriai uses. The largest danand for plaîinum, paîldium md rhodium
is in the automobile industry (Cowley and Matthey, 1996). These three met& are used in
the automobile catalyst convaters for the conversion of toxic exhaust gases f?om
automobiles into non-poUuting gases.
Table 1.1 PIatinum metals and theu neigbbors in the periodic table

Group 6 Group 7 Group 11

Atomic Number 24 25

Elernent Cr Mn
Atomic Weight 52.0 54.9

Atomic Nwnber 42 43

Element Mo Tc
Atomic Weight 95.9 98.9

Atornic Number 74 75

Element W Re

Atomic Weight 183.8 186.2

 Table 1.2 Physical prope!rties of the platinun group elements.
. Rn Rb B!
1

Latrice stnicnire' HCP FCC FCC HCP FCC FCC

Mclting point, OC 2334 1%7 1555 3030 2454 1768.4
I

Boiling point, OC 3900 3727 3140 5027 4130 3827

First ionization potemiai, ev 7,364 7.46 8.33 8.7 9 8

L

Dcnsity a i 20°C, ~ g m . ~W* 3 12.2 12.4 12.0 22.5 22.4 21.45

1

Specitïc heat ai O°C, JKS'F' 230.5 26.4 244.3 129.3 128.4 131.2
1

Resistivity microhman 7.60 4.51 10.5 9.50 3.30 10.6

I

Hardness, anneaiecl, VHN 200-350 100-102 404~ 300670 2001210 -2

C d n t radius, A 1.241 1.247 1.278

Atomicradius,A(12-foldCoordinotion) 1336 1.342 1.373

Modulus of elanicity in tension, lcNms* lad 416 3 16 117

I

Tcosile men@, annealeû, kNmm2*

10-~ 4% 688 172
L

Note:

a) HCP = hexagonal cl&-packed

FCC = fii-tered cubic
1.2 AUTOCATALYST
COMPOSIT~ONAND CWRACTEREATION

Automobile cataiysts are essdally comprised of a d b t o r y olride canier on

which two or more pncious metais are dispersed in very low concentrations. T w o types
of carriers (or substrates) are wmmonly used. The monoiithic (or honeycomb) type whose
body comprises cordierite (2Mg0.2A12a.SSi&) with a su& coating (1% by weight
of cordierite) of predorninantly y-Ai& to provide a hi@ mufiace area film on which the
PGE is dispersed. The bead type catalyst is comprised of individual W s (either 3.2 mm
spheres or 3.2mm x 6.3mm cylinders) made of y-Al2@ (Mîshra, 1993 ). The PGE loading
and weight of autocatdyst is dependent on the size and make ofthe automobile. nie ratio
of Pt, Pd, and Rh also varies widely. Typicaiiy the content of the POE is shown in Table
1.3 (Mishra, 1993 ).

Table 1.3 The typical content of autocatalyst (in pg/g).

Bead (2-Way) 350 150 -

Bead (3-Way) 850 300 60
Honeycomb (2-Way) 900 300 -
Honeycomb (3-Way) 1100 300 100

The catalyst wiil sometimes contain other proprietary components such as nickel
oxide (NiO) and cerium oxide (CeO) to help stabilkhg the bigh surdice area of Aiz03.
The spent autocataîyst also contciins various types of impurities. Lead, Manganese,
Carbon, Sulfiir and Phosphonis are picked up Born p w h e and oil additives. Süica, bon,
and Chromium are picked up h m the d d g operation. The pcesence of these
elements mua be taken into rccount when devishg anaiytical rnethods since they wül play
a large role in the deteInhaîion of the PGE dements. Table 1.4 below üsts the non-
certifieci results ofthe m a t x composition of both standard derence rnatds (SRMs). It
is estimateci that in 1985.50 percent ofdl catalytc convertersw a e recycled.

Table 1.4 MatrUt composition (non-certified results) as reportai by National Iristinite of

Standards and Technology in Gaithersburg, MD (1993)

Element Concentration, Method

wt % (mgKgx lo4) of analysis
SRM 2556 SRM 2557
(Pellet) (Honeycomb)

AIuminum (Al) XRF, INAq ICP-MS

Barium (Ba) XRF, ICP-MS
Calcium (Ca) XRF, ICP-MS
Cenum (Ce) XRF, INAq ICP-MS
Iron (Fe) XRF, INAA, ICP-MS
Lanthanum (La) XRIF, INAq ICP-MS
Magnesium (Mg) ??
Nickel (Ni) XIRF
Silicon (Si) XRF, ICP-MS
Element Concentration, m f l g Method of Aaalysis

Barium (Ba) 100 NIA XRF, ICP-MS

Cadmium (Cd) N/A 44 XRF
Zinc (Zn) 600 IO00 ;WF, INAq ICP-MS
Zirconium (Zr) 300 300 XRF
 As mentioned earlier, the automobile industry is the p h u y indu- that uses
Platinum, Palladium, and Rhodium in automobile d y s t s . The purpose of the utdyst is
to convert toxk exhust gases h m fbel oornbustion into a non-toxk and less pobthg
form. In 1975, aii North Amencan vehicles were required by Law to be fitted with catalytic
converters foiiowing environmental pmblems cesuithg bom 'automobile use in large U.S.
dies (Brown et al., 1991). Similar actions have now been taken in lapan, Europe and also
Mexico. A large amount of platinum, palladium and rhodium is used annually in the United
States and Canada for this purpose, representing a major source of consumption for these
elements.

The old cataiytk converters were peIIet fom 2-way catalytic converters. These
catalytic converters contained d quantities of platinum and palladium and were used
for the oxidation of the hydrocarbons (HC) and carbon monoxide gas. Both hydrocarbon
and carbon monoxide are dangerous gases but the oxidized forms Ca or HB are
acceptable pon combustion by-products. The conversion of the gases is show in the
unbalanced reactions (1) and (2).

2c0+o2 PtSd
P 2 C a (Acceptable gases) (1)
HC + 0 2 PtJd
CO2+ HzO (Acceptable gases) (2)

With the advent of the Clean Air Act in 1985, it was requind that engine emissions
drop by 35% for hydrocarbon and carbon monoxide and also 60% for NOK. Therefore the
two-way converters were no longer &ectve. As a result of the Clean Air Act, rhodium
was now required for the reduction of NOx into the Iess toxic N2gas as seen with the
unbalanced ceaction (3).
 NO + 2 CO --k, N2+ 2 C a (acceptable gases) (3)

The 3-way catalytic converters have dm changed in fom The PGEs are now
deposited omto a honeycomb sûucture composeci ofcordierite. A diagram of the two fonn
of catalytic convertas can be seen in fip1.1. Ali automotive companies now use the
three-way catalyîic converters and mat the autocataiytic honeymmb ma& with a 0.2%
platinum, palladium and Rhodium solution.

Various wmpanies purcbase quantities of these used autocatalysts for the recovery
of these platinum group metais. Figure 1.2 is a flow chart iiiustrating the recycling of
catalytic converters. Due to contractual obligations, analytical results are of parmount
importance since they dictate the purchase valw of the recyclable matenals.
Figure 1.1 Diagram ofthe two types ofautomobite caîaiytic convatas. The t
h (top
picture) is the peuet type catalytic converter whüe the second (bottom
pi-) is the monoüthic type d y t i c converter.
Figure 1.2 Flow-Chart iiiustrating the recyciing pathway ofused catalytic
converters.

Catalyst Manufacturer

Con

Production Swap

Junk Yard
Big Collector
Swap Yard
Small Collector
Auto Crusher ,
 METHODS FOR THE DETERMINATION OF THE E
1.4 ANALYTICAL E

Most instrumentai techniques listeû below require the amples to be dissolved or

undago some type of sample hancihg pnor to instnunental adysis. For PGE
daermination, the most popuiar technique iwoIves a sample pre-concentration aep
foiiowed by instrumental detemination of POE oonentrstions. The most cornmon and
widely used pre-concentration technique is the ciassical fireassay technique @ugbee,
1981, Smith, 1987). Fire-assayhg is a highly sensitive pre-concentration mahod for
plathum, paiiadiwn and rhodium detemination. A brief account of the h a s s a y
procedure is given in section 1.4.1.

There are some reports of alternative methods to fie-assay for sample preparation
in autocatalyst analysis. Beary and Padsen (1995) of the National Institute of Standards
and Technology (NIST) used a hot chîorine Carius Tube dissoiution method in the
certification of SRM 2557 (monolith), and SRM 2556 @elle$). This was followed by
isotope dilution inductively coupled plasma mass spectrometq (ID-ICP-MS)
determination of Platinum and Palladium and an intemal standard ICP-MSdetermination
of Rhodium. This dissolution method does not readily lend itseif to routine application, so
other techniques were explored. The dissolutioa techniques investigated in this work focus
on a hot plate atid dissolution technique, microwaveassisted dissolution technique, and
the sodium paoxide fusion technique. Each of these dissolution techniques will be briefly
discussed.

1.4.1 THE FIRE ASSAY PRE-CONCENTRATION METHOD

Procedures to perfonn a basic fire assay were published by Vannoccio Biringuccio

in the sDaeaah cenhiry. In most cases, it is used as a methoci of qumtitative analysis of an
ore - that is, to detemine the amounts of gold, silver, and 0th- vehies in ore in the ounce
per ton range. Fie assay is dso appropriaîe for samples that are inhomogeneous in nature
wbich therefore rquire large sample size to ensure quantitative rapresentative r d t s . The
material for analysis is nised in a ttrnaca with a flux mixture. The method is applied t d y
principally to the detamination of PGEs. Sihw. gold, tin, coppa, and merauy in ores
may alsa be detennined by fireassay m&ods. In each instance, an d o y phase tbat
contains the dissolved anaiyte is produceci. The d o y phase is then dissoived and anaiyzed
using a variety of chemical or instrumental techniques to establish q d a t i v e l y the
andyte content.

The collector that is used for the alloy phase plays a large role in the quantitative
detennination of PGEs. nie most popular coilectors are sîlver and lead or a combination
of the two. In 1975, Steele reportcd that 92 % of all platinun concentration
determinations for the South Afncan Ore Certification program used lead as the cokctor
in their fire assay (Steele et al., 1975). Lead comb'ied with silver as a fire assay coilector
has dso been used for the isolation of platinun, palladium and rhodium (Beamish, 1966).
Unfominately neither of these colîectors proved effective as an isolator for rhodium. Ti
(Sn) has also been used as a fie assay collector for PGE with disappointhg results (Faye
1965). In 1992, Tuwati used gold as a collector for the isolation of platinum, palladium
and rhodium fiom autocatalyst (Tuwati, 1992). He reported a collection of 99+ % of the
platinum and palladium and 99% of the rhodium. A disadvantage of his tezhnique is the
relative high cost of gold as a collector. In addition to the above mahoâs, fie-assaying
procedures using nickel sulfide have been widely used (Robert, 1971). In 1987, Date et
al., also studied the use of nickel suffide as a collector for POE in geological samples pnor
to ICP-MS analysis (Date, Davk, et Cheung, 1987). Keyworth (1982) descnied a detded
listing of cost, loss, operating ranges, seprational losses of PGEs while using various
collectors. The nickel &de tire assay pre-concentration technique for the determinafion
of PGEs in used autocatalyst and 0 t h samples foliowed by ICP-OES and AAS analysis is
comidered one of the most precise and accurate methods avaiIabk for PGE
determinations.
 The 4amount of PGEs tbrt stay in the da$ during tâe nickel &de Mon step
are anaiyzed through a lead bead wliection procedure and a h a i meastarement is done by
ICP. The results ofthe lead b e d analysis are then added to the nickel sulfide rdts.

1.4.2 ACIDDlSSOLunoN TECHNIQUES ON USED AUTOCATALYST

Noble m d s wae thus designated because of their relatively high resistance to

anack by chemical agents. Single minerai &d attack on properly aatlealed noble m d s
shows little effect on the metals. Van Loon (1977) reported thgt wen a quantitative attack
with aqua regia showed littie e&ct on a platinum w h . Howewer, it has b e n show that
hely divided palladium metallic residue was completely dissoived ushg hot HCI.
Therefore the degree of division, degree of compaction, metallurgical histoory and the
presence of hnpurities will play a large rok in sample dissolution. Thae exist a number of
prefened approaches for metals decomposition but the choiw of one of these is dependent
on the partidar metal as well as the factors listed above.

Aqua regia is the most commonly used combination. This consists of 3 parts
hydrochloric acid and 1 part nitric acid. It is thought to contain unstable mixture of Eiee
chlorine, nitrosyl chioride (NOCI), NO, gases and âee HCI and H N 0 3 . Its &cacîty is
attributed to the oxidïzing power of fiee C ~ I O M ~
in aqueous solution as wefl as the
complexing power of the chloride ion Accordhg the American Standard Materials (MM-
1994), aqua regia wiil dissolve platinum and palladium quite readily if they are fhely
devided. Unfortunately, q u a regia also oxidizes rhodium thus forming an insoluble
rhodium oxide @ha).Strong and Murray-Smith (1974) used aqua regia to dissolve
geological samples for the detemimation of gold. Aqua regia has been mixed with other
acids to increase geological sample dissolution. Gowing and Potts (1991) examined h o w
aqua regia dissolveci geological samples for the determination of gold and PGE's. They
reported 100 % dissolution of gold and palladium, 18 % dissolution of platiwm and
rhodium, and littie attraction of the remahhg PGE's. Kuo-Yrng et crl. (1993) anaiipted
various acid combinations for the dissolution of PGE's in an eutomobile catalyst. AU but
two acid combïitions werc ineffiective extractors for rhodium while aii provided
quantitative extraction of phtinum, aad p d d à i m The two acid combinations were a
HClE@OJH& combination and the second was a H&)/HCVHZSOr/H2& combomtionR

1.4.3 TEE MCROWAVE ASSISTED DISSOLUTION TECHNIQUE AND

AUTOCATALYST SAMPLES

The micr~wave~assisted
sample prepmtion technique is r a p i e becoming a widely
used analyticai tedmique due to its ability to quickly d i d v e inwutable geological
matrices consisting of refhctory materials which are normaily resistant to acid attack. The
introduction of microwave assisteci pressure dissotution has been a mjor advance in
geochemicd Pnalyois and it is now regarded as a substitute for acid dissolution, pressure
bomb dissolution, Carius tube dissolution and alkali fusion dissolution for geological
samples. The principle is simple. A sample is weighed and placed into a PTFE vessel.
Acids are then addecl and the mixture is then agitated to promote thorough ming. Once
the initial reactions are complete, the vessel is d e d . The seal contains a membrane that is
mptured if the pressure within the vessel becornes too hi*. The vessels are then put into a
carousel that can hold twelve PTFE vessds and placed into the microwave oven. The
contents are irradiatecl with microwave mergy and the contents of the vessel are quickly
heated. At the same tirne, the pressure withîn the vessei rises. This aliows the acid attack
on the samples to take place at considerably higher temperatures which inmeases its

Several references exists which cover the applicab'ity of this technique to

geological samples. Kokot et al. (1992) have thoroughly d e d the applicab'rlity of
microwave dissolution to various samples as weii as various acid combinations and
microwave programming. Ginepro et aL (1996) have used the microwave oven for the
daennination of heavy metals in seâiments using miaowave desorption and Tessier
sequential extemai oxidation of metai aquatic sediments. Yi and Msswida (1995) and
Beary a al. (1994) both studied the use of microwave dissolution and isotope dilution
ICP-MSto the anaiysis of PGEs in gwlogid samples. Nowinski and Hodge (1994)
studied the applicability of rniaowave dissolution of ore samp1es for gold and platinm
group metals prior to ICP-MS anaiysis. Totluid a al., (1995) have wmpued microwave
dissolution results to o h dissolution techniques u s d for geologid ample aailysis.
Sample dissolution via the rnicrowave has ais0 k e n extensiveiy miewed by Smith and
Anenault (1996).

There appear to be no reports in the literature of the microwave dissolution

technique appiied to the analysis of autocataiyst samples.

