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QUANTIFICATION OF GALLIUM, INDIUM AND THALLIUM IN METEORITES AND OTHER GEOLOGICAL MATERIALS BY GRAPHITE
FURNACE ATOMIC ABSORPTION SPECTROMETRY
A Thesis Presented in Partial Fulfilment of the Requirements for the Degree of Doctor of
_ Philosophy at Massey University
MASSEY UNIVERSITY NEW ZEALAND
Xun Guo 1993
ABSTRACT
Methods of so lvent extrac t i o n have been deve l oped for the determinat ion of ga l l ium , indium , and tha l l ium in meteorites a nd other geological mater i a l s . The extract ion of ga l l ium is bas ed on forming a chloro comp lex i n HC l s o lut ion and extraction into
MIBK . I nd ium was extracted into the s ame so lvent a s an i odo complex i n an HBr + KI med ium to wh ich KOH had been added .
Tha l l ium was a l so extracted a s an i odo comp l ex from a H2S04 + K I medium with addition of K2HP04 as a s a lt ing out agent . Ser i ou s
interference from iron ( I I I ) w a s e l iminated by addi ng KI to reduce this e l ement to its d iva lent state that was not extractabl e i nto the organi c phase .
Graphite furnace atom i c absorp t i on spectromet r i c techniques were emp l oyed to determine thes e three elements in the MIBK phase
after extract ion from the aqueous phase . Very low l imits of detect ion ( l . o . d . ) were obta ined with these methods . It wa s poss ible to lower the l . o . d for these e l ements e ither by
increasing the aqueou s j organic phase rat io before extract ion , or by mult i p l e l oading i n j ect ions .
Us ing the deve l oped methodo l ogy , ga l l ium , ind ium , and thal l ium were quant i f ied in iron and chondr itic meteor ites as well as in Cretaceous/Tert iary boundary clays , and some volcanic emi ss ions .
The data for thallium abundances in 4 9 iron meteorites were the f irst ever recorded for th i s type of meteorite and a l lowed for taxonomi c separation of the var i ous groups of irons .
Indium abundances were only r ecorded in s ix chondrites because of the very l ow concentrat i ons in iron meteorites .
My data for tha ll ium and other e l ements were u s ed to class ify the previous ly non- stud i ed Manitouwabing i ron meteorite .
A l l three Group I I IA e l ements were determined i n
Cretaceou s / Tertiary boundary clays and it was shown that these
and other chalcoph i l e elements have an abundance greater than that whi ch wou ld have been expected from e ither a vo lcanic or impact-derived source . Poss ible s ources of thi s enr ichment are discus sed .
ACKNOWLEDGEMENTS
I wou ld l ike to acknowledge the fol lowing persons:
Grateful thanks are due to my supervi sors, Profe s sor Robert R. Brooks and As soc iate Profes sor Roger D . Reeves, for accepting me as a PhD student in 1990. I appreciate their advice, a s s i stance, and encouragement dur ing all my studies . I shall never forget their kind help, particularly w ith my English that was de f ic ient in the earl ier stages of the work .
I thank Dr . T . N . M . Waters, Vice-Chancel lor of Mas sey Univers ity, for h i s encouragement, a s s i stance a n d his kind h e l p s ince I arr ived in New Zealand, particu l arly in providing me with a Vice-Chance l lor's PhD research Scholarship to enable me to comp lete th i s project .
My thanks are a l so due to members of my f amily: my w i fe, Xiaohong Fan and my son, Tony F. Guo for the ir continual mora l support in every way . I am also grate ful to my parents, Linying Zhou and Zishong Guo, a s well as my s i ster Chu n Guo for the ir encouragement and support, particularly for initially taking care of my son when my wife and I f irst l e f t China .
Fina l l y I would l ike to thank a l l the people I have worked with for the ir fr iendship and encouragement.
