This action might not be possible to undo. Are you sure you want to continue?
An exploration of sample preparation techniques for the rapid sequential multielementai 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
O Mark Payeîte, June, 1997
The author has gnaaed a nonexclusive Licence allowing the National Li'brary of Canada to reproduce, loan, distri'bute or sel1 copies of this thesis in microform, paper or electronic formats.
L'autem a accordé une licence non
Bibliothèqye nationale du Canada de re~foduire,fêter, distnam ou venûre des copies de cette thèse sous la forme & microfiche/i%n, de reproduction sur papier ou sur f m t électroniquee.
L'auteur conserve la propriété du &oit d'auiem qui protège cette thèse.
The author retains ownership of the copyright i this thesis. Neaher the n thesis nor substantial exîracts h m it
reproduced without the author's
N la thèse ni des extraits substantiels i
de celle-ci ne doivent être miprimes ou autrement reprodinits sans son
The project was to d m l o p a f and irisxpaisive mabod to eil'ièctively d e t h e a the concentration of platinum, pailadiwn and rbodium i new and used crushed automob'ie n 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 i necessary, the resuits obtawd by a referee f
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, m & a
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
affects are minimized
interferences are no longer of great SiBaificance, samp1e preparation techniques other than f ~ e a s s havebem învestigated in this snidy, including ~y acid dissolution, microwaveasisteddigestion and alkali fùsion.
interferences. Since mat*
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. As a r d t . acid dissolution and microwaveassisted digestion were able to effectively extract platinum and pailaâiwn (> 98%) but d d wt be used to extract rhodium (. 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.Of the three methods listed above. .gû?!). On the other b d . the extraction of platinum. aikali fusion wu the only m t o that muid ehd effectively dissolve the supponiag autocatalyst matrix. palladium. 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-MS andysis.
Without such support many snidents would n t have the o opportunity to do graduate research degnes. Bo&. BeIzüe. and you know who you are. Mark Payette . 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.. For those aot listed here. 1 am very much indebted to you and 1thank you from the bottom of my heart.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. and D . Carmen for his ICP analysis. and al1 those who have directly or indirectly s i e d my grad studies. To begin with I wouid like to thank Inco Limiteci for pamitting me to use th& facilities for my research. Phil Gougeon for his extra tirne. There are also many other individuais h m hco L d Central Process Technology Laboratory that L would like t. 1 would also Lastly I would like to thPnk Dr. Dennis and John for their insight. to thank. kindness and helpfilness. like to thank Zbig Waszczylo for his guidance and profound knowledge of chemistry. J. F. D . N. and aiso ali Laurentian Chemistry Faculty for allowing me to pursue my cûeam. S i h for r r mt accepting me as a graduate student. Dave Maskery for bis insight and impeccable memory.
Acknowledgments Table of contents Table of Figures Table of Tables Chapter 1 Introdudion 1.1 The fire Assay pre-concentration method 1.2 Acid dissolution techniques on used autocatalyst 1 -4.5 Analytical methods for PGE determinationin catalytic converters 1. occurrence and importance of platinum group elements 1.5-3 GravUnetrîc analysis 1.5.3 The microwave assisted dissolution technique and autocatalyst samples i .4 X-Ray fluorescence @RF) spectroscopy .4 Analytical methods for the determination of the PGE 1.2 Spectrophotorneük (Colorimetric) methods 1.3 Two-way and three-way catalytic systems 1.4.1 Introduction 1-5.1 The history.4.2 Autocatalyst composition and chmcterization 184.108.40.206 The alkaline fusion techaique for used autocatalyst 1.
8 Selection of intemal standard 220.127.116.11 Isotope preparation .3 Test Method #2 :Microwave-assisteci dissolution 2.6 ICP-MSanalysis (Optional Parameters) 2.7 Emission speztroscopy (ICP-OES) 1.3 Sample weighing 2.8 Inductively coupled plasma mass spectroscopy (ICP-MS) 20 22 24 25 1.2 Sarnple calcination 2.4 Test Method #3 :Zirconium fusion of autocatalyst samples 18.104.22.168 Test Method #1 :Acid dissolution method prior to ICP-MSanalysis 2.5.1 Sample preparation 2.5 Fnl sarnple preparation step prior to ICP-MS utilizing isotope dilution ia and interna1 standard techniques 2.5.6 Purpose and scope of this project 27 Chapter 2 Experîmental Procedures for Autocatalyst Quantification 2.7 instrumental caiibration and interkence removal 2.1 Sample pre-treatment 2.1.6 Atomic absorption spectroscopy (AU) 1.5 Neutron activation anaiysis (NU) 1 -5.
2.4 T e effect ofleaching time in open beaker digestions h 3.5 Effects of sample Ne and qumtity offlux 3.3 E f c of the addition of HF to the microwave samples fet 3.2.4 Test Method #3 : Sodium peroxide fusion of samples 3 -4.2 Problems arising from alkali m & a composition 3 -4.4.5 Studying the various acid cornbitions 3.Chapter 3 Results and Discussion 3. vii .3.6 Automated fluxing 3.3. 3.2.1 Assessrnent o f ma& interferences 3.1 Introduction 3 3 2 Effect ofvarying the microwave digestion time .2.3 Problems due to interna1 standard selection 3 -4. 1 Ts rnethod #3A :Discussion of remlts ftom mass match4 et internai standards.S.2 Autocatalyst type affects on acid dissoiution 3.5 Sample fision rmlts and discussion 3 .2 Test Method #1 :Acid dissolution of autocatalyst ssmpls 3.1 Introduction 3 -4.3 Test Method $2 :Microwave-assisteddigestion of autocatdyst samples 3..1 Introduction 3.4 Sample drying prior to dissolution 3 -4.
S.3 .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 .
9 Effect of varying flux weight on PGE d o n on dried autocatalyst 81 samples(2 Hours @ 500°C) (NIST2557 Honeycomb) . Figure 3. 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. Figure 3. Figure 3.Table of Figures Figure 1.1 The effect of eutocatalyst type on the extracfion of PGEs in new and spent catalyst ushg an aqua regia dissolution to sample dryneu.5 Calcination nsults from LECO and water analysis of NIST 2556 (Pellet) autocatalyst. Figure 3. The fimt (top picture) is the pellet type catalytic converter while the second (bottom pichue) is the monolithic type cataiytic converter.2 T e percent extraction of PGEs in aushed autocatalyst (NET 2557) h and using aqua regi'a over a 4 hour period.4 Calcination r d t s from LECO and water analysis of NIST 2557 (honeycomb) autocatalyst.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. Figure 3.6 Effea ofvarying sample weight on PGE extraction on dned autocataiyst samples(2 Hours @ 500°C) (NIST 2556 Pellet) Figure 3. Figure 1.3 PGE recoveries from a variety of acid combinations in open-beaker digestions of MST 2557 (Honeycomb).2 Flow-Chart illustrating the recychg pathway of new and used catalytic convertas.1 Dia- of the two types ofautomobile catalytic converters.
1 The percent extraction of PGEs in crushed autocatalyst (NET 2557) and using aqua regia over a 4 hour period. Sr.4 Relative abundance of natural isotopes used in this project. Table 2.5 Percent Werence for NIST 2556 samples disrolved using microwave dissolutiontreated with HF. m Table 1.1 Platinun metals and their neighbors in the periodic table Table 1. . - Table 2. 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 1. 1O gm catalyst ample.2 Pirysical properties of the platiaum group elements. Y.4 Matrix composition (non-certified results) as reported by National Institute of Standards and Technology În Gaithersbug.Table of Tables Table 1. Table 3. and Pb. MD (1993) Table 2.3 Spectral removal of possible Merences fiom Cu.2 Operational parameters used on ICP-MSfor the anaiysis of sodium peroxide fiision samples Table 2.3 The typical content of autocatalyst C Mg). Table 3.1 Operathg conditions for the microwave digestion of a O.
8 Repeatability ofmicrowave resutts for MST 2556 and 2557 samples wiîhout HF. Table 3. F Table 3.7 Percent Werence for MST 2557 saxnples dissolved ushg microwave dissolution treated with HF. Table 3.13 Percent difference of ICP-MSresults using indium and indium intemal standards. Table 3. Table 3. Table 3.9 Repeatability of microwave redts for MST 2556 and 2557 samples with H .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.12 Precision of ICP-MSresults using nithenium and thallium intemal standards.6 Percent differeuce for MST 2557 samples dissolvecl using microwave dissolution and not a a e d with HF. Table 3. .1 1 Percent merence of ICP-MSresults using Ntheniurnand thallium intemal standards.Table 3.
23 ICP-MSresults for Rh detemûnation compared to the nickel sulfide fie-assay results and the phosphoric acid/fire-assay results.15 Wata concentration of previoudy dned and d y z e d a u t d f i c samples.21 ICP-MSresults f r Pt determination compared with nickel sulfide o fire-assay and phosphoric acidffire assay.20 Repeatabüity associated with the automatic fusion of autocataiyst Table 3. disotopes ' ~ and ~ d ' "isotopes and .18 Percent Ilifference involved with the automatic fision of standard rderence rnatezials Table 3. Table 3.17 Relative error involved with hand &ion ofstandard al reference materials Table 3.14 Precision of I P M m u h s ushgiridium and indaun intanal C-S standards.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. Table 3.Table 3.19 Repeatabiliîy associated with hand fusion of autocatalyst Table 3.25 Precision of ICP-MSresults using indium internai standards.24 Percent difference of ICP-MSresults using ptlggand ~ and indium intemai standards Table 3. Table 3. Table 3.16 ICP-MSresults fiom wet and dried NIST samples T b e 3.
in what is now named the Merensky r d This new deposit helped to bll the plaîinum demand. The next piatinum deposit to corne into production was in the Ural mountains in Northern Russia in 1824. osmium. and mthenium and w s* t of a is platinuni. Unfortunately. As a r d t of the Russian revohrtion. The £ k treference to the metal was i a commentary by Julius Caesar Scaliger published n 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. pktinum was found by Merensky in South A f b . rhodium. highly resistant to corrosion. and bave high melting temperatures (Bugbee. 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). OCCURRENCE AM)IMPORTANCE OF PLATINUM GROUP ELEMENTS The platinum group elanents (PGE) iridium. They are best known for their s p d c traits. other platinum containhg ore bodies were required to Satie the growing demand for the PGE metals. 1981). At the the. Generally al1 PGE elements are very rare. of these metals generdy occut together i nature n (Vines. the Russian revolution intemipted the much d e d platinwn supply. The first known people to recognize platinum as a separate elernent were the ReColumbian Indians of Enrador who worked the metai into most of their native jewelry. 1941).Chapter 1Introduction 1. white to grayish-white in color. 1982). heavy. This platinum was a byproduct of the copper-nickeI'deposits found in the Sudbury district of . Canada d m joined in the -011 and rehhg of platinum. the Ural mountains were rnined for gold but at a later date platinum was aiso extmcted. Swn after. In 1930.1 THE HISTORY. palladium. This platinum was to be the first water-borne grains of platinum found to be interlaced with a gold deposits.
and 1 of the 2d and îd 0 transition periods. Russia. 1996).9. petroieum. 1981). South Afnca and Cohnnbia refbe and seif platinum metals. The piatinum m a s include the elements in groups 8. The largest danand for plaîinum. and chemicai industries but as well have many rninor industriai uses.Canada and it was mined and r&ed by Inco Limited and Falconbridge Limited.1 (Lide. 1991). paîldium m rhodium d is in the automobile industry (Cowley and Matthey. medical. These three met& are used in the automobile catalyst convaters for the conversion of toxic exhaust gases f?om automobiles into non-poUuting gases. Their position within the paiodic table as well as t & local neighbors h can be seen in Table 1. To this date. 1996). Thy an mostly used in the automobile. Some of the reiated physicai properties to the POE metals are üsted in Table 1. The industrial utüuetion of the platinum metais is continually expanding which increases the demand for the already scarce metals (Cowley and Matthey. .2 (Cabri. oniy Canada.
1 PIatinum metals and theu neigbbors in the periodic table Group 6 Atomic Number Group 7 2 5 Group 11 24 Elernent Atomic Weight Cr 52.9 74 75 Element Atomic Weight W 183.8 Re 186.9 T c 98.Table 1.0 M n 54.2 .9 Atomic Nwnber Element Atomic Weight Atornic Number 42 43 Mo 95.
241 1336 416 4% L 1.51 100-102 244.60 200-350 9.4 B ! FCC 1555 Latrice stnicnire' HCP 2334 HCP 3030 5027 8. A Atomicradius.A(12-foldCoordinotion) Modulus of elanicity in tension.373 117 Tcosile men@. JKS'F' 1 26.Table 1.45 Dcnsity a i 20°C.5 404~ 128.4 4. .7 22.6 -2 Resistivity microhman I 7. annealeû. ~ * 3 W 1 Specitïc heat ai O°C.2 Physical prope!rties of the platinun group elements.5 129. anneaiecl.342 3 16 1.0 4130 9 22. O C I Boiling point.30 2001210 131.2 230.50 300670 Hardness. O C First ionization potemiai.364 12.4 3. ev L 3900 7.2 10.5 3140 8. lcNms* lad I 1.46 12. kNmm2* 10-~ 688 172 Note: a) HCP = hexagonal cl&-packed FCC = fii-tered cubic .247 1.33 12.4 3827 8 21.3 FCC 2454 FCC 1768. VHN C d n t radius. 1 Rn Rb FCC 1%7 3727 7.3 10.4 Mclting point.278 1. ~ g m .
2A12a. Carbon.SSi&) with a s& u 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. 1993 ).3 (Mishra. The PGE loading and weight of autocatdyst is dependent on the size and make ofthe automobile. Table 1. b n o. and Rh also varies widely. nie ratio of Pt.3 The typical content of autocatalyst (n pg/g). Sulfiir and Phosphonis are picked up Born p w h e and oil additives.2mm x 6. The spent autocataîyst also contciins various types of impurities. The monoiithic (or honeycomb) type whose body comprises cordierite (2Mg0.2 mm spheres or 3. and Chromium are picked up h m the d d g operation. T w o types n of carriers (or substrates) are wmmonly used.2 AUTOCATALYST COMPOSIT~ON AND CWRACTEREATION Automobile cataiysts are esal sdly comprised of a d b t o r y olride canier on which two or more pncious metais are dispersed i very low concentrations. Lead. Typicaiiy the content of the POE is shown i Table n 1. Süica. Manganese. i Bead (2-Way) Bead (3-Way) Honeycomb (2-Way) 350 150 60 850 900 300 300 300 100 Honeycomb (3-Way) 1100 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 Aiz03.3mm cylinders) made of y-Al2@ (Mîshra. The pcesence of these . Pd. 1993 ).1.
ICP-MS Calcium (Ca) Cenum (Ce) Iron (Fe) XRF. Table 14 below üsts the non.elements mua be taken into rccount when devishg anaiytical rnethods since they wül play the PGE dements.50 percent ofd catalytc convertersw a e recycled.WF. s n l Table 1. wt % (mgKgx lo4) SRM 2556 (Pellet) Method of analysis SRM 2557 (Honeycomb) XRF. ICP-MS XRF . INAq ICP-MS AIuminum (Al) Barium (Ba) XRF. ICP-MS XRIF. ICP-MS Element Barium (Ba) Concentration. It i estimateci that i 1985. INAq ICP-MS NIA 44 Cadmium (Cd) Zinc (Zn) N/A 600 IO00 300 Zirconium ( r Z) 300 XRF . ICP-MS XRF. INAq ICP-MS ?? Lanthanum (La) Magnesium (Mg) Nickel (Ni) Silicon (Si) XIRF XRF. INAq ICP-MS XRF. certifieci results ofthe m a t x composition of both standard derence rnatds (SRMs).4 MatrUt composition (non-certified results) as reportai by National Iristinite of Standards and Technology in Gaithersburg. m f l g 100 Method of Aaalysis XRF. MD (1993) a large role in the deteInhaîion of Element Concentration. INAA.
palladium and rhodium i used annually in the United s States and Canada for this purpose. Palladium. representing a major source of consumption for these elements. Therefore the two-way converters were no longer &ectve. 1991). The conversion of the gases is show in the unbalanced reactions (1) and (2). the automobile industry i the p h u y indu. rhodium was now required for the reduction of NOx into the Iess toxic N2gas as seen with the unbalanced ceaction (3). it was requind that engine emissions drop by 35% for hydrocarbon and carbon monoxide and also 60% for NOK. 2c0+o2 HC + 0 2 PtSd PtJd P 2 C a (Acceptable gases) CO2+ HzO (Acceptable gases) (1) (2) With the advent of the Clean Air Act in 1985. Both hydrocarbon and carbon monoxide are dangerous gases but the oxidized forms C or HB are a acceptable pon combustion by-products. As a result of the Clean Air Act. A large amount of platinum. aii North Amencan vehicles were required by Law to be fitted with catalytic converters foiiowing environmental pmblems cesuithg bom 'automobile use in large U. .. Europe and also n Mexico. The purpose of the utdyst is to convert toxk exhust gases h m fbel oornbustion into a non-toxk and less pobthg form.S.that uses s Platinum.As mentioned earlier. dies (Brown et al. These catalytic converters contained d quantities of platinum and palladium and were used for the oxidation of the hydrocarbons (HC) and carbon monoxide gas. and Rhodium in automobile d y s t s . In 1975. Similar actions have now been taken i lapan. The old cataiytk converters were peIIet fom 2-way catalytic converters.