1.4.4 THE ALKALINE FUSION TECIINIQUE FOR USED AUTOCATALYST

There exist a large number of matenals that are resistant to the strongest hot
mineral acid attacks. Even using a combination of concentrated hot mineral acids has
proved inefG6Ctive for the dissolution of these matenals. Among these matenals is
cordierite which is the supporthg matrix used in the production of honeycomb automobile
catalya. Unlike the Y-alumlliia used in the pelle$fom of the autocatalyst, wbich is readily
dissolved using concentmted hydrofluonc acid, cordiente is artremely resistant to mineral
acid anack. Therefore altemative techniques are required for sample decomposition.
Alkali fbsion is one technique that can be used. This meîhod rquires the sample to be
finely ground and mixed with an acidic or basic flux. The proporiion of sarnple to aux
varies fiom 1:2 to 15 0 and the sample and flux are bseûin various types of crucible. The
choice of crucible is dependent on the flux chosen as descrihi by Anderson (1987). The
crucible, sample and flw are then heated into a clear melt and cooled. Next the samples
are dissolved in a concentrated mineral acid combination und then diluted for instrumental
analysis. For our purpose, the flux chosai was the basic sodium peroxide flux which is one
of two fluxes capable of disso1ving cordierite.The extrane oxidizing nature of the sodium
peroxide flw required the utili2ation of a zirconium crucible as d e s c r i i by Anderson
(1 987).
 The use of an elkali h i o n to digest Uwluble residues prior to PGE detemination
has been used with varying degree of sucass. Brown and Biges (1994), Hodge et al.
(1986)' SenGupta (1989) and SenGupta and m o i r e (1989) have all used aIkali fusion to
dissolve geological amples prior to Pa's and Au determination. Totland et ai. (1995)
studied and comparexi resuhs from an aikali hion on refmence materials to those of
mimwave dissolution of the saxne samples. In most cases, Plkali &sion gave excellent
sensitivity, and results compareci extmnely w d mth the certifieci vaiues. Enzweiler et al.
(1995) studied the applicability of aikali fwion for the determination of PGE's in
geological samples. There appears to be no published reports covering the use of all<ali
fiision to the daennination of PGEs in autocatalyst.

Alkali fusion provides a means of dissolvhg autocatslyst samples but does not
provided the abiüty to separate the PGEs fiom the supporting maaix. Its applicability to
AAS and ICP-OESrequires caution to avoid various interferences of extemal elements
found within the samples' supporting rnatrUr. On the other han& fused samples and@
by ICP-MSdo not d e r Eoom the sarne spectral interferenas that affect the ICP-OES and
AAS and can therefore be used to detamine PGEs in dissolved alkali fused samples. One
problem with the use of ICP-MSanalysis for dissolved alkali fised samples arises from
salt fomtion. The sarnple solution contains high sodium and chloride concentrations
which can lead to salt formation. Salt can plug the ICP/mass spectrometer interface so
sample solutions require considerable dilution prior to sample anaiysis.
1.5 ~ ~ A L Y T I c AMETHODS
L FOR PGE DETERMINATION IN CATALYTIC
CONVERTERS

Platinum group elements are present in most esrth-dace materials at trace

concentrations. The PGEs play an extremely important role in seversil major industries.
Therefore, the ability to d e t h e these elanente is important for researchers linked to
PGE utiiization. A variety of anaiytical methods have been appüed to POE analysis in
various samp1e types. These methods inchide spectrophotometric (colorimetrîc),
gravimetric and titrimetric detenninations, x-ray fluorescent spectrosopy m),neutron
activation analysis (NAA), atomic absorption spectroscopy (AAS), emission spectroscopy
and inductively coupled plasma mass spectrometry (ICP-MS).
(ICP-OES),

1.5.2 SPECTROPHOTOMETRIC (COLORIMETRIC)METHODS

Spectrophotometric methods were the mainstay of trace maals analysis pnor to

the introduction of modem instrumental techniques. Spectrophotometry is a mature and
inexpensive method for analyzing PGEs. It is ohn considered to be one of the best
methods for analyzing PGEs.It is carried out by way of absorbance measurements d e r
the appropnate reagents are added to develop a chatactezistic d o r . Depending on the
sample composition, several steps may be required More quantitative analysis can take
place. An example of the spectrophotometrîc detennination of platinun, palladium and
rhodium is as folows.

Platinum is quantifieci using a concentrated HCI solution with the subsequent

addition of tin 0 chlonde. The quantitative absorbance of the platinum chlonde is
measured at 403 nm. The sensitivity for this platinun determination is 0.03 ppm whüe
using a 10 g sample (Wagner, 1955). Another specaophotometric determination for
platinwn determination requires the use of gnitrosodimethyianaiine (Yoe rnd Kirkland,
1954). In this case, the smsitivity was 0.0029 pg and a working d i of 0.015ppm
was found while using a lm ceil. The optimum range for platinun detennination ranges
between 0.7 to 2.4 ppm and the precisioa for this technique ranges ôetween 1.4 and 3.û%.
The c o l d solution shows absorbrma maxima a 550 and 525 nm, the latter being used
for the absorbance measurement. The color is due to two diffamt comp1exes, one bang
Pt[(CH&N.C~O]~Cl2.

Many reagents can be used for the spectrometric detemination of patladium

concentration. The most promising of these is 2,2-dipyridUieketoxime which was
developed by Holland and Bozic (196%).Palladium reacts with the reagent to fom a water
insoluble chelated complex whkh can be readily extracteci by the use of chloroform at a
pH of 4-5. Beer's Law is followed oves a concentration range between 0.5 to 10 ppm with
the maximum at 410 nm being used for analyticai quantification of palladium. hie to the
possibility o f interferences, ethylene diaxnine tetracetic acid (EDTA) is used to mask
nickel, copper, iron, and cobalt.

To determine the rhodium concentration by spectrometry, one d d use a 1-to-1

mixture of 1,44iphenylcarbazide and 1,4-diphenylcarbazone. This mixture would react
with the dominant rhodium @I) salts to fom a purple complex of unknown structure
(Ayres and Johnson, 1960). The optimum range is 0.3 to 1.5 ppm while using a lm
optical path and the optimum wavelength for absorbame measurement is 565 am. The
color is developed in a perchloric acid m e b of pH 3.0. Reported imerfkrences are Ir,
Fe, Co, Ni Pb, and Cu. Both the acidity and concentration are criticai.

These methods are often quite difncult to carry out successfûliy, with a variety of
criticai factors. Some of these are pH, reagent concentration, time, temperature, order of
mixing reagents, stab'iiity, masking of interférences, organic solvents and salt
concentrations. However, under favorable conditions, the colorimetric methods offer good
seositivity in the microgramrange (Beamish 1965).
1.5.3 G R A ~ANALYSIS
C

Gtavimetn0cmethods have hktoncally played a large role in the daetmination of

PGE metals; but due to their relative costs (manpower, and time), many iaboratork~have
opted for the more rapid instrumental anaiyticai methods. As a resuit, there has been a
generai move away h m the relatively slow but extremely accurate precr*pitationmethods.
Nevertheless, gravimetic methods still play an important role as the final arbita of
quantitative composition, in the appropriate concentrationrange (> 1% PGE).

Generally, platinwn group met& do not occur aione in samples. Therefore when
exploring gravimetric methods, one must employ severai isolation steps for the final
concentration detedation of aii PGEs. The foiiowing will demonstrate how isolation
and gravimetric analysis can help to d e t e d e the concentration of platinum in a platinum,
palladium and rhodium mamire in a chlorinateci solution. The first step involves the
addition of sodium bromate pnor to boiling foUowed by solution neutraliuition (pH= 7.0).
This aep causes the precipitation of palladium and rhodium as hydrated dioxides thus
leaving platinum in solution done. The next step involves the bubbling of hydrogen suifide
(&S) gas into the platinum containhg solution. This r d t s in the formation of a black
plathum sulfide precipitate. The platinum sulfde is then separated and heated to 750°C
leavhg the Pt metd for quantitative anaiysis (Güchrist and Wichers, 1935). Mooiman
(1993) has reviewed the various published techniques for noble metal extraction by use of
organic solvents in dilute solution. De a al. (1970) also wver many dserent solvent
extractions for noble metals in theù book

The use of x-ray fluorescmce specaoscopy is often the favored method due
to t s speed and also because of its abi1it.y to anaîyze simples non-destructively. The main

19
drawback to this method is b ladr of sedivity for the PGE m a s where it is limited to
samples with milligram or higher concentrations and the neeâ for simiiar standards that
closely match the matri.< of the samples. XRF can be used to anaiyze !amples with no
prior pre-concentration steps. One such example is Giauque a al. (1977) who apptied
XRF to the detemination of 40 elernents including PGEs in various sample matrices.
Many methods have been developed for the x-ray fluorescence anaiysis of noble metaIs,
after separation and pre-concentration of the elements has been achieved. Predominaat
among these is lead bead fire assay pre-concentration of aoble metals foilowed by a
tlattening and annealing of the bead which is then piaceâ into the ample holda and is
anaiyzed for PGE concentrations. Tnere are dso reports of PGE analysis on impregnated
fiiter paper containing the pre-concentrateci noble met& (MacNevin & Hakkita, 1957).

Neutron Activation Analysis (NAA) has played a major role in establishg the
geochemical data base for PGE in rocks. The main reason for this is that NAA is very
sensitive towards PGE's and it can avoid most of the contamination problems typical of
wet chemical analysis in the ppb range. For example, NAA is d c i e n t l y sensitive to
measure the six PGEs in moa un-aiineralized ultramafic rock on samples of 100 mg or
less without any type of pre-concentration of the metais (Cabri, 1981). The acairacy
obtained h m this anaîysis is typically 11 5%. In practice, rhodium is not detemiiwd due
to its derivative's short haElif'e (4.4 minutes). Otherwise, activation techniques are
probably unqualled for the detemination ofsubmicrograin traces ofmost maals. Using a
flux of 5x10~'neutrodcm2.qneutron activation is at least one order of -tude more
sensitive for most platinum group elements then the k s t spectrophotometric method.
With this flux, the sample absorbs the neutron to fom artificial short-We radionuclides .
The radioactive spectnim of the radionuclides, once fomeâ, are memureci and interpreted
in ternis of guantity of the various elements present.
 For used automobile cataiyst, there exist no pubüshed reference methods focusing
on NAA d y s i s , but thae are a iixnited number of publications which review the
application of NAA on PGE anaiysis for geological samples. Crocket et al., (1968). De
Wet et ai., (1971), Gijbeis and Hoste (1971). Millard and Bartel (1971), Nadkami and
Momson (1974). Gilbert et al., (1977) and Hofnnaa a al. (1978) have (in pubfished on
NAA d y s i s for PGEs in rock and ore samplos. GjWs and Hoste (1971), Crocket
(1968), Gjbels and Govaens (1973) have al- mviewed the application of NAA analysis
to the PGEs.In their researches, they have presented two separete methods of NAA for
the detennination of PGEs.The first method is Radionuclides Neutron Activation Analysis
(RNAA) which requires no prior sampIe preparation. The second is Instnimental Neutron
Activation Analysis @UA) and requires some sort of prior sample preparatioa such as

Radionuclide Neutron Activation Analysis (RNAA) has been extensively applied to

geological studies of un-mineralized rocks. It hes proven highly effaaive for Pd and In but
is somewhat less usefùl to Os, Ir, and Pt and totally ineffectve for Rh (Cabri, 1981, De
Soete et al., 1972). Crocket et al., (1968) developed an RNAA method for the analysis of
Ru. Pd, Os,Ir, Pt, and Au in geological sarnples. Small arnounts of sarnples (100-200 mg)
where first mixed with non-radioactive carriers of those elernents and irradiated (Crocket
et al., 1968). The results reported by Crocket et al. showed RNAA's inability to
efktively d e t e d e Pt, Os, Ir. Nadkami and Momson (1974) also stuclied the use of
RNAA for the detennination of Au, Ru, Pd, Os, Ir, and Pt in gedogicai materials while
ushg a Strafion N.M.R @olycyclc-NBL47) ion exchange resin. Again, the results
indicate a Wted abiiity to eîZ&vely m a u r e Ir, and Os. There are o t k reports
descnig RNAA analysis of geologicai samples, but MM report good results for
platinun, and rhodium which suggests that RNAA may not be appropriate when analyzing
automobile catalytic converters.

Instrumental neutron activation anaiysis (INA)is the second method. This

method generaîiy requires a p r e - c o n d o n step prior to quantitative analysis of various
materiais. It has proven higbiy efEective for the PGE determination in &de beMag
rocks. Turkstra et el. (1970) were able to deterxnine Rh, Pd, Au, Pt, Ir, and Ag in fused
ores, concentrated mattes and lead fie-assay beads via INAA. In thgr research, th- were
able to quantitatively measure Ir, Pt, and Au in South A£ncan ores, and hi&
concentrations (15-500 ppm.) Rh, Pd, Ag, Ir, Pt and Au in mattes. Lead firr-assay beads
nom the South African ores allowed for the high concentration determinations of Rh, Pd,
Ag, Ir, Pt and Au. H o h et al., (1978) demonstratecl tbat INAA could show supaior
accuracy and precision than most d y t i c a i methods present in 1978, exclucihg ICP-MS.
There are no reports of INAA for the anaiysis of autocatalyst sarnples.

The only major disadvantage of NAA techniques are the instrumental costs,
availability of suitable irradiation sources, and the tirne requued for dyti*cai analysis. It
has also proven to be ineffeaive in determinhg platinum and rhodium quantitatively
(RNAA) and also lacks sensitivity (INAA) for all three PGEs in autocatalyst.

ABSORPTIONSPECTROSCOPY(AAS)
1S.6 ATOMIC

Atomic absorption spemoscopy ( A M ) is the measurement of the absorption of

opticai radiation by atoms in their gaseous state. The phenornenon of light absorption by
liquids and crystals dates to the 18" century. It was not for many years that the maiytical
applications and instrumentation became avdable to perform empirîd anaiyticai
determinations In 1963, Walsh and Haussman (1963) developed a method for the analysis
of PGE's by AAS. This is considered to be one of the major landmarks in noble metal
analyticd cherni-. Although not enthusiastically received in North Awrica until 1964,
the technique was ixnmediately investigated for noble metai analyses partidarly by
Austraiian and South Afncan researchers. At the present tirne atomic absorption
spectroscopy is the most widdy u d detemimion tool for these metais. The basic
hctionality AAS is quite simple. A dissolved somple is aspirated h o a hot flme where it
is atomited. Upon atomization, the atoms absorb the characteristic iight emitted fiom a
holiow cathode lamp WCL) and the difference between the incident light and the
absorbeci light is subtracted and used to empiricaiîy quanti@ the concentration of the
element wncerned.

The depressive intetzlementd interferences orperienced in aiomic absorption

qectroscopy in the determination of noble metals are more cornplex than for most other
elements and therefore serious problems have Mm (Janssen and Urnland, 1970).
Fortunately there exist extensive interfîmnce studies that propose a wide variety of
remedies to help in the analysis of PGEs. The d e s t remedy is to use releasing agents to
block extemal inter-elemental interfierenceswiih the noble metals. One mch case is the use
of vanadium to help in determining Pt, Pâ,Rh, Ru and Au in geologicai sample~.

The second possibiiity to overcoming the depressive inter-elemental interfierences

is through the separation of the noble maals tiom their interfering mat& This approach
has attained the greatest popularity for noble metals determination. Neo-classical fire assay
is by far the most widely used sepadonal technique. Mer sepmtion, a releasing agent is
added to block noble metals fiom interfering with one another. Le HouiXer and De Blois
(1986) used silver to collect Pt, Pd, and Rh îrom geological samples foilowed by an
alkaline cyanide solution dissolution Vanadium was used to correct for eIemental
interferences. The remlts were promising with the exception of Rh which is aot properly
coiiected by silver. Schnepfe and Grimaldi (1969) used gold to wUect Pt, Pd and Rh ftom
a geologicai semple followed by an aqua regia dissolution. They fomd tbat wpper sulfate
can enhance the Pt sensitivity by as much as 5W and that lanthanum chlonde could also
be used to prevent Rh interferences with Pt. In thQr research they showed that PGE
extraction fiom the AAS anaîysis samples showed an excellent correlation to
spectrochemical and chernicd results. The copper and Lanthanum combination has also
been shown to eüminate Pt, Pd,and Rh interferkg with one another.