Table I-1 Table I-2
Table I I - 1 Table I I-2
Tab le I I -3 Tab le I I-4 Tab le I I-5 Table I I I-1
Tab le I I I -2 Table I I I -3 Table I I I-4
LIST OF TABLES
Me lt ing and Boil ing Po int s of Ga, I n and Tl • . • • . • . . . • . • 10 D i stribut ion Coeffic ient s of Group I I I B Element s
in Mineral Acid Med i a on Strongly Ac idic Cat ion
Exchangers • . . . • . . • . . • . . • • • . • . . . . • • • . . • • . . • 1 6 Period ic Tab le Posit ions of Hydride Forming E l ements that
Can be Quant ified by HGAAS . . . • • . • . . . • . . . • • . . . • • • . . 28 The Me lting and Bo i l ing Po int s of Hydrides of
G a l l ium , I nd ium and Thal l ium . . . • . . . • . • . . . • • • • 30 Operat ing Cond it ions for Ho llow Cathode Lamps • . • . . . • . . • . . . • • • 32 HCl Ac id Mo l arit ies for Generat ing Hydrides of G a l l ium ,
I ndium and tha l l ium 36
Prec i s ion and Accuracy for I ndium Determinations as
Estab l i s hed by Analy s i s of a St andard Reference Rock • • . . . • • . • 40 Compari son of G a l l ium Absorbances i n the M I BK phase
after Manu al and Mechanical Shaking . . . 61 Extract ion of Ch loro Complexe s of G a l l ium . . . 6 1 Ab sorbances of Gal l ium Standard Solut ion s . . . • • 63 Precis ion and Accuracy of GFAAS Gall ium
Determinations as Obtained by Analysis of
Standard Reference Mater i a l s ... 65 Table I I I-5 Maximum Amounts of El ement s that Do Not I nterfere with the
Determination of Gall ium by GFAAS . . . • . 66 Table III-6 Instrumental Parameters for GFAAS Determination
of Gall ium in MIBK Extracts ... 67 Table I I I -7 Prec i s ion and Accuracy for the Indium Method as
Determined by Ana lys is of Standard Reference
Rock (MP-1a ) . . . • . . . 75 Tab le I I I-8 I nstrumental Parameters for GFAAS Determinat ion
of I ndium i n MIBK Extrac t s . . . • . . 76 Tab le I I I-9 The Phy s ical Propert ies of Tha l l ium Hal ides . . . • . . • 79 Table I I I-10 Compar ison of Standard Addit ion and Convent ional Cal ibrat ion
Methods for Qu ant ification of Thall ium i n t he Toluca Iron
Meteorite . . . 84 Tab le I I I- 1 1 Precis ion and Accuracy of Method for Quant ification
o f Thallium i n Geological Samples a s Determined
from Analy s i s of St andard Rocks . . . • . . . . • . . • • . . . . • • . . • • • . 85 Tab le IV-1 Meteor ite Classes and Numbers . . . • . . . ;. 88
Table IV-2 Table IV-3 Table IV-4
Table I V-5 Tab l e I V-6 Tab l e I V-7
Tab le I V-8 Table I V-9 Tab le IV-10 Tab l e I V- 1 1 Tab l e IV-12 Table V-1 Tab le V-2
Chondr ite Classes and Mean Propert ies . . . • . . . 90 Structural Cl a s s i f icat ion of Iron Meteorites . . . • . . . 92 Comparison Between the Structural and Chemical
C l a s s i f i c at ions o f I ron Meteorites . • . • . . . . • • • . . • • • • . . . . • . • . . . 93 Chemical Clas s i f icat ion of I ron Meteorites . . . • • . . . • . . . 93 Compari son of Dif ferent Treatment Methods for Quant i f ic at ion of G a l l ium in the canon Diablo I ron Meteorite • • . . . . • • . . . • 9 6 G a l l ium Abundance s ( �g/g ) i n Iron Meteorit e s a s