2 is a flow chart iiiustrating the recycling of catalytic converters.1.NO + 2 CO --k. analytical results are of parmount importance since they dictate the purchase valw of the recyclable matenals. N2+ 2 C a (acceptable gases) (3) The 3-way catalytic converters have dm changed i fom The PGEs are now n deposited omto a honeycomb sûucture composeci ofcordierite. Figure 1. . Various wmpanies purcbase quantities of these used autocatalysts for the recovery of these platinum group metais. A diagram of the two fonn of catalytic convertas can be seen in f p Ali automotive companies now use the i 1. Due to contractual obligations. three-way catalyîic converters and mat the autocataiytic honeymmb m & a with a 0. palladium and Rhodium solution.2% platinum.
.1 Diagram ofthe two types ofautomobite caîaiytic convatas. The t (top h picture) is the peuet type catalytic converter whüe the second (bottom pi-) is the monoüthic type d y t i c converter.Figure 1.
Catalyst Manufacturer Con Production Swap Junk Yard Swap Yard Small Collector Big Collector Auto Crusher .2 Flow-Chart iiiustrating the recyciing pathway ofused catalytic converters.Figure 1. .
There are some reports of alternative methods to fie-assay for sample preparation in autocatalyst analysis. and SRM 2556 @elle$). 1987). For PGE daermination. In most cases. and 0th.4. Fire-assayhg is a highly sensitive pre-concentration mahod for plathum. Each of these dissolution techniques will be briefly discussed. 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. and the sodium paoxide fusion technique. paiiadiwn and rhodium detemination. so hs other techniques were explored.1 THE FIRE ASSAY PRE-CONCENTRATION METHOD Procedures to perfonn a basic fire assay were published by Vannoccio Biringuccio in the sDaeaah cenhiry.that is. 1. The most cornmon and widely used pre-concentration technique i the ciassical fireassay technique @ugbee.vehies in ore in the ounce .1. The dissolutioa techniques investigated in this work focus on a hot plate atid dissolution technique. Smith. the m s popuiar technique iwoIves a sample pre-concentration aep ot foiiowed by instrumental detemination of POE oonentrstions. microwaveassisted dissolution technique. A brief account of the h a s s a y procedure is given in section 1. T i dissolution method does not readily lend itseif to routine application.4 ANALYTICAL METHODS FOR THE DETERMINATION OF THE E E Most instrumentai techniques listeû below require the amples to be dissolved or undago some type of sample hancihg pnor to instnunental adysis. it is used as a methoci of qumtitative analysis of an ore .4. silver. to detemine the amounts of gold. s 1981.1. 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).
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 . In each instance. seprational losses of PGEs while using various collectors. The material for analysis is nised in a ttrnaca with a flux mixture. 1992). A disadvantage of his tezhnique is the relative high cost of gold as a collector. 1987). In 1992. 1971).. palladium uai and rhodium fiom autocatalyst (Tuwati. gold. 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. 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. loss. Unfominately neither of these colîectors proved effective as an isolator for rhodium. andyte content. tin. T w t used gold as a collector for the isolation of platinum. The method is applied t d y principally to the detamination of PGEs. fie-assaying procedures using nickel sulfide have been widely used (Robert. Date et al. palladium and rhodium (Beamish. Keyworth (1982) descnied a detded listing of cost. and merauy in ores an d o y phase tbat contains the dissolved anaiyte is produceci. operating ranges. also studied the use of nickel suffide as a collector for POE in geological samples pnor to ICP-MS analysis (Date.per ton range.. T i (Sn) has also been used as a fie assay collector for PGE with disappointhg results (Faye 1965). . 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 may alsa be detennined by fireassay m&ods. In 1987. In 1975. 1966). et Cheung. He reported a collection of 99+ % of the platinum and palladium and 99% of the rhodium. Lead comb'ied with silver as a fire assay coilector has dso been used for the isolation of platinun. Sihw. 1975). The collector that is used for the alloy phase plays a large role in the quantitative detennination of PGEs. coppa. In addition to the above mahoâs. nie most popular coilectors are sîlver and lead or a combination of the two. Davk.
They reported 100 % dissolution of gold and palladium. (1993) anaiipted various acid combinations for the dissolution of PGE's in an eutomobile catalyst. 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. metallurgical histoory and the presence of hnpurities will play a large rok in sample dissolution. Its &cacîty is e attributed to the oxidïzing power of fiee C ~ I O M aqueous solution as wefl as the i ~ n complexing power of the chloride ion Accordhg the American Standard Materials (MM- are fhely devided. nitrosyl chioride (NOCI). Unfortunately. Therefore the degree of division. 18 % dissolution of platiwm and rhodium. Kuo-Yrng et crl. gases and â e HCI and H N 0 3 . degree of compaction. Aqua regia has been mixed with other acids to increase geological sample dissolution. Gowing and Potts ( 9 1 examined h o w 19) aqua regia dissolveci geological samples for the determination of gold and PGE's. Single minerai &d attack on properly aatlealed noble m d s shows little effect on the metals. Aqua regia is the most commonly used combination.The 4amount of PGEs tbrt stay in the da$ during tâe nickel &de ICP. The results ofthe lead b e d analysis are then added to the nickel sulfide Mon step rdts.4. This consists of 3 parts hydrochloric acid and 1 part nitric acid.2 ACIDDlSSOLunoN TECHNIQUES ON USED AUTOCATALYST Noble m d s wae thus designated because of their relatively high resistance to anack by chemical agents. AU but 1994). NO. h ) Strong and Murray-Smith (1974) used aqua regia to dissolve geological samples for the detemimation of gold. aqua regia wiil dissolve platinum and palladium quite readily if they . are anaiyzed through a lead bead wliection procedure and a h a i meastarement i done by s 1. it has b e n show that hely divided palladium metallic residue was completely dissoived ushg hot HCI. Howewer. q u a regia also oxidizes rhodium thus forming an insoluble rhodium oxide @ a . and littie attraction of the remahhg PGE's. Van Loon (1977) reported thgt wen a quantitative attack with aqua regia showed littie e&ct on a platinum w h . It is thought to contain unstable mixture of Eiee chlorine.
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. Carius tube dissolution and alkali fusion dissolution for geological samples. A sample is weighed and placed into a PTFE vessel. Acids are then addecl and the mixture i then agitated to promote thorough ming. (1994) both studied the use of microwave dissolution and isotope dilution . 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. The no contents are irradiatecl with microwave mergy and the contents of the vessel are quickly heated. Y and Msswida (1995) and i Beary a al. Once s the initial reactions are complete.two acid combïitions werc ineffiective extractors for rhodium while aii provided quantitative extraction of phtinum. (1992) have thoroughly d e d the applicab'rlity of microwave dissolution to various samples as weii as various acid combinations and microwave programming. The vessels are then put into a carousel that can hold twelve PTFE vessds and placed i t the microwave oven. the pressure withîn the vessei rises. The seal contains a membrane that is mptured if the pressure within the vessel becornes too hi*. The principle is simple. The introduction of microwave assisteci pressure dissotution has been a mjor advance i n geochemicd Pnalyois and it is now regarded as a substitute for acid dissolution. At the same tirne. the vessel is d e d .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.4. Kokot et al. pressure bomb dissolution. 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.
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 9 7 . T i meîhod rquires the sample to be hs finely ground and mixed with an acidic or basic flux. 8) . the flux chosai was the basic sodium peroxide flux which is one of two fluxes capable of disso1ving cordierite. cordiente is artremely resistant to mineral acid anack. sample and flw are then heated into a clear melt and cooled. Totluid a al.4. (1995) have wmpued microwave dissolution results to o h dissolution techniques u s d for geologid ample aailysis. Therefore altemative techniques are required for sample decomposition. wbich is readily dissolved using concentmted hydrofluonc acid. Nowinski and Hodge (1994) studied the applicability of rniaowave dissolution of ore samp1es for gold and platinm group metals prior to ICP-MS anaiysis. Among these matenals is cordierite which is the supporthg matrix used in the production of honeycomb automobile catalya. Even using a combination of concentrated hot mineral acids has proved inefG6Ctive for the dissolution of these matenals. Alkali fbsion is one technique that can be used. 1.. Sample dissolution via the rnicrowave has ais0 k e n extensiveiy miewed by Smith and Anenault (1996). The sû n choice of crucible is dependent on the flux chosen as descrihi by Anderson (1987).ICP-MSto the anaiysis of PGEs in gwlogid samples. The crucible. There appear to be no reports in the literature of the microwave dissolution technique appiied to the analysis of autocataiyst samples. Next the samples are dissolved in a concentrated mineral acid combination und then diluted for instrumental analysis. The proporiion of sarnple to aux varies fiom 1:2 to 15 0 and the sample and flux are be i various types of crucible. Unlike the Y-alumlliia used in the pelle$fom of the autocatalyst. For our purpose.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.
Hodge et al. Plkali &sion gave excellent sensitivity. (1995) studied the applicability of aikali fwion for the determination of PGE's i n geological samples. (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. Salt can plug the ICP/mass spectrometer interface so sample solutions require considerable dilution prior to sample anaiysis. (1995) studied and comparexi resuhs from an aikali hion on r f e c materials to those of emne mimwave dissolution of the saxne samples. In most cases. Brown and Biges (1994). . On the other han& fused samples and@ by ICP-MSdo not d e r E o the sarne spectral interferenas that affect the ICP-OES and om AAS and can therefore be used to detamine PGEs in dissolved alkali fused samples. There appears to be no published reports covering the use of all<ali fiision to the daennination of PGEs in autocatalyst. One problem with the use of ICP-MSanalysis for dissolved alkali fised samples arises from salt fomtion. Alkali fusion provides a means of dissolvhg autocatslyst samples but does not provided the abiüty to separate the PGEs fiom the supporting maaix. The sarnple solution contains high sodium and chloride concentrations which can lead to salt formation.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. Its applicability to AAS and ICP-OESrequires caution to avoid various interferences of extemal elements found within the samples' supporting rnatrUr. Enzweiler et al. and results compareci extmnely w d mth the certifieci vaiues. Totland et ai.
5 ~ ~ A L Y T I c AMETHODS FOR PGE DETERMINATION IN CATALYTIC L CONVERTERS Platinum group elements are present in most esrth-dace materials at trace concentrations. These methods inchide spectrophotometric (colorimetrîc). palladium and rhodium is as folows. Therefore. Platinum is quantifieci using a concentrated HCI solution with the subsequent addition of tin 0 chlonde. several steps may be required More quantitative analysis can take place.1.5. Depending on the sample composition. The sensitivity for this platinun determination is 0. emission spectroscopy (ICP-OES). gravimetric and titrimetric detenninations. The PGEs play an extremely important role in seversil major industries. atomic absorption spectroscopy (AAS). the ability to d e t h e these elanente is important for researchers linked to PGE utiiization. The quantitative absorbance of the platinum chlonde i s measured at 403 nm. Spectrophotometry is a mature and inexpensive method for analyzing PGEs. 1955). Another specaophotometric determination for . inductively coupled plasma mass spectrometry (ICP-MS). x-ray fluorescent spectrosopy m).It is carried out by way of absorbance measurements d e r the appropnate reagents are added to develop a chatactezistic d o r .03 ppm whüe using a 10 g sample (Wagner. It is ohn considered to be one of the best methods for analyzing PGEs.2 SPECTROPHOTOMETRIC (COLORIMETRIC) METHODS Spectrophotometric methods were the mainstay of trace maals analysis pnor to the introduction of modem instrumental techniques. A variety of anaiytical methods have been appüed to POE analysis in various samp1e types. and 1. An example of the spectrophotometrîc detennination of platinun. neutron activation analysis (NAA).
under favorable conditions. organic solvents and salt concentrations. To determine the rhodium concentration by spectrometry. The c o l d solution shows absorbrma maxima a 550 and 525 nm. order of mixing reagents. Co. with a variety of criticai factors.44iphenylcarbazide and 1.015ppm was found while using a lm ceil.5 ppm while using a lm optical path and the optimum wavelength for absorbame measurement is 565 am.4-diphenylcarbazone. However.4 and 3. Both the acidity and concentration are criticai. Some of these are pH. iron. and cobalt.3 to 1. one bang Pt[(CH&N. the colorimetric methods offer good seositivity in the microgramrange (Beamish 1965). Fe. Reported imerfkrences are Ir. masking of interférences. temperature. In this case.C~O]~Cl2.7 to 2.4 ppm and the precisioa for this technique ranges ôetween 1. and Cu. Beer's Law is followed oves a concentration range between 0. Ni Pb. 1960).5 to 10 ppm with the maximum at 410 nm being used for analyticai quantification of palladium. Many reagents can be used for the spectrometric detemination of patladium concentration. stab'iiity. The color is due to two diffamt comp1exes.2-dipyridUieketoxime which was developed by Holland and Bozic (196%). copper. The most promising of these is 2. The optimum range is 0. reagent concentration. . ethylene diaxnine tetracetic acid (EDTA) is used to mask nickel.0.0029 pg and a working d i of 0. The optimum range for platinun detennination ranges between 0.platinwn determination requires the use of gnitrosodimethyianaiine (Yoe rnd Kirkland. These methods are often quite difncult to carry out successfûliy. one d d use a 1-to-1 mixture of 1. the latter being used 1954). hie to the possibility o f interferences.û%. for the absorbance measurement. This m x u e would react itr with the dominant rhodium @I) salts to fom a purple complex of unknown structure (Ayres and Johnson. The color is developed in a perchloric acid m e b of pH 3. time. 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. the smsitivity was 0.
3 G R A ~ANALYSIS C Gtavimetn0cmethods have hktoncally played a large role in the daetmination of PGE metals.1. This r d t s in the formation of a black plathum sulfide precipitate.y to anaîyze simples non-destructively.5. The platinum sulfde is then separated and heated to 750°C leavhg the Pt metd for quantitative anaiysis (Güchrist and Wichers. This aep causes the precipitation of palladium and rhodium as hydrated dioxides thus leaving platinum in solution done. (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. one must employ severai isolation steps for the final concentration detedation of aii PGEs. many iaboratork~ have opted for the more rapid instrumental anaiyticai methods. platinwn group met& do not occur aione in samples. in the appropriate concentrationrange (> 1% P E . G) Generally. The first step involves the addition of sodium bromate pnor to boiling foUowed by solution neutraliuition (pH= 7. The m i an 19 . Nevertheless. A a resuit. Mooiman (1993) has reviewed the various published techniques for noble metal extraction by use of organic solvents in dilute solution. and time). palladium and rhodium mamire in a chlorinateci solution. gravimetic methods still play an important role as the final arbita of quantitative composition. Therefore when exploring gravimetric methods. De a al. The next step involves the bubbling of hydrogen suifide (&S) gas into the platinum containhg solution.0). but due to their relative costs (manpower. there has been a s generai move away h m the relatively slow but extremely accurate precr*pitationmethods. 1935). 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.
qneutron activation is at least one order of -tude more sensitive for most platinum group elements then the k s t spectrophotometric method. Tnere are dso reports of PGE analysis on impregnated fiiter paper containing the pre-concentrateci noble met& (MacNevin & Hakkita. The radioactive spectnim of the radionuclides. Using a flux of 5x10~'neutrodcm2. 1981). With this flux. n .4 minutes). One such example is Giauque a al. In practice. For example. (1977) who apptied XRF to the detemination of 40 elernents including PGEs in various sample matrices. 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. XRF can be used to anaiyze !amples with no prior pre-concentration steps. after separation and pre-concentration of the elements has been achieved. The acairacy obtained h m this anaîysis is typically 11 5%. 1957). Otherwise. the sample absorbs the neutron to fom artificial short-We radionuclides . The main reason for this i that NAA is very s sensitive towards PGE's and it can avoid most of the contamination problems typical of wet chemical analysis in the ppb range.< of the samples. activation techniques are probably unqualled for the detemination ofsubmicrograin traces ofmost maals. Many methods have been developed for the x-ray fluorescence anaiysis of noble metaIs. 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.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. once fomeâ. rhodium i not detemiiwd due s to its derivative's short haElif'e (4. are memureci and interpreted i ternis of guantity of the various elements present. Neutron Activation Analysis (NAA) has played a major role in establishg the geochemical data base for PGE in rocks.