As with 1 AAS work, noble metais also d e r Born problems associated with
elemental determinations. These problems are : Doppler and pressure h e broadening,
resonance broadenuig, limitations imposed by the absorption cocfncient of transition that
gives rise to the particular line u
d (flame temperature innuences it), interferences due to
inwmplete isolation of the emitted opticai h e , and the dependence of sensitivity on
opticai path length and other events in the flame. The background due to absorption by
molecular species also poses problems (Koirtyohann and Pickett, 1966).

This technique requires a srnail amount of the solutioa to pass into a plssma where
it is not ody atomired but also energized to emit al1 possible spectral lines through
electronic excitation. The intensity of the spectral lines is proportional to the concentration
of the species in solution. This provides one large advantage over atomic absorption
qectroscopy in that it pennits simuhaneous multi-element d y s i s over a large linear
dynarnic range of concentrations.

There are a lirnited number of literature reports involving the use of ICP for the
anaiysis of Pt and Pd in geological samples. Brown and Biggs (1984) applied ICP to the
analysis of Pt and Pd in geological samples. They used an ion exchange chromatography
step as a possible aiternative to the lengthy fie-assay procedure. Their research looked at
both high and low grade materials. The low grade materials were concenmted by nickel
sulfide fie assay. Extensive interference midies were perfonned and the accufacy of the
method was estimated using sample materials previously anaiyzed by AAS. The detection
b i t s for Pt at 265.9 nm, Pd at 340.5 nrn and Rh ot 343 -5 nm were O. 1, 0.03 and 0.03
pB/mL respectively (Wemyss and Scott, 1978). Aberwmbia (1982) investigated the
possibility of using ICP-OES for the determination of Pt, Pd, and Au in geoiogical
samples. His research showed that the Pt band at 265.9 mn showed signifiant problems
due to interferences by Mo, Ni Cu,V, Si, Mn, Fe and Mg. As a result of these problems,
samples with low Pt lewls were suôjected to lead fire-assay prior to ICP anaiysis. Richard
Brown (1982) descriied extensively the use of ICP-OES for the anaiysis of various sampte
matrices for precîous metais. He examineci how dissolveâ sdds affected the extractions,
how silver could be used as an intemal standard for the precious metais, how matrix
dements can cause spectral interferences with certain noble metals and how ICP-OES
f i a g a reeree values on the geological suaples. Rao and Bridger (1982) examine
the possibiity of pefiorrning a dina detemination of process soiution with both high
dissolved solids and SiBnificant amounts of PGEs. Their research look at torch
assemblies,alum interfaaices on Pt,as weli as possible spectral overlaps with the Pt üaes.

Inductively coupled plasma mass spectroscopy (ICP-MS)is a =Iy new technique

for elemental and isotopic anaiysis. The technique combines the characteristics of the ICP
for atornization and ionizing injected material with the sensitivity of m a s spectrornetry
(sensitivity limit 0.03-0.22 ng w').There are two distinct advantages to ICP-MS
analysis. Fudy, the spectra are very simple and inter-elemental interferences are largely
absent. Secondly, the technique provides for the sequential analysis of both elemental and
isotopic ratios, the latter previously being restricted to thermal ionization mass
As a M e r refinement to this method, isotope dilution techniques
spectroscopy (TI-MS).
may be employed.

Sample preparation is the critical step in the trace analysis procedure; fiequently, it
is responsible for establishing the lower detection limits of an d y s i s through its influence
on the analytical blank This is panicularly important in ICP-MS as the technique requires
that the sample be in liquid form with the total amount of dissolved solvents being less
then 0.1 %. The least popuiar method for sample preparation is alkalllie fision foiîowed by
acid dissolution due to introduction of additional extenial eiementai interfaences aot
found in the initial ssmple matrix. Wet-digestion m*hoâs are often employed but they
require close attention by the a d y s t to avoid unintentional b o h g over or evaporation of
the sample to dryness. Thuq a more rapid and e f f i v e digestion method for trace metal
analysis hes been sought. Microwave assisteci sample dissohttion may be the answer for
fast, clean sample preparation. AU of these are discussed in this th&
 Inductively coupled plasma mass spectroscopy has beai widely used for the
detemination of PGEs in geological sample due to the iarge danand for these noble
metals. Date and Oray (1989) descriibe the many advantages of ICP-MSfor gcolo@d
samples and d e m i e ais0 vPiaus sample prepantion techniques. Pary et al., (1995)
describe the appücability of ICP-MSfor the determination of PGEs and gold on various
sample matrices in geological sarnples, biological samples, botanid samples, and water
samples. Their paper looked at the detection Mts in each of the sampIe types while u&g
various digestion methods and ample preparation methods and tt provides many
refemices for additionel information on ICP-MS anaîysis for noble metals and gold. Piotr
Nowinski (1994) looked at the applicab'ity of using a microwave oven for the digestion of
geological samples foliowed by ICP-MS and Totland et d (1995) looked at an aikali
fusion and microwave assisted preparation procedure for the deternllnation of POE and
Au in geological matenals. Their results were genedly in agreement with the reference
results but showed a tendency to bias on the high side.

Isotope Dilution ICP-MS(D-ICP-MS) has also been extensively applied to noble

metals detemination in geological samples. This method can provide the analyst with up
to a ten-fold increase in accuracy in PGE determination in various sample types. Cattenck
et al. (1995) used isotope dilution ICP-MSor ID-MSfor the determination of various
metals in various types of matrices with exallent results. Nowllisky and Hodge (1994)
and Enzweiler et al., (1995) studied the appücability ofvarious digestion techniques in the
detemination of PGEs and Au in geologicai samples folowed by ID-ICP-MS. Nowinsky
and Hodge (1994) showed that microwave assisteci dissolution of samples foUowed by ID-
ICP-MSis a viable methods for geologid samples -sis whik Enzwda et al., (1995)
showed that ID-ICP-MS of a peroxide nised and teiiurium coprecipitated sample also
gave acceptable results. Yi and Massuda (1995) paformed a sequentid determination of
Ru, Pd, Ir, and Pt et ultratrace l d s by ID-MSon various geologid samples. Their
method proved to be quite reiiable in cornparison with otha d y t i c a l techniques. Beary
et ai., (1994) explorecl different sample pnpatation approaches for isotope dilution ICP-
MS of c e d e d materiais. Their paper helped to dsveiop the sensitivity, prcision and
accuracy reqWred for autocatalytic PGE detenninatiom et Inco Limited, Sudbury
Division.

As a result of the analytical data provided fiom the authors above, both the h t d
standard and isotope dilution ICP-MS techniques were gcplored for the daennination of
PGEs in used outocatalyst. It is hoped that one of these techniques can provide EghS
accurate, sensitive and precise resuîts as rquired for the determination of PGEs in useâ
autocatalyst while elirninirting soma of the interferences with ICP-MSas seen in Evans and
Giglio's (1 993) research paper.

1-6 PURPOSEAND SCOPE OF THIS PROJECT

The ah of this project was to develop a simple, fast and sensitive method for the
determination of platinum, palladium and rhodium content withui usd automobile
cataîyst. A well emblished method involves a combination of nickel suifide fie-assay pre-
concentration foliowed by another pre-concentration step using lead on the nickel suifide
slag (Appendix A). The PGEs collected fiorn both techniques are dissolvecl ushg
concentrated mineral acids, then sarnples are d y z e d both by ICP-AES and AAS. The
results are combined and reponed. The fie-assay is a highly accurate method and well
developed technique, but the pre-concentration steps are time consuming, costly, and very
labor intensive.

The three methods exploreci in this study are: (1) concentmted a h d acid
dissolution, (2) microwave assisteci dissolution, and (3) Zirconium cniaile sodium
peroxide fùsion M e r the automobile catalyst samples are dissolveci, the arialysis is
pafonned using a Perkin-Elmer Elan 6000 ICP-MSand the resuits an compareci to the
classical methods: Nickel sulfide coiiestion and ICP and AAS finish (haLimited) and the
Ledoux A-1 method consisting of an acici digestion plus fire assay digestion method with
ICP finish.
 CEAPTER2 EXPERIMENTAL
PROCEDURESFOR
AUTOCATALYST
QUANTIFICATION

In this project, thne sample preparation methods were explorecl as possiile

replacement for the present Nickel-SuEde fire-assay technique. These three methods w m
concentrated acid digestion on a hot-plate, microwave assistai digestion, and alkaii fusion.
The basic procedure in dl three techniques foilowed the same steps. First the samples
were dried and cmoled. Next a h o w n amount was weighed into an appropriate vessd
The samples were digested ushg one of the three methods. Following sample trament,
the samples were ali dissolved accordingiy and fïnaliy pnpared for sample d y s i s on the
Inductively Coupled Mass Spectrometry (ICP-MS) instniment. Each of these methods will
be descnbed individuaiiy below.

Prior to sarnple dissolution using one of the three methods descllied above, (acid
dissolution, or microwave assisted dissolution, or dkaii fision) the autocaîalytic samples
were ail pre-treated in the sarne way. The fint step was to cmsh the samples which is
elaborated in section 2.1.1, then al samples were dried as outlined in section 2.1.2, Finally
the samples were weighed ushg one of two methods listed in section 2.1.3 and then
dissolved ushg one ofthe three studied methods.
 The samples used throughout this work were &&y pulverized (-200 mesh or 75
pm) and thoroughiy mixed. Two catincd amples wae used as conaol monitors. The first
standard reférace material (SRM) is SRM 2556 which is the pellet fom of the
autocataiyst and the second is SRM 2557 which is the honeycomb fonn Sampk
composition for both standards can be oan in Appendot C. The standards are pnpared in
the same fmhion as nonnd autocatalyst samples.

The autocatalyst like many other semples arrive in the damp or wet state.
Anderson (1987) descn'bed how wet samples can affect the accuracy of the resdts in a
negative way. Therdore, fiom an atialytid point of view, this means that the samples
contain potentially large amounts of water associated to them which ~ u l give
d rise to
unwanted quantitative analytical mors. As a redt, samples were calcined in a
temperature controlled Cole Palmer muflle b a c e for 2 hours at 500°C prior to sample
analysis for platinum palladium and rhodium. This removes unwanted water associated
with the samples and carbon which c m also cause anaiytical problems. Calcination in this
manner is the accepted way to dry autocataiyst samples Peary and Paulsen, 1996, Beary
et al., 1994).
 Sample wcjghing was pafonneâ foilowhg Anderson's (1987) technique. Two
Merent methods of sample weighiDg were uwd in tbis pmject, the choice of method
king dependent on the type of Mettk balance that was used. Gaie*, for ail alkali
fùsions, the samples were diredy weigùed into the zirconium auables. Sample weighg
involved the use of a weighing plate.
for both microwave dissolution and acid dissolutio~~
Samples were added to the plate atta the baiance was tard Then the sample was
transfured to the digestion vessels and the weigbing plate was once again weiaed to
ensure accurate results. Great care was taken with di weightings.

2.2 TESTMETHOD #1: ACIDDISSOLUTION METHOD USING

BEAKEM~OTPLATE

Acid dissolution provides an easy way of dissolvtig most materials (Anderson,

1987). The choice of digestion vesse1 for acid dissolution is dependent on the nature of the
acid. AU dissolutions which useci hydrofluoric acid (HF) were carriecl out in Tefion
beakers due to the ability of HF to dissolve Borosüicete glass. û t h d s e , aii other acid
dissolutions were perfonned ushg Boros3cate gkssware. A 0.25 g sample of catalyst was
weighed using the Mettler 100 or 166 electronic balance as descn'bed in section 2.1.3. The
weighed samples were traasferred to the proper digestion vessels and the vessets were
washed d o m with a miall mount ofdeionwd water (DI)to ensure that al1 the cataiysî
sample would be in contact with the acids. Then a 45 mL concentrateâ hydrochloric and a
15 mL portion of concentrateci nitric acid was added (3:1 qua regk solution). Other
acids, aich as hydrofluoric aci4 sulfiuic Md, and percblonc a d , wae then added to the
aqua regia mixture to belp dissoive rhoàium Î f it was repuireci*After the addition of the
last acid, the contents of the beakers w a e thorougbhl mhed and placed onto a hotplate.
 The simples once placecl on the hot plate wouid nmaia there d dl the a i d s had
evaporated. The beakers were then removed and aüowed to cool. Once coold, a 10 mL
aliquot of D.I. water was added followed by the addition of 50 mL of comentrated
hydrochioric acid. The contents w a e thomugbly mixed aad the sunples were re-beated
for a couple of minutes. ûnce the solution was clear, the dUsohnd srmples w a e moved
fiom the hot plate and cooled d o m Mer cooling the contents of the beakas were
emptied imo a 500 mL glas vo1umetnc fîask. The sample beal<er was repeatedly wmhd
with D.I. water and the wasbings were transfensd to the 500 mL volurnetric flask. DI.
water was added to just below the 500 mL. The fiasks were thai aansferred to a coobg
bath for 20 minutes. M e r cooling for 20 mimites, the samples were removed fom the
coolhg bath and allowed to accliudze to room temperature. At tbis point the s ~ p l t s
were dissolveci to the 500 mL m k e r and the vesse1 were placed on an automaticagitation
plate for proper solution -g. Atta about 5 minutes, a 50 mL aüquot was p h a d into a
50 mL Falcon tube as the stock solution for fbture ICP-MSdysis. These Falcon tubes
permittecl the samples to be stored for up to 2 months with no ample degraâation or salt
precipitation.

The samples were digested with the Hoyd RMS-150 electronidy oontrolied
microwave digestion unit. Sample weights mged between 0.100 to 0.200 gm of used
were weighed (section 2.1.3) in a
automobiie atalyst or refierence mataîals. The sa~~ples
plastic weighing dish and then acinsfaed to the 120 mL Tefion iiiicrowave digesti0on
vessel. The weighing dish was thai raweighed as d e s c f l i in sedon 2.1.3. A 20 gm
aliquot of aqua regia (3:l HCVHNCh) was then added to the digestion vessei and in some
cases a 1 mL aliquot of HF was also added te maease the -*on of rhodium. The

31
microwave carousel can hold 12 vessels and most runs iSvoIved 11 srmples and 1 ftagent
blank. AU analyses were pafomed whüe using ail 12 vessels as the microwave oven
power was calibraed on this basis. Af?er the addition of the acids (qua regia or a c p
regia + hydrofluoric acid) the catalyst samples were mked and aliowed to react at room
temperature momentady (until any visible reaction had subsideâ). The vesseis were then
capped with a 120 PSI rupture membrane and placed into the microwave carousel. The
oven was operateci at d m u m powa for 10 to 20 minutes (se Table 2.1 below). Mer
the power was tumed O& the ve~selswere Ieft in the microwave for 15-20 niinutes and
then cooled in a cold water bath. Once the vessels had co01ed Suflscientiy, they were then
removed and carefully vented in a fUme hood.

With the vessels vented and cooled, the contents were anptied into a 200 m .
voIumetric flask. The Teflon microwave vesse1 was repeatedly washed with DI water and
the washings were transferred to the volumetric flask. Additional DI water was added to
just below the 200 mL. Since the solution was still warm, the volumetric flask and its
contents were transferred to the cooüng bath for 20 minutes. A f k coohg, the flasks
were placed on the counter top and la to acclimatize to room temperature. The solution
was diluted to the 200 mL mark and then mixeci using a magnetic stirring bar and an
automatic stirring plate. A 50 mL portion of the flask was ttansferred to a 50 rnL Falcon
tube for storage. Stored samples remained in soIutîon for severai months with no sarnple
precipitation. This was the concentrat4 stock sohition for that the finai ICP-MS analysis.
 -
Table 2.1 Operating conditions for the microwave digestion of a 0.10 g (~1tocatalyst
sample.