Determined b y GFAAS and Other Methods . . . • • . . . • . • . . . 100 Ind ium Abundances in Some I ron Meteorites . . . . • . . . • . . . • 102 I nd ium Abundances in Chondritic Meteorites • • • . . . • • . • • • • • • • . • 102 Tha l l ium and Nicke l Abundances in I ron Meteor i t e s • • . • . . . 107 Thal l ium Abundances in Chondritic Meteorites • • . . . . • . . • . • . . . . 108 E l ementa l Con�entrat ions in the Manitouwab ing and Madoc Irons 1 10 E l emental Abundances ( ng/g ) (ppb] for In and I r and �g/g(ppm)
for G a and T l ) in K/T Boundary and Other Geolog i c a l S amples . 123 Mass Balance for Chal cophiles in the F l axbourne River
and Woods ide Creek K/T Boundaries , New Zea l and . • . . . • . . 124
LIST OF FIGURES
Fig. I-1 P lot Showing t he D istribution of the Three I sotopes
of 0 in Meteorites . . . • . . . . • . . . • . . . • • . . . • . . . 25 Fig. I -2 Logarithmic Plot of Ni vs. Ge i n Iron Meteorite Groups . • . . . • . . . 25 Fig. I I-1 Reaction Apparatu s for Generation of Hydride . . . • • . . • . • . 31 Fig. I I -2
Fig. I I-3 Fig. I I -4
Des ign of S i l ic a Tube for Atomisat ion of Hydrides . . . • • . . . 34 Flow Rates of F l ame Gases for Quant ific at ion of I nd ium • • . • . • . • • 34 Effect of Carrier Gas Flow Rate for Hydride Generat ion
Quantification of I ndium . . . • . . . . • . . • . . . • • . • • . . • . • . . . . • . . . 35 Fig. I I-5 Effect of Ac idity for Hydride Generat ion of G a l l ium ,
I ndium and Thall ium . . . • . . . • . • . . . • . • . . . • • • • . • . . • • 37 Fig. I I-6 Effect of Vo lume of Sample Solution, Ac i d , and Sodium
Borohydride on Ab sorbance of I nd ium Solution . . • . . . • . . . 37 Fig. I I-7 Effect of Concentrat ions of Sodium Borohydride o n
Generat ion o f I ndium Hydride . . • . . . • . . . • . . 37 Fig. I I-8 Effect of Vo lume of Sodium Borohydride on Format ion
of I ndium Hydrides . . . • . . 38 Fig. I I-9 Effect of Temperature on Hydride Generat ion of I ndium 38 Fig. I I-10 Des ign of Connect ing Tube between the Burner and
Generator for Hydride Generat ion ... 39 Fig. I I- 1 1 Typical Absorbance S ignal s for Hydrides of Gal l ium,
Fig. I I I-1 Fig. I I I -2 Fig. I I I -3 Fig. I I I-4 Fig. I I I-5
I nd ium and Tha l l ium . . . • 39 GF 1000 Workhead . . . • . • • 48
-
Sample I nject ion Probe Geometries ... 48 A Typical Furnace Cyc le . . . • . • . . . 53 Typ ical GFAAS Absorbance S ignals for Gal l ium, Ind ium
and Tha l l ium . . . 53 GFAAS Absorbance of Ga Extracted into M I BK from
5M HCl in the Presence of Various Concentrat ions
of Iron (I I I ) . . . • . . . 5 6 Fig. I I I-6 Effect o f the Ascorbic Acid Concentrat ion on
the GFAAS Absorbance S ignal for Gall ium with and
without the Pre sence of Iron . . . • . . . • 57 Fig. I I I-7 Effect of Sod ium Borohydride on the GFAAS Ab sorpt ion
S ignal for 1 �g/mL Gall ium in the Pre sence of Iron ... 57 Fig. I I I-8 Effect of the K I Concentrat ion on the Extract ion of
Iron and Gal l ium from 5M HCl into M I BK ... 58 Fig. I I I-9 Effect of Mo l arity of Several Acids on the Extraction