For used automobile cataiyst. It hes proven highly effaaive for Pd and In but is somewhat less usefùl to Os. Again. (1968) developed an RNAA method for the analysis of 92. Crocket j s (1968). Millard and Bartel (1971). De Soete et al. and Pt and totally ineffectve for Rh (Cabri. This I A method generaîiy requires a p r e . the results indicate a Wted abiiity to eîZ&vely m a u r e Ir. Crocket et al. 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. Instrumental neutron activation anaiysis (N )is the second method. The results reported by Crocket et al. Ir. Os.M. NAA d y s i s for PGEs in rock and ore samplos.R @olycyclc-NBL47) ion exchange resin.In their researches. and Os. Os.Ir. R . Os. Ir. and rhodium which suggests that RNAA may not be appropriate when analyzing automobile catalytic converters. (1977) and Hofnnaa a al. l.mviewed the application of NAA analysis to the PGEs. showed RNAA's inability to efktively d e t e d e Pt. Nadkami and Momson (1974) also stuclied the use of RNAA for the detennination of Au. Gjbels and Govaens (1973) have al. There are o t k reports descnig RNAA analysis of geologicai samples... (1971). Gijbeis and Hoste (1971). P . Pd. and Au i geological sarnples. Small arnounts of sarnples (100-200 mg) u t n where first mixed with non-radioactive carriers of those elernents and irradiated (Crocket et al.The first method is Radionuclides Neutron Activation Analysis (RNAA) which requires no prior sampIe preparation. ( 9 8 . and Pt in gedogicai materials while ushg a Strafion N. GW and Hoste (1971). Pd. 1981. Nadkami and e Momson ( 9 4 . De 16) Wt et ai. Ir.. 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. Gilbert et a. 1 7 ) Crocket et a.c o n d o n step prior to quantitative analysis of various . (1978) have (in pubfished on 17) l. but M M report good results for platinun. 1968). they have presented two separete methods of NAA for the detennination of PGEs.. Ru.
The phenornenon of light absorption by liquids and crystals dates to the 18" century. P . Turkstra et el. Ir. and hi& concentrations (15-500 ppm. exclucihg ICP-MS.6 ATOMIC ABSORPTIONSPECTROSCOPY(AAS) Atomic absorption spemoscopy ( A M ) is the measurement of the absorption of opticai radiation by atoms in their gaseous state. th. Pt and Au in mattes. Ag. 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. The only major disadvantage of NAA techniques are the instrumental costs. availability of suitable irradiation sources. This i considered to be one of the major landmarks in noble metal s analyticd cherni-. Upon atomization. Au. the technique was ixnmediately investigated for noble metai analyses partidarly by Austraiian and South Afncan researchers. H o h et al. (1970) were able to deterxnine Rh. nom the South African ores allowed for the high concentration determinations of Rh. concentrated mattes and lead fie-assay beads via INAA. There are no reports of INAA for the anaiysis of autocatalyst sarnples. and the tirne requued for dyti*cai analysis. and Ag in fused t ores. Pt and Au. Pd. 1S. and Au in South A£ncan ores. It has proven higbiy efEective for the PGE determination i &de n beMag rocks. Walsh and Haussman (1963) developed a method for the analysis of PGE's by AAS. (1978) demonstratecl tbat INAA could show supaior accuracy and precision than most d y t i c a i methods present in 1978. Pt. It was not for many years that the maiytical applications and instrumentation became avdable to perform empirîd anaiyticai determinations In 1963. Lead firr-assay beads Ag. A dissolved somple is aspirated h o a hot flme where it is atomited.were able to quantitatively measure Ir. The basic hctionality AAS is quite simple.) Rh.. Although not enthusiastically received in North Awrica until 1964.materiais. Pd. At the present tirne atomic absorption spectroscopy is the most widdy u d detemimion tool for these metais. Ir. In thgr research. the atoms absorb the characteristic iight emitted fiom a holiow cathode lamp WCL) and the difference between the incident light and the . Ir. Pd.
limitations imposed by the absorption cocfncient of transition that . As with 1 AAS work. Neo-classical fire assay is by far the most widely used sepadonal technique. The remlts were promising with the exception of Rh which is aot properly coiiected by silver. Fortunately there exist extensive interfîmnce studies that propose a wide variety of remedies to help in the analysis of PGEs. Pd and Rh ftom a geologicai semple followed by an aqua regia dissolution.absorbeci light is subtracted and used to empiricaiîy quanti@ the concentration of the element wncerned. noble metais also d e r Born problems associated with elemental determinations. resonance broadenuig. The copper and Lanthanum combination has also been shown to eüminate Pt. One mch case is the use of vanadium to help in determining Pt. Pd. M r sepmtion. In thQr research they showed that PGE ih extraction fiom the AAS anaîysis samples showed an excellent correlation to spectrochemical and chernicd results.Rh. Le HouiXer and De Blois (1986) used silver to c l e t Pt. Schnepfe and Grimaldi (1969) used gold to wUect Pt. 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. a releasing agent is e added to block noble metals fiom interfering with one another. These problems are : Doppler and pressure h e broadening. 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 wt Pt.and Rh interferkg with one another. and Rh îrom geological samples foilowed by an olc alkaline cyanide solution dissolution Vanadium was used to correct for eIemental interferences. The d e s t remedy is to use releasing agents to block extemal inter-elemental interfierenceswiih the noble metals. Pâ. Ru and Au in geologicai sample~. Pd. 1970). 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.
The background due to absorption by molecular species also poses problems (Koirtyohann and Pickett.03 . There are a lirnited number of literature reports involving the use of ICP for the anaiysis of Pt and Pd in geological samples. Pd. inwmplete isolation of the emitted opticai h e . Mn. He examineci how dissolveâ sdds affected the extractions. 1. Ni Cu.9 nm. 1966). Pd at 340. They used an ion exchange chromatography step as a possible aiternative to the lengthy fie-assay procedure. His research showed that the Pt band at 265. 0 0 and 0. and the dependence of sensitivity on opticai path length and other events in the flame.V. 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.5 nrn and Rh ot 343 -5 nm were O. Si. The low grade materials were concenmted by nickel sulfide fie assay. Fe and Mg.gives rise to the particular line u d (flame temperature innuences i) interferences due to t. 1978). samples with low Pt lewls were suôjected to lead fire-assay prior to ICP anaiysis. 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. Extensive interference midies were perfonned and the accufacy of the method was estimated using sample materials previously anaiyzed by AAS. how silver could be used as an intemal standard for the precious metais. As a result of these problems. how matrix . Richard pB/mL respectively (Wemyss Brown (1982) descriied extensively the use of ICP-OES for the anaiysis of various sampte matrices for precîous metais. Their research looked at both high and low grade materials. Brown and Biggs (1984) applied ICP to the analysis of Pt and Pd in geological samples. The detection b i t s for Pt at 265.9 mn showed signifiant problems due to interferences by Mo. Aberwmbia (1982) investigated the possibility of using ICP-OES for the determination of Pt. and Au in geoiogical samples.3 and Scott.
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.alum interfaaices on P .dements can cause spectral interferences with certain noble metals and how ICP-OES f i a g a reeree values on the geological suaples. R o and Bridger (1982) examine a the possibiity of pefiorrning a dina detemination of process soiution with both high dissolved solids and SiBnificant amounts of PGEs. clean sample preparation. fiequently.1 %. AU of these are discussed in this th& .There are two distinct advantages to ICP-MS analysis. 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. Sample preparation is the critical step in the trace analysis procedure. a M e r refinement to this m t o . isotope dilution techniques As ehd may be employed.22 ng w'). Microwave assisteci sample dissohttion may be the answer for fast. the spectra are very simple and inter-elemental interferences are largely absent. the latter previously being restricted to thermal ionization mass spectroscopy (TI-MS).03-0. the technique provides for the sequential analysis of both elemental and isotopic ratios. Secondly. Their research look at torch a s m l e . 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.as weli as possible spectral overlaps with the Pt üaes. sebis t Inductively coupled plasma mass spectroscopy (ICP-MS) a =Iy new technique is for elemental and isotopic anaiysis. 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. Fudy. Thuq a more rapid and e f f i v e digestion method for trace metal analysis hes been sought.
Inductively coupled plasma mass spectroscopy has beai widely used for the detemination of PGEs in geological sample due t the iarge danand for these noble o m t l . and P et ultratrace l d s by ID-MSon various geologid samples. Ir. Beary et ai.. Date and Oray (1989) descriibe the many advantages of ICP-MSfor gcolo@d eas samples and d e m i e ais0 vPiaus sample prepantion techniques.. Pd. (1995) used isotope dilution ICP-MSor ID-MSfor the determination of various metals in various types of matrices with exallent results. Their results were genedly in agreement with the reference results but showed a tendency to bias on the high side. Yi and Massuda (1995) paformed a sequentid determination of Ru. Isotope Dilution ICP-MS (D-ICP-MS) has also been extensively applied to noble m t l detemination in geological samples. Nowllisky and Hodge (1994) and Enzweiler et al. showed that ID-ICP-MS of a peroxide nised and teiiurium coprecipitated sample also gave acceptable results. (1995) l. 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. Their t method proved to be quite reiiable in cornparison with otha d y t i c a l techniques. biological samples. and water samples. Nowinsky and Hodge (1994) showed that microwave assisteci dissolution of samples foUowed by ID- ICP-MSis a viable methods for geologid samples -i ss whik Enzwda et a. (1995) describe the appücability of ICP-MSfor the determination of PGEs and gold on various sample matrices in geological sarnples. Pary et al. 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. botanid samples.. (1995) studied the appücability ofvarious digestion techniques in the detemination of PGEs and Au in geologicai samples folowed by ID-ICP-MS. This method can provide the analyst with up eas to a ten-fold increase in accuracy i PGE determination in various sample types. Cattenck n et al. (1994) explorecl different sample pnpatation approaches for isotope dilution ICP- .
It is hoped that one of these techniques can provide EghS accurate. costly. The results are combined and reponed. 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. fast and sensitive method for the h determination of platinum. both the h t d standard and isotope dilution ICP-MS techniques were gcplored for the daennination of PGEs in used outocatalyst. The three methods exploreci in this study are: (1) concentmted a h d acid dissolution. but the pre-concentration steps are time consuming. and very labor intensive. and (3) Zirconium cniaile sodium peroxide fùsion M e r the automobile catalyst samples are dissolveci. A well emblished method involves a combination of nickel suifide fie-assay preconcentration foliowed by another pre-concentration step using lead on the nickel suifide slag (Appendix A). The fie-assay is a highly accurate method and well developed technique. As a result of the analytical data provided fiom the authors above. prcision and accuracy reqWred f r autocatalytic PGE detenninatiom et Inco Limited. . palladium and rhodium content withui usd automobile cataîyst. The PGEs collected fiorn both techniques are dissolvecl ushg concentrated mineral acids. Their paper helped to dsveiop the sensitivity.MS of c e d e d materiais. 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 ( a h Limited) and the Ledoux A-1 method consisting of an acici digestion plus fire assay digestion method with ICP finish. 1-6 PURPOSEAND SCOPE OF THIS PROJECT The a of this project was to develop a simple. then sarnples are d y z e d both by ICP-AES and AAS. (2) microwave assisteci dissolution. Sudbury o Division.
3 and then dissolved ushg one ofthe three studied methods. First the samples l were dried and cmoled. 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.1. Prior to sarnple dissolution using one of the three methods descllied above. Each of these methods will be descnbed individuaiiy below.1. Following sample trament. These three methods w m concentrated acid digestion on a hot-plate. The basic procedure in d three techniques foilowed the same steps.1. Finally the samples were weighed ushg one of two methods listed in section 2. .CEAPTER 2 EXPERIMENTAL PROCEDURES FOR AUTOCATALYST QUANTIFICATION In this project. (acid dissolution. microwave assistai digestion. Next a h o w n amount was weighed into an appropriate vessd The samples were digested ushg one of the three methods. and alkaii fusion. thne sample preparation methods w r explorecl as possiile ee replacement for the present Nickel-SuEde fire-assay technique. then al samples were dried as outlined in section 2. or dkaii fision) the autocaîalytic samples were ail pre-treated i the sarne way.1. The fint step was to cmsh the samples which is n elaborated in section 2. or microwave assisted dissolution.2.
pulverized (-200 mesh or 75 pm) and thoroughiy mixed. 1994). Calcination in this manner is the accepted way to dry autocataiyst samples Peary and Paulsen. As a redt. This removes unwanted water associated with the samples and carbon which c m also cause anaiytical problems. The first The samples used throughout this work were &&y 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. Two catincd amples wae used as conaol monitors. . Anderson (1987) descn'bed how wet samples can affect the accuracy of the resdts in a negative way. Beary et al. 1996.. Therdore. The autocatalyst like many other semples arrive in the damp or wet state. 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. fiom an atialytid point of view. The standards are pnpared i n the same fmhion as nonnd autocatalyst samples. this means that the samples contain potentially large amounts of water associated to them which ~ u l give rise to d unwanted quantitative analytical mors.
A 0. Great care was taken with d weightings. û t h d s e .1. . i 2. Other acids.Sample wcjghing was pafonneâ foilowhg Anderson's (1987) technique. wae then added to the d 15 aqua regia mixture to belp dissoive rhoàium Î f i was repuireci*After the addition of the t last acid. Then a 45 mL concentrateâ hydrochloric and a mL portion of concentrateci nitric acid was added (3:1 qua regk solution).25 g sample of catalyst was weighed using the Mettler 100 or 166 electronic balance as descn'bed in section 2. AU dissolutions which useci hydrofluoric acid (HF) were carriecl out in Tefion beakers due to the ability of HF to dissolve Borosüicete glass. Two Merent methods of sample weighiDg were uwd in tbis pmject.3. and percblonc a d . the choice of method king dependent on the type of Mettk balance that was used. 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) ensure that al1 the cataiysî to sample would be in contact with the acids. Sample weighg for both microwave dissolution and acid dissolutio~~ involved the use of a weighing plate.2 TESTMETHOD #1: ACIDDISSOLUTION METHOD USING BEAKEM~OTPLATE Acid dissolution provides an easy way of dissolvtig most materials (Anderson. the samples were diredy weigùed into the zirconium auables. The choice of digestion vesse1 for acid dissolution is dependent on the nature of the acid. 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. Gaie*. the contents of the beakers w a e thorougbhl mhed and placed onto a hotplate. for ail alkali fùsions. 1987). aich as hydrofluoric aci4 sulfiuic M . aii other acid dissolutions were perfonned ushg Boros3cate gkssware.
