Separation Preconcentration and Spectrophotometry in Inorganic Analysis

526 Pages·2002·26.62 MB·english

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Analytical Spectroscopy Library 10
Separation, Preconcentration and
S pectr op h otometr y in In orga n ic Analysis
Analytical Spectroscopy Library
A Series of Books Devoted to the Application of Spectroscopic Techniques to Chemical Analysis
Volume 1 NMR for Liquid Fossil Fuels, by L. Petrakis and D. Allen
Volume 2 Advances in Standards and Methodology in Spectrophotometry, edited by
C. Burgess and K.D. Mielenz
Volume 3 Introduction to Inductively Coupled Plasma Atomic Emission Spectrometry, by
G.L. Moore
Volume 4 Sample Introduction in Atomic Spectroscopy, edited by J. Sneddon
Volume 5 Atomic Absorption Spectrometry. Theory, Design and Applications, edited by
S.J. Haswell
Volume 6 Spectrophotometry, Luminescence and Colour; Science and Compliance, edited by
C. Burgess and D.G. Jones
Volume 7 Applications of Synchrotron Radiation to Materials Analysis, edited by
H. Saisho and Y. Gohshi
Volume 8 Methods for Structure Elucidation by High-Resolution NMR, edited by Gy. Batta, K.E.
K6ver and Cs. Sz~.ntay, Jr.
Volume 9 Flow Analysis with Atomic Spectrometric Detectors, edited by A. Sanz-Medel
Volume 10 Separation, Preconcentration and Spectrophotometry in Inorganic Analysis, by
Z. Marczenko and M. Balcerzak
Analytical Spectroscopy Library- 10
Separation, Preconcentration and
Spectrophotometry in Inorganic Analysis
by
Zygmunt Marczenko and
Maria Balcerzak
Department of Analytical Chemistry, Warsaw University of Technology,
Naokowskiego 3, 00-664 Warsaw, Poland
Translated by Eugeniusz Kr
2000
ELSEVIER
Amsterdam - Lausanne - New York - Oxford - Shannon - Tokyo
This work is an enlarged translation of
Spektrofotometryczne metody w analizie nieorganicznej by Zygmunt Marczenko and Maria Balcerzak
(cid:14)9 Wydawnictwo Naukowe PWN, SA, Warszawa, 1998
Published by arrangement with Polish Scientific Publishers PWN
(cid:14)9 2000 Elsevier Science B. V. for the English edition only
ELSEVIER SCIENCE B.V.
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First edition 2000
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ISBN: 0 444 50524 5
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Printed in The Netherlands.
Contents
Preface ...................................................................................................................................... 3
Abbreviations ........................................................................................................................... 4
Part I. General
Chapter 1. Separation and preconcentration of elements ..................................................... 5
Chapter 2. Principles of spectrophotometry ........................................................................ 26
Chapter 3. Spectrophotometric methods ............................................................................. 39
Chapter 4. Spectrophotometric reagents ............................................................................. 53
Part II. Determination of Elements
Chapter 5. Alkali metals ..................................................................................................... 77
Chapter 6. Aluminium ........................................................................................................ 83
Chapter 7. Antimony .......................................................................................................... 92
Chapter 8. Arsenic .............................................................................................................. 99
Chapter 9. Beryllium ........................................................................................................ 107
Chapter 10. Bismuth ......................................................................................................... 113
Chapter 11. Boron .............................................................................................................. 121
Chapter 12. Bromine .......................................................................................................... 129
Chapter 13. Cadmium ........................................................................................................ 133
Chapter 14. Calcium .......................................................................................................... 140
Chapter 15. Carbon ............................................................................................................ 147
Chapter 16. Chlorine .......................................................................................................... 152
Chapter 17. Chromium ....................................................................................................... 159
Chapter 18. Cobalt ............................................................................................................. 167
Chapter 19. Copper ............................................................................................................ 177
Chapter 20. Fluorine .......................................................................................................... 189
Chapter 21. Gallium ........................................................................................................... 198
Chapter 22. Germanium ..................................................................................................... 204
Chapter 23. Gold ................................................................................................................ 210
Chapter 24. Indium ............................................................................................................ 216
Chapter 25. Iodine .............................................................................................................. 222
Chapter 26. Iron ................................................................................................................. 226
Chapter 27. Lead ................................................................................................................ 238
Chapter 28. Magnesium ..................................................................................................... 247
Chapter 29. Manganese ...................................................................................................... 253
Chapter 30. Mercury ..........................................................................................................2 62
Chapter 31. Molybdenum and tungsten ............................................................................. 270
Chapter 32. Nickel .............................................................................................................2 84
Chapter 33. Niobium and tantalum .................................................................................... 293
Chapter 34. Nitrogen ..........................................................................................................3 04
Chapter 35. Oxygen ...........................................................................................................3 15
Chapter 36. Palladium ........................................................................................................3 18
Chapter 37. Phosphorus .....................................................................................................3 26
Chapter 38. Platinum ..........................................................................................................3 34
Chapter 39. Rare-earth elements ........................................................................................3 41
Chapter 40. Rhenium .........................................................................................................3 50
Chapter 41. Rhodium and iridium ......................................................................................3 57
Chapter 42. Ruthenium and osmium ..................................................................................3 65
Chapter 43. Scandium ........................................................................................................3 75
Chapter 44. Selenium .........................................................................................................3 79
Chapter 45. Silicon .............................................................................................................3 85
Chapter 46. Silver ..............................................................................................................3 92
Chapter 47. Strontium and barium .....................................................................................3 99
Chapter 48. Sulphur ..........................................................................................................4. 03
Chapter 49. Tellurium ........................................................................................................4 12
Chapter 50. Thallium ........................................................................................................4. 18
Chapter 51. Thorium ..........................................................................................................4 24
Chapter 52. Tin .................................................................................................................4. 31
Chapter 53. Titanium ........................................................................................................4. 38
Chapter 54. Uranium ..........................................................................................................4 46
Chapter 55. Vanadium .......................................................................................................4 56
Chapter 56. Zinc .................................................................................................................4 66
Chapter 57. Zirconium and hafnium ..................................................................................4 74
Appendix .............................................................................................................................4. 83
Index ....................................................................................................................................5. 14
Preface
Spectrophotometry enables to determine, with a good precision and sensitivity, almost all the
elements present in small and trace quantities in any materials. The method is particularly
useful in the determination of non-metals.