of Gall ium into MIBK . . . • . . • . . . • . . . 5 9
Fig . III- 10 Stab i l ity of the G a l l ium Chloro Complex in the Organic Phase after Separat ion from t he
Aqueou s Phase • . • • . . . • . • . • . . • • . . . • . • . • . . . 60 F ig . III- 1 1 Effect of Shaking T ime on the Extract ion of G a l l ium
from 5 M HCl into MIBK . • . . • . • • • • . . . • . • . • • • • • . • . . . . • . . . . 60 Fig . III- 12 Effect of Acidity on t he Extract ion of Indium
into MIBK . . • • . • . . . • • • • • . • . . . • . . . • . • • . . . • 70 Fig. III- 13 Effect of KI Concentrat ion on the Extract ion of
Ind ium in the Presence of Iron . . . • . . . • . • • • • • • • • • . • • . . . • • • 71 Fig. III- 14 Effect on Addit ion of Salts and E l ectro lytes on
Extract ion of Indium into MIBK . . . • . . . 72 Fig . III- 15 Effect of the Concentrat ion of KOH on Extract ion
of Ind ium into MIBK . . . • • • • . . • . • . • . • • • • • . • . • . • • . . • . . 72 Fig. III- 1 6 Effect of Shaking T ime on Extraction of Indium
into MIBK . . . • . . . • . • • • . . . • • . • . • . • • • . • • • . . . . • . . . 73 Fig . III- 17 Stab i l ity of the Indium Iodo Complex in the Organi c
P h a s e after Separat ion from t h e Aqueous Phase ... . ... 73 Fig . III- 18 Analyt ical Curv e s for Indium . . . • . . . • . . . • . . . • • . . . 74 Fig . III- 19 Effect of Varying Iod ide Concentrat ion on t he
Extract ion into MIBK of Tha l l ium . . . 79 Fig. III-20 Effect of the H2S04 Concentrat ion on Extract ion
of Thall ium into MIBK . . . • . . . • • . . • . • • . . . • . . • . • . . . • . . 80 Fig. III-21 Effects of Variou s Agent s on Extract ion of Tha l l ium • . . . 80 Fig . III-22 Effect of Varying K�HP04 Concentrat ions on the
Extract ion of Tha l l ium into MIBK . • . . . 80 Fig . III-23 Effect of Shaking T ime on the Extract ion of Tha l l ium
into MIBK . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81 Fig . III-24 Stab i l ity of Tha l l ium Iodo Comp lex in the Organic
Phase after Separat ion from the Aqueou s Phase . . . • . . . • 81 Fig . III-25 Cal ibrat ion Curve for GFAAS Absorbance of Tha l l ium .. . ... . .. . 82 Fig. IV-1 Effect of D ifferent Acid Mixtures and Sample D igest ions
on the D i s solut ion of G a l l ium from the Al lende Chondritic
Meteorite . . . • . . . 97 Fig . IV-2 Comparative Ab sorbance Data for Gallium in Iron
Meteorites as Determined by NAA and GFAAS • . . . • . . . 9 9 Fig . IV-3 Group Separat ions o f Iron Meteorites from a Thallium
v s . Nickel Abundance P lot . . . • . . . • . . . 105 Fig. V-1 Locat ion Map Showing the Fl axbourne River and Woods ide
Creek K/T Boundary S ites in Re l at ion to Other S im i l ar Fig. V-2
S it e s in New Zea l and . . . • . • . • • . . . • . . . 1 1 6 E lement al Rat ios i n K/T Boundary Cl ays Compared with
those in Vo l cani c Emi s s ions . . . • . . • • • • . • • . . . • . . . 122
CONTENTS
PART ONE
GENERAL INTRODUCTION
1
I - 1 INTRODUCTI ON 8
I - 1 - 1 D i s covery o f Group I I IB E l ements • • • • • • • • •• • • • • • 8 I - 1 - 2 Chem i s try of Group I I I B E l ements • • • • • • • • •• • • • • • 9 I - 1 - 3 Geochem i s�ry o f Group I I I B E l ement s • • • . • • • • • • • • 12