The sample beal<er was repeatedly wmhd with D. water and the wasbings were transfensd to the 500 mL volurnetric flask.1. ûnce the solution was clear. water was added to just below the 500 mL. water was added followed by the addition o 50 mL of comentrated f hydrochioric acid. The beakers were then removed and aüowed to cool. Once coold. Sample weights mged between 0.3) in a were plastic weighing dish and then acinsfaed to the 120 mL Tefion iiiicrowave digesti0on vessel. The contents w a e thomugbly mixed aad the sunples w r re-beated ee for a couple of minutes. Atta about 5 minutes. The sa~~ples weighed (section 2.I. T e weighing dish was thai raweighed as d e s c f l i in sedon 2. a 10 mL aliquot of D. The fiasks were thai aansferred to a coobg bath for 20 minutes.100 to 0. M e r cooling for 20 mimites.The simples once placecl on the hot plate wouid nmaia there d d the a i d s had l evaporated. DI. At tbis point the s ~ p l t s w r dissolveci to the 500 mL m k e r and the vesse1 w r placed on an automaticagitation ee ee plate for proper solution -g.I.200 gm of used automobiie atalyst or refierence mataîals. These Falcon tubes permittecl the samples to be stored for up to 2 months with no ample degraâation or salt precipitation. the samples were removed fom the coolhg bath and allowed to accliudze to room temperature.1. The 31 . a 50 mL aüquot was p h a d into a 50 mL Falcon tube as the stock solution for fbture ICP-MSdysis. The samples were digested with the Hoyd RMS-150 electronidy oontrolied microwave digestion unit. the dUsohnd srmples w a e moved fiom the hot plate and cooled d o m Mer cooling the contents o the beakas were f emptied imo a 500 mL glas vo1umetnc fîask.3. A 20 gm h aliquot of aqua regia (3:l HCVHNCh) was then added to the digestion vessei and in some cases a 1 mL aliquot of H was also added te maease the -o F *n of rhodium.
they were then removed and carefully vented in a fUme hood. 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). This was the concentrat4 stock sohition for that the finai ICP-MS analysis. the flasks were placed on the counter top and l to acclimatize to room temperature. voIumetric flask. A 50 mL portion of the flask was ttansferred to a 50 rnL Falcon tube for storage. A analyses were pafomed whüe using ail 12 vessels as the microwave oven U power was calibraed on this basis. e the power was tumed O& the ve~sels were Ieft in the microwave for 15-20 niinutes and then cooled in a cold water bath. With the vessels vented and cooled.microwave carousel can hold 12 vessels and most runs iSvoIved 11 srmples and 1 ftagent blank. Once the vessels had co01ed Suflscientiy. Since the solution was still warm. The vesseis were then capped with a 120 PSI rupture membrane and placed into the microwave carousel. M r al . The oven was operateci at d m u m powa for 10 to 20 minutes (se T b e 21 below). A f k coohg. The solution a was diluted to the 200 mL mark and then mixeci using a magnetic stirring bar and an automatic stirring plate. Additional DI water was added to just below the 200 mL. Stored samples remained in soIutîon f r severai months with no sarnple o precipitation. . the volumetric flask and is t contents were transferred to the cooüng bath for 20 minutes. The Teflon microwave vesse1 was repeatedly washed with DI water and the washings were transferred to the volumetric flask. the contents were anptied into a 200 m .
The autocatalyst and flux were then fised on a LEC0 FX-503 automatic fluxer for 3 minutes. 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. During the addition of water.1 Operating conditions for the microwave digestion of a 0.4 TESTMETHOD #3 :ALKALIFUSION OF AüTûCATALYST SAMPLES A 0.Table 2.25 g portion of the dried autocataiya sample was weighed into a dned zirconium crucible. cace was taken to avoid sample loss through sputtering.10 g (~1tocatalyst - sample.. The automatic fluer was u d to aisure that d sampies were fused in the exact same way. The addition of 50 mL of concentrated hydrochloric foiiowed by 50 mL of concentrated nitric acid took place only affa alî reactions were complete. Microwave Power Output Microwave Power Duration thne : Maximum Pressure Estimated Temperature Volume of Digestion solvent : 500 W 10-20 minutes 120 psi 180 2 O C O0 - 20 mL aqua regîa (withlwithout HF) 2.5 g portion of sodium peroxide flux was added. The auOble rad Tdon beaker . The samples w m thoroughly mixeci With the Cole P a m r automatic agitator for 3-5 Mnutes. 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. The weight was recorded and then a 2.
water. the samples w a e removed fiom the coolhg bath and allowed to acclimatk to r o m temperature. 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.I. The stock solution. STANDARD TECHMQüES From the 50 mL concentrated stock solutions stored in the Falcon tubes..w a e repeatedly washed with D I water and the washings wae also tradiared to the . . The operatiord parameters for the ICP-MS are listed in Table 2. Pd. 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. as describeci in m ' o n 2.2. was diluted as appropriate pnor to o ICP-MS analysis.5.-ter. to just below the 500 mL tnarker with DJ. 2. Atta cooling for 20 minutes.The placement of these samples was done accordhg to a prepared asset fiSe as s a n in Appendix B. The flasks were then W i e d to a coobg bath for 20 minutes.S FINAL+ SAMPLE PREPARATlON STEP PRIOR TO ICP-MS UTILIZING ISOTOPIC DILUTiON AND INTERNAI. Each one of t these components was added to the 50 rnL Falcon Tube and diluted to the 50 mL mark with D. mL fiask. then the samples were thoroughly mixed and they were now r d y for introduction into the Perlrin Elmer Elan 6000 ICP-MS. Dependhg on the type of ICP-MSanalysis. 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. M r the Ûansfer of the mixture to the voluxnetri*~ the mixture wts düuted e flask. s obtained. and Rh) to repliate samples. one could also add 1 mL of ~ t ' ~ / ~ d ' " interna1 standard as w e l as a 1 rnL spike isotope (containhg known concentrations of P. Once all the components wat nWed in. After about 5 minutes.
i 2.The sample file sewed as a ternplate for the Elan 6000 ICP-MS software package.6 ICP-MS ANALYSIS (OPERATIONAL P )- Before the analysis of the dissolveci PGEs in solution.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 d samples were thoroughly mixed. An example is given in Appendk B.1. .2 below. 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. a sampie file was generated using the weights transcnied fkom section 2.3 iato a PC software package.
15 mm orifice Skimmer Cone : Nebuliter Type : Solution Uptake : Nickel with O.2 Volts Ion Lens Setting : . 1O mm orifice Cyclonic Spray Chamber 15 Urnin Peak Scan Parameters : Reading Replicates : Discriminator Threshold : Number of Scans : Peak Hopping 1 55 mV0lts 3 40 seconds Sample Sweep : Mass Spectrometer : Detector : Quad Mass Spectrometer Dual Detector 6.O2 U i mn -2.2 Operational Parameters useâ on the ICP-MS for the Analysis of Sodium Peroxide Fusion Sampks RF forward power : Argon Gas Flow (Nebuber): Analog Stage : Sample Cone : 1o O Watts .300 Volts Nickel with a 0.O 1.Table 2.
This single ulIbration soiution was composed of -4 p f i Rhodium.3.The detection b i t for the ICP-MShtmment for d elements in the periodic table l can be seen in APPENDIX C. When the samples are analyzed. 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. the intensities of the species imrolved i the molecular ion n interferences are measured. . palladium and rhodium. . removal of these Uaerrence is imporîant for the high accuracy and precise determination of platinum. Such interferences can affect the determination of the three PGEs and are rernoved rnathematically usïng the corrections Iisted in Table 2. Mer the calibration of the ICP-MS with the PGE calibrating solution. Once measured. yttrium and H u m . was mixed with the indium . 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. copper. h strontium. the n a t step is to calibrate for the removal of possible intederences. The caiibration solution was rnonitored using an indium and i i i m internai standard prepared from purchased rdu Certifieci Spectral Standards. Using three solutions of hown concentrations of rnercury. the intensities for each of these element are measured for the blank solutions and inputted into the ICP-MS software.lead. t .20 pfi of palladium and 40 CcglL of platinum which - and iridium intemal standard. The .
and rhodium. Strontium comb*med with oxygen f o m a strontium oxide which iwbacically interferes with rhodium and palladium.3 Spectral removal of possiie interfierences from C .Table 2. Ytim oxide formed tru within the ICP torch will also isobaricafiy interfiere with palladiwn.Y. Copper combined with the argon gas in the piasma gas f o m a copper argide (~uAr+*) isobaricaily intetferes with rhodium and pallaâium dements dependiag on which which copper isotope is present. strontium. Double charged lead . yttrium. The ICP-MS software WU moaitor the copper. u and Pb. and hafhîum for possible isobaric and double charged spectral interfierences of platinum.Sr. palladium.
W~th d the g up of these iaterference removals tiom the sample. Pd and Rh in new and used automobile catalya CM use a wide variety of internai standards. The analysis of platinum can be doue either through isotope dilution (Sa Table 2. 2. The final choice was to use a platinum isotope. t 118 will interfere with indium which is used as intemal standard and mercury h U n a r e s lightiy with the detetmitllltion of I d . Another t . Another possible choice was T m but it was obsewed to drift on the ICP-MS and to affect the l' o detefmination of platinum. s it was not used. This is chemicaily dissirnilar to Pt but close in rmw. The isotope was p u r c M âom O k Ridge National a h Laboratory as a metai powder containhg 95. s Palladium not behg mononuclidic in nature caild also be d y z e d through either isotope dilution (See Table 2. The determination of Pt. u m F M y . Pd. A semiquantitative -5s of fused catalyst (sa Appendix A) showed that Pt1% almost nonexistent and therefote was chosen as our was isotope interna1 standard. Therefore each element is discussed separately.9. the d y s i s of autocataiytic snmples can now p r d . The choice of isotope was largely dependent on its avaüability as weil as its natural abundance within the catalyst.204 wül intetfere with the monoisotopic rhodaim 104 species and W u pre!sent within m the zirconium nuciales forms a W oxide speck that interfères with platinun 195.4) or through the utiiization of intemal standards. T e method for the dissolution of this metal powder i giwn in section 2. For this research.8 SELECTION INTERIVAL STANDARD OF The choice of intemal standards for the determination of Pt.3 1% of ptm abmdant. the intemal standard hlg3 was used at first. and Rh in n m and used automobile catalyst is dependent on the element.4) or with an intemai standard The interna1 standard chosen was inNs which is chemidy metent fiom Pd but i is relatively dose in mass.
The dissolution procedure for tbis metai was simüar to that of the Ptlm isotope (section 2.Wh of the isotope. The first involves the use of ~ dwhich is one mass unit removed fiam ' ~ pdl*' and chemically similar t the Rh. As a result.possible choice for interna1 standard was R " U' irregularities during Jnrnple but this element showed miwr d y s i s and was therefore not used. the isotope was purchased from Oak Ridge Natiod Moratory as a metal powder which wntained 94. Finally. hl1' was chosen as the intemal standard for rhodium determination. for the daennination of the mononuclidic Rh there are three possible intemal standards. ~ a seen in AppendUr A and w s *&ore a d was ody ' ~ found in trace amounts in a semiquantitative analysis of the fused outomobite cataiyst as chosen.9). accmcy and precision to the detemidon of palladium. . The second is with ~ t ' "which is again chemicaily o similar to Rh but has a large mass difference and W y there is I' which is chemically n" different from rhodium but close in mass and naturally absent in autocataiyst. Internai standards provideci excellent d y t i c a l resuits but i was believed that isotope dilution muid provide t additional sensitivity. Tûaefbre the isotope diution ICP-MS detemination of pallnAium w s attempted. Of these.
4 Relative abundance of naturai isotopes used i this project. n Element Ru Measured Mass 99 101 102 1O 3 10s Relative abundance 12.Table 2.72 Ru Ru Rh fd Pd Pd Ir 106 108 191 Ir P t 193 194 P t P t P t In 195 196 198 113 115 In .
. . 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. Sudbury Division. The concentration of the two isotopes w e n deternwied with an ICP-OES analysis which was then comlated to ICP-MS detenninations. package developed at INCO Ltd.31% abtsndant) w r purchased fkom ee Oak Ridge National Laboratory as a metd powders. 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.The pdlM (94.000?abundant) and ~ t "(95.
fie assay pre-concentration generally r e e s a large amount of acid to be used for sample preparation. precise and sensitive analytical determinations of the PGEs. labor intensive. Ii addition to the above.Chapter 3 Results and Discussion The use of nickel sulfide fie aswy collection for Pt. Many sample dissolution methods are available but the method chosen should be low cost. and is subject to experimental e m due to the large amount of sarnple handliag (Beamish. The methods considered in this project were: hot plate acid dissolution. relatively simple. microwave assisteci dissolution. and highly accurate. most autocatalytic samples d y z e d on the ICP-MS were andyzed dong with . a look at possible problems that could 3. assisted dissolution). this project l o o b for altemative sample preparation methods that could be used for the simultaneous determination of Pt.3 (Microwave . These will be seen in section 3 2 (Acid dissolution).4-3. ftsion) respedively. 1966). Pd and Rh in both new and used autocataiyst.1 ASSESSMENT MATIUX INTERFERENCES OF In an effort to provide the best conditiong and analyticai resuits f r the recovery of o PGE's. As a result. dependent on the anaiyst laboratory skül level. T i new method would be used in hs combination with a Perkin-Elma Elan 6000 ICP-MS for highly accurate. section 3. Pd and Rh in the pteconcentration of autocatalyst sampfes is a highly accurate procedure but it i d m time s consuming.5 aEkct the ICP-MSresults is warranted. The ICP-MSprovides many advantages in that the analyst can predict possible interences. and z r o i m aucible icnu alkali frisions. sample analysis are rapid and not hindend with emission peak oveilaps and the instrument is fully autornated. and sections 3. its provides a broad iinear dyaamic range. Prior to explorhg each dissolution method and its results.
and strontium show M e or no ih affects on the anaiytical results Born the ICP-MS. pdlW also suffers nom isobiuic interferences fiom various isotopes of strontium and oxygen as shown with S ~ ~ ' O 'But ? again strontium is found i trace concentration and poses very M e problems in Pd n 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. saniquantitative d y s i s (Appendix A 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. and as such mat& interferences and other sources of instrumentai error were of concem during sample d y s i s . The first two mors are fkom interferences &sing Born either molecular ions ancilor doubly charged ions present within the prepared solution. F i d y .criii standard reference matenCaIsS etfa (R) autocatalytic samples (NIST 2556 @dl&). In addition to using d e d materiais. The ICP mass spectrometer is a non-specific ionization source. For Pt. Pd. the use of isotopes as interna1 standards wouid a b provide with extremeiy sensitive d y t i d results. Both of these two interferences are readily identified by the anaiyst and are easiiy c o r r d for. NIST 2557 (honeycomb)). catain ~ m p l were e~ spiked with a known concentration of Pt. Generaiiy this last source of error affects the rnid-rnass measurements of several elements and it is vey dficult to identify. The third source of error is due to the drifthg of the ICP-MSover a period of tirne. . there was no sigaificant elemental isobaric intaference other than a stight interference fiom Ht"*0" @ 8 ' Hwith the ultra-trace levels of and 7 0 6 f hafhium originating fiom the zirconium crucible. The wpper @des will also interfére wt Pd but h&ium. copper. There exists thtee possible sources ofanaiyticai error that can a the ICP-MS é c t results. The last source of error can be correcteci for but it generdy requires special software development. and Rh solution and recoveries for each element were caiculated to assess the vaiidity of the analyticai resuits. Molecular ion interferences (isobaric interferences) affect aU PGEs i autocatalyst n in varying degrees.
Through the Elan 6000 ICP-MSsoftware. If lead is present in detectable amounts. tbis type of error is vey diacult to identiQ and requires specïaliy developed software. The extent of the interference i dependent on operational conditions as well as s the presence of the doubly charged Iead species. doubly charged ions kom the percent level of Pb in the sample will produce an interference at n/z 104 (M'Pb'2)with ~ d and also at n/t 103 fkom ?b+* ' ~ with Rh. Therefore. The second possible interfirence originated fion double charged @s e such as g lead. 3. P is unaffected by this type of interference but Pd and Rh are affected to m t extents. T i drift correction eliminates this source of emr during ICP-MSanalysis of hs PGEs but it is propnetary and therefore the mathematical details are not covered in this thesis. software was developed to correct for the instrumental driAing and all resuits are reported after a d i t conecti*on rf cakulation. The last source of error is due to instrumental driffing which generally affkctsthe measunment of heavy elerneats.2 TESTMETHoD # 1 :ACID DISSOLUTION OF AUTOCATALYST SAMPLES The fkst method of autocatalyst sample dissolution requires the use of concentrated acids to digest the samples on a hotplate. interference fiom lead is virtually eliminated for the PGE analytical nsults. 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. Doubly charged interferences are dso monitored within this project through the ELAN 6000 ICP-MS sohare and for specially prepared celibrating interference solutions. Udortunately. As a result. There are many factors that can affect the extraction of Pt group met& fiom the autocatalytic matrix Among these .
These two classes of catalyst are the monolithic and the peiîet types. The supporting matrix win affect the rmvery of PGEs in new and used autocatalyst. (1993) briefly disaissed how recoveries fiom acîd dissolutions were affected by mat& composition type.1. Presentiy there are a nwtlber of supporting matrices for the PGEs in autocatalyst and these fiill essentiaiiy into two classes. 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. Wu a al. the sample particle size. 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. . AU of these fàctors play a role in PGE recoveries so each will be discussed in detail. and the various acid combinations.factors are the type of autocatalyst. the leaching tirne.
.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.