Microwave Power Output 500 W

Microwave Power Duration thne : 10-20 minutes

Maximum Pressure 120 psi

Estimated Temperature -
180 2OO0C

Volume of Digestion solvent : 20 mL aqua regîa (withlwithout HF)

2.4 TESTMETHOD #3 :ALKALIFUSION OF AüTûCATALYST SAMPLES

A 0.25 g portion of the dried autocataiya sample was weighed into a dned
zirconium crucible. The weight was recorded and then a 2.5 g portion of sodium peroxide
flux was added. The samples w m thoroughly mixeci With the Cole P a m r automatic
agitator for 3-5 Mnutes. The autocatalyst and flux were then fised on a LEC0 FX-503
automatic fluxer for 3 minutes. The automatic fluer was u d to aisure that d sampies
were fused in the exact same way. The mass was allowed to cooi., then the cruaile was
tranderred to a 250 mL Teflon beaker and 100 mL of distilled and deionized water was
added to the vessel. During the addition of water, cace was taken to avoid sample loss
through sputtering. The addition of 50 mL of concentrated hydrochloric foiiowed by 50
mL of concentrated nitric acid took place only affa alî reactions were complete. Care was
again taken when adding the concentrated hydrocbionc acid to avoid sputiaiDg of the
sarnples. The addition of concentrated niüic acid posed no problems in temis of sputtering
as the reaction continued at a much gentier me. The samples were trderred to a 500
mL glas volumetric flask d e r the bubbluig had ceased. The auOble rad Tdon beaker
w a e repeatedly washed with D.I.water and the washings wae also tradiared to the
flask, the mixture wts düuted
mL fiask. Mer the Ûansfer of the mixture to the voluxnetri*~
to just below the 500 mL tnarker with DJ.-ter. The flasks were then W i e d to a
coobg bath for 20 minutes. Atta cooling for 20 minutes, the samples w a e removed fiom
the coolhg bath and allowed to acclimatk to r o m temperature. At this point the
solution was made up to the 500 mL mark and thm transferred to an automatic agitation
plate for proper solution mixing. After about 5 minutes, a 50 mL aliquot was pl& hto a
50 mL Falcon tube for fiihire ICP-MS analysis. These Falcon tubes permitted the samples
to be stored for up to 2 months with no sample degradation or salt prexipitation. The
stock solution, so obtained, was diluted as appropriate pnor to ICP-MS analysis, as
describeci in m ' o n 2.5.

2.S FINAL+SAMPLE PREPARATlON STEP PRIOR TO ICP-MS UTILIZING ISOTOPIC

DILUTiON AND INTERNAI, STANDARD TECHMQüES

From the 50 mL concentrated stock solutions stored in the Falcon tubes, a 1 rnL
portion ofsample was combined with 3 mL of concentrated hydrochloric acid and 1 rnL of
intemal standard into a 50 mL Falcon Tube. Dependhg on the type of ICP-MSanalysis,
' " interna1 standard as w e l as a 1 rnL spike
one could also add 1 mL of ~ t ' ~ / ~ disotope
(containhg known concentrations of Pt, Pd, and Rh) to repliate samples. Each one of
these components was added to the 50 rnL Falcon Tube and diluted to the 50 mL mark
with D.I. water. Once all the components wat nWed in, then the samples were
thoroughly mixed and they were now r d y for introduction into the Perlrin Elmer Elan
6000 ICP-MS.The placement of these samples was done accordhg to a prepared asset
fiSe as s a n in Appendix B. The operatiord parameters for the ICP-MS are listed in Table
2.2.
 It should be noted h t the nnel Mmpk p r e p d o n was only p a f o d
immediately pnor to ICP-MS anaiysis and îhat di samples were thoroughly mixed.

2.6 ICP-MS ANALYSIS (OPERATIONAL

)-P

Before the analysis of the dissolveci PGEs in solution, a sampie file was generated
using the weights transcnied fkom section 2.1.3 iato a PC software package. An example
is given in Appendk B.The sample file sewed as a ternplate for the Elan 6000 ICP-MS
software package. The samples were then loaded accordhg to the sequence üsted in the
sample file and then analyzed on the P a h Elmer Elan 6000 ICP-MS f o M n g the
operational parameters listed in Table 2.2 below.
Table 2.2 Operational Parameters useâ on the ICP-MS for the Analysis of
Sodium Peroxide Fusion Sampks

RF forward power : 1,oOO Watts

Argon Gas Flow (Nebuber): 1.O2 Umin

Analog Stage : -2,300 Volts

Sample Cone : Nickel with a 0.15 mm orifice

Skimmer Cone : Nickel with O. 1O mm orifice

Nebuliter Type : Cyclonic Spray Chamber
Solution Uptake : 15 Urnin

Peak Scan Parameters : Peak Hopping

Reading Replicates : 1

Discriminator Threshold : 55 mV0lts

Number of Scans : 3

Sample Sweep : 40 seconds

Mass Spectrometer : Quad Mass Spectrometer

Detector : Dual Detector

Ion Lens Setting : 6.2 Volts
 The detection b i t for the ICP-MShtmment for dl elements in the periodic table
can be seen in APPENDIX C.

Since the ICP-MScalibration w e is iinear through to zero* a single d % d o n

solution was used for the caliiration of the instrument. This single ulIbration soiution was
composed of -4 p f i Rhodium, - 20 pfi -
of palladium and 40 CcglL of platinum which
was mixed with the indium and iridium intemal standard. The caiibration solution was
rnonitored using an indium and iridium internai standard prepared from purchased
Certifieci Spectral Standards.

Mer the calibration of the ICP-MS with the PGE calibrating solution, the n a t
step is to calibrate for the removal of possible intederences. Such interferences can affect
the determination of the three PGEs and are rernoved rnathematically usïng the corrections
Iisted in Table 2.3. Using three solutions of hown concentrations of rnercury, th,lead,
strontium, copper, yttrium and H u m . , the intensities for each of these element are
measured for the blank solutions and inputted into the ICP-MS software. When the
samples are analyzed, the intensities of the species imrolved in the molecular ion
interferences are measured. Once measured, they are psssed through the mathematid
f o d a e listed in Table 2.3 and then removed fiom the s p d c PGEs in solutions. The
removal of these Uaerrence is imporîant for the high accuracy and precise determination
of platinum, palladium and rhodium,
Table 2.3 Spectral removal of possiie interfierences from Cu,Y,Sr, and Pb.

The ICP-MS software WUmoaitor the copper, strontium, yttrium, and hafhîum for
possible isobaric and double charged spectral interfierences of platinum, palladium, and
rhodium. Copper combined with the argon gas in the piasma gas f o m a copper argide
(~uAr+*) which isobaricaily intetferes with rhodium and pallaâium dements dependiag on
which copper isotope is present. Strontium comb*med with oxygen f o m a strontium
oxide which iwbacically interferes with rhodium and palladium. Yttrium oxide formed
within the ICP torch will also isobaricafiy interfiere with palladiwn, Double charged lead
204 wül intetfere with the monoisotopic rhodaim 104 species and Wm pre!sent within
u
the zirconium nuciales forms a Wm oxide speck that interfères with platinun 195.
u
F M y , th 118 will interfere with indium which is used as intemal standard and mercury
U n a r e s lightiy with the detetmitllltion of I d . W~ththe d g up of these iaterference
removals tiom the sample, the d y s i s of autocataiytic snmples can now p r d .

2.8 SELECTION
OF INTERIVAL STANDARD

The choice of intemal standards for the determination of Pt, Pd, and Rh in n m and
used automobile catalyst is dependent on the element. The determination of Pt, Pd and Rh
in new and used automobile catalya CM use a wide variety of internai standards.
Therefore each element is discussed separately.

The analysis of platinum can be doue either through isotope dilution (Sa Table
2.4) or through the utiiization of intemal standards. For this research, the intemal standard
hlg3was used at first. This is chemicaily dissirnilar to Pt but close in rmw. Another
possible choice was Tlm' but it was obsewed to drift on the ICP-MS and to affect the
detefmination of platinum, so it was not used. The final choice was to use a platinum
isotope. The choice of isotope was largely dependent on its avaüability as weil as its
natural abundance within the catalyst. A semiquantitative -5s of fused catalyst (sa
Appendix A) showed that Pt1%was almost nonexistent and therefote was chosen as our
isotope interna1 standard. The isotope was p u r c M âom Oak Ridge National
Laboratory as a metai powder containhg 95.3 1% of ptm abmdant. The method for the
dissolution of this metal powder is giwn in section 2.9.

Palladium not behg mononuclidic in nature caild also be d y z e d through either

isotope dilution (See Table 2.4) or with an intemai standard The interna1 standard chosen
was inNs which is chemidy metent fiom Pd but it is relatively dose in mass. Another
possible choice for interna1 standard was RU"' but this element showed miwr
irregularities during Jnrnple d y s i s and was therefore not used. Internai standards
provideci excellent d y t i c a l resuits but it was believed that isotope dilution muid provide
additional sensitivity, accmcy and precision to the detemidon of palladium, Tûaefbre
the isotope diution ICP-MS detemination of pallnAium was attempted. ~ d was
' ody
~
found in trace amounts in a semiquantitative analysis of the fused outomobite cataiyst as
seen in AppendUr A and was *&ore chosen. As a result, the isotope was purchased
from Oak Ridge Natiod Moratory as a metal powder which wntained 94.Wh of the
isotope. The dissolution procedure for tbis metai was simüar to that of the Ptlm isotope
(section 2.9).

Finally, for the daennination of the mononuclidic Rh there are three possible
intemal standards. The first involves the use of ~ dwhich
' is~ one mass unit removed fiam
pdl*' and chemically similar to the Rh. The second is with ~ t ' "which is again chemicaily
similar to Rh but has a large mass difference and W y there is In'" which is chemically
different from rhodium but close in mass and naturally absent in autocataiyst. Of these,
hl1' was chosen as the intemal standard for rhodium determination.
Table 2.4 Relative abundance of naturai isotopes used in this project.

Element Measured Mass Relative abundance

Ru 99 12.72

Ru 101

Ru 102

Rh 1O3

fd 10s

Pd 106

Pd 108

Ir 191

Ir 193

Pt 194

Pt 195

Pt 196

Pt 198

In 113

In 115
 The pdlM (94.000?abundant) and ~ t "(95.31% abtsndant) were purchased fkom
Oak Ridge National Laboratory as a metd powders. The powden were dissolveci in
concentrateci aqua regia on a hot-plate and then once cooled they were storeâ in a 2moK
ultra-pure HCl solution. The concentration of the two isotopes w e n deternwied with an
ICP-OES analysis which was then comlated to ICP-MS detenninations. The
concentration of the isotopes is continuously king moaitored during sample d y s i s on
the ICP-MS and th& concentrations are tabuiated using specincally dmloped software.
package developed at INCO Ltd., Sudbury Division.
 Chapter 3 Results and Discussion

The use of nickel sulfide fie aswy collection for Pt, Pd and Rh in the pte-
concentration of autocatalyst sampfes is a highly accurate procedure but it is d m time
consuming, labor intensive, dependent on the anaiyst laboratory skül level, and is subject
to experimental e m due to the large amount of sarnple handliag (Beamish, 1966). Ii
addition to the above, fie assay pre-concentration generally r e e s a large amount of
acid to be used for sample preparation. As a result, this project l o o b for altemative
sample preparation methods that could be used for the simultaneous determination of Pt,
Pd and Rh in both new and used autocataiyst. This new method would be used in
combination with a Perkin-Elma Elan 6000 ICP-MS for highly accurate, precise and
sensitive analytical determinations of the PGEs. The ICP-MSprovides many advantages in
that the analyst can predict possible interences, its provides a broad iinear dyaamic
range, sample analysis are rapid and not hindend with emission peak oveilaps and the
instrument is fully autornated.

Many sample dissolution methods are available but the method chosen should be
low cost, relatively simple, and highly accurate. The methods considered in this project
were: hot plate acid dissolution, microwave assisteci dissolution, and zirconium aucible
alkali frisions. These will be seen in section 3.2 (Acid dissolution), section 3.3 (Microwave
assisted dissolution), and sections 3.4-3.5 ftsion) respedively. Prior to
explorhg each dissolution method and its results, a look at possible problems that could
aEkct the ICP-MSresults is warranted.

3.1 ASSESSMENT
OF MATIUX INTERFERENCES

In an effort to provide the best conditiong and analyticai resuits for the recovery of
PGE's, most autocatalytic samples d y z e d on the ICP-MS were andyzed dong with
certifiai standard reference matenCaIs(SR-) autocatalytic samples (NIST 2556 @dl&),
NIST 2557 (honeycomb)). In addition to using d e d materiais, catain ~ m p l were
e~
spiked with a known concentration of Pt, Pd, and Rh solution and recoveries for each
element were caiculated to assess the vaiidity of the analyticai resuits. F i d y , the use of
isotopes as interna1 standards wouid a b provide with extremeiy sensitive d y t i d
results.

The ICP mass spectrometer is a non-specific ionization source, and as such mat&
interferences and other sources of instrumentai error were of concem during sample
d y s i s . There exists thtee possible sources ofanaiyticai error that can a
ét the ICP-MS
c
results. The first two mors are fkom interferences &sing Born either molecular ions
ancilor doubly charged ions present within the prepared solution. Both of these two
interferences are readily identified by the anaiyst and are easiiy c o r r d for. The third
source of error is due to the drifthg of the ICP-MSover a period of tirne. Generaiiy this
last source of error affects the rnid-rnass measurements of several elements and it is vey
dficult to identify. The last source of error can be correcteci for but it generdy requires
special software development.

Molecular ion interferences (isobaric interferences) affect aU PGEs in autocatalyst

in varying degrees. For Pt, there was no sigaificant elemental isobaric intaference other
than a stight interference fiom Ht"*0"and @780'6Hfwith the ultra-trace levels of
hafhium originating fiom the zirconium crucible. pdlW also suffers nom isobiuic
interferences fiom various isotopes of strontium and oxygen as shown with S ~ ~ ' O 'But
?
again strontium is found in trace concentration and poses very M e problems in Pd
determinations W ' 0 3 on the other hand is isobaridy interfered by copper argîdes such as
Cu63Ar4û which is present in traceto ultra-trace lewel in the dissolved samples. The wpper
@des will also interfére with Pd but h&ium, copper, and strontium show M e or no
affects on the anaiytical results Born the ICP-MS.A saniquantitative d y s i s (Appendix
B) of fûsed samples showed that the PGEs consists of hudred of thousands of counts per
second whiie the isobaric intafaing species account for hundreds of counts per second.
Through the Elan 6000 ICP-MSsoftware, these dernents were cali'brated using specially
prepared interference solutions and subtracted fiom the PGE anaiytical r d t s
automatidiy pnor to reporthg of the resuits.

The second possible interfirence originated fion double charged @es such as
lead. Pt is unaffected by this type of interference but Pd and Rh are affected to m g
extents. The extent of the interference is dependent on operational conditions as well as
the presence of the doubly charged Iead species. If lead is present in detectable amounts,
doubly charged ions kom the percent level of Pb in the sample will produce an
interference at n/z 104 (M'Pb'2)with ~ ~ at n/t 103 fkom ?b+*
d and' also with Rh.
Doubly charged interferences are dso monitored within this project through the ELAN
6000 ICP-MS sohare and for specially prepared celibrating interference solutions.
Therefore, interference fiom lead is virtually eliminated for the PGE analytical nsults.

The last source of error is due to instrumental driffing which generally affkctsthe
measunment of heavy elerneats. Udortunately, tbis type of error is vey diacult to
identiQ and requires specïaliy developed software. As a result, software was developed to
correct for the instrumental driAing and all resuits are reported after a drift conecti*on
cakulation. This drift correction eliminates this source of emr during ICP-MSanalysis of
PGEs but it is propnetary and therefore the mathematical details are not covered in this
thesis.

3.2 TESTMETHoD # 1 :ACIDDISSOLUTION OF AUTOCATALYST SAMPLES

The fkst method of autocatalyst sample dissolution requires the use of

concentrated acids to digest the samples on a hotplate. There are many factors that can
affect the extraction of Pt group met& fiom the autocatalytic matrix Among these
factors are the type of autocatalyst, the sample particle size, the leaching tirne, and the
various acid combinations. AU of these fàctors play a role in PGE recoveries so each will
be discussed in detail.