I - 2 REVI EW O F ANALYTI CAL METHODS 1 4
I -2 - 1 S eparat ion and Enr i chment • • • • • • • • • • • • • • . • • • . • • • 1 4 i . Coprec ip i tat ion • • • • • • • • . • • • • • • • • • • • • . • • • • • • • 1 5 i i . I on Exchange • • • . . • • • • • • • • • • • • • . • • • • • . • • • • • • • 1 5 a . s eparation b y cation Exchange • • • • • • • . • • • . 1 5 b . S eparation by Anion Exchange • • • • • • • • • • • . . 1 7 i i i . Other Chromatograph i c Methods . • • • • • • •• • • • • • • • 1 7 iv. Extrac t ion • • . • • • • • • . • . . . • • . • . . • . • • • . . . • • • . • • 1 8 I - 2 - 2 Gravime tric Methods • • • . . • . . • . . . . . • • • • • • . . . • • . • • • 1 8 I-2-3 T i t r imetric Methods • . • . . . . • • . • . . . • • • • • . . • • . . • • • 19 I - 2 - 4 Sp e ctrophotometr i c Methods . • • • • • . . • • . • • . • • . . . • • • 2 0 I -2-5 Ele ctro chemi cal Methods . . . . • . • . • • . . • • • • . . • . . • • • • 2 0 I - 2 -6 Sp e c trof luorimet r i c Methods • . • . . • . . . • • • . . . • • • • • • 2 1 I - 2 -7 Atom i c S p e ctrome tr i c Methods • • . . . . • . • • • • . • • • . • • • 2 2 I - 2 - 8 Neutron Act ivat ion Ana lys i s • . . • • • • • . • • . . • • . • • • • 23 I - 2 -9 Ma s s Spectrometr i c Method s • • • . • • • • • • • • • . • • • • • • • . 2 3 I -2 - 1 0 X-ray F luores cence Spectrometr i c Methods • •• • • • • • 2 4 I - 2 - 1 1 Conc lus ions . • • • • •• • • • • • . . • • • • • . • . • • • • • • • • • • • • • • 2 4
I -3 AIMS OF THI S WORK 2 5
I - 3 - 1 Clas s i f i cat ion of Meteor ites • • • . • • • • • • . • • • •• • • • • 25 I -3-2 The Use of Group I I IB E l ementa l Abundances to
Eva luate the Impact Theory o f Ma s s Ext inct ions at the Termina l Creta ceous • • . • • • • • • • • • • . . • • . • • • • 26 I - 3 - 3 Deve lopment o f an Analyt i c a l Procedure to
Determine Group I I I B E l ements • • . • • • • • • • • • • • • • • • 2 7
PART TWO
DETERMINAT ION OF GROUP I I I B ELEMENTS BY HYDRIDE GENERATION ATOMIC ABSORPTI ON S PECTROMETRY
I I - 1 INTRODUCT ION
I I - 2 EQUIPMENT AND REAGENTS
2
2 8
3 1 I I - 2 - 1 Hydr ide Generator . • . . • . • • • • • . • • . . . • . • . • • • . • . . • 3 1 I I -2 -2 Instrumentat ion • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 3 2 I I - 2 - 3 Atomisat ion • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • . • 3 3 i . Direct F lame Atom i s at ion • • • • • • • • • • • • • • • • • • • • • 3 3 i i . Heated S i l i c a Tube Atom i s a t ion • • • • • • • • • • • • • • • 3 3 I I - 2 - 4 Co l l ect ing Un i t • . • . . • • • • • • • • • • • • • • • • • • • • • • • • • • 3 4 I I - 2 - 5 F lame F l ow Rat e s • • • • • • • • • . • • • • • • • • • • • • • • • • • • • . 3 4 I I -2 - 6 Carrier G a s F l ow Rates . • • • • • • • . • • • . • • • • • • • • • • • • 3 5 I I - 2 - 7 Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . 3 5
I I - 3 EXPERIMENTAL 3 5