Since aii samples in this project were prepmed in the same fmhion. The particles that were larger than 75 or -200 mesh are trapped in the sieve and cannot p a s through. However.The y .3 EFFECT SAMPLE PARTICLE SIZE OF Sampie size can play a sigdlcant role i the extraction of noble metals. the sample size should be the same in ali cases. Thus the dEerence in solubility of the two matrix components is most likely to be the cause for the bata recoveries âom the pellets. thae are signifiant diffefences in the recoveries fiom the two types of ~IW&S. s i regardless of the matrix type. ali the autocatalytic samples were pulverized to 75 pm or -200 mesh and to prevent larger particles fiom entering into the sarnpk bettle. 1995). Each of the seven acid combations used an aqua regia (3:1 HCVHNa) mixture but additional acids were added to improve . (1995) describeci how extraction times affect PGE recoveries âom various sample matrices. Generally. Their results indicate that extraction time can have a major out using the autocatdyst samples with influence.It i apparent that the aqua rea digestion gives >85% recovery in d instances.2. and so a study ofthis &kt was &ed aqua regia digestion. it should be appreciated that sarnple size can affect the percent extraction of that particular element (Ferry et al.4 THE EFFECT OF LEACHING TIME IN OPEN BEAKER DIGESTIONS Peny et al. al1 the crushed samples were thoroughly sifted. 3 2. This is probably b s e the PGEs fom a Surface coaîing and are not an integrai part of the matrix itself. 3. The percent of extraction for a range of digestion times was measured using the dried and d e d MST 2557.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. Anderson n (1987) described how the padcle size of noble metal samples af!f'iected acid dissolution results. But in cases where the sample sire may vary.
2 The percent extraction of PGEs in cnashed autocatalyst (NIST2557) and using aqw regia over a 4 hour period.5 3.the recoveries of the PGEs. Atta mcasured t h e intervals. Percent Extraction (%) 1 1.5 2 3 Digestion Time (Houn) 2. the sarnples were removed Born the hotplate.1 . Figure 3. cooled and then diluted to 500mL. . The d t s of this study are shown Figure 3 2 and Table 3.5 4 .
2.5 STUDMNG VARIOUS ACID COMBINATIONS THE A study of the various acid combinations on the spent autocatalyst samples was performed to explore the possibility of improving the rmveries of Pt.3. Acid dissolution does not effectvely extract ail PGEs like the alkaü fiinon technique cm. Seven different acid combinations were tried. 3.2% was the best rwvery ochieved. 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.00! of Rh was extracted while after 4 houn 90. The results of these experiments are shown in Figure 3.Table 3. Several attempts w m made to improve the Rh extraction but for wet acid dissolution 90. only 82.1 The percent dos of PGEs kt d e d autocatalyst (MST 2557) and using aqua regia over a 4 hour period. . Pd and Rh.2% Rh was actracted.
- Percent Extraction (%) Rhodium Palladium Sample # Note: Sarnple # 1) HCI+HN03(3 :1) .3 PGE ncoveries fkom a variety ofacid coaibUiation~ opai-begkm in digestions ofNIST 2557 (Honeycomb).Figure 3.
5 mL nitric aci4 2 mL bydrofluonc acid.2 EFFECT VARMNG THE MICROWAVE DIGESTION TIME OF The e f f i of varying rnicrowave digestion time was studied on the two different certified reference catalyst sarnples. A 0.From the figure above. Ail other acid combination showed infaor t extraction results to this acid combination.3 TEST METHOD :MICROWAVE-ASSISTED #2 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. A bnef discussion of these midies are a follows. and 5 mL of 1:1 suifùric acid showed the best recoveries of the PGEs ( 97% of P and Pd and 91 % Rh). 3. . Autocatalyst samples were digested using various digestion times and two Werent acid combinations.3.2 as compand to their cemfied values. The resuhs obtained with two different dissolution times are shown in Table 3. 10 mL perchioric acid. i is o b s m d that none of the various acid combinatiom t was able to extract 1 / of P . The five acid Wo t wmbination (#7) using 15 mL hydrochloric iiaâ. 3. 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 H was studied due to the F improved Rh extraction resuIts when digested via the hot-plate technique.15 g autocatalyst samples of reference s matenals was used in each study since it yielded the highest POE recoveh. Thus it appears that open-beaker digestion is not a satisfactory option for the dissolution of spait autocatalyst samples. Pd and Rh from the autocatalyst.
O%) * 71 1. Average of triplicate results.3 Palladium values in ppm (% recovery) 326.8 (99.5 Found (ICP-MS) 10 minutes Fould (ICP-MS) 20 minutes * 715.4 i 1.1%) SRM 2557 (honeycomb type) certified values Found (ICP-MS) 10 minutes Found (ICP-MS) 20 minutes values in ppm (% recovery) 1131 i 11 1125.6 i 0. .% 1128.0%) * Results are expressed in pprn and based on dry weight (500°C for 2 houn).5 values in ppm (% recovery) 135.7 (9 1.2 * 2.2 î 1.8%) 327.6 Rhodium values i ppm n (% recovexy) 51.6 & 8.0 I 2.1 (100.2 Effect of varying the miaowave digestion thne on S R .3%) 46.9 f 9.1 121.4 (102.2 I 0.1 (96) 9.5 k 1.3%) 233. 2556 (Peuet) and SRM 2557 (honeycomb) wbile digesting with aqua regia and HF mixnue.8%) (99.9 231.3 0.8 (102-6%) 328.Table 3. Platinurn SRM 2556 (pellet type) certified values d u e s i ppm n (% recovery) 697.9 * 2.3%) 126.5 (94.8 values in ppm (% recovery) 233.4 2.9 i 1.9 (100.9 I 2.0 f 1.0 (100.9 (90.5%) 46.3%) (90.9 2.7 * 1.
The ie results do show a slight but bignifiant improvement which can be amibuted to Uistnimental drifting of the ICP-MS. but Rh results were wnsistently low. The microwave oven was set to identical power setting for each of the digested autocataîytic samples. 3. The cornpuison of the microwave results for the two NIST samples a f k M f n dissolution time showed that ee t an increase in dissolution tm wiii not increase the extraction of the Pt. On the other hand. It has ken obsecved tbat independent of the dissolution time chosen. The resuits are given in Tables 3.3. fist reason The might be related to the oxidation of the Rh to Rh oxide (RhZ&) which is largely insoluble in almost al1 acid combinations. Pt and Pd are weli extracted through microwave dissolution. The poor Rh extractions could be due to two re8~011~. If this method is employed. Rh shows poor recoveries via miaowave dissolution evai afta varying the digestion time.In this investigation. the percentage of Rh recovered was increased significantly. Pt and Pd resuits were acceptable. digesting the samples for 20 minutes could correct for some low PGE results and was therefore chosen for all samples. a correction fâctor needs to be appiied to the Rh recovery values. the previously drieâ autocataiytic samp1es were digested witb an aqua wgia mixture for eïther 10 or 20 minutes.3 EFFEC~ THE ADDlTION OF HF TO THE MICROWAVE SAMPLES OF It has been observed that with the addition of conceatrated HF to samples dissolved via the open-beaker acid digestion technique. 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 microwaveassisted digestions. Therefore. . The second possibility for poor Rh recoveries is probably due to the inwmplete digestion autocatalyst samples. 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.3. Pd and Rh.
9 î 3. Platinum SRM 2556 (pellet type) Palladium values in ppm (% recovexy) Rhodium values in ppm (% recovery) values in ppm (% recovery) certified values Found (ICP-MS) Aqua regia with no HF Found (ICP-MS) Aqua regia with 0.6%) values i ppm n (% recovery) 233.9 2.1 k 1 9 .1 (97.O%) 1125.3 W c of adding HF to the microwave digestion for amples of SRM 2556 et (Pellet) and SRM 2557 (honeycomb). . Average of aipticate resuits.0%) Found (ICP-MS) Aqua regia with no H F Found (ICP-MS) Aqua regia with 0.9 k 2 8 .8%) * 1 6 4 I 15 2.5 mL HF F O U (ICP-MS) ~ Aqua regia with 1.3%) 233. .2 1 9 .8 (99.9f 17 .5 (96 -7%) * values in ppm (% recovery) 135.3%) 121. 225.0 mL H F 1128.6 î 1. 114.1 (99.7 (85.Table 3.5 mL HF 231.5 î2.6 f 2. (94.0 (100.0%) Results are expresseci in ppm and based on dry weight (500°C for 2 hours).0mLHF SRM 2557 (honeycomb type) c e d e c i values values i ppm n (% recovery) 1131 Il1 1096.8 f 1. (99.3%) Found (ICP-MS) Aqua regia with 1. (90.
5h9. . The cornparison of the percent difference for NIST 25 56 samples treated and not treated w*th caa be seen in tables 3. P t 697. W . NIST 2556 . Sarnples treated wt HF showed Rh fecoveries of 91 to 94% and up wbile those ih with or@ aqua regia showed Rh recoveries ranging around 78 to 85%.32 Note: Results presented above are the average of triplicate results.4 Percent difference for NIST 2556 samples dissolved using microwave dissolution and not treated with HF.4 and 3.From the resuits in Tables 3.28 d g Pd Rh 51.1 +1.9 + 0.3.6 33025.2 1.4*2.2=t0.3 695.4 4.O NIST Value MicrowaveACP-MS DEerence Percent Merence compared to NIST 326k1. 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.5 below.29 - -2 13 . . HF Table 3. Therefore it cui be concluded that HF does help in the extraction of Rh.5 3 9 . Another advantage of using HF m the miaowave dissoIutioa i that the r d t s s fiom the samples treated with HF showed a better p&sion and accuracy over the samples treated with only aqua regïa.28.
the recovery of Rh i s still too l w and therefore requires a correction.2M.5 Pacent Merence for NIST 2556 sampIes dissoIved using microwave dissolutiontreated witb HF. Although HF helped in the further o extraction of Rh but stiü does not solve the low recovery problem.7%with HF).6 MST Value Percent merence compared to NIST 1 .31 1 . it also helps in the recovery of Pt (99.0. .9% with HF) and Rh F (779% without HF compared to 87.11 1 Note: Results presented above are the average of triplicate results. These results can be seen in Table 3. At the m e time.3 ~g/g 1 Rh 51.0.12 1 .Table 3.4*2.7%without H compared to 99. Unfortunately.00h without HF compared to 99. it cm be obsmed that the addition of HF does help to improve the PGE relative percent error.12.7 below.6 and Table 3. the NIST 2557 autocatalyst samples shows a slightiy dbierentresults. When cornparhg the results fkom the hvo tables above. Unlike the NIST 2556 (Pellet) autocatalyst sample. NIST 2556 1 P t 697.9% with HF) but it shows a negative effect 4 t h Pd (101.5 Pd 326I1.
2 + 0. . Microwave/ICP-MS Merence -35 .6I3.111 . 91. Therefore HF plays a major role in the extraction of & Pd and Rh in used autocatalyst samples.15. Pd (96. HF is useful for improving the percent relative error for the MST 2557 autocatalyst ssmples.9 114. Table 3.0 -20.7 -7.O .30 Rh 135.9 135.9 . 9 Merence Percent difference c o m p d to NIST .36 -0.2 NIST Value 1131kl l 1096.8 .6% witb HF).7 Percent dEerence for NIST 2557 samples dissolved using microwave dissolution treated with HF.8*5.6 Percent diffecence for NIST 2557 samples dissolved using microwave dissolution and not treated with HF.6 3. While improving the acwracy. MST t NIST Value 1131k11 +6.W wiîhout HF compared to F.9I13.1*1.3 Note: Results presented above are the average of tripiicate nsults.30 Percent ciifference compared to - . As seen in the two tables above. + 1.66 -1 1. the r d t s for Rh extraction are d too low i and therefore require a correction. NIST 2557 dg .O0! with HF).M without HF wmpared to 100.2k22.214.171.124% without HF compared to 99.7 Note: Results presented above are the average of triplkate results.55 233.Table 3. P t Pd 233211.9 225.7% with H ) and Rh (85. Unfortunately. it also helps with the recovery of Pt (97.
2 RSD% A 2.9 3-7 5.In addition to helping improve the m c y of the microwave dissolution nwilts.8 and Table 3 9 below. .3 9 . 3.5 P t Pd Rh SRM 2556 (Pellet) 12 12 1096-9 225.1 Results reported with a 95% confidence intefval. This i s obsemd when compaMg the r d t s in Table 3. Table 3.4 3 .O Pt Pd Rh A 12 12 12 695.0 3. F - le ment SRM 2557 (Monolith) n 12 Mean @g@ SD 13.5 330. HF has alw improved the repeatability of the microwave digestion technique.8 Repeatabidity of microwave resuits for NIST 2556 and 2557 semples without H . .6 148 1.O 2-6 3 -3 15. 99 9.1 5.
2 1.8 0.6 325.3 . microwave assiaed dissolution was not explored in any great detail.1 2. Unfortuaately.0 45 . HF was added to all subsequun samples to aid in the PGE dissolution.6 1.9 Results reported with a 95% confidence interval. The present rnicrowave apparatus can only go to 120 PSI which is not high enough to digest the samples aad Rh properly.1 1. two Limitations of this technique and instrumentation need to be changed. To improve Rh recoveries. 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. SampIe w o n could prevent such hardware problems but it is not required since the cordierite and y-aluminia .1 1.4 6 1. because of the very Iow Rh recoveries. P t Pd Rh A 6 6 6 696. Samples treated with HF and then digested via the rnicrowave have shown excellent repeatability.6 P t Pd Rh SRM 2556 (Pellet) 1137.4 123. but also the precision of PGE dissolution h m the two types of sample matrices (Honeycornb and Peiiet). The first limitation is due to the temperature and pressure required for sample dissolution.2 232.8 1.7 1.O 3.Table 3 -9 Repeatabüity of microwave results for NIST 2556 a d 2557 samples with Element SRM 2557 (Monoiith) I n 6 6 Mean SD 13.2 2. As a result of these hdings. 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.
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. Since each of these plays an extremely important role in quantitative analysis of autocatalyst by fision preparation. The first method explorecl in this project was sodium peroxide fusion of dned autocatalyst. 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. There are five areas of possible conceni when preparing samples by alkali fusion. The f i d problem deals with how the samples are fused. Pd and Rh. each will be discussed in detail. The problem of choosing proper sample weight and flux weight i also important in the s determination of Pt. 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 .precipitate to the bottom of the JO mL Falcon Tube and thus are not trpnsférred to the final aspirated solution. the use of sodium combined 6th concentrateci hydrochlonc acid does provide for the possiûiility of forrning salts within the ICP-MSinstrumentation and dso i the dissolved n .4. It is one of few dissolution rnahoâs that can effectively dissolve the honeycomb's cordiente m & a as discussed by Totland et al. 3. d e s s the method is properly developed. fùsion prepsration d l not provide accurate and pranalytical results. (1995).. Udortunately. But.2 PROBLEMS ARISING FROM ALKALI MATRIX COMPOSïïiON Sodium peroxide alkali tiision is by fiu the best m t o for dissolving the ehd autocatalyst 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 . Several attempts were made to correct for the analytical bias but none were successful. This dilution kctor has proven very effective and no further exploration into sample dilution bas been attempted. Due to the excellent sensitivity of the ICP-MS. . the present samples were diluteci with deionid -ter Usng extrane care and caltirateci glassware. another fkctor affecting the analytical results is the concentration of acids within asphted samples. The problem was later solved when a 2-3 mL aliquot of concentrated hydrochloric acid was added to the aspirated sample. Initially analyzed samples contained 0. Along with interferences resulting fiom salt formation. This is w y ICPh MS is the desirecl instrument for PGE Bnalysis in used autocataiytic sarnpla. Pd and Rh results were mostly t biased low. The results âom the addition of 2 rnL of HCI to the aspirated samples can be seen in Table 3. the Pt was precipitathg as Pt chloride species. To avoid possible salt formation problems.4% (vlv) dissolved acid and the P .samples. the Pt could n o longer precipitate and the bias was no longer apparent.10 below. this is a possible solution to preventing salt forniaton but not for most other anaiytical instnunents. With the addition of concentrated hydrochloric acid. It was established that due to the initiaiiy Iow concentration of acid within the aspirated samples.
