A Manual for the i ~ ~i¸ , TH OMAS R DULS KI ~' i/i i " llI ~!i ~ K i ~ ~i' ! ,¢i~ > ,> i~ i~ ?~L~III" i ~ • i ~ - ~ 'á,~ i ~,, "~ ~ ,' ~ ã i ¸¸ L I b e l !i~'~ ~:~/i ~i ~i~ ', i~i'll i~! ~iii~:?! ~ii :!'i i i '! i ~:L £~._ ~ , ~,~7 ~ f" ': "~ '7 r , ~L¸II~IG4!!i ~!i.i "al,~ ¸ ~• A Manual for the Chemical Analysis of Metals Thomas R Dulski ASTM Manual Series: MNL 25 ASTM P~blication Code Number (PCN) 28-025096-50 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959 L i b r a r y of Congress Cataloging-in-Publication Data Dulski, Thomas R., 1942A m a n u a l for the chemical analysis of metals/Thomas R Dulski p cm. -(ASTM m a n u a l series; MNL 25) Includes bibliographical references (p ) and Index ISBN 0-8031-2066-4 Metals Analysis Handbooks, manuals, etc I Title II Series QD132.D85 1996 669'.92-dc20 96-1836 CIP Copyright © 1996 AMERICAN SOCIETY FOR TESTING AND MATERIALS All rights reserved This material may not be reproduced or copied, in whole or in part, in any printed, mechanical, electronic, film, or other distribution a n d storage media, without the written consent of the publisher Photocopy Rights Authorization to photocopy items for internal, personal, or educational classroom use, or the internal, personal, or educational classroom use of specific clients, is granted by the American Society for Testing and Materials (ASTM) provided that the appropriate fee is paid to the Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923, Tel: 508-750-8400 online: http://www.copyright.com/ NOTE: This manual does not purport to address (all of) the safety problems associated with its use It is the responsibility of the user of this m a n u a l to establish appropriate safety a n d health practices a n d determine the applicability of regulatory limitations prior to use Printed in Ann Arbor, MI M a r c h 1996 Dedication THIS BOOK IS DEDICATED to m y father, F r a n k Dulski, w h o w a s b o t h a g e n t l e m a n a n d a gentle man Acknowledgments THERE ARE three levels of indebtedness that I would like to acknowledge First, there are those individuals, living and deceased, who for over 32 years have taught me from their deep knowledge of classical and instrumental analysis: Charles J Byrnes, Silve Kallmann, Ralph M Raybeck, James O Strauss, Alfons Suk, and George Vassilaros These cherished friends have contributed to this book in countless unrecognized ways Next, there are those who have given their time and their effol ts in the review of the manuscript: their names and affiliations are listed below The suggestions and corrections of these individuals have been an invaluable aid in the preparation of the final text Finally, there are my friends, coworkers, and associates, including the members of ASTM Committee E-1, and my family my wife, Grace, my daughter, Brittany, and my mother, Stephanie who have in their respective ways supported and sustained me in this work Thank you, all Terry F Beckwith Zinc Corporation of America Monaca, PA Charles M Beck NIST Gaithersburg, MD Charles J Byrnes Crucible Materials Corp.-Research Center Pittsburgh, PA D A Flinchbaugh Bethlehem Steel Corp Bethlehem, PA Robert N Smith, retired American Cast Iron Pipe Co Birmingham, AL Jeffrey C Morrow Colonial Metals Co. Lab Columbia, PA Charles K Deak C K Deak Technical Services, Inc Warren, MI Foreword THIS PUBLICATION,A Manual for the Chemical Analysis of Metals, was approved by ASTM Committee E-1 on Analytical Chemistry for Metals, Ores, and Related Materials This is Manual 25 in ASTM's manual series Cover photo from the collection of Isabel and Alfred Bader Disclaimer MUCH OF THE METHODOLOGYdescribed in