The supporting matrix win affect the rmvery of PGEs in new and used
autocatalyst. Wu a al. (1993) briefly disaissed how recoveries fiom acîd dissolutions
were affected by mat& composition type. Presentiy there are a nwtlber of supporting
matrices for the PGEs in autocatalyst and these fiill essentiaiiy into two classes. These two
classes of catalyst are the monolithic and the peiîet types. The fist type has the PGEs
sprayed onto a cordiente m a t h while in the second the PGEs onto a y-silica substrate. A
cornparison of an aqua regia dissolution (3: 1 HCVHN03) on the two types of NIST
sarnples (NIST2556 -pellet and NIST 2557 -Monolith) is shown in Figure 3.1.
Figure 3.1 The effect of autocatalyst type on the extmtion of PGEs in new and spent
catalyst using an aqua regia disso1ution to sample dryaess.
 It is apparent that the aqua rea digestion gives >85% recovery in di instances,
regardless of the matrix type. This is probably b s e the PGEs fom a Surface coaîing
and are not an integrai part of the matrix itself. However, thae are signifiant diffefences
in the recoveries fiom the two types of ~IW&S.The y - a l d a in the pelleîs is pdally
soluble in aqua regia whereiu the cordierite of the honeycomb type catalyst is impervious
to acid attack. Thus the dEerence in solubility of the two matrix components is most
likely to be the cause for the bata recoveries âom the pellets.

3.2.3 EFFECTOF SAMPLE PARTICLE SIZE

Sampie size can play a sigdlcant role in the extraction of noble metals. Anderson
(1987) described how the padcle size of noble metal samples af!f'iected acid dissolution
results. Since aii samples in this project were prepmed in the same fmhion, the sample size
should be the same in ali cases. Generally, ali the autocatalytic samples were pulverized to
75 pm or -200 mesh and to prevent larger particles fiom entering into the sarnpk bettle,
al1 the crushed samples were thoroughly sifted. The particles that were larger than 75
or -200 mesh are trapped in the sieve and cannot p a s through. But in cases where the
sample sire may vary, it should be appreciated that sarnple size can affect the percent
extraction of that particular element (Ferry et al. 1995).

3 2.4 THE EFFECT OF LEACHING TIME IN OPEN BEAKER DIGESTIONS

Peny et al. (1995) describeci how extraction times affect PGE recoveries âom
various sample matrices. Their results indicate that extraction time can have a major
influence, and so a study ofthis &kt was &ed out using the autocatdyst samples with
aqua regia digestion. The percent of extraction for a range of digestion times was
measured using the dried and d e d MST 2557. Each of the seven acid combations
used an aqua regia (3:1 HCVHNa) mixture but additional acids were added to improve
the recoveries of the PGEs. Atta mcasured t h e intervals, the sarnples were removed
Born the hotplate, cooled and then diluted to 500mL. The d t s of this study are shown
Figure 3.2 and Table 3.1 .

Figure 3.2 The percent extraction of PGEs in cnashed autocatalyst (NIST2557) and
using aqw regia over a 4 hour period.

Percent Extraction (%)

1 1.5 2 2.5 3 3.5 4

Digestion Time (Houn)
Table 3.1 The percent dos of PGEs kt d e d autocatalyst (MST 2557) and
using aqua regia over a 4 hour period.

From the results above it can be seen that there was no improvement in the
extraction ofPt and Pd when extending the dissoIution t h e 6om 1 hour to 4 hours. There
was an improvement with Rh where &er 1 hou, only 82.00! of Rh was extracted while
after 4 houn 90.2% Rh was actracted. Acid dissolution does not effectvely extract ail
PGEs like the alkaü fiinon technique cm. Several attempts w m made to improve the Rh
extraction but for wet acid dissolution 90.2% was the best rwvery ochieved.

3.2.5 STUDMNG
THE VARIOUS ACID COMBINATIONS

A study of the various acid combinations on the spent autocatalyst samples was
performed to explore the possibility of improving the rmveries of Pt, Pd and Rh. Seven
different acid combinations were tried. The results of these experiments are shown in
Figure 3.3.
Figure 3.3 PGE ncoveries fkom a variety ofacid coaibUiation~in opai-begkm
-

digestions ofNIST 2557 (Honeycomb).

Percent Extraction (%)

Rhodium
Palladium

Sample #
Note: Sarnple #
1) HCI+HN03(3 :1)
 From the figure above, it is o b s m d that none of the various acid combinatiom
was able to extract 1W/o of Pt, Pd and Rh from the autocatalyst. The five acid
wmbination (#7) using 15 mL hydrochloric iiaâ, 5 mL nitric aci4 2 mL bydrofluonc acid,
10 mL perchioric acid, and 5 mL of 1:1 suifùric acid showed the best recoveries of the
PGEs ( 97% of Pt and Pd and 91 % Rh). Ail other acid combination showed infaor
extraction results to this acid combination. Thus it appears that open-beaker digestion is
not a satisfactory option for the dissolution of spait autocatalyst samples.

#2 : MICROWAVE-ASSISTED
3.3 TESTMETHOD DIGESTIONOF
AUTOCATALYST SAMPLES

A study was carried out to check whether the dissolution of the autocatalyst
semples would be improved when using the microwave-assisted digestion technique.
Autocatalyst samples were digested using various digestion times and two Werent acid
combinations. The variation of digestion tirne was midieci to sa if Rh could be fiilly
extnicted while the use of aqua regia and aqua regia with HF was studied due to the
improved Rh extraction resuIts when digested via the hot-plate technique. A bnef
discussion of these midies are as follows. A 0.15 g autocatalyst samples of reference
matenals was used in each study since it yielded the highest POE recoveh.

3.3.2 EFFECTOF VARMNG THE MICROWAVE DIGESTION TIME

The e f f i of varying rnicrowave digestion time was studied on the two different
certified reference catalyst sarnples. The resuhs obtained with two different dissolution
times are shown in Table 3.2 as compand to their cemfied values.
Table 3.2 Effect of varying the miaowave digestion thne on S R ,2556 (Peuet) and
SRM 2557 (honeycomb) wbile digesting with aqua regia and HF mixnue.

Platinurn Palladium Rhodium

SRM 2556 d u e s in ppm values in ppm values in ppm
(pellet type) (% recovery) (% recovery) (% recovexy)
certified values *
697.4 2.3 326.0 f 1.6 51.2 I 0.5

Found (ICP-MS) 715.2 * 2.8 328.5 k 1.9 *

46.3 0.9
10 minutes (102-6%) (100.8%) (90.5%)

Fould (ICP-MS) 71 1.9 I2.4 327.0 I 2.1 46.6 i 0.7

20 minutes (102.1%) (100.3%) (9 1.O%)

SRM 2557 values in ppm values in ppm values in ppm

(honeycomb type) (% recovery) (% recovery) (% recovery)
certified values 1131 i 11 233.2 î 1.9 135.1 * 1.9
Found (ICP-MS) 1125.9 f 9.8 231.5 * 2.1 121.9 i 1.7
10 minutes (99.6%) (99.3%) (90.3%)

Found (ICP-MS) 1128.6 & 8.8 *

233.9 2.0 126.4 i 1.5
20 minutes (99.8%) (100.3%) (94.0%)

Results are expressed in pprn and based on dry weight (500°C for 2 houn). Average of
triplicate results.
 In this investigation, the previously drieâ autocataiytic samp1es were digested witb
an aqua wgia mixture for eïther 10 or 20 minutes. The q u a regia combination gave
e x d e n t open-beaka r d t s which were comparable to d other rcid combinations used
in the open-beaka hot-plate digestion studies. The microwave oven was set to identical
power setting for each of the digested autocataîytic samples. The cornpuison of the
microwave results for the two NIST samples a f k Mefent dissolution time showed that
an increase in dissolution time wiii not increase the extraction of the Pt, Pd and Rh. The
results do show a slight but bignifiant improvement which can be amibuted to
Uistnimental drifting of the ICP-MS. It has ken obsecved tbat independent of the
dissolution time chosen, Pt and Pd are weli extracted through microwave dissolution. On
the other hand, Rh shows poor recoveries via miaowave dissolution evai afta varying
the digestion time. The poor Rh extractions could be due to two re8~011~.The fist reason
might be related to the oxidation of the Rh to Rh oxide (RhZ&) which is largely insoluble
in almost al1 acid combinations. The second possibility for poor Rh recoveries is probably
due to the inwmplete digestion autocatalyst samples. Therefore, digesting the samples for
20 minutes could correct for some low PGE results and was therefore chosen for all
samples.

Pt and Pd resuits were acceptable, but Rh results were wnsistently low. If this
method is employed, a correction fâctor needs to be appiied to the Rh recovery values.

OF THE ADDlTION OF HF TO THE MICROWAVE SAMPLES

3.3.3 EFFEC~

It has been observed that with the addition of conceatrated HF to samples

dissolved via the open-beaker acid digestion technique, the percentage of Rh recovered
was increased significantly. Thus a series of experiments were made in which HF was
added to the r d o n mDmûe composeci of the sample an q u a regia in microwave-
assisted digestions. The resuits are given in Tables 3.3.
Table 3.3 Wect of adding HF to the microwave digestion for amples of SRM 2556
(Pellet) and SRM 2557 (honeycomb).

Platinum Palladium Rhodium

SRM 2556 values in ppm values in ppm values in ppm
(pellet type) (% recovery) (% recovexy) (% recovery)

certified values

Found (ICP-MS)
Aqua regia with
no HF
Found (ICP-MS)
Aqua regia with
0.5 mL HF
F O U (ICP-MS)
~
Aqua regia with
1.0mLHF

SRM 2557 values in ppm values in ppm values in ppm

(honeycomb type) (% recovery) (% recovery) (% recovery)
c e d e c i values 1131 Il1 *
233.2 1.9 135.1 k 1.9

Found (ICP-MS) 1096.9 î 3.1 225.6 f 2.5 114.8 f 1.7

Aqua regia with (97.O%) (96 -7%) (85.0%)
no HF
Found (ICP-MS) 1125.9 k 2.8 231.5 î2.1 121.9f 1.7
Aqua regia with (99.6%) (99.3%) (90.3%)
0.5 mL HF
Found (ICP-MS) 1128.6 î 1.8 *
233.9 2.0 126.4 I 1.5
Aqua regia with (99.8%) (100.3%) (94.0%)
1.0 mL HF

Results are expresseci in ppm and based on dry weight (500°C for 2 hours). Average of
aipticate resuits.
 From the resuits in Tables 3.3, it can be seen that samples treated with HF and
aqua regia (3 :1 HCVWNa) showed betta Rh recoveries than those treated with just qua
regia. Sarnples treated with HF showed Rh fecoveries of 91 to 94% and up wbile those
with or@ aqua regia showed Rh recoveries ranging around 78 to 85%. Therefore it cui be
concluded that HF does help in the extraction of Rh.

Another advantage of using HF m the miaowave dissoIutioa is that the r d t s

fiom the samples treated with HF showed a better p&sion and accuracy over the
samples treated with only aqua regïa. The cornparison of the percent difference for NIST
25 56 samples treated and not treated w*thHF caa be seen in tables 3.4 and 3.5 below.

Table 3.4 Percent difference for NIST 2556 samples dissolved using
microwave dissolution and not treated with HF.

NIST . d g
2556 Pt Pd Rh
NIST Value 697.4*2.3 326k1.6 51.2=t0.5
MicrowaveACP-MS 695.5h9.1 33025.4 3 9 . W .O
DEerence +1.9 4.2 -2 1.3
Percent Merence compared to + 0.28 -
1.29 - 28.32
NIST

Note: Results presented above are the average of triplicate results.

Table 3.5 Pacent Merence for NIST 2556 sampIes dissoIved using
microwave dissolutiontreated witb HF.

NIST 1 ~g/g 1
2556 Pt Pd Rh
MST Value 697.4*2.3 326I1.6 51.2M.5

Percent merence compared to - 0.12 - 0.31 - 12.11

NIST 1 1 1 1
Note: Results presented above are the average of triplicate results.

When cornparhg the results fkom the hvo tables above, it cm be obsmed that the
addition of HF does help to improve the PGE relative percent error. At the m e time, it
also helps in the recovery of Pt (99.7%without HF compared to 99.9% with HF) and Rh
(779% without HF compared to 87.9% with HF) but it shows a negative effect 4 t h Pd
(101.00h without HF compared to 99.7%with HF). Unfortunately, the recovery of Rh is
still too low and therefore requires a correction. Although HF helped in the further
extraction of Rh but stiü does not solve the low recovery problem.

Unlike the NIST 2556 (Pellet) autocatalyst sample, the NIST 2557 autocatalyst
samples shows a slightiy dbierentresults. These results can be seen in Table 3.6 and Table
3.7 below.
Table 3.6 Percent diffecence for NIST 2557 samples dissolved
using microwave dissolution and not treated with HF.

NIST dg ,
2557 Pt Pd Rh
NIST Value 1131kl l 233211.9 135.1*1.9
. Microwave/ICP-MS 1096.9I13.9 225.6I3.7 114.8*5.2
. Merence -35 ,O -7.6 -20.3
Percent ciifference compared to + 1.30 - 3.30 - 15.0
Note: Results presented above are the average of tripiicate nsults.

Table 3.7 Percent dEerence for NIST 2557 samples dissolved

using microwave dissolution treated with HF.

MST
t
NIST Value 1131k11 233.2k1.9 135.111 .9

Merence +6.2 -0.8 -1 1.7

Percent difference c o m p d to + 0.55 - 0.36 - 8.66
NIST

Note: Results presented above are the average of triplkate results.

As seen in the two tables above, HF is useful for improving the percent relative
error for the MST 2557 autocatalyst ssmples. While improving the acwracy, it also helps
with the recovery of Pt (97.M without HF wmpared to 100.6% witb HF), Pd (96.7%
without HF compared to 99.7% with HF), and Rh (85.W wiîhout HF compared to
91.O0! with HF). Therefore HF plays a major role in the extraction of & Pd and Rh in
used autocatalyst samples. Unfortunately, the r d t s for Rh extraction are d
i too low
and therefore require a correction.
 In addition to helping improve the m c y of the microwave dissolution nwilts,
HF has alw improved the repeatability of the microwave digestion technique. This is
obsemd when compaMg the r d t s in Table 3.8 and Table 3.9 below.

Table 3.8 Repeatabidity of microwave resuits for NIST 2556 and 2557 semples
without HF.
-

le ment -n Mean @g@ -

SD RSD% A
SRM 2557 (Monolith)
Pt 12 1096-9 13.9 2.5
Pd 12 225.6 3-7 3.3
Rh 12 114.8 5.2 9 .O

SRM 2556 (Pellet)

Pt 12 695.5 9.1 2-6
Pd 12 330.0 5.4 3 -3
Rh 12 39.9 3 .O 15.1

A Results reported with a 95% confidence intefval.

Table 3 -9 Repeatabüity of microwave results for NIST 2556 a d 2557 samples with

Element -n Mean -
SD
SRM 2557 (Monoiith)
I
Pt 6 1137.2 13.2 1.2
Pd 6 232.4 2.6 1.1 ,

Rh 6 123.4 1.6 1.3

SRM 2556 (Pellet)

Pt 6 696.6 3.8 1.1
Pd 6 325.0 1.8 1.1
Rh 6 45 .O 0.7 2.9

A Results reported with a 95% confidence interval.

Samples treated with HF and then digested via the rnicrowave have shown
excellent repeatability. The repeatability of these samples was calculated at about half of
the repeatability of those samples no treated with HF which indicates that HF is beneficial
to both the accuracy as seen, but also the precision of PGE dissolution h m the two types
of sample matrices (Honeycornb and Peiiet). As a result of these hdings, HF was added
to all subsequun samples to aid in the PGE dissolution. Unfortuaately, because of the very
Iow Rh recoveries, microwave assiaed dissolution was not explored in any great detail.
To improve Rh recoveries, two Limitations of this technique and instrumentation need to
be changed. The first limitation is due to the temperature and pressure required for sample
dissolution. The present rnicrowave apparatus can only go to 120 PSI which is not high
enough to digest the samples aad Rh properly. The second limitaîion to microwave
assisted dissolution is its inabiliîy to M y dissolve the cordierite and y-aluminia which
could pose as a possible problem for the ICP-MS hardware. SampIe w o n could
prevent such hardware problems but it is not required since the cordierite and y-aluminia
precipitate to the bottom of the JO mL Falcon Tube and thus are not trpnsférred to the
final aspirated solution.