99.and 100 f 03 % for Rh.10 Compan*son ICP-MS resulto vaiidnting the addition of 2 ILof of concentrated HCI to the aspirated sample to help improve the acairacy of PGE detennination and remove the bias.7 f 0.33 f 0. Pd and Rh.4% for Rh.70 f 0. 99.Table 3.8 % extraction for Pt. Aspirated Sample results with no prior addition of concentrated HCI. Thdore it is observed . The simples with hydrochioric acid added to the aspirated samples showed a 100 f 0. For the MST 2557 autocataiytic sample. the ICP-MSresuhs with no hydrochloric acid added had 99.0 f 0. Aspirated samples redts with concentrated HCl added (2-3d) From the table above. /g 1 SRM 2557 (Hontycomb) ( SRM 2556 (Pcllct) A) B) C) NIST certified results.1 % irnprovement for Pt and Pd and 0. 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.5 f 0. that hydrochloric acid did help in the determination o f the PGEs for the howycomb type catalyst since there w s 0.3 k 0.5 % for Pd.1 % a improvement for Rh.6 % for Pd and 99. .8 % extraction for Pt.
sampfes not treated with hydrochloric acid saw a 99. the addition of hydrochloric acid dso helps in the determination of Pt. Rhodium is monoisotopic and therâore required the first type of internai standard for moaitoring. Pd and Rh. Samples treated with hydrochloric acid pnor to aspiration showed extraction of 99. 99.9 % extraction of Pt. Pd. Pd. Thae was a 0.9 f 0. As mention& the first type of interd standards were used because they w r not ee present in the sample solutions and they were closely matched in ~MSSto the PGEs. A brief discussion of these two types of internal standards foiiows. 3 -4. and 98.3 f 0. The first type included elements not found withh the dissolved niatrix but whose m a s closely matched those of Pt. Due to the improvement in PGE results. In this case four elements were chosen as internal standards and these were Indium and llullium for Pt and Iridium aad Ruthenium for Rh.7 f 0. The second type of internal standards were isotopes of the elements Pt and Pd.2 I 0.6 f 0.5 % for P4 and 99.1 % improvement for Rh. Thus. 99.6 f 0. The dection of these initial four standards . Two types of internal standards were tried. 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.1 M 6 % -o .3 PROBLEMS TO INTERNAL STANDARD SELECTIûN DUE The selection of an internai standard plays a vital role in the determination of Pt.For the NIST 2556 autocatalytic ample.5 % extraction of Rh.4 % for Rh. *n of Pd. 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. Pd and Rh in new and used autocatalyst. and Rh in pellet type autocatalyst samples.5 I 0.1 % improvement for Pt and Pd and a 0.7% for Pt.
11.5 50AM.89 51.9 131.00 323.80 +l .46. As for the MST 2556 sample.1 1 above show that Rutheniium and Thallium give good PGE determinations but slightly outside acceptable range. It was found that the use of two of these intemai standards failed to produce satisfactory nsults. SRM 2557 N S T Value FusioriICP-MS DBerence Percent difference compared to NIST 1 P t 1131.311.72 % relative enor and Pd and Rh showed an average 1. it can be concludeci that Ru is not an acceptable intemal standard for the determination of Pd and Rh. Therefore.90 -0. Thallium still is an .80 -1 -56 -0.3 326*1.4*2.12.was due to their relatively close masses to the PGE elements.1G.04 % for Pt and an average of 2. fireassay &'bit a 1.2M.81 NIST Value FusionnCP-MS Difference Relative Error (%) compared to NiST 697. Thallium and Ruthenium both gave inconsistent resuits w e used as intemai standards as shown in hn Table 3.5I3. nie average relative percent error for the MST 2557 samples was found to be 1.6 -0.2 -2 -70 -1.72 The results in Table 3.1 1 Percent ciifference of ICP-MS results using ruthenium and thallium interna1 standards.0% for both Pd and Rh.9 1 1 1 142. Generaily.0*11 1 1 Pd 23321. The precision associateci with these two intemai standards is shown in Table 3. Pt had a 0.4 -2.1*1. Table 3.0 % relative error.2 % relative error.3 -5.16 Rh 135. fiom the data presented above.O4 - 230.8*1 1 +11.6 692.4 -3 -80 -2.
The general n accuacy and precision associated with the use of indium and iridium as intenial standards can be seen in Tables 3. other elements w r tried as interd standards.12 Precision of ICP-MS resuits using Nthenium and thallium intenial standards.acceptable interna1 standard for the determination ofPt but shows the same =tic of Ru. nature 1 Element SRM 2557 (Monolith) 1 1 n 1 1 Mean h @ g 1 . the precision is found to be above this target. For both the Ru and T internai i standards. Since nithenhm and thallium gave unacceptable results when used as interna1 standards.12 below. Ru and T l possibly can not be possibly used as internal standards for the detemination of Pt./ SD 1 1 RSD NA SRM 2556 (Pellet) A Precision based on a 95% confidence interval The target precision for this study was < 2%. and Rh.Pd. Therefore a more suitable set of internal standards is required.This erratic behavior is rsadüy seen in Table 3. also not presait i the dissohred autocatalyst samples.14 below.13 and 3. This is largely due to the erratic behavior of the intemal standards and as a result of this erratic behavior. The second set consisted of ee iridium and indium. . Table 3.
69 +OS2 Mid&! P t 697.13 Percent merence of ICP-MS resuits using iridium and indium intenial standards.515.2a. and Rh t determinations in autocatalyst.4*2. SRM 2557 I Pt 1131.90 50.9 -0.6 +0.03 -0.46 -0.0111 Pd 233.5 MST Value Aikali Fusion/ICP-MS DEerence 696.3I6.512.70 +0.30 135. al .5 -0. The recovenes for each of the PGEs are also much better then those of Ru and T interna1 standards.111.0 Rh 51.13 -0. -1. Since indium and iridium show good relative i percent errors as compared to the certifieci results.40 .811.2I1.7 -1. Pd.Table 3.60 Rh u NIST Value 135.8 +0.8&0.14.50 Percent Merence compared to NIST -0.78 The relative percent errors associated with the use of i d u and indium as nim internai standards are found to be wi below the 1% ei k t for P .3 Pd 32611.9 231. the precision of these two standards is shown in T b e 3.6 324.9 Aîkali FusionfICP-MS Merence Percent merence compared to SRM 2556 1131.6~1.
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.Table 3. Pd. 1996). Therefore. Rh is monoisotopic and therefore required the first type of internal standard.3 S D 6. Element 1 a 16 Mean (-&& 1131.36. i d u and indium seem to be nim the appropnate choice as intemal standards for Pt. Pd and Rh are below the 2%limit .8 RSD % A 1. and Rh t determinations.14 Precision o f ICP-MSr d t s using indium and indium k t d standards.. Pd and Rh determination for new and used autocatalyn samples. the precision associated with the determination of Pt.2 SRM 2557 (Monohth) P t I SRM 2556 (Pellet) 1 A Precision based on a 2 or 95% confidence interval a From the results above. The isotopes were dissolved a . The next set of internal standards tested not ody matched the Pt and Pd through mass but also chemicaliy. The accuracy and sensitivity for isotope dilution is better then that of NAA with P . Iridium w s used to detemine Rh by ICP-MS. 1994). Isotope dilution ICP-MS is considend to be the most accurate and sensitive anaiytical method available for PGE determinations (Beary et al.
.I.5) . the samples were âried by the method used by MST in the certification of autocatalyst materiais (Beary et al.4. T e acid concentrations ofthe disdohted stock solution of isotopes were h closely matched to those of dissdved autcsataiyst to ensure totai compatiiüity between the two samples and elimlliate ma& effects. w 3. Once the samples are dried. T i elhinates hs both carbon and water fiom within the certined MST 2557 (honeycomb) and NIST 2556 (Pellet) samples. One problem with the u e ofthis second set s of intemal standarâs was that the software needed to be developed and the method only became available at the end ofthis project. In the NIST dryiag process. 1987).4 and 3.4 SAMPLE DRYING PRIOR TO DISSOLUTION The autocataiyst. (See Figures 3. although previously drkd arrives at the laboratory in a wt or e darnp state and must therefore be dried (Anderson. they should be then stored in a d e s i ~ o to prevent them fiom picking up water fkom the r atmosphere. so f resuits were obtained.ushg ultra-pure nitric and hydrochloric acid (Aldrich) over a hot-plate and were dihited with D. the sarnples are dried at 500°C for 2 houn and then cooled in a desiccator. water. 1994). In this project.
Figure 3.4 Calcination redts fiom LEC0 and water anaiysis of MST 2557 (honeycomb) autocataiyst. .
Carbon Perceni -+-Percent SiiWr .5 Calcination results from LEC0 and water d y s i s ofNIST 2556 (Peuet) autocatalyst.Figure 3. + Percent Water ----#----.
15 below. The samples are used to validate the rllraü fision n preparation technique.2097 2. Water was determined ushg the weight Merence method.01 0. (P) is the pellet autocatdyst fom. a Al1 water results are reported averages of tripiicate d y s i s .0666 2.1856 3.99 I 1.21 i 1.0126 2.9926 2.09 I 1. Sample Sample Number (#) ID Smple Added Dry Sample Wei@ Percent water ' (%) (BI (BI 4 5 6 7 S24350) 52471( ) M S2427(P) S24600 2. Table 3.15 Water concentration of prwiously dned and analyzed autocataiytic samples.The water content of several autocatdyst samples prevïouely analyzsd by firr assay can be found i Table 3.95 I 1.0078 1.1515 2.11 1.05 3. .03 0 is the monolithic autocatdyst fom.0743 2.
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 f o 2 4 % bowd water. Although the concentration im of b o n d water is quite mail, Ï t does play a large rote in t e d y t i c a l resuits on the 1 8 h 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)
P t -
P t -
1118.6f8.8 230.9f1.9 133.8I1.8
1130.8I6.8 233.2f1.7 135.111.6
697.1f5.9 326.1f2.0 51.2f0.5
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~calcination in the sample step 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 N is particularly important when dealing with PGE-containhg e
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 i section n
2.2. The resuits fiom NIST 2556 (Pellet) and MST 2557 (Honeycomb) can be seen i n
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)
The results are shown in Figures 3.9 (NIST 2557 Honeycomb). p d I y because there was inainiCient hvr amilable. The flux weights ranged between 1 to Sg additions. The r d t s for the NIST 2557 samples compared weli to those of MST 2556. and Rh) whüe ushg 2. The samples were nised using the method iisted in section 2. a 0.5 g sodium peroxide aikali fim. and 3.25 g autocatalyst sample size is used for the remainder of this study.3 % Rh) and MST 2557 (100 percent aarsction of Pt.25 g for NIST 2556 (100 percent extraction ofPt.7. Consequently. Using the standard reference materials MST 2556 (pellet) and NIST 2557 (honeycomb). Pd and 99. a 0.2. it was obseved thaî the minhum weight n 36 required for effèctive autocataîyst saxnple fisions was about 0. it is dso important to observe how the amount of flux affects analytical renilts. Along with varying the sample weight.8 (NIST 2556 . It was ais0 observeci that larger samples do not fise es well.25 g autocatalyst sample was tUsed using various sodium peroxide weights.Pellet) and 3. - . Pd.From the results i Fi~ufes.
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) .
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) .Figure 3.
2 % of Pd.3 % of Pd. 93 t and 100.17 Relative error involved with hand fbsion of standard reference materials SRM 2557(Honeycomb) NIST Value s P t 1131 +9 . n Table 3.2 Rh 135. % of P.1 Merence Relative error (%) compared to -2-7 -1.2 1 Relative enor (%) compared to 1 1 NIST 1 -1-76 1 1 -7.The resuits seen in Figures 3.80 ~ I NIST SRM 2556 (Pellet) NIST Value 1 1 697. Since an automatic fluxer was available.17 -1.8 % of Rh was t achieved. some experiments were carrieci out to compare results using this method with the slower manu81 fluxing method.87 Pd 233. These resuIts are shown i Tables 3.1 1 1 1 -5 -45 .4 1 1 326 1 51.1 -0.18.0 % of Rh. the results indicate that a 2.99.9 +0.5 g of fiwt i d c i e n t for use s with a 0. Thadore.8 and 39 show aimost identicai results. 2556 (Pella) samples. so this was used for these studies. 99. NIST 2557 (Honeycomb) r d t e d in extradons of 9 .25 g sample. It was anticipated that the automatic fluxer would show a greater wnsistency of results.17 and 3. and 99.6 % P. the extradon of 99. For NIST .
18 Relative error involveciwith the automatic fision of standard reference materials SRM .9 135.70 +OS2 -0.40 -0.4~2.13 NIST A comparison of the two tables above shows that a smaller relative percent error compared t NIST i achieved when usîng the autornatic fiuxer for ail PGEs.Table 3.111. A comparison ofthe repeatability of each of these two sample preparation methods may provide for additionaf information.36.2*1. The repeatabiiity for the two methods of fision are seen i Tables 3.19 and 3 -20below.515.&1. 2557(Honeycomb) NIST Value Alkali Fusion/ICP-MS DifEerence 1 Relative emor (%) compared to NiST SRM 2556 (Pellet) NIST Value Alkali Fusion/ICP-MS Difference Relative error (%) compared to Pt 1 131.8G.03 Pd 233.5*2.90 -0.7 -1 -60 Rh 135. The o s improved results on more noticeable with the MST 2556 (Pellet) samples than those of NIST 2557 (Honeycomb) sarnples.5 50.50 -0.78 696.0 -1.3 Pd 326*1.W11 1131.6 324.9 -0.2a.69 P t 697.8 +0.5 -0.46 Rh 5 1.6 +0.30 +0. n .8k1.9 231.
5 50.7 .3 1. Table 3.9 1.0 5.20 Repeatability associated with the automatic fusion of autocatalyst SD 1131.6 RSD % ' 1.4 Rh SRM 2556 (Pellet) 15 Pt Pd Rh a 16 16 15 696.1 302. .8 0.7 4.5 324.8 6.6 135.9 1.2 1.8 26.1 n Mean ( & u 1 SD %RSDa SRM 2556 (Pellet) Pt Pd 16 16 685.5 2. Resuits reporteci on a 95% confideme interval.6 a Results reported on a 95% confidence interval.7 1.6 1 17.8 15.3 23 1.5 2.19 Repeatabüity associated with hand fision of autocatalyst Element l 1 .8 1.Table 3.
and sample spülage. it is important to compare the d y t i c a l results from each of these two types of intemal standard. Since two types of internal standard were used in this project. This technique cannot be used for monoisotopic elements such as Rh. 3. ail samples were fiised using a LEC0 automatic fluer. so a cornVition of the two internai standards was required where Rh detenninations were needed. loss.From the resuits in the pmcision tables above. or sputtering due to overheating. Pd or Rh and is discussed in Test Method 3G The second set of intenial standards was made of isotopes of Pt and Pd. 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. Such errors are due to the improper sample agitation wbich varies W e e n samples. The second method is seen in T s Method #3B. .5 SMLE FUSION RESULTS AND DISCUSSION The deternination o f Pt. i is observed that the automatic t 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. the various flux temperatures due to the changing cnicible location over the fiame. As a result of the findings above. An et exploration of the results fkom the two test rnethods foiIows. The firsî type of intemai standard included elements not present in the dissolved autocatalyst mat& but that closely matched the mass of either Pt. An examination of the reailts suggests that they are clearly dependent on the choice of internal standard used to monitor each of the PGEs. 1996). 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.
The results pre~ntedin the two tables above show no bias with good recoverks and repeatabilities. 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.13 and 3.3. 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.14. Two sets of internai standards were d e d . As a result. Thus the choice of indium aad iridium as internai standards proved effective. The platinum redts are considered first.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. 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. Table 3.21 presents results obtained for Pt analyses using this test method dong wt correspondiig results obtained using the ih rnethods dedbed in Appendix B.5. 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. 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.1 TESTMETHOD #3A :DISCUSSION RESULTS FROM MASS MATCHED OF INTERNAL STANDARDS. .
12 2.35 1.1 fin-assay and phosphoric acid/fire assay.56 -0.52 851.00 885.16 O.88 644.14 872.86 921.76 886.O8 673-93 -0.95 914.12 895.3 1 665.07 570.70 -1.80 666.00 679.23 -1.89 922.Table 3 2 ICP-MS resuhs for Pt detemidon compared with nickel sulfide . Results are an average of quintupla assays.71 2.23 913.45 0.98 585. Results an of tripliate assays.71 694. Sample # N S Fr Phosphoric ICP-MS i ie Assay A cd 18 % Diffaaice % Merence acidfireas=Y = dg CiB/g to NiS Mahod to Acid/Fiue Assay Method 0.12 643.92 718.19 -6.05 A Anaiysis done with Nickel sulfide fue assa.09 658.10 -0.04 911.28 922.71 -0. ICP-MS redts fiom alkaü fused samples foilowed by anaiysis on a Perkin Elmer Elan 6000 ICP-MS using Indium and Iridium intemal standards.89 -2.04 424.58 0.37 6.95 463.99 655.26 0.9 1 6.38 798.04 976.02 -6.90 717.05 -0.83 739.t 7 3 .46 -0.09 925.78 677.13 0.32 934.07 934.99 0.42 0.08 0.41 0.66 864.12 893.09 650.64 420.55 937.05 0.15 folowed by ICP-OESand AAS spectd analysis.26 915.83 692.78 845.18 869.86 696.72 -0.04 856.51 -0.0 1 915.02 -0.04 686.32 -1.77 802.89 870.61 656.07 0.12 663.84 913.92 643.80 0.11 0.98 673.42 -0.94 -0.34 937.62 -1.18 852.95 0.06 1002.78 -0.89 665.83 629.95 663.50 -9.54 0.49 705. 10 -2.2 1 -2. and teiiuriurn CO-praipitation 2427 2428 2435 2443 2445 2460 247 1 2475 2484 2493 2495* 2502 2970 2935 295 1 2912 2962 298 1 303 1 3048 3007 3004 3025 3016 583.18 889.06 882.08 914.12 915. Anaiytical r d t s reporteci f o phosphoric acid dissolution plus h a s s a y rm digestion combinations foliowed by ICP-OES specnal d y s i s .1 1 2.58 417. .O3 689.27 1.71 707.15 570.37 22.20 603.29 976.35 934.5 1 1.