this book is potentially hazardous The author, his affiliation, Carpenter Technology Corporation, and the publisher, ASTM, assume no liability whatsoever for any material, financial, or personal loss or injury incurred from the implementation of the equipment, chemicals, or procedures described herein Contents ix Introduction PART I: MATERIALS Chapter l~Laboratory Design Chapter 2~Equipment 15 Chapter 3~Reagents 29 PART II: SAMPLES Chapter Sampling 51 Chapter 5~Sample Preparation 61 Chapter -Dissolution in Acids 70 Chapter 7mMiscellaneous Dissolutions 82 PART III: S E P A R A T I O N S Chapter 8~Separation by Precipitation 95 Chapter 9~Separation by Miscellaneous Techniques 110 Chapter 10 -The Separation of the Elements 125 PART IV: M E A S U R E M E N T Chapter l Gravimetry 141 Chapter 12 Titrimetry 147 Chapter 13mAbsorption Spectrophotometry 158 Chapter 14~Emission Spectroscopy 169 Chapter 15 Other Measurement Techniques 177 PART V: QUALITY Chapter 16 -Reference Materials, Calibration, and Validation 189 Chapter 17mStatistics and Specifications 196 Chapter 18 -Good Laboratory Practices 203 ooo viii CONTENTS Chapter 19 Good Administrative Practices 213 Chapter 20 -Personnel 219 Afterword 223 Glossary 224 Bibliography 226 Appendix I: A Brief Chronology 231 Appendix II: The Chemical Behavior of Analytes 234 Appendix IIA: The Alkali Metals 242 Appendix IIB: The Rare Earths 243 Index 245 Introduction WHILE THE ANCIENTSWERE intuitively aware of the particulate nature of matter and had developed a keen understanding of proportions and mathematics, it was not until the eighteenth century, when the mists of alchemy began to clear, that mankind first peeked into the heart of a substance The insights that followed were in every sense as profound as those that followed the somewhat earlier ponderings of force and light Analytical chemistry, as a more or less clearly defined discipline, has been around now for about 200 years The intimate connection between the analysis of materials and the understanding of the laws governing their nature has remained a hallmark and an impetus of both since that time Among the earliest insights of those nascent days was the very notion that certain substances were, in fact, divisible Air, for example Leonardo da Vinci had suspected and Joseph Priesfley had proved that it was a mixture, hut Antoine Lavoisier gave quantity to its components And today, watching those two perfectly proportioned peaks emerge when a sample of air is injected into a gas chromatograph, who can deny a key historical role to compositional analysis? The analysis of metals was among the earliest applications of analytical chemistry, but it is also interesting to note that fire assay techniques used to assess the purity of gold antedated the scientific discipline by 3000 years In the nineteenth century, the Bessimer process (introduced in 1856) made the large-volume production of steel a reality This was followed shortly by the open-hearth (1864) and electric furnace (1890) processes The latter led to the production of high-purity alloy steels and the need for accurate quantitative measurement of product composition Brass and bronze foundties, derived from a centuries-old tradition, began to employ new processes and to produce new alloys And in the 1890s the Hall process gave birth to the aluminum industry Each of these developments required innovations from analytical chemistry to analyze their products and raw materials, to assess their recoveries, and to fine tune their processes In the second half of the twentieth century, nickel- and cobalt-base high-temperature alloys came into their own