The first method explorecl in this project was sodium peroxide fusion of dned
autocatalyst. This method provides the analyst with a f'kt and labor s a h g analfical
method for prepuing autocatalyst samples prior to ICP-MS d y s i s . But, d e s s the
method is properly developed, fùsion prepsration d l not provide accurate and pr-
analytical results. There are five areas of possible conceni when preparing samples by
alkali fusion. The first problem is due to rnatrix interférences fiom interferhg species in
the dissolved matrix or the matrix itseif while the second problem is fiom the choice of
intemal standards used with the ICP-MSfor accurate and precise PGE daennination.
Samples that have not been prevhusly dned and therefore have water bound to them c m
also be a major concem for PGE detemination in new and used autocatalyst samples. The
problem of choosing proper sample weight and flux weight is also important in the
determination of Pt, Pd and Rh. The f i d problem deals with how the samples are fused.
Since each of these plays an extremely important role in quantitative analysis of
autocatalyst by fision preparation, each will be discussed in detail.

3.4.2 PROBLEMS
ARISING FROM ALKALI MATRIX COMPOSïïiON

Sodium peroxide alkali tiision is by fiu the best method for dissolving the
autocatalyst samples. It is one of few dissolution rnahoâs that can effectively dissolve the
honeycomb's cordiente ma& as discussed by Totland et al., (1995). Udortunately, the
use of sodium combined 6th concentrateci hydrochlonc acid does provide for the
possiûiility of forrning salts within the ICP-MSinstrumentation and dso in the dissolved
samples. Sdt formation prevents the proper detection of PGEs în successive samples
thereby affècting the d y t i c e l r d t s . To avoid possible salt formation problems, the
present samples were diluteci with deionid -ter Usng extrane care and caltirateci
glassware. Due to the excellent sensitivity of the ICP-MS, this is a possible solution to
preventing salt forniaton but not for most other anaiytical instnunents. This is why ICP-
MS is the desirecl instrument for PGE Bnalysis in used autocataiytic sarnpla. This dilution
kctor has proven very effective and no further exploration into sample dilution bas been
attempted.

Along with interferences resulting fiom salt formation, another fkctor affecting the
analytical results is the concentration of acids within asphted samples. Initially analyzed
samples contained 0.4% (vlv) dissolved acid and the Pt, Pd and Rh results were mostly
biased low. Several attempts were made to correct for the analytical bias but none were
successful. The problem was later solved when a 2-3 mL aliquot of concentrated
hydrochloric acid was added to the aspirated sample. It was established that due to the
initiaiiy Iow concentration of acid within the aspirated samples, the Pt was precipitathg as
Pt chloride species. With the addition of concentrated hydrochloric acid, the Pt could no
longer precipitate and the bias was no longer apparent. The results âom the addition of 2
rnL of HCI to the aspirated samples can be seen in Table 3.10 below.
Table 3.10 Compan*sonof ICP-MS resulto vaiidnting the addition of 2 ILof
concentrated HCI to the aspirated sample to help improve the acairacy of
PGE detennination and remove the bias.

/g
1 SRM 2557 (Hontycomb) ( SRM 2556 (Pcllct)

A) NIST certified results.

B) Aspirated Sample results with no prior addition of concentrated HCI.
C) Aspirated samples redts with concentrated HCl added (2-3d)

From the table above, it is apparent that the addition of 2 to 3 mL of conantrated

HCI to the aspirated solution helped in improving the determination of Pt, Pd and Rh. For
the MST 2557 autocataiytic sample, the ICP-MSresuhs with no hydrochloric acid added
had 99.7 f 0.8 % extraction for Pt, 99.0 f 0.6 % for Pd and 99.5 f 0.4% for Rh. The
simples with hydrochioric acid added to the aspirated samples showed a 100 f 0.8 %
extraction for Pt, 99.3 k 0.5 % for Pd,and 100 f 0.3 % for Rh. Thdore it is observed
that hydrochloric acid did help in the determination o f the PGEs for the howycomb type
catalyst since there was 0.33 f 0.1 % irnprovement for Pt and Pd and 0.70 f 0.1 %
improvement for Rh.
 For the NIST 2556 autocatalytic ample, sampfes not treated with hydrochloric
acid saw a 99.7 f 0.9 % extraction of Pt, 99.1 M.6 % -*on of Pd, and 98.6 f 0.5 %
extraction of Rh. Samples treated with hydrochloric acid pnor to aspiration showed
extraction of 99.9 f 0.7% for Pt, 99.5 I 0.5 % for P4 and 99.2 I 0.4 % for Rh. Thae
was a 0.3 f 0.1 % improvement for Pt and Pd and a 0.6 f 0.1 % improvement for Rh.
Thus, the addition of hydrochloric acid dso helps in the determination of Pt, Pd, and Rh in
pellet type autocatalyst samples.

The addition of 2-3 mL of concentrated hydrochioric acid does help improve the
ICP-MSresults for the three PGEs in autocatalyst but shows little 8 k c t on improving the
instrumental precision. Due to the improvement in PGE results, al1 subsequent aspirated
samples were spiked with a 2-3 mL addition of concentrated hydrochloric a d pnor to
sample analysis on the ICP-MS.

3 -4.3 PROBLEMS
DUE TO INTERNAL STANDARD SELECTIûN

The selection of an internai standard plays a vital role in the determination of Pt,
Pd and Rh in new and used autocatalyst. Two types of internal standards were tried. The
first type included elements not found withh the dissolved niatrix but whose m a s closely
matched those of Pt, Pd and Rh. The second type of internal standards were isotopes of
the elements Pt and Pd. Rhodium is monoisotopic and therâore required the first type of
internai standard for moaitoring. A brief discussion of these two types of internal
standards foiiows.

As mention& the first type of interd standards were used because they were not
present in the sample solutions and they were closely matched in ~MSSto the PGEs. In this
case four elements were chosen as internal standards and these were Indium and llullium
for Pt and Iridium aad Ruthenium for Rh, Pd. The dection of these initial four standards
was due to their relatively close masses to the PGE elements. It was found that the use of
two of these intemai standards failed to produce satisfactory nsults. Thallium and
Ruthenium both gave inconsistent resuits when used as intemai standards as shown in
Table 3.11. The precision associateci with these two intemai standards is shown in Table
3.12.

Table 3.1 1 Percent ciifference of ICP-MS results using ruthenium and thallium
interna1 standards.

SRM
2557 Pt 1 Pd 1 Rh
N S T Value 1 1131.0*11 1 23321.9 1 135.1*1.9
FusioriICP-MS 1 142.8*1 1 230.5I3.2 131.311.4
DBerence +11.80 -2 -70 -3 -80
Percent difference compared +l .O4 -1.16 -2.81
to NIST -

NIST Value 697.4*2.3 326*1.6 51.2M.5

FusionnCP-MS 692.46.3 323.1G.4 50AM.6
Difference -5.00 -2.90 -0.80
Relative Error (%) compared -0.72 -0.89 -1 -56
to NiST

The results in Table 3.1 1 above show that Rutheniium and Thallium give good
PGE determinations but slightly outside acceptable range. Generaily, fireassay &'bit a
1.0 % relative error. nie average relative percent error for the MST 2557 samples was
found to be 1.04 % for Pt and an average of 2.0% for both Pd and Rh. As for the MST
2556 sample, Pt had a 0.72 % relative enor and Pd and Rh showed an average 1.2 %
relative error. Therefore, fiom the data presented above, it can be concludeci that Ru is not
an acceptable intemal standard for the determination of Pd and Rh. Thallium still is an
acceptable interna1 standard for the determination ofPt but shows the same =tic nature
of Ru.This erratic behavior is rsadüy seen in Table 3.12 below.

Table 3.12 Precision of ICP-MS resuits using Nthenium and thallium intenial
standards.

Element 1 -n 1 Mean hg@ 1 -

SD / RSD NA
1 SRM 2557 (Monolith) 1 1 1 1

SRM 2556 (Pellet)

A Precision based on a 95% confidence interval

The target precision for this study was < 2%. For both the Ru and Ti internai
standards, the precision is found to be above this target. This is largely due to the erratic
behavior of the intemal standards and as a result of this erratic behavior, Ru and Tl
possibly can not be possibly used as internal standards for the detemination of Pt,Pd, and
Rh. Therefore a more suitable set of internal standards is required.

Since nithenhm and thallium gave unacceptable results when used as interna1
standards, other elements were tried as interd standards. The second set consisted of
iridium and indium, also not presait in the dissohred autocatalyst samples. The general
accuacy and precision associated with the use of indium and iridium as intenial standards
can be seen in Tables 3.13 and 3.14 below,
Table 3.13 Percent merence of ICP-MS resuits using iridium and indium
intenial standards.

SRM
2557 Pt Pd Rh
I u

NIST Value 1131.0111 233.2I1.9 135.111.9

Aîkali FusionfICP-MS 1131.3I6.8 231.6~1.7 135.811.6
Merence +0.30 -1.60 +0.70
Percent merence compared to +0.03 -0.69 +OS2

SRM Mid&!
2556 Pt Pd Rh
MST Value 697.4*2.3 32611.6 51.2a.5
Aikali Fusion/ICP-MS 696.515.9 324.512.0 50.8&0.5
DEerence -0.90 -1.50 -0.40
,
Percent Merence compared to -0.13 -0.46 -0.78
NIST

The relative percent errors associated with the use of indium and indium as
internai standards are found to be weii below the 1% k t for Pt, Pd, and Rh
determinations in autocatalyst. The recovenes for each of the PGEs are also much better
then those of Ru and Ti interna1 standards. Since indium and iridium show good relative
percent errors as compared to the certifieci results, the precision of these two standards is
shown in Table 3.14.
Table 3.14 Precision o f ICP-MSr d t s using indium and indium k t d standards.

Element
1
-a Mean (-&& -
SD RSD % A
SRM 2557 (Monohth)
Pt 16 1131.36.3 6.8 1.2

I
SRM 2556 (Pellet) 1

A Precision based on a 2a or 95% confidence interval

From the results above, the precision associated with the determination of Pt, Pd
and Rh are below the 2%limit . The relative standard deviations associateci with the use of
indium and iridium are well within acceptable lisnits and are even lower then those
reported by NIST (Beary and Paulsen, 1996). Therefore, indium and indium seem to be
the appropnate choice as intemal standards for Pt, Pd and Rh determination for new and
used autocatalyn samples.

The next set of internal standards tested not ody matched the Pt and Pd through
mass but also chemicaliy. Isotope dilution ICP-MS is considend to be the most accurate
and sensitive anaiytical method available for PGE determinations (Beary et al., 1994). The
accuracy and sensitivity for isotope dilution is better then that of NAA with Pt, Pd, and Rh
determinations. Rh is monoisotopic and therefore required the first type of internal
standard. Iridium was used to detemine Rh by ICP-MS. The isotopes were dissolved
ushg ultra-pure nitric and hydrochloric acid (Aldrich) over a hot-plate and were dihited
with D.I. water. The acid concentrations ofthe disdohted stock solution of isotopes were
closely matched to those of dissdved autcsataiyst to ensure totai compatiiüity between
the two samples and elimlliate ma& effects. One problem with the use ofthis second set
of intemal standarâs was that the software needed to be developed and the method only
became available at the end ofthis project, so fw resuits were obtained.

3.4.4 SAMPLE
DRYING PRIOR TO DISSOLUTION

The autocataiyst, although previously drkd arrives at the laboratory in a wet or

darnp state and must therefore be dried (Anderson, 1987). Once the samples are dried,
r prevent them fiom picking up water fkom the
they should be then stored in a d e s i ~ o to
atmosphere. In this project, the samples were âried by the method used by MST in the
certification of autocatalyst materiais (Beary et al., 1994). In the NIST dryiag process, the
sarnples are dried at 500°C for 2 houn and then cooled in a desiccator. This elhinates
both carbon and water fiom within the certined MST 2557 (honeycomb) and NIST 2556
(Pellet) samples. (See Figures 3.4 and 3.5)
Figure 3.4 Calcination redts fiom LEC0 and water anaiysis of MST 2557
(honeycomb) autocataiyst.
Figure 3.5 Calcination results from LEC0 and water d y s i s ofNIST 2556
(Peuet) autocatalyst.

+Percent Water
Perceni Carbon
----#----.
-+--
Percent SiiWr
 The water content of several autocatdyst samples prevïouely analyzsd by firr assay
can be found in Table 3.15 below. The samples are used to validate the rllraü fision
preparation technique.

Table 3.15 Water concentration of prwiously dned and analyzed autocataiytic samples.
Sample Sample Smple Dry Sample Percent
Number ID Added Wei@ water '
(#) (BI (BI (%)

4 S24350) 2,0743 2.0078 3.21 i 1.01

5 52471(M) 2.0126 1.9926 0.99 I 1.05
6 S2427(P) 2,1515 2.0666 3.95 I 1.11
7 S24600 2.2097 2.1856 1.09 I 1.03

0 is the monolithic autocatdyst fom.

(P) is the pellet autocatdyst fom.
a
Al1 water results are reported averages of tripiicate d y s i s . Water was determined ushg
the weight Merence method.
 As with the certified standards, the results in Table 3.15 show that the monoIithrtc
type of autocatalyst generally contain around 1% bound water whaeas the pellet fom of
catalyst general contains anywhere fiom 2 4 % bowd water. Although the concentration
of b o n d water is quite mail, Ï t does play a large rote in the d y t i c a l resuits on the 1 8 -
MS. This is seen when cornparhg the wet and dried ICP-MSresults ofNIST 2556 (Pellet)
and NIST 2557 (honeycomb) as seen in Table 3.16 below.

Table 3.16 ICP-MSresults fiom wet and dned NIST samples

SRM 2557 (Honeycomb) SRM 2556 (Pellet)

-
Pt -
Pd -
Rh -Pt Eé -
Rh

A 1131*11 233.211.9 13s.la1.9 697.4k2.3 326I1.6 51.2*0.5

B 1118.6f8.8 230.9f1.9 133.8I1.8 683.3k6.4 317.1f2.2 50.2f0.8

I l
c
I I
1130.8I6.8 233.2f1.7 135.111.6
II I
697.1f5.9 326.1f2.0 51.2f0.5
I
A NIST Certifieci Results
B Wet sample ICP-MS results
C Dned samples for 2 hours at 500°C and analyzed by ICP-MS

These results illustrate the importance of a dryin~calcinationstep in the sample

preparation process.
3.4.5 EFFECTSOF SAMPLE SIZE AND QUANTITY OF FLUX

A series of experiments were carrieci out to investigate how a variation in

the sample and flux weights would affect the recovery of Pt, Pd and Rh from used
autocatalyst. The sample Ne is particularly important when dealing with PGE-containhg
samples, as the metals are often unevenly distributecl so the Iarger the sample, the more
homogeneous and representativc the resulrs wiii be. To find the smallest ample size for
effective analysis, the standard refereace materiais MST 2556 (pellet) and MST 2557
(honeycomb) were fuseci ushg various weights ranging between 0.1 g to 0.5 g. AU these
samples were fised with 2.5 g of sodium peroxide foilowing the mahod listed in section
2.2. The resuits fiom NIST 2556 (Pellet) and MST 2557 (Honeycomb) can be seen in
Figures 3.6 and 3.7.
Figure 3.6 Effect ofvarying m p l e weight on POE extradon on dned autocatalyst
samples(2 Hours @ 50o0C)(NIST 2556 Petlet)

Percent Extraction ofAnaïyte (%)

Wei@ Of Autocatalyst Sample (gm)

 Figure 3.7 EEect of varying sample wught on PGE d o n on dried eutocatalyst
samples(2 Hours @ 500°C) (NIST 2557 Honeycomb)

Percent extraction of analyte (%)

Weight of autocatalyst sample (gm)

 From the results in Fi~ufes3.6 and 3.7, it was obseved thaî the minhum weight
required for effèctive autocataîyst saxnple fisions was about 0.25 g for NIST 2556 (100
percent extraction ofPt, Pd and 99.3 % Rh) and MST 2557 (100 percent aarsction of Pt,
Pd, and Rh) whüe ushg 2.5 g sodium peroxide aikali fim. It was ais0 observeci that larger
samples do not fise es well, p d I y because there was inainiCient hvr amilable. The
r d t s for the NIST 2557 samples compared weli to those of MST 2556. Consequently, a
0.25 g autocatalyst sample size is used for the remainder of this study.