A compatison of the test method results to the acidlfire-assaymethod resulted in a 1 ta1 of 2.0025 = 2. The exception is #2495 which is about 2% lower then both of the results. 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).2970.22) 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 t23.069 (Khazanie.763. and 3004.057. the nickel suifide and phosphoric acid/fkassay resuhs themsebes difib by more tban 2% for samples #s 2427. The average precision for quintuplet a~says a t e d with these 24 values was d found to be 1.2962. From this perspective.13% on a 95% coufidence interval.01325 was found to be 2. T i is also true for the 99% confidence interval (t23. These values show that there are no significant dierences between the test method of the student method and the nickel sulfide and phosphonc hs acid/fire-assay standard methods at the 95% confidence level. 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.807). The palladium test results are considered next (Table 3.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.2981. 1990). Howeva. .2445.0. A cornparison of the test method r d t s and the nickel suifide results found a 1 ta 1 of 1. ' a 2% Merence in one nsult suggests the method compares f o d y with the standard method.2951.2935.
Anaiyiical resuits reporteci âorn phosphorîc acid dissoIuti011 fie-assay plus digestion combinations foiioweâ by ICP-OESspearal anaiysis. Resuits are of tripiicate assays. 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.Phosphori ICP-MS % Merence % Diffefetlce Assay A cacidJfireassay # ~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.Table 3. Sample NiS Fire.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. . Resuits are an average of quintuplet assays.
521.3 dong with conesponding resuits obtained ushg the nickel sulnde and phosphonc acidlfire assay standard methods described in Appendix B. even aAa repeated alkali fùsions and ICP-MS analysis. The ta. 1990). therefore it was removed nom our sample populations by using the Dkon & Dean outliner test (1951). the sample is beüeve to be mothm prepared autocatalyst mple. The average precision for quintuplet assays associated with these 24 values was found to be 1.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.m was found to be 2 0 9 . These results are given in Table 3 2 . 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.09% on a 95% confidence inteoral. This is also tnie for the 99% confidence intervai (t23. 0.0025 = 2. A cornparison of the test method results to acidfire-assaymethod resulted in a 1 t 1 of 0. 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.0. the Pd results never came close to either the nickel d d e nor the acid/fire-asay resuhs. Unfortunately.021. The exception is #2495 which is about 2% bigha then both the nickel d i d e and phosphoric acid/fire-assay results.807). A cornparison of the test method results and the nickel suffide results found a 1 ta 1 of 1. . As a result.6 (Khazanie. The lest two columns give the percent dEerence in result between the test method and the other two standard methods. The rhodium results are now considerd.
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. M y t i c a i results reported f o phosphoric acid dissolution plus fireassay rm digestion combinations foliowed by ICP-OES spearal analysis.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. R d t s are an average of quintupkt assays. .Table 3. . Sample # N S Fire.Phosphoric ICP-MS i AssayA % M f n e K Difference ee c acidlfire assay ~E d5 pgig to N S Method to AciWie i 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.
5%. a 2.5% diffmnce in one result suggests the rnethod cornpans f o d y with the standard method.0. 2502.5% are 2427.025 was found to be 2. 2495 and 2435. As a result. the nickel sulnde and phosphoric acid/&easay resuhs themseives mer by more than 50% for sample 2445 and more than 9. and 9. and 2495 which are respectively 27 ' %. As a result. and 2443. 2443.069 (Kbazanie. A cornparison ofthe test method results and the nickel sulfide method results found a 1 ta 1 of 0.O. 2475. 2445.oOZS = 2-807)- . The tu. the samples are believed to be another pnpared autocatalyst sarnple but due to the disappearance of the original sample container. As for the other hHO samples.5% variation. A cornparison oftbetest method results to phosphoric acid/fireassay method resuited in a 1 h 1 of 0. There are t h e exceptions whkb are #s 2435. 2493. 2935.2 % for samples 2427. For a 2. and 3031.11. the foUowing INCO and Ledoux samples that vary by more than 2.A doser examination of the Rh d t s i the table shows that in aimost m r y n instant the test method is close (within 1%) to one or both of the standard methods. 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. 3004. Tbis is also m e for the 99% coddence interval (t23.2 % lower or higha than both the other two method nsults. the Rh results never came close to either the nickel suifide nor the a c i d / h assay results. 1990). The average precision for quïntuplet assays associated with these 24 values was found to be 1. 2.23% on a 95% confidence interval. this will never be confimed. 2428. 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. even &er repeated alkali fiisions and ICP- MS analysis.2428. the sample were removed fiom Our sarnple populations by using the Dixon & Dean outliner test (1% 1). From this perspective. However.17.
5.24 Percent difference of ICP-MSresults using ~ t ' * pdlWisotopes and and indium internai standards NIST Value 1 1131.07 1 -1.2I0.35 1 1 -0. The percent difference associated wîth the m a s matched indium and indium standards is seen i the Table 3.2 TESTMETHOD 3B:DISCUSSION RESULTS FROM ISOTOPE DïLüTïON ON W R N A L STANDARDS Before the isotope dilution studies could be tested.96 NIST Value 1 697.5 Percent merence compared to NIST 1 -0.3 1 32611.24.211. Test method #3B i now considered.6 51. s 3.13 while those using the ushg ~ t ' * n and ~ disotopes and Iridium interna1 standards are seen in Table 3.9 Percent Merence compared SRM 1 -0.111. it was necessary to develop the required software for the instrument.65 1 1 +Os8 .9 1 135. ' ~ Table 3.0*11 1 233.4k2. This method will look at the results achieved with the NIST autocatalyst samples.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.
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 i Table 3.13 for the In and Ir intemal standards. As a result, this test method n
muid be explored even fiutha.
s 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 and iridium provide excelient d
indium intenial standards.
Element SRM 2557 (Monolith)
l ~ e a (u&l n
- 1 SD
SRM 2556 (Pellet)
Precision redts (%MD) reportecl on a 95% confidence interval for aii are
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)
autocataiyst samples than ushg the i n ~ u i d i u m intemal standards. On the other han4
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
Chapter 4 Conclusion
Three test methods were studied for the dissolution of autoccitalyst saxnples pnor
to ICP-MSanaiysis. These thme m*hods w r open besker acid digestions, microwaveee
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
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.
pp.Abercombia.E. S. 3193. p66 Bugbee. 6. Chem. Characterization of automobile catalyst and using inductively coupled m s spectroscopy: sample preparation. RK. P. Brown. S.1363. R (1987). Winter confierence on Plasma Spectrochemistry. F. Brown.F.R. Brown. Rh. 9. E.N..E.. 393. P J . Anal. Acta.. Chim.56. E.The Analytical Chernistry of the Noble Metais. (1982).E. and Paulsen. pp. Paulsen. New York. Development of hi&-accuracy ICP mass spectromeaic procedures for the quantification of Pt. J. (1984). .. Sample Pretreatment and Separation. Kunz. Determination of platinum and palladium in gsolagic samples by ion exchange chromatography with inductively coupled plasma atomic emission spectrometric detection. Sample preparation approaches for . 11. 743. RK. Analyticd Chemistq by Open Leaming. 43.(1 W6).. London. pp.p . Atom. . USA. 23. and Smith. Wdey 3d edition. J. 1 6 ) sym-Diphenylcarbazont. Orlando. J D . Talanta 1 . Thames Polytechnic. Spect.. Beary. J. Anderson.(1 isotope dilution inductively coupled plasma mass spectmmetric certification of reférence matenals. (1966).pp. pp. pp. Beary. 47. - . Anal. E. Anal. Pd.393. (198 l A Texibook ofFie Assaying.. and Johnson. New York.. and Biggq W. London.(199 l). pp. ( 9 0 . Talanta. pp.J.A. Horida. 67. F. and Pb in used auto catalysts. F. 448.(1982). At. Arsenault. 60. Beamish. 1207. 4 .(1 W6).and Fassett. RJ. Abstract No. ) . Spect.(1 96S). Chem-. . 994). F.E. Microwave-assisted sample preparation in A analytical chemistry. E. Spectrometric detemination of rhodium with ye. Anal. F L Jr.H. Belitz.608. Anal. 2 Beamish.W. A r s G. Intemational Precious M d s Institute (IPhrII)-l982. pp. Pergammon Press.. A critical evaluation of colorimetric methods for determination of noble metals. as pp. Analysis of precious metals ushg inductively coupled argon plasma (ICAP) spectroscopy..
.(l981 Platinum group elements mineralogy. A.. W. 120. London. W. 187. London England..Keays. (1Wl). . AK. ruthenium and iridium in geological samples by isotope dilution UiductkeLy coupleci plasma mass spearometry ushg a sodium peroxide fûsion and teiiurium copresipitation. Chapter 6. pp. pp. J. Solvent Extraction of Maals. Cabri. Cowlq. Analyst. Great Bntain. pp. 229. G.S. geology.. England. 59. rock and ultrabasic rocks. J. Detemination of sorne precious metals by neutron activation analysis. (1968).V. Radioanalyt. B d e l t . RR. Cabri. pp. S. pp. ûroup Elements: Mineraiogy. J H .. Applications of Inductively Couplecl Mass ry Spectrometry. and Dean.. Davis. De Wet. Osochim. Potts. PP*4Crocket.B. Spect. 1 12. Division of C. Detefmination ofplatinum. L. Chern. Ottawa. Crocket. Enzweiler. Neutron Activation analysis. pp. J H and Skippen. and reco~ery~ ). and Merson. (1 W2). Analyst.. Anaiyticai aawacy in ICP-MS using . Turkstra. . Date. pp. At. Platinum. New Garden House. Chem. Oslq pp. and Janiis (1995). Ed By L. Analyticai methods for the pliitinum-group elements In: PlatinumJ. The potential of fire assay and indudvely coupled plasma source mass spectroscopy.. (1987). pp 1217. J. pp. A and Matthey. S M . and Hoste. CIM Special Volume 23. A O and Steinnes E. Hmdley. Van . Chalmers.(1989).Y. (195 l). Vol. pp. Gijbelq R. Geology. 23.F. isotope dilution and its application to derence materials.J.. editors.487. Direct cietennination of the noble metals by activation analysis u t W g high resolution gamma spectroscopy. . S.A... (1995). Et. (1996). De. E.. WileyInterscience. R. and Hsieh.37 1. 1391. Catterick. (198 1). De Soete. and G a .. RB.R. palladium. 1n:Advation Analysis in Geochemisuy and Cosmochemistty. D. and Toenen. Date. Blackie and Son Ltd. . 636. 30.. and Cheung Y. 23. J. Khopkar. Anal. 32. England. Ont.487. (1 968).J. Cosmochim. 1. Universitetesforlaget. Dixon. L. Acta.Cabri. Rk(1970). T .J. Chichester. . Recovery.A. Simplitied statistics for small nunibers of observations.AL. Radioactivation determination of Pd in basaltic .and Nostrand Reinhold Company.J..LM. 73.
Radioanalyt. Van Loon. 57.Dept. pp. Faye. R B .. Chem. C. A review. Gilchrist.. R and Govaerts. 157.J. Spect.. Bnisseb.. A.D. 147.V..Evans. Analyst. pp.. Zelano. pp.. Chem.. Mines Tech-S w e y s . (1977). Stallard.Y. Anaf. R and Wkhers. (1986). A procedure for the sepmtion of the s platinum x i met& fiom one another and for their gravimetric determination. V. Anal.J. W..N. pp. L. Anal. (1 977). Koide. Anal. Interferences in inductively coupled plasma mess and spectrometry. 1012. Chem. V. C. 63. Th collection scheme for the determination of the platinum-group metais and gold.H. Neutron Activation detennination of noble metah for the analysis of technologicai and naturai materials. Veriovkin. (1935). Chem... M. J. Hodge. B & J. Garrett. 6 16. Chem. Practical aspects of neutron activation detemination of platinum metals. Giauque. J. 116. Determination offorty elements i n geochemical sampIes and coal fly ash by x-ray fluorescence speztroscopy. 773. M. 2565. and Nikitin.J..27. and G. A (1973).7. Hoiland. Chem. J. and Goda. Nuciear auaiytical methods in the produaion and industnai use of noble metals: posaiilities for the apptication of neutron ZLCfiVation analysis. pp. (1Wl).E. 108. Ostacoli. 8. dipyridylketoxime. Environ. pp. Anal. 16. Gowing.. Acta. Mines Branch Research R154. Ginepro.433. V. (1%8). Giglio. 58. Amer. G. Hoffman. pp. E L ... R and Hoste. Spectrophotosnetrïc detenninationof palladium with 2.. Radioanalyt.B. Anai. 49. Makhailov. (199 l). 38. Gddberg. E. RG-V. P. J-C. J.H. Int. E. (1996).2*o. M.... Ottawa. Potts. l'TE66.1. J. 102. Chern. Gulmini. M. Gijbels. Eurisotop office. 40. At. (1965). pp. RD.. E. Gijbels. J. and Maason A (1978). sediments and organisms.. . . Evaluation of a rapid technique for the and determination of precious met& in geological amples based on a selective aqua regia Ieach. . Soc. Han Cock. V... rept.. Determination of platinum and indium in marine waters. 147. pp. The determimiion of the platinun-group elements and gold i rocks and ore by n neutron activation d y s i s a f k preconcentrationby a nickel-sulnde fie assay technique on large samples. Commission of the European Communities.A.J. Chem. pp. Naîdrett. pp. J J (1993). pp. Gilbert.. Microwave desorption treatment after the oxidation step in Tessier'ssequeniid extraction scheme.
The solvent d o n of precious m d s .R. and Hakkita.1019. Scoot. A R h of platinum group mads recovery fiom automobile cataiytic convertors. 3"'KZtion. Johnson Matthey. Chem.Janssen. CRC Press Inc. 0 Kokot. D. and Bartel. USA. Barry (1982).W. Chim. pp. A. iridium. Gienview Illinois. Mooiman. G. Mishra.pp.585. L.353.(1957).B. D. Determination of mudl mounts of rhodium. Rhode Island. 29.O.and Picket. F (1970). 509.J. pp..W... FreseniusZ. pp. MacDonald. pp. Long. P I M1993. 11 Lide. platinwtl and palladium Mri. Millard. Pt. Rh and Ir. HT. (1966). E. recovery from new and spent automotive catalysts. London. Keller. Hew Porte. Anal. EE.& (1993). Le Houillier.(1993). and Massart. a t n A. pp. C. S.. Allryl cyanide medium for the daennination of 8) precious metais by atomic absorption spectroscopy. 19) Foresman. H. (1 9 6 . pp. EIementmy Stdstics in a world of cppiications. Analy~t~ 1.A Review. 251. 259.and Hunt. 17" Confcrmce.M. Chem. A History ofplatinum and its aiîied metals. Keith. 267. BBNnlt. pp. IPMI-1993. MacNevin..A. editors. Kuo-Ying. " The role of pyrometalurgy in the recovery of preciou metals fiom secondary materials".. A. S. Rajesh Kumar (1993). R and De Blois. Europa Publications Limiteci. 101. D. Little. International Precious Maals lastmite (PMI)-1993. Acta. Oslo. Koirtyohann. Anal. Brown Higher Education. England. 449. 343.(1991).(1 W ) Microwave Digestion: an 2. Acta. In Acrivation Am&sis in Geochemistry md Cosmuchemi$try. DL. Chim. Keyworth. .38. Universitetesfortaget. A neutron activation adysis procedure for the detemination of noble metds in geological samples. W. Spectral interfèrences in atomic absorption spectroscopy.. MB. Rhodium.(1982). Fluorescent x-ray spectroscopy estimations of Pd. A.P. d y s i s of procedures Anal. Anal. England. and Steinnes E. pp.292. Khasanie.. 71' Edition. R ( 9 0 . King. Determinaiion of the platinum metais in presence of each other by atomic absorption flame photometry. and platinum ushg CU'^ and Na*as spec~oscopic bfler. CRC Handbook of Chemistry and Phvsics. palladium. A and Urnland. Intanationai Precious Metals Institute (PMI)-1982.