for critical aerospace applications, followed closely by titanium alloys The nuclear industry required zirconium and beryllium alloys These and other metals industries made unprecedented demands on the analytical chemist for accuracy, precision, and sensitivity And at the same time, the new high-speed production processes in "traditional" industries the basic oxygen furnace, the argon-oxygen decarburization (AOD) vessel, the continuous caster were adding a new demand for nearly instantaneous results The evolution of techniques for the analysis of metals and alloys followed these metallurgical developments very closely.1 Late nineteenth and early twentieth century metals analysis laboratories employed gravimetric and titrimetric methods As the demand for timely reports increased, time-honored approaches were modified Factor weights and burets calibrated in element percent circumvented time-consuming hand calculations A major innovation at the time was the color intensity comparator, a subjective application of Beer's law In the 1920s and 1930s instrumentation began to ease the analyst's burden: pH meters, filter photometers, electrogravimetric analyzers But it was in the 1940s that instrumental approaches began to dominate Spectrophotometers extended molecular absorption approaches to new levels of sensitivity and 1For a brief chronology of the developments in both fields, see Appendix I 238 CHEMICAL ANALYSIS OF METALS Element Nickel (Ni) 28 58.693 +2 Niobium (No) 41 92.906 (+3), +5 Osmium (Os) 76 190.23 + , +6, +8 Useful precipitations Dimethylglyoxime: (p) NaOH: (p) NH4OH: (s) Basic sulfide: (p) after removal of acid sulfide group NaOH: (p) NH4OH: (p) Cupferron: (p) Acid sulfide: (p) Basic sulfide: (p) Useful solvent extractions Dimethylglyoxime-CHCla: (o) Useful volatilizations/ distillations OsO4 (b.p 130°C) Other useful separations/ comments Ion Exchange (C1- system)-from Fe, Co, Cu Mercury cathode: (a) Ion exchange (C1-/F- system)-from Mo, Ti, W, Ta, etc OsC14: yellow Highly toxic, especially as oxide vapor Best methods at high concentrations Gray.: as dimethylglyoximate Volum.: excess EDTA, back titr with Bi(NOs)3 Gray.: as Nb205, after precip with cupferron and ignition Gray.: as the metal after distillation of OsO4 and reduction in H2 Best methods at low concentrations FAA: 232.0 nm ICP-OES: 231.6 nm (Intf.: Co) Color: Ni-dimethylglyoxime complex (in presence of I2) Color: H202 in conc H2SO4; hydroquinone in conc H2SO4 ICP-OES: 309.4 nm (Intf.: V) Color: thiourea; ephedrine-HC1 ICP-OES: 225.6 nm Element Palladium (Pd) 46 106.42 +2, +4 Phosphorus (P) 15 30.974 4-3, 4-5,-3 Platinum (Pt) 78 195.08 4-2, +4 Useful precipitations Dirnethylglyoxime: (p) from weak acid sol Cupferron: (p) NaOH: (s) NaOH + Na202: (s) Accompanies Fe + NH4OH: (p) Acid sulfide: (p) Basic sulfide: (s) Useful solvent extractions Pd-dimethylglyoximate CHC13: (o) Phosphomolyddate c o m p l e x N-butanol: [ox. yellow: (o); reduced blue: (a)] Useful volatilizations/ distillations PC13 (b.p 76.1°C) Other useful separations/ comments PdI2: black precipitate (soluble in NH4OH + iodide) Highly toxic volatile compounds Ion exchange (alumina column) Pt ° appears as a red colloid if reduced with SnC12, or as a black precip, if reduced with formaldehyde in basic sol Best methods at high concentrations Grav.: as Pddimethylglyoximate from weak acid sol Grav.: as Mg2P207 after precip with MgC12 + NH4OH Volum.: Precip as ammonium phosphomolybdate, add excess std NaOH and backtitr, with std HC1 Grav.: as Pt metal after acid sulfide precip, and ignition to the metal Fire Assay Best methods at low concentrations ICP-OES: 229.7 