I I - 3 - 1 Effect o f A c i d s o n Hydride Generat ion • . • . • • . • • 3 6 I I - 3 - 2 Effect o f the Total Reac t ion Vo lume • . • • • • • • • • • 3 7 I I - 3 - 3 The Opt imum Amount o f Sod ium Borohydride • • • • • • 3 7 I I - 3 - 4 The Op t imum Reaction Temperatur e • • • • • • • • . • • . • • 3 8 I I - 3 - 5 Des ign o f the Connect ing Tub e • . • • • • • • • • • • • . . . • 3 8 I I - 3 - 6 Fina l Ana lyt i c a l Proc edur e s . . . . . . . . . • . . . . . •• • . 3 9 I I - 3 - 7 The Form and Magni tude o f Ana lyte s igna l s • • . • • 3 9 I I - 3 - 8 Pre c i s ion and Ac curacy . . . • . • • • • • . . . • . • . . . . • • . . • 39
I I - 4 DISCUSSION AND CONCLU S I ONS 4 0
PART THREE
DEVELOPMENT OF SOLVENT EXTRACTION PROCEDURES FOR ATOMI C AB SORPT ION SPECTROMETRIC QUANT IFICATION OF
GROUP I I I B ELEMENTS
3
I I I - 1 INTRODUCTION 4 2
I I I - 1 - 1 Pr incip l e s o f S o lvent Extract ion • • • • • • • • • • • •• 4 3 I I I - 1 - 2 C la s s i f i cat ion o f Extraction Systems • • • • • • • • • 4 4 I I I - 1 - 3 Cho i c e o f S o lvent • • • • • •• • • • • • • • •• • • • • • • • • •• • • 4 5 I I I - 1 - 4 S o lvent Extraction i n Tra c e Ana lys i s •• • • • • • • •• 4 6
I I I - 2 INSTRUMENTATI ON I I I - 2 - 1 Equipment I I I - 2 - 2 G l as sware
4 7 4 8 4 8 I I I - 2 - 3 Reagents . • . . . • . • • • • • • • • • • • • • • • • • • • • • • • • 4 8 I I I - 2 - 4 Ho l low Cathode Lamp s •• • • • • • • • •• • • • • • • • •• • • • • • 4 9 I I I - 2 -5 Graphite Furnace • • . • • • • • • • • • • • • • • • • • • • • • • • • • • 5 0 I I I - 2 -6 Sample Injection T ip A l i gnment • • • • •• • • • • • • • • • 5 1 I I I - 2 -7 The Samp l e Vial · · · · · · · · · · · · · · · • • • • • • • • • • • • • • • 5 1 I I I - 2 - 8 Mult iple Load ings • . • • . • • • • • • • • • • • • • • • • • • • • • • • 5 2 I I I - 2 - 9 Furnace Heat ing Programme s . • • . • • • • • • • • • • • • • • • • 5 2 I I I - 2 -10 Ab sorp t ion S ignals and Background No i s e • • • • • • 5 3
S ECTION I I I - 1 GALLIUM
I I I - 3 DEVELOPMENT O F A PROCEDURE FOR QUANT IFICATION OF
GALLIUM 5 4
I I I - 3 - 1 Experiment a l . • • • • • • • . . • • • • • • • • • • • • • • • • • • • • • • • 5 5 i . S ample Pur i f ication and Reduct ion o f
Inter f erences • • • • • •• • • • • • • • • •• • • • • • • • • • • • • • • • 5 5 a . U s e o f Ascorb i c Acid . . . 5 6 b. U s e o f Sodium Borohydr i d e . . . 5 7 c . U s e of Other Reductants • • • • • • • • • •• • • • 5 7 d . Reduct ion o f Iron ( I I I ) w i th
Pota s s ium Iodide • • • • • • • • • • • • • • • • • • • • • 5 8 i i . Acid Typ e and Concentration • • • • • • • • • • • • • • • • • • 59
4
i i i . Stab i l i ty o f the Ga l l ium Comp lex i n the
organi c Pha s e . . . 59 iv . Shak ing T ime o f Extrac t ion • • • • • • • • • • • • • • • • • • 6 0 v . Compar i son o f Manua l and Mecha n i c a l Shaking • • 6 1 v i . Values o f the D i s t r ibut ion Rat i o • • • • • • • • • • •• • 6 1 I I I - 3 -2 L imit o f Detect ion • • • • • • • • • • • • • • • • • • • • • • • • • • • 6 2 I I I - 3 - 3 U s e o f the standard Add i t ion Procedure • • • • • • • 6 4 I I I - 3 - 4 Pr e c i s ion and Accura cy • • • • • • • • • • • • • • • • • • • • • •• 6 4 I I I - 3 - 5 Interfer enc e s from Other E l ements • • • • • • • • • • • • 6 5 I I I - 3 - 6 F ina l Ana lyt i c a l Procedure • • • • • • • • • • • • • • • • • • • 6 6 I I I - 3 - 7 Conc lus ions . . . 6 7