Along with varying the sample weight, it is dso important to observe how the
amount of flux affects analytical renilts. Using the standard reference materials MST 2556
(pellet) and NIST 2557 (honeycomb), a 0.25 g autocatalyst sample was tUsed using
various sodium peroxide weights. The flux weights ranged between 1 to Sg additions. The
samples were nised using the method iisted in section 2.2. The results are shown in
-
Figures 3.8 (NIST 2556 - Pellet) and 3.9 (NIST 2557 Honeycomb).
Figure 3.8 Effect ofvwng flw waght on PGE extraction on dned autocatdyst
samples(2 Hours @ 500°C) (NIST 2556 Pellet)

Percent Extraction (%)

Sodium Peroxide Wei@ (gm)

Figure 3.9 Effect of vaiying flw< weight on PGE extraction on dried autocatalyst
samples(2 Hours @ 5ûû"C) (NïST 2557 Honeycomb)

Percent Extraction (%)

Weight Sodium Peroxide (gm)

 The resuits seen in Figures 3.8 and 3.9 show aimost identicai results. For NIST
2556 (Pella) samples, the extradon of 99.6 % Pt,99.2 % of Pd, and 99.8 % of Rh was
achieved. NIST 2557 (Honeycomb) r d t e d in extradons of 99.3 % of Pt, 99.3 % of Pd,
and 100.0 % of Rh. Thadore, the results indicate that a 2.5 g of fiwt is d c i e n t for use
with a 0.25 g sample, so this was used for these studies.

Since an automatic fluxer was available, some experiments were carrieci out to
compare results using this method with the slower manu81 fluxing method. It was
anticipated that the automatic fluxer would show a greater wnsistency of results. These
resuIts are shown in Tables 3.17 and 3.18.

Table 3.17 Relative error involved with hand fbsion of standard

reference materials

SRM s
2557(Honeycomb) Pt Pd Rh
NIST Value 1131 233.2 135.1

Merence +9 .9 -2-7 -1.1

Relative error (%) compared to +0.87 -1.17 -0.80
NIST
~ SRM
2556 (Pellet) 1 1
I NIST Value 1 697.4 1 326 1 51.2

1 Relative enor (%) compared to 1 -1-76 1 -7.1 1 1 -5 -45

1 NIST 1 1 1
Table 3.18 Relative error involveciwith the automatic fision of
standard reference materials

SRM .
2557(Honeycomb) Pt Pd Rh
NIST Value 1 131.W11 233.2*1,9 135,111.9
Alkali Fusion/ICP-MS 1131.36.8 231.&1,7 135.8k1.6
DifEerence 1 +0.30 -1 -60 +0.70
Relative emor (%) compared to +0.03 -0.69 +OS2
NiST
SRM
2556 (Pellet) Pt Pd Rh
NIST Value 697.4~2.3 326*1.6 5 1.2a.5
Alkali Fusion/ICP-MS 696.515.9 324.5*2.0 50.8G.5
Difference -0.90 -1.50 -0.40
Relative error (%) compared to -0.13 -0.46 -0.78
NIST

A comparison of the two tables above shows that a smaller relative percent error
compared to NIST is achieved when usîng the autornatic fiuxer for ail PGEs. The
improved results on more noticeable with the MST 2556 (Pellet) samples than those of
NIST 2557 (Honeycomb) sarnples. A comparison ofthe repeatability of each of these two
sample preparation methods may provide for additionaf information. The repeatabiiity for
the two methods of fision are seen in Tables 3.19 and 3 -20below.
Table 3.19 Repeatabüity associated with hand fision of autocatalyst

l
Element 1 -n 1 Mean (u& 1 -
SD %RSDa

SRM 2556 (Pellet)

Pt 16 685.1 15.8 4.6 1
Pd 16 302.8 26.7 17.6

a
Results reported on a 95% confidence interval.

Table 3.20 Repeatability associated with the automatic fusion of autocatalyst

-
SD RSD % '

1131.3 6.8 1.2

23 1.6 1.7 1.5
Rh 15 135.8 1.6 2.4

SRM 2556 (Pellet) .

Pt 16 696.5 0.5 1.9
Pd 16 324.5 2.0 1.3
Rh 15 50.8 5.9 1.7

a
Resuits reporteci on a 95% confideme interval.
 From the resuits in the pmcision tables above, it is observed that the automatic
fùsion of autocatalyst samples d a s provide for a Mer mahod of sarnple prepmtion
The method repeatabiiity for automatic fùsions are much betta thai those ofmanuai hand
fisions since automatc sample fùsion treats all samples equally thus eliminating the
possiiüay of randorn errors d a t e d with the inaaualRision of samples. Such errors are
due to the improper sample agitation wbich varies W e e n samples, the various flux
temperatures due to the changing cnicible location over the fiame, and sample spülage,
loss, or sputtering due to overheating. As a result of the findings above, ail samples were
fiised using a LEC0 automatic fluer.

3.5 SMLE FUSION RESULTS AND DISCUSSION

The deternination o f Pt, Pd and Rh in both NIST and routine production samples
relied h e d y on the ability of ICP-MS to provide highly acairate and precise
determinations of the PGEs in the new and used autoatalyst sampies. An examination of
the reailts suggests that they are clearly dependent on the choice of internal standard used
to monitor each of the PGEs. Since two types of internal standard were used in this
project, it is important to compare the d y t i c a l results from each of these two types of
intemal standard. The firsî type of intemai standard included elements not present in the
dissolved autocatalyst mat& but that closely matched the mass of either Pt, Pd or Rh and
is discussed in Test Method 3G The second set of intenial standards was made of
isotopes of Pt and Pd. The use of this isotope düution technique is expected to give
excelient resuits since the standards match tk analyte elements in both mass and chernical
properties (Beary and Paulsen, 1996). This technique cannot be used for monoisotopic
elements such as Rh, so a cornVition of the two internai standards was required where
Rh detenninations were needed. The second method is seen in Test Method #3B. An
exploration of the results fkom the two test rnethods foiIows.
3.5.1 TESTMETHOD #3A :DISCUSSION
OF RESULTS FROM MASS MATCHED
INTERNAL STANDARDS.

Two sets of internai standards were d e d . The first set consisted of

Ruthenium for Pd and Rh detenninatiom and Thallium for Pt determinatiom wbile the
second type consisted of Indium for Pd and Rh determinations and Iridium for Pt
detenninations. The R f l combinations gave poor resuits and so was not used m e r .
Indium and iridium wexe selected as the internal standards for PGE analysis on the ICP-
MS.The accuracy and precision of the tesuIts for the two NIST samples d y z b d with
indium and iridium as internal standards can be seen in Tables 3.13 and 3.14.

The results pre~ntedin the two tables above show no bias with good recoverks
and repeatabilities. Thus the choice of indium aad iridium as internai standards proved
effective. As a result, 24 separate and previously anaiyzed autocatdyst samples were
selected and analyzed for PGE determination using this alkali fusion dissolution technique
followed by ICP-MS analysis. The results fkom both the nickel suifide fue assay method
and Ledoux's (A-1) acid dissolution and fire assay method (see Appendix) are compared
with the resuhs fiom thîs project.

The platinum redts are considered first. Table 3.21 presents results obtained for
Pt analyses using this test method dong with correspondiig results obtained using the
rnethods dedbed in Appendix B. The last two columns give the percent difference in
result between the test method and the standard methods employed nickel ailfide
collection and acid dissolutionlfire ssay cokction.
Table 3.21 ICP-MS resuhs for Pt detemidon compared with nickel sulfide
fin-assay and phosphoric acid/fire assay.

Sample NiS Fire Phosphoric ICP-MS % Diffaaice % Merence

Assay A acidfire-
as=Y =
# c1d8 dg CiB/g to NiS Mahod to Acid/Fiue
Assay Method

2427 583.89 603.09 585.10 0.2 1 -2.98

2428 922.64 925.04 922.46 -0.02 -0.28
2435 420.00 424.12 417.41 -0.62 -1.58
2443 885.95 893.15 886.37 0.05 -0.76
2445 463.89 570.18 570.56 22.99 0.07
2460 870.86 869.84 864.08 -0.78 -0.66
247 1 921.95 913.04 915.42 -0.71 0.26
2475 663.78 686.06 679,t 7 2.32 -1.00
2484 845.49 882.86 872.80 3 .23 -1.14
2493 705.95 696.0 1 707.89 0.27 1.71
2495* 914.99 915.09 895.70 -2.1 1 2.12
2502 655.55 650.06 644.34 -1.71 -0.88
2970 937.38 1002.18 937.54 0.02 -6.45
2935 798.18 889.04 802.19 0.50 -9.77
295 1 852.35 911.32 851.94 -0.05 -6.52
2912 934.23 934.29 934.9 1 0.07 0.07
2962 913.04 976.12 976.51 6.95 0.04
298 1 856.12 915.09 914.37 6.80 -0.08
303 1 663.78 658.98 666.11 0.35 1.O8
3048 677.83 673.O3 673-93 -0.58 0.13
3007 692.92 689.83 694.72 0.26 0.71
3004 643.90 629.83 643.16 -0.12 2.12
3025 717.61 739.89 718.3 1 O. 10 -2.92
3016 656.20 665.15 665.5 1 1.42 0.05
A Anaiysis done with Nickel sulfide fue assa, and teiiuriurn CO-praipitation
folowed by ICP-OESand AAS spectd analysis. Results an of tripliate assays.
Anaiytical r d t s reporteci from phosphoric acid dissolution plus h a s s a y
digestion combinations foliowed by ICP-OES specnal d y s i s .
ICP-MS redts fiom alkaü fused samples foilowed by anaiysis on a Perkin Elmer Elan
6000 ICP-MSusing Indium and Iridium intemal standards. Results are an average of
quintupla assays.
 A doser examination of the resuits in the tabk shows tbat in plmost every instant
the test method is close (within 1%) to one or both of the standard rnethods. The
exception is #2495 which is about 2% lower then both of the results. Howeva, the nickel
suifide and phosphoric acid/fkassay resuhs themsebes difib by more tban 2% for
samples #'s 2427,2445,2970,2935,2951,2962,2981, and 3004. From this perspective,
a 2% Merence in one nsult suggests the method compares f o d y with the standard
method.

The average precision for quintuplet a~saysd a t e d with these 24 values was
found to be 1.13% on a 95% coufidence interval. A Students t-Test was pedormed to
measure signincant difference between the test mahod resuits to those of the nickel
sulfide and phosphoric acidlfireassay methods. A cornparison of the test method r d t s
and the nickel suifide results found a 1 ta 1 of 1.763. A compatison of the test method
results to the acidlfire-assaymethod resulted in a 1 ta1 of 2.057. The t23,01325 was found to
be 2.069 (Khazanie, 1990). These values show that there are no significant dierences
between the test method of the student method and the nickel sulfide and phosphonc
acid/fire-assay standard methods at the 95% confidence level. This is also true for the 99%
confidence interval (t23,0.0025 = 2.807).

The palladium test results are considered next (Table 3.22) using this test method
dong with corresponding results obtained using the nickel s a d e and phosphonc
adfire-assay standard methods descri'bed in Appendix B. The lest two columns give the
percent difference in result between the test method and the standard methods employed
by the nickel suIfide method (column 5) and the acidlfire-assay method (column 6).
Table 3.22 ICP-MS r d t s for Pd determination c o m p d with the nickei sulfide
fire-assay r d t s and the phosphoric ricidiire-assay iesults.

Sample NiS Fire- Phosphori ICP-MS % Merence % Diffefetlce

Assay A cacidJfire-
assay
# ~d6 ~d8 pg/g to NiS Method to AcidFie
Assay Method

A Anaiysis done with Nickel sulade fire assay and tciiuriurn co-precipîtation
foUowed by ICP-OES and AAS spectral 81181ysiis. Resuits are of tripiicate assays.
Anaiyiical resuits reporteci âorn phosphorîc acid dissoIuti011plus fie-assay
digestion combinations foiioweâ by ICP-OESspearal anaiysis.
ICP-MSresuhs h m alkali fùsed samples fdowed by d y s i s on a P e r h Elwr Elan
6000 ICP-MSusing Indium and Iridium i n t d standards. Resuits are an average of
quintuplet assays.
 A closer examination of the Pd results in the table shows that in almost mry
instant the test method is close (witbin 1%) tto one or both of the standard methods. The
exception is #2495 which is about 2% bigha then both the nickel d i d e and phosphoric
acid/fire-assay results. Unfortunately, even aAa repeated alkali fùsions and ICP-MS
analysis, the Pd results never came close to either the nickel d d e nor the acid/fire-asay
resuhs. As a result, the sample is beüeve to be mothm prepared autocatalyst mple,
therefore it was removed nom our sample populations by using the Dkon & Dean outliner
test (1951).

The average precision for quintuplet assays associated with these 24 values was
found to be 1.09% on a 95% confidence inteoral. A Students t-Test was performed to
measure sisnificant diierence between the test method results to those of the nickel
sulfide and phosphoric acidlfire-assay results. A cornparison of the test method results and
the nickel suffide results found a 1 ta 1 of 1.521. A cornparison of the test method results to
acidfire-assaymethod resulted in a 1 t 1 of 0.021. The ta, 0.m was found to be 2.069
(Khazanie, 1990). These values show that there are no signifiant ciiffierences baween the
test method of the student method and the nickel sulnde and the phosphonc acidfireassay
standard methods at the 95% confidence Ievel. This is also tnie for the 99% confidence
intervai (t23.0.0025 = 2.807).

The rhodium results are now considerd. These results are given in Table 3.23
dong with conesponding resuits obtained ushg the nickel sulnde and phosphonc acidlfire
assay standard methods described in Appendix B. The lest two columns give the percent
dEerence in result between the test method and the other two standard methods.
Table 3.23 ICP-MS r d t s for Rh detaaiiaation compareci to the nickel d d e
fire-assay redts and the phosphoric acid/hassay resuits.

Sample NiS Fire- Phosphoric ICP-MS % Mefence K Difference

AssayA acidlfire
assay
# ~dE5 pgig to NiS Method to AciWie
Assay Method

M y s i s done with Nickel sulfide fbe assay and teIIUnun CO-precipitation

followed by ICP-OES and AAS s p d anaiysis. Resufts are of triplïcate assays.
M y t i c a i results reported from phosphoric acid dissolution plus fireassay
digestion combinations foliowed by ICP-OES spearal analysis.
ICP-MSresuits âom alkali fùsed samp1es followed by d y s i s on a Pakin Elmer Elan
6000 ICP-MS using indium and Iridium intenial standards. R d t s are an average of .
quintupkt assays.
 A doser examination of the Rh d t s in the table shows that in aimost m r y
instant the test method is close (within 1%) to one or both of the standard methods.
There are t h e exceptions whkb are #'s 2435, 2445, and 2495 which are respectively 27
%, 2.5%, and 9.2 % lower or higha than both the other two method nsults. However,
the nickel sulnde and phosphoric acid/&easay resuhs themseives mer by more than
50% for sample 2445 and more than 9.2 % for samples 2427,2428, and 2443. For a 2.5%
variation, the foUowing INCO and Ledoux samples that vary by more than 2.5% are 2427,
2428, 2443, 2475, 2493, 2502, 2935, 3004, and 3031. From this perspective, a 2.5%
diffmnce in one result suggests the rnethod cornpans f o d y with the standard method.
As for the other hHO samples, 2495 and 2435, even &er repeated alkali fiisions and ICP-
MS analysis, the Rh results never came close to either the nickel suifide nor the a c i d / h
assay results. As a result, the samples are believed to be another pnpared autocatalyst
sarnple but due to the disappearance of the original sample container, this will never be
confimed. As a result, the sample were removed fiom Our sarnple populations by using
the Dixon & Dean outliner test (1% 1).