nm FAA: 247.6 nm Color: a-furfuraldoxime; bromide after extraction of phenylthiourea complex Color: phosphomolybdate; phosphomolybdovanadate ICP-OES: 214.9 nm (Intl.: Cu) ICP-OES: 214.4 nm FAA: 265.9 nm Color: p nitrosodimethylaniline APPENDIX H Element Rhenium (Re) 75 186.207 +4, +6, +7 Rhodium (Rh) 45 I02.906 +3, +4 Ruthenium (Ru) 44 101.07 +3, +4, +6, +8 Useful precipitations Nitron: (p) Tetraphenylarsonium chloride: Acid sulfide: (p) Basic sulfide: (p) Acid sulfide: (p) Basic sulfide:(p) Bismuthiol: [Ru(III)] (p) (p) 239 a-Benzoinoxime: (s) from Mo Useful solvent extractions Ethyl ether/HCl: (o) Useful volatilizations/ distillations Re207 (b.p 362°C) - from Mo Other useful separations/ comments Ion exchange from Mo Yields yellow-brown precip with HC1 + SnC12 + KCNS RhC13: red Yields yellow color with thiocyanate Highly toxic volatile compounds RuCI3: dark brown Best methods at high concentrations Grav.: as tetraphenylarsonium perrhenate; as nitron perrhenate ICP-OES: 197.3 nm Grav.: as Rh metal after precip as the acid sulfide and reduction in H2 ICP-OES: 233.5 nm Grav.: as Ru metal after precip as the acid sulfide and reduction in H2 ICP-OES: 240.3 nm Best methods at low concentrations ICP-OES: 197.3 nm ICP-OES: 233.5 nm FAA: 343.5 nm Color: sodium hypochlorite ICP-OES: 240.3 nm FAA: 349.9 nm Color: pnitrosodimethylanaline; rubeanic acid Element Selenium (Se) 34 78.96 + , +6,-2 Silicon (Si) 14 28.086 +4 Silver (Ag) 47 107.868 +1 Useful precipitations Hydrazine sulfate: as the element (p) Accompanies Fe + NH4OH: (p) Fuming with HC104 or H2SO4: as silicic acid (p) NaOH: (p) NHaOH: (s) Chloride: (p) Acid sulfide: (p) Basic sulfide: (p) Useful solvent extractions RuO4 (decomp 108°C) RuOF (b.p 184°C) Silicomolybdate-N-butanol: [ox.: yellow(o); red.: blue (a)] SiF4 (gas at R.T.) H2SiF6 (b.p 300°C) Useful volatilizations/ distillations SeOC12 (b.p 175.5°C) H2Se (gas at R.T.) Other useful separations/ comments Best methods at high concentrations Highly toxic Carries down B as it precipitates as SiO2 Pb 2+, H ~ +, T1+, Bi a+, Sb 3+ may contaminate AgC1 Grav.: as the element, reduced by H2SO3, SnC12, or hydroxylamine-HC1 Grav.: as SiO2 after dehydration with HC104 and/ or H2SO4 Fire Assay Volum.: titr with thiocyanate Grav.: as AgC1 (protect from light); as metal electroplate out of oxalate or persulfate SO1 ICP-OES: 196.0 nm (Intf.: A1, Co, Fe, Mn, Mg) FAA:/GFAA: 196.0 nm Color: 3, 3'-diaminobenzidine Color: silicomolybdate FAA: 251.6 nm ICP-OES: 251.6 nm FAA/GFAA: 328.1 nm ICP-OES: 328.1 nm Best methods at low concentrations 240 CHEMICAL ANALYSIS OF METALS Element Useful precipitations Strontium (Sr) 38 87.62 +2 Oxalate: (p) from Ba and Mg NaOH fusion/H20 leach: (p) Sulfate: (p) Sulfur (S) 16 32.066 +4, +6,-2 BaC12: as BaSO4: (p) Tantalum (Ta) 73 180.948 +5 Cupferron: (p) NH4OH: (p) NaOH: (p) Hydrolysis with H2503 after fuming with HCI04: as hydrous Ta2Os: (p) Useful solvent extractions Usefltl volatilizations/ distillations Other useful separations/ comments Mercury cathode: (a) Scarlet red flame test H2S is highly toxic Ion exchange (alumina column) F-/C1- system anion exchange No color with H202 (unlike Nb in H2SO4 and Ti in dilute acid) Best methods at high concentrations ICP-OES: 407.8 nrn Gray.: as oxalate Gray.: as BaSO4 first oxidize S with Br2 reduce Fe before adding BaC12 Volum.: Ignite in 02 to SO2, titr iodimetrically Grav.: as Ta205 after ion exchange separation, cupferron precipitation and ignition Best methods at low concentrations FAA: 407.8 nm ICP-OES: 407.8 nm IR abs: ignite to SO2 Color: pararosaniline (after ignition to SO2) Color: pyrogallol ICP-OES: 240.0 nm (Intf.: Co, Fe) Element Tellurium (Te) 52 127.60 +4, +6,-2 Hydrazine sulfate or sodium hypophosphite: as the element (p) Accompanies Fe + NH4OH: (p) Acid sulfide: (p) Basic sulfide: (s) TOPO-MIBK: (0) Thallium (T1) 81 204.383 +I, +3 Thorium (Th) 90 232.038 +4 Chromate: as Tl2CrO4: (p); Iodide: as TII (p); Chloride : as T1C1(p); Weak acid sulfide: (p); Basic sulfide: (p) NH4OH: (p) NaOH: (p) Fluoride: (p) Oxalate (pH 3-4): (p) Iodate: (p) (NH4)2HPO4: (p) Cupferron-butyl acetate/0.5M H2SO4: (0) Useful precipitations Useful solvent extractions H2S (gas at R.T.) Useful volatilizations/ distillations Other useful separations/ comments TeC12 (b.p 328°C) H2Te (gas at R.T.) Highly toxic; Se can be distilled away from Te (HCI/H2SO4) Best methods at high concentrations Volum.: titr with K2Cr207 (diphenylamine ind.) Gray.: as the element (H2SO3 + hydrazine - HC1 reduction) Best methods at low concentrations FAA/GFAA:214.3 nm ICP-OES: 214.3 nm Color: iodine complex Ethyl ether/HCI: (0) TOPO-MIBK: (0) Highly toxic; Imparts emerald-green color to colorless flame; Fluoresces in NaC1 under short k UV Gray.: as T12CrO4from NH4OH sol Volum.: Titr with Ce(IV) ICP-OES: 190.9 nm Highly toxic; H202:(p) in HNO3 medium FAA/GFAA:276.8 nm ICP-OES: 190.9 nm ICP-OES: 283.7 nm Gray.: as ThO2 after precip with oxalic acid ICP-OES: 283.7 nm APPENDIXII 241 Element Tin (Sn) 50 118.710 +2, +4 Titanium (Ti) 22 47.88 +3, +4 Tungsten (W) 74 183.84 (+3), +6 Useful precipitations Acid sulfide: (p) Basic sulfide: (s) NH4OH: (p) NaOH: (s) Cupferron: (p) NH4OH: (p) NaOH: (p) Cupferron: (p) Na2CO3 fusion/H20 leach: (p) NaOH: (s) NH4OH: (s) Basic sulfide: (s) a-Benzoinoxime (coprecip with excess Mo only): (p) Useful solvent extractions TOPO-MIBK: (0) Useful volatilizations/ distillations Other useful separations/ comments SnC14 (b.p 114.1°C) SnL (b.p 364.5°C) May be electrodeposited from acid oxalate sol Cinchonine aids precip, of WOa by dilute acid hydrolysis Best methods at high concentrations Volum.: Titr with I2 after reduction with metallic Pb, Ni, A1, or Zn Gray.: as SnO2 from HNOa Best methods at low concentrations FAMGFAA:286.3 nm ICP-OES: 189.9 nm Color: phenylfluorone Ti(III): violet Ti(IV): colorless Phosphate is insoluble Grav.: as TiO2 after ion exchange, NaOH sep from W, cupferron precip, and ignition Volum.: Jones reductor into excess std ferric sulfate; back-fir, with KMnO4 FAA: 364.3 nm ICP-OES: 334.9 nm Color: H202 in dil H2SO4; diantipyrlmethane; hydroquinone in conc H2SO4 Element Useful precipitations Useful solvent extractions Uranium (U) 92 238.029 +4, +6 NaOH: (p); NH4OH: (p) must be V & CO2-free; Cupferron: (p); (NH4)2CO3: (s) from Fe, A1 & Cr which precip Grav.: as WO3 after ion exchange and precip, with cinchonine (diss in NaOH and weigh impurities) ICP-OES: 207.9 nm (Intf A1) Color: hydroquinone in conc H2SO4; toluene-3,4-dithiol; thiocyanate Vanadium (V) 23 50.942 +3, +4, +5 Zinc (Zn) 30 65.39 +2 Zirconium (Zr) 40 91.224 +4 Na202 + NaOH: (s) Cupferron: (p); Accompanies Fe + NH4OH: (p) NH4OH: (s) NaOH: (s) NH4OH: (s) NaOH: (s) Acid sulfide: (s) Basic sulfide: (p) (NH4)2HPO4: (p) NaOH: (p) NH4OH: (p) Cupferron: (p) p-Bromomandelic acid: Ethyl ether/HNO3: UO2 + - (0) Dithizone-CHC13 (p) (NH4)2HPO4: (p) In all cases Hf accompanies TOPO-Cyclohexane/ HNO3: (0) Hf accompanies Useful volatilizations/ distillations Other useful separations~comments Highly toxic U(VI): yellow U(IV): green Forms soluble complex with CO2- Best methods at high concentrations Grav.: as U3Os after NH4OH precip, and ignition Volum.: Titr with KMnO4 Best methods at low concentrations ICP-OES: 386.0 nm Fluorimetry: of fused NaF + sample with UV (