. F. . P. Geostand.409.. Steele. U.B. 13.. V. The sampling and analysis of the precious metais.M.. Johannesburg. spectromeûy for the detennination of platinum group elements and golâ. R (1 971). Improved performance using i n t d standardidon i n ICP-AES. Chan. South Afiica. Smith.. NadRA and Momson. (1974).G.197. Johannesburg. Tracy.Myers. Rao. pp. (1982). Robert. ores and related rdu materials by isotope dilution inductively coupled plasma-mass spectrometry. pp. 1. and Cape* 1 (1975). J C (1995).. South Afnca. Chem. pp. Concentration of the noble metals . 344. (1987). M. B. Peny. by fire assay technique ushg nickel sulfide as the coliector. Vah Wyk.C. and Van Loon. Talanta. Boulder. SA. National Iiistitute for Metallurgy Report 1696. 65 1.S.V. Newsl.. Detennination of the noble metals in geologicai materials by neutron activation analysis Anal. and Hodge.. 16.. Nowinski. Bridger. 232. Speot.(1969). pp.R (1974). At. The preparation and certification of a . International Precious Metals Imîtute (IPW-1982.. USA Schnepfe. Evaluation of ICP-MS/Minowave oven preparation for the rapid analysis of ore samples for gold and the plathum-group metals. T. pp. 591. Strong. and Gregoire. Talanta. Trends in Anal. and Murray-Smith. Determination of palladium.J. E . 21. pp.388. J G (1989). GH. E.(1989). Met-Chem Research Inc. Anal. 8. 46. SenGupta. SenGupta. reference sarnple of a precious-metai ore. D.W. Chem. Detennination of precious m d s in solutions and contaking high dissolved soüds ushg ICP-AES. Detennination of gold in copper-behg suEde and metaliurgicai flotation products by atomic absorption spectrometry*Talanta. pp. 1253. 14. 50. (1994).... Detemination of nithdum. eas n geologicd and related materials by graphite-fùmace atodc-absorption spectroscopy after separation by ion-exchange or cuprecipitation with tehuiurn. 36. Grimaldi. and i i i m in 27 international reference silicates and iron-formation rocks. pp. Colorado. Barefoot..D.. J. 109. Inductively coupled plasma mass . R. pp. D e t e d t i o n of trace and ultra-trace amounts of noble m t l i . pp. pp.A. RR. D B (19833. and platinum by atomic spectroscopy.Le@ J. palladium. P. and Palmer. National Institute of Metalluru Report 1371.V.
and Scott. RH. A colorimetric determination of platinum in plate-focming catalysts. 18. A (1993). and DeWet. ChernicalGeology. (1978). International Precious Metals Insiitute. M. Anal. Simultaneous detennination of ruthenium. pp.J.Z.) Part II. 1694. (1995). Vines. W (1970). in ores and related plant materials by inductively coupled plasma-optical emission spectrometry. E.. Yi Y.V. F. 27. Anal.. LM. pp. 68.. New York.J. Wisecarver. 26. The International Nickel Company. 49. 50..(1941). Wagner. Turkstm P. Chem. R. Laurentian University. Chem. C h . Tuwati. subsequent colorimetric determination with p-Nitrosodimethylaniline. vol. M.835. J. Ch=. 1444. Non-destructivedetemination of . Separation of platinum and palladium and their . 42. Treatise on Analfical Chernistry.(1955). Rhodium. (1 977).Y. 343. Jan& I. .B.Kolhoff and P.. platinum. Chem.2 1. pp. T. Analytical chernistry of noble m t l . and lead fire-assay beads by reactor activation analysis and high nsolution gamma spectrometry.and Abraham. and Kirkland.Masters Research Paper. Simultaneous detennination of platinum group rnetals and gold. 379. recovery nom new and spent automotive catalysts.J..Anal. pp. usina a nold bead coiiection method with final d y i s bv ICP.and Hausmaan. pp. Inc. A (1995). 1335. Anal.A. Massuda. palladium. (1963).. Walsh. Van Loon. 2. 1 4 pp. pp. mattes. (1 954). Wu. USA. A. Microwave digestion and all<ali fiision procedures for the detennination oft&eplatinum-group elements and gold in geological materiais by ICP-MS. Wemyss R. and palladium . Chim. Anai. Yoe. H.Pure App.J. pp. Pretorius J. The Piatinum Metals and their alloys. and iridium. 2. Wiley. 8.Totland. New York. platkum metals in ores. and platinum at ultratrace levels by isotope düution inductively coupled plasma mass spectroscopy in geological samples. and Janis. pp.M. (1993). E.Elving (eds. A. K . K.. eas 1495.
The procedure Uivolves the foilowing steps: 1. Inco Ltd. Cumntly. (1 97 1). Table-Al Fire assay flux for nickel suifide coilection Inaredient Wei@ ( @ 60 30 Borax Sodium carbonate Silica Nickel S u b r Powder 15 18 9 2. A O.9174g) of the autocatalyst sample was weighed out in a weighing dish. 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. and transferred to the loaded cruciile. The components of the fusion mixture ( shown in Table Al) were added to a 40g clay cnicible. .Appendix A Autocatalyst The nickel sulnde dieaion of the PGE was adapted fiom the method ofRobert et al. 1 Assay ton (2.
15 mL of tellurium tetrachloride (TeCL) were added.The mixture was caretiilly stimd with a spahili until it was thoroughly mixeci. the beaker was removed fiom the heat and aliowed to cool slightly. This subsequeat analysis was cMied out by a lead- collection analysis fire asssy. the auaile was removed fiom the fimace and the fusion melt was quickly poured into a mold. The watch glass. . wvered with a kat resistant lid and allowed to cool domi to room temperature. The manire was then filtered through a Whatman glas fibers filter grade F and the tiltrate discarded. and the mixture was boiled for 5 minutes. The nickel suEde (-27g) button containhg the PGE's was sepmted from the slag. The slag was saved i the original pot and manalyzed for any losses of n PGE's in the NiS fusion step. Note: The purpose of the addition oftelluriun tetrachloride and starmous chloride was to ensure wmplete removal of pS Pd.of starnous chloride (SnCI*) were added &er allowing the mixture to cool slighîiy. When the dissolution of the button was complete. The button was transferred to a 1000-mLbeaker. and @ter fiinne1 were washed with (vh) K I . The crucible was placed in an electric fiiniaceand heatd at 980 O for 90 minutes. HCl were added and the mixture left overnight on a hot plate at low heat to dissolve the button.and Rh h m solutio~ 9. beaker. The solution was placed back on the hot plate and boiled for another 10 minutes. C After the fiision was complete. 6 0 0 rnL of cunc. 4 0 m .
and tbm the m*xturewas Wied for 1 hou. The proadure involves the foliowing steps: . and heated to dryness over low heat on a padded hot plate. cupellation to 100mg Pb bead. The filtrate was placed back on the hot plate. were addeâ. 15. 11. The method layout for this thesis orighates fiom a fjur dating to Aprii 19. The solution was transferred to a 100 rnL volumetric flask and diluted to the mark with deionized water and mixed well. The PGE's lost to the slag in the MS fiision step were recoverd through a Pb collection. HCI and 5 mL of conc. and Rh by ARL 34000 ICP. The filter contaking the PGEiswas transfened back into the origmal beaker. and digestion with aqua regia.10. The mcthod can use either or both AAS or ICP or DCP. Pd. Final measurement was done by ICP-OES. 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. and the mixture was heated gentiy until the POE'Swere completely dissolved. 12. HN03 were added to the residue. The Ledoux mahod is a combination of acid dissolution and fireassay. 13. 14. 25 mL of conc. DO mL of HCl and 4 0 mL of HNO. The solution was then anaiyzed for Pt. 1989.
and t r d e r to 200mL volumetnc flasks.75 mL ofHF. Any residue srnd in the case of pellet.1. and combine with the main solution.1 mg and dried at 125OC. 35 mL HISOh 35 mC H o 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. The samples are weighed to the nearest 0. Clean the pipet with water. boil and filter into reserve filtrate nom the previous step. 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. Pd. Treat with aqua regia and combine with the rnain solutions. add about 5 g of sodium thiosuIfate. Dilute to 400 rnL. 3. 4. Boil to a minimum of 1 hour to convert rhodium to the chloride form. Filter and wash thoroughly with cold 1% HCl. 5 . T the @et sarnples m the 800 mL beaker. 8. pour hot dilute (1:2) aqua regia through paper. Allow to settle for minimum of 3 hours. heat to b i i g and just keep at boiling oln. 9. about 100 mL of HCl and 50 mL of brornine water. larger in the case of monoliths is treated as foilows: A) Pellets: Fume paper with HNO3 and HCI04 to dryness. Wash precipitate back into original 800 mL beaker. To the salts in the 800 mL g l a s . and 15 mL ofH2S04. Take fkom each flask a 15 mL aüquot with dry pipet and check the approxhate Pt. Dhsolve aqua regia and check on plasma or AAS for ntaineâ Pt. and the exact Rh content by AAS. Pd and/or Rh. Pd. Palladium present : Transfer to sepraratory bels and extract the pdladium by repeated treatments witb chlorofonn and sodium dirnethyl glyoxime soluti~ns~ . scorify in presence of about 25 mL of Au and cupel. Evaporates to fumes of H2S04. add about 100 rnL of water. To the monolith samples in 800 mL in tdon beakers. 7. and respective teflon beakers. 6. and Rh. Evaporate the aqua regia solution wntaining the bullr of Pt. add 50 mL of H20. B) Monolith: Ignite in a scarifier. 2. point for 2 hours.
Evaporate to 100 mL. 13. Compare the Pt content of the smaples and standards by Merenta! spectrometry. In the absence of Pd. in aqua regia t Add appropriate amounts of Rh chlorine solution nitric acid-free. 14. wt the intm*ttent addition of s m d ih amounts of HCI. Dissolve in a fiw mL ofaqua regiLa. Add small moullfs of nitric and perchloric acids and again evaporate to dryness. Repare standards by dissolvhg pure Pt. 10 mL of percbloric acid and 5 mL SuKiinc acid. 15. (See previous AAS determination). to cover the range of P determination. omit the DMG chloroform extraction. Six milümeter ofthe SnClz solution per 200 mL. . (Maximum for 200 g. Dissolve residue in 50 mL of 3-% (VN) HCl and transfer to volumetric flasks of proper size. add 25 mL of nitric aciâ. 10 mg of Pt). T d e r the aqueous phase (Pd removed) to 600 mL beakers. Dilute to approhtely 800/0 of the volume of the flasks with 300/. Add 30 mL. 11. Evaporate to dryness. Evaporate twice to dryness. HCl. but otherwise following the procedure as written. 12. transfer to 100 mL volumetrk fiasks and determitle Pd by AAS or DCP.IO. Evaporate the chloroform phase soiutions to byness. 28% stannous chloride (VN) in 1 :1 HCI.
SAM S P U ID - 04-16-1997 WEIOHT 03:07:0 1 VOLUME SPLE DESC .ANALYST: MP Po6 Simple FUtniw R:UcP-MSUri970127.
ANALYST :MP 04-16-1997 POS 03:07:01 VOLUME SPLE ID SPLE DESC WElQHT .
3anuaiy 27.1997 15:54.Original Data File: 3MTUlzr.ntr Analyzed On: Monday.09 Anatyred In: mgMg 9 TO: MP Analyreci By: MP SAMPLE IDENT. #Drift i Rh Standard Drift 1 Pd Pt .
OFU-3 246ûFU-4 246OFU-5 2495FU-1 2495FU-2 2495FU-3 2495FU-4 2495FU-5 2428FU-1 2428FU-2 2428FU-3 2428FU-4 2428FU-5 2475FU-1 2475FU-2 2475FU-3 2475FU-4 2475FU-5 2502FU-1 2502FU-2 2502FU-3 ritme rime Standard check rime Sample Bbnk Dry Dry Dry Dry Dsr Dry Dry Dry Dty Dsr Dry Dry Dry Dry Dry 2556-1 2557-2 Dry Dry Dry Dry Dry Dry Dly Dry Dry Dly Dry Dry Diy Dw Dly Dry Dry Dry Dry Dry Dry Dry Dry Diy Diy Dry Dry Diy .tinse RINSE #DR!FT 1 R1NSE mhnk 2435FU-1 2435FU-2 2435FU-3 2435FU-4 2435FU-5 2493FU-1 2493FU-2 2493FU-3 2493FU-4 2493FU-5 2471FU-1 2471FU-2 2471FU-3 2471FU4 2471FU-5 S2556-1 S2557-2 2427FU-1 2427FU-2 2427FU-3 2427FU4 2427FU-5 246OFU-1 2460FU-2 246.
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 .
09956 21.08100 lntensity H He Li Be B C lntensity Units Not Measured Not Measured N O 2.08519 T i v C r Mn Fe Co .00000 792.00 1199717.00 0.00 0*00 346.07515 31357185.201 42 563.O0 4178.00 57.52578 17. November 13.00 Not Measurd 9131173.00 325017.1 996 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.dac Response File: C:\elandata\System\cunent.00 2909.00 F Ne Na Mg Al Si P S CI Ar K Ca SC 46.ûû 2442899.00000 1.00 1071.00 20276.028 Tuning File: defauktun Optimization File: default.97555 4978.88298 56.Sample ID: sample blank Sample Datemme: Wednesday.61098 1647.00 37159.00 456.15930 7130577 266.00 52379444.55234 65.00 1OS51.00427 0.26787 1.04093 147870028.00 22û35723.27708 0.00 111713.00 23762.00 323374.31570 2258.00 6922034135.91161 1.23790 35iï952.mth Dataset File: C:\elandata\DatasehTotalQuant Analysis\sample blank.rsp Analyte Intensities Analyte Concentration 0.00 211257.00 618002.
TotalQuant Equations Analyte Equation .
3~~1~llt FIQnt H g ICP GFAA J 3 h h ICP- AA 15 .02 15 .f-SeaL.e-S34.05 l with a Systan 2 eicciro&lcss dbchqc lamp. e - d-Ni60.ûûf lig1L with an amaIgdon acœsoxy .0 AU detection iimits are given in micrognimsper lits and were detamined using elcmcntal standards i n dilute aqueous solution Al1 detcction limits are based on a 98% conGdaice lcvcl(3 standard deviations).0 AA Hw& M o 45 00 . a L'vov platfarm and fiill STPFcooditiolls(ModelS100FC with5100~7riarisnF~Moda)eaModcl4100ZL). ICP-MS detectionlimits were detamincd ushg an ELAN 5000.8 hdS 003 .0 003 . (ThcHg detaction limit with i a tfitdcdi~~tedFIMS-100mFIMS~maciaydyzasis<O. ih holow cathode b p . Atomic absorption (Mode1 5 100) and ICP mission (Plasma 2000) dctectionWs wcre &termineci using t instrumental peramctas optimi7Ldfbr the individual clcm~ltICP anission d t c i m Iimits obtained dMng cctc muitieiem~lt auaiyscs wiii typidy b within a k t o r of2 of the values s h o w c Cold vapor mercury dctecticmlimits wat dctamid with a M l 0 0 or FIAS400flowinjection systan with amaigamation accemq. Lettas foITowingan ICP-MS deîectionfimit value dr to the use of a less abundant mass for the detanmationas foiiows:a. Graphite ~dctectimlimitscanbtfiPthcraihwirnlbythrwofnp1icateinjccti0ll~. d Fe 54. 0. w t a s. The detection limit without an amaigamation acmsoxy i 0 2 iigII. 114 . bCa 44. HvQide deteftionlgaits wcre dctamuacd ) USinganMHS-IOMaciayDIydridt qswm.0 H Q d GFAA Jbhsion MS yie 0.(213. Graphite W AA deteciion limits were d c t c d d ushg 50-ILL sample volmes.O1OPGlLwithoutrinamd~ti~1 accessory and < O.
This action might not be possible to undo. Are you sure you want to continue?
We've moved you to where you read on your other device.
Get the full title to continue reading from where you left off, or restart the preview.