The average precision for quïntuplet assays associated with these 24 values was
found to be 1.23% on a 95% confidence interval. A Students t-Test was performed to
measure significant difference between the test method results to those of the nickel
suifide and phosphoric acid/fireassay resuits. A cornparison ofthe test method results and
the nickel sulfide method results found a 1 ta 1 of 0.11. A cornparison oftbetest method
results to phosphoric acid/fireassay method resuited in a 1 h 1 of 0.17. The tu,0.025 was
found to be 2.069 (Kbazanie, 1990). These values show that there are no signifiant
ciifferences between the test method of the student method and the other two standard
methods at the 95% confidence level. Tbis is also m e for the 99% coddence interval
(t23,O.oOZS = 2-807)-
 The results presented above indicate that the fint test method @vas acceptable
redts and could be used to replace the nmeat standard nickel sulfide method. Test
method #3B is now considered.

3.5.2 TESTMETHOD 3B:DISCUSSION

ON RESULTS FROM ISOTOPE DïLüTïON
W R N A L STANDARDS

Before the isotope dilution studies could be tested, it was necessary to develop the
required software for the instrument. This method will look at the results achieved with
the NIST autocatalyst samples. The percent difference associated wîth the m a s matched
indium and indium standards is seen in the Table 3.13 while those using the ushg ~ t ' *
and ~ ' ~ and Iridium interna1 standards are seen in Table 3.24.
disotopes

Table 3.24 Percent difference of ICP-MSresults using ~ t ' *and pdlWisotopes and
indium internai standards

NIST Value 1 1131.0*11 1 233.211.9 1 135.111.9

Percent Merence compared 1 -0.07 1 -1.35 1 -0.96

SRM

NIST Value 1 697.4k2.3 1 32611.6 1 51.2I0.5

Percent merence compared to

NIST 1 -0.65
1 1 +Os8
 Table 3.24 shows that isotope dilution shows no bias and provides excelient
results. The relative error of this method compareci to the MST fesults is under the one
percent imposed INCO limit for PGE deteminations in autocatalyst for most uialytes
(except NlST 2557 - Pd (1.35%)). The isotope dution resuits are a h closely match
those listed in Table 3.13 for the In and Ir intemal standards. As a result, this test method
muid be explored even fiutha.

Indium and iridium provide excelient d es and at the same time really good
instrumentai precision. The precision rissociated with the use of these two internai
standards is seen in Tables 3.14 and 3.25 below.

Table 3.25 Precision ofICP-MS results ushg ~ tand' ~ d~' "isotopes and
indium intenial standards.

Element 1 -n l ~ e a (u&l
n -
SD 1 RSD%*
SRM 2557 (Monolith) 1 1 1 1 1

SRM 2556 (Pellet) 1 1 1 1

A Precision redts (%MD)are reportecl on a 95% confidence interval for aii

of the 8 independently determined ICP-MSr d t s .
 A cornparison of the pre'sion for the two test rnethoâs shows thaî isotope dilution
can provide for a more p h s e determination of PGEs in MST 2557 (honepmb)
intemal standards. On the other han4
autocataiyst samples than ushg the i n ~ u i d i u m
the indiumiidium internai standards provide for a better precision detemhations of
PGEs in MST 2556 (pellet) autoataiyst samples. With fbrther n f i n e n t of the isotope
dilution method, the method may be worth deveioping. It provides for both good 8ccu~cy
and precision.
 Chapter 4 Conclusion

Three test methods were studied for the dissolution of autoccitalyst saxnples pnor
to ICP-MSanaiysis. These thme m*hods were open besker acid digestions, microwave-
assisted digestion, and allrali nision fhious. Of these three methods, two methods (acid
digestion and microwaveassisted digestion) were not able to M y dissolve the
autocatalyst snatrix and the third method (alkali hion) was the oniy m e h d capable of
dissolving the autocatalyst matrix. Both acid dissolution a . miaowave digestion wuld
effeaively extract Pt (>97% acid dissolution and >99% microwave dissolution) and Pd
(>97% acid dissolution and >99% microwaw dissolution) but would require a correction
factor to report Rh (>91% acid dissolution and H(r/o rnicrowave dissolution)
concentrations. Alcali tùsion was able to dissolve the matrix and extract all PGEs in the
autocatalyst samples (-10M Pt and Pd, and Rh). When d y z i n g the îùsed samples two
types of intemal standards can be used. The first is mass-matched intenial standards and
the second is isotope dilution intemal standards. Although much of this project fonised on
the development of the mas-matched intenial standard technique, both interna1 standards
could be readily used to effhvely analyze trace PGE concentrations afker sample fusion.

As a result of the alkali fbsion r d t s , a fiist, simple, sensitive and cost4èctive

method was developed for the analysis of PGEs in autocatalyst.
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 Appendix A Autocatalyst

The nickel sulnde dieaion of the PGE was adapted fiom the method ofRobert et
al. (1 97 1). Cumntly, Inco Ltd. staff use this method for the determination of PGE in
autocatalyst and other samples foiiowed by AA or 1 8 . This method was carried out as
well in our present work for the cornparison of accuracy 4 t h our proposed method. The
procedure Uivolves the foilowing steps:

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

Table-Al Fire assay flux for nickel suifide coilection

Inaredient Wei@ (@

Borax 60
Sodium carbonate 30
Silica 15
Nickel 18
S u b r Powder 9

2. A O. 1 Assay ton (2.9174g) of the autocatalyst sample was weighed out in a

weighing dish, and transferred to the loaded cruciile.
 The mixture was caretiilly stimd with a spahili until it was thoroughly mixeci.

The crucible was placed in an electric fiiniaceand heatd at 980 OC for 90 minutes.

After the fiision was complete, the auaile was removed fiom the fimace and the
fusion melt was quickly poured into a mold, wvered with a kat resistant lid and
allowed to cool domi to room temperature.

The nickel suEde (-27g) button containhg the PGE's was sepmted from the
slag. The slag was saved in the original pot and manalyzed for any losses of
PGE's in the NiS fusion step. This subsequeat analysis was cMied out by a lead-
collection analysis fire asssy.

The button was transferred to a 1000-mLbeaker, 6 0 0 rnL of cunc. 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
fiom the heat and aliowed to cool slightly.

15 mL of tellurium tetrachloride (TeCL) were added, and the mixture was boiled
for 5 minutes. 4 0 m .of starnous chloride (SnCI*) were added &er allowing the
mixture to cool slighîiy.

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

Note: The purpose of the addition oftelluriun tetrachloride and starmous chloride was to
ensure wmplete removal of pS Pd,and Rh h m solutio~

9. The manire was then filtered through a Whatman glas fibers filter grade F and the
tiltrate discarded. The watch glass, beaker, and @ter fiinne1 were washed with
(vh) K I .
10. The filter contaking the PGEiswas transfened back into the origmal beaker,
DO mL of HCl and 4 0 mL of HNO, were addeâ, and tbm the m*xturewas Wied
for 1 hou.

11. The solution was then fdtaed through a Whatman glas microfibre fïiter paper and
then the beaker and filter holder were Msed with 50% (vhr) HC1.

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. HCI and 5 mL of conc. HN03 were added to the residue, and the
mixture was heated gentiy until the POE'Swere completely dissolved.

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

15. The PGE's lost to the slag in the MS fiision step were recoverd through a Pb
collection, cupellation to 100mg Pb bead, and digestion with aqua regia. Final
measurement was done by ICP-OES.

The Ledoux mahod is a combination of acid dissolution and fireassay. The

method layout for this thesis orighates fiom a fjur dating to Aprii 19, 1989. The mcthod
can use either or both AAS or ICP or DCP. The proadure involves the foliowing steps:
1. Four portions of the sample (100 me&) weighing between 8 and 15 gm are a a n s f d to a
800 mL beakers, The samples are weighed to the nearest 0.1 mg and dried at 125OC.

2. To the @et sarnples m the 800 mL beaker, 35 mL HISOh 35 mC H a 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 tdon beakers, add 50 mL of H20.75 mL ofHF, and
15 mL ofH2S04. Evaporates to fumes of H2S04. To the salts in the 800 mL g l a s , and
respective teflon beakers, add about 100 rnL of water, about 100 mL of HCl and 50 mL of
brornine water. Boil to a minimum of 1 hour to convert rhodium to the chloride form.
4. Dilute to 400 rnL, add about 5 g of sodium thiosuIfate, 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 nom the previous step.
7. Any residue srnd in the case of pellet, larger in the case of monoliths is treated as foilows:
A) Pellets: Fume paper with HNO3 and HCI04 to dryness. Treat with aqua regia and combine
with the rnain solutions.
B) Monolith: Ignite in a scarifier, scorify in presence of about 25 mL of Au and cupel. Dhsolve
aqua regia and check on plasma or AAS for ntaineâ Pt. Pd and/or Rh.

8. Evaporate the aqua regia solution wntaining the bullr of Pt, Pd, and Rh, and t r d e r to
200mL volumetnc flasks. Take fkom each flask a 15 mL aüquot with dry pipet and check the
approxhate 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 sepraratory bels and extract the pdladium by repeated

treatments witb chlorofonn and sodium dirnethyl glyoxime soluti~ns~

IO. Evaporate the chloroform phase soiutions to byness. Add small moullfs of nitric and
perchloric acids and again evaporate to dryness. Dissolve in a fiw mL ofaqua regiLa,transfer
to 100 mL volumetrk fiasks and determitle Pd by AAS or DCP. T d e r the aqueous phase
(Pd removed) to 600 mL beakers.
11. Evaporate to 100 mL, add 25 mL of nitric aciâ, 10 mL of percbloric acid and 5 mL SuKiinc
acid. Evaporate to dryness. Evaporate twice to dryness, with the intm*ttent addition of s m d
amounts of HCI. Dissolve residue in 50 mL of 3-% (VN) HCl and transfer to volumetric
flasks of proper size. (Maximum for 200 g, 10 mg of Pt).
12. Repare standards by dissolvhg pure Pt, to cover the range of Pt determination, in aqua regia
Add appropriate amounts of Rh chlorine solution nitric acid-free. (See previous AAS
determination).
13. Dilute to approhtely 800/0 of the volume of the flasks with 300/. HCl. Add 30 mL. 28%
stannous chloride (VN) in 1 :1 HCI. Six milümeter ofthe SnClz solution per 200 mL.
14. Compare the Pt content of the smaples and standards by Merenta! spectrometry.
15. In the absence of Pd, omit the DMG chloroform extraction, but otherwise following the
procedure as written.
ANALYST: MP
-
Simple FUtniw R:UcP-MSUri970127.SAM 04-16-1997 03:07:0 1
Po6 S P U ID SPLE DESC WEIOHT VOLUME
ANALYST :MP
04-16-1997 03:07:01

POS SPLE ID SPLE DESC WElQHT VOLUME

Original Data File: 3MTUlzr.ntr
Analyzed On: Monday, 3anuaiy 27,1997
15:54.09
Anatyred In: mgMg

9
TO:
MP
Analyreci By:
MP

SAMPLE IDENT. Rh Pd Pt
#Drift i Standard Drift 1
tinse ritme
RINSE rime
#DR!FT 1 Standard check
R1NSE rime
mhnk Sample Bbnk
2435FU-1 Dry
2435FU-2 Dry
2435FU-3 Dry
2435FU-4 Dry
2435FU-5 Dsr
2493FU-1 Dry
2493FU-2 Dry
2493FU-3 Dry
2493FU-4 Dty
2493FU-5 Dsr
2471FU-1 Dry
2471FU-2 Dry
2471FU-3 Dry
2471FU4 Dry
2471FU-5 Dry
S2556-1 2556-1
S2557-2 2557-2
2427FU-1 Dry
2427FU-2 Dry
2427FU-3 Dry
2427FU4 Dry
2427FU-5 Dry
246OFU-1 Dry
2460FU-2 Dly
246.OFU-3 Dry
246ûFU-4 Dry
246OFU-5 Dly
2495FU-1 Dry
2495FU-2 Dry
2495FU-3 Diy
2495FU-4 Dw
2495FU-5 Dly
2428FU-1 Dry
2428FU-2 Dry
2428FU-3 Dry
2428FU-4 Dry
2428FU-5 Dry
2475FU-1 Dry
2475FU-2 Dry
2475FU-3 Dry
2475FU-4 Diy
2475FU-5 Diy
2502FU-1 Dry
2502FU-2 Dry
2502FU-3 Diy
2502FU-5
#Drift 1
rime
RINSE
#DRIFT 1
RINSE
#Blank
2484FU-1
2404FU-2
2484FU-3
2484FU-4
2484FU-5
244SFU-1
2445FU-2
2445ÇU-3
2445FU-4
2445FU-5
2443FU-1
2443FU-2
2443FU-3
2443FU-4
2443fU-5
S2556-1
S2556-2
S2556-1+SPK
S2557-1
S2557-2
#Drift l
Sample ID: sample blank
Sample Datemme: Wednesday. November 13.1 996 I3:42:3l
Sample Desciption: sample blank
Solution Type: Sample
Blank File:
Number of Replkates: 1
Peak Processing Mode: Average
Signal Profile Proœssing Mode: Average
Dual Detector Mode: Dual
Dead Time (ns): 70

Sample File:
Method File: C:\elandata\Method\TotaIQuant.mth
Dataset File: C:\elandata\DatasehTotalQuant Analysis\sample blank.028
Tuning File: defauktun
Optimization File: default.dac
Response File: C:\elandata\System\cunent.rsp

Analyte Intensities
Analyte Concentration lntensity lntensity Units
H Not Measured
He Not Measured
Li 0.00427 2.00
Be 0.00000 0*00
B 1.31570 346.00
C 2258.04093 211257.00
N 147870028.08100 1199717.00
O Not Measurd
F 9131173.00
Ne 57.00
Na 46.52578 37159,O0
Mg 17.15930 4178.00
Al 7130577 20276.00
Si 266.55234 111713.00
P 65.23790 2909.00
S 35iï952.07515 52379444.00
CI 31357185.61098 22û35723.00
Ar 6922034135.00
K 1647.20142 618002.00
Ca 563,09956 325017.00
SC 21.27708 1OS51.00
Ti 0.00000 0.00
v 792.88298 323374.00
Cr 56.91161 23762.00
Mn 1.97555 1071.ûû
Fe 4978.26787 2442899.00
Co 1,08519 456.00
TotalQuant Equations
Analyte Equation
 3~~1~ llt
FIQnt Hg ICP ICP-
AA HyQide GFAA Jbhsion MS AA Hw& GFAA J 3 h h hdS
1.50 0.02 1.50 0.003 Mo 45 0.08 0.003

AU detection iimits are given in micrognimsper lits and were detamined using elcmcntal standards in
dilute aqueous solution Al1 detcction limits are based on a 98% conGdaice lcvcl(3 standard deviations).
Atomic absorption (Mode1 5 100) and ICP mission (Plasma 2000) dctectionWts wcre &termineci using
instrumental peramctas optimi7Ldfbr the individual clcm~ltICP anission dctccticm Iimits obtained dMng
muitieiem~ltauaiyscs wiii typidy bc within a k t o r of2 of the values s h o w
Cold vapor mercury dctecticmlimits wat dctamid with a M l 0 0 or FIAS400flowinjection systan
with amaigamation accemq. The detection limit without an amaigamation acmsoxy is 0.2 iigII, with a
holow cathode b p , 0.05 l a with a Systan 2 eicciro&lcss dbchqc lamp. (ThcHg detaction limit with
i
tfitdcdi~~tedFIMS-100mFIMS~maciaydyzasis<O.O1OPGlLwithoutrinamd~ti~1
accessory and < O.ûûf lig1L with an amaIgdon acœsoxy .) HvQide deteftionlgaits wcre dctamuacd
USinganMHS-IOMaciayDIydridt qswm.
Graphite W AA deteciion limits were d c t c d d ushg 50-ILL sample volmes, a L'vov platfarm and fiill
STPFcooditiolls(ModelS100FC with5100~7riarisnF~Moda)eaModcl4100ZL). Graphite
~dctectimlimitscanbtfiPthcraihwirnlbythrwofnp1icateinjccti0ll~.
ICP-MS detectionlimits were detamincd ushg an ELAN 5000. Lettas foITowingan ICP-MS deîectionfimit
value d
e -
r to the use of a less abundant mass for the detanmationas foiiows:a- (213, bCa 44, d Fe 54,
d-Ni60,e-S34,f-SeaL,
114