SECTION I I I -2 INDIUM
I I I - 4 DEVELOPMENT O F A PROCEDURE FOR THE QUANT I F I CAT I ON OF OF IND I UM
I I I - 4 - 1 Exp erimental . . . . . . . . . . . . . . . . . . . . . . 6 9 7 0 i . Acids and The ir Concentrat ions • • • • • • • • • • • • • • 7 0 i i . Effect o f Iodide o n Extraction o f Indium
from Hydrobromi c Acid S o lution • • • • • • • • • • • • • • 7 1 i i i . - Effect o f Add i t ion o f Pota s s ium Hydroxide
and the Acidity o f the S o lut ion • • • • • • • • • • • • • 7 2 iv . Shaking T ime . . . 7 3 v . The Di str ibut ion Rat io • • • • •• • • • • • • • • • • • • • • • • 7 3 v i . stab i l i ty of the Ind ium Comp lex i n the
Organ i c Pha s e . . . 7 3 v i i . Limit o f Detect ion • • • • . • • . • • • • • • • • • • • • • • • • • • 7 4 I I I - 4 -2 Cho i c e o f Ana lyt i c a l Method for
Determin ing I nd ium • • • • • • • • • • • • • • • • • • • • • • • • • • • 7 4 I I I - 4 - 3 Pr e c i s ion and Ac curacy • • • • • • • • • • • • • • • • • • • • • • • 7 4 I I I - 4 - 4 Final Ana lyt i c a l Pro c edure • • • • • • • • • • • • • • • • • • • 7 5 I I I - 4 - 5 Conc lus ions . . . 7 6
5 SECTION I I I - 3 THALL I UM
I I I - 5 DEVELOPMENT OF A PROCEDURE FOR QUANTI F I CAT I ON OF 77 THALLIUM
I I I - 5 - 1 Exper iment a l • • • • • • • • • • • • •• • • • • • • • • • • • •• • • • • • • • 7 8 i . So lvent Extraction Sys tems • • • • • • • • • • • • • • • • • • • 7 8 i i . E f f e c t o f the Amount o f Iod ide Added • •• • • • • • • 7 9 i i i . E f f e c t of A c i d s and The i r Concentrat ions •• • • • 8 0 iv . E f f e c t o f Salt ing out • • • • • • • • • • • • • •• • • • • • • • • • 8 0 v. Extraction Shak ing T ime • • • • • • • • • • • • • • • • • •• • • • 8 1 vi. Stab i l i ty o f the Iodo Tha l l ium ( ! ) Comp l ex • • • • 8 1 v i i . The D i s tr ibution Ratio for Extr a c t ion o f
Tha l l ium . . . 8 1 v i i i . Effect of Other E l ements • • • • . • • • • • • • • • • • • •• • • 8 1 I I I - 5 - 2 L imit o f Detection • . • • • • • • • • • • • • • • • • • • • • • • • • • • 8 2 I I I - 5 - 3 Cho i c e of Analyt i c a l C a l ibrat ion Method • •• • • • • 8 3 I I I - 5 - 4 Pr e c i s ion and Accuracy • • • • • • • • • • • • . • • • • • • • • • • • 8 4 I I I - 5 - 5 D i s cu s s ion . . . 8 5 I I I -6 CONCLUS IONS AND DI SCUS S I ON
IV- 1 INTRODUCTION
PART FOUR
GROUP I I I B ELEMENTS IN METEORITES
8 6
8 7 IV- 1 - 1 Chondrites . . . 89 IV- 1-2 Iron Meteor ites • . • • • • • • • • • • • • • • •• • • • . • • • •• • • • • • 9 1
IV- 2 QUANT IFICAT I ON OF GROUP I I I B ELEMENTS I N METEORITES 9 4 IV-2 - 1 Treatment o f Samp l e • • • • • • • • • • • • • • • • • • • • • • • • • • • • 9 4 i . Iron Meteor ites . . . . . . . . . . . 9 4 i i. Chondr ites . . . 9 6 IV- 2 - 2 Quant i f i cat ion of Group I I I B E l ements in
Meteo�i tes .. . . . . . . . . . . . . . • . . . . . . . . 9 7