In the book, much attention has been paid to separation and preconcentration methods,
since they play an essential role in increasing the selectivity and sensitivity of
spectrophotometric methods. The separation and preconcentration methods have been utilised
also in other determination techniques.
Modern spectrophotometers, supplied with data-processing capabilities, enable the
treatment of absorption spectra in the derivative spectrophotometry. The spectrophotometric
methods can be easily automatized, e.g. in the flow injection analysis.
Chapters 1-4 provide the characteristics of the separation and preconcentration methods:
solvent extraction, flotation, coprecipitation with collectors, volatilization, ion exchange etc.
These chapters deal also with the fundamentals of spectrophotometry, spectrophotometric
methods of analysis, and most important chromogenic reagents. Chapters 5-57 have been
devoted to individual elements or groups of related elements.
In the monograph much attention has been paid to the application of the methods in
analytical practice. The references, listed at the end of each chapter and critically selected,
cover the works published until the end of 1999.
The book has been designed for analytical chemists dealing with environment protection,
geology, biology, many branches of industry, etc. It will also be a useful guide for students
interested in becoming specialists in analytical chemistry.
Zygmunt Marczenko and Maria Balcerzak
Abbreviations
BPHA N-benzoyl-N-phenylhydroxylamine
5-Br-PADAP 2-(5-Br-2-pyridylazo)-5-diethylaminophenol
CAS Chrome Azurol S
CP cetylpyridinium ion (or salt)
CTA cetyltrimethylammonium ion (or salt)
DAM diantipyrylmethane
DAPM diantipyrylpropylmethane
DDTC diethyldithiocarbamate
DIPE di-isopropyl ether
DMF dimethylformamide
ECR Eriochrome Cyanine R
EDTA ethylenediaminetetraacetic acid (or disodium salt)
g molar absorptivity
FIA flow-injection analysis
HzDm dimethylglyoxime
H2Dz dithizone, diphenylthiocarbazone
HTTA thenoyltrifluoroacetone
wavelength
MIBK methyl isobutyl ketone
NTA nitrilotriacetic acid
oxine 8-hydroxyquinoline, 8-quinolinol
PAN 1-(2-pyridylazo)resorcinol
phen 1,10-phenanthroline
ppb parts per billion
ppm parts per million
REE rare-earth elements
SPADNS 2-(4-sulphophenylazo)chromotropic acid
sp. abs., a specific absorptivity
TAN 1- (2- thiaz olyl azo)- 2- naphthol
TAR 4-(2-thiazolylazo)resorcinol
TBP tri-n-butyl phosphate
TEA triethanolamine
TOA tri-n-octylamine
TOPO tri-n-octylphosphine oxide
TPTZ 2,4,6-tri(2'-pyridyl)-s-triazine
Chapter 1. Separation and preconcentration of elements
The spectrophotometric determination of elements is usually preceded by their separation
from major components (matrix) and from interfering elements, the effects of which cannot
be eliminated by other methods such as masking or change of pH of the medium. In the trace
analysis of high-purity materials, separation from the matrix involves simultaneous
concentration of the trace components. General methods of preconcentrating and separating
elements have been outlined in several monographs and reviews [1-4].
The present Section provides a discussion of the following separation and
preconcentration methods: solvent extraction, precipitation and co-precipitation with
collectors, volatilization, and methods based on the use of ion-exchangers and other
sorbents. These methods are used not only with spectrophotometry, but also in conjunction
with other methods of determination.
1.1. Solvent extraction
1.1.1. Introduction
The extraction process and extractive methods for separation and preconcentration of
elements are described in several monographs and reviews [5,6].
Solvent extraction separation is based on differences in the solubilities of elements and
their compounds between two immiscible liquid phases. Usually, the initial phase is an
aqueous solution and the second phase is an organic solvent, immiscible with water. Some
properties of the more common organic solvents are listed in Table 1.1. The ion to be
extracted into the non-aqueous phase should first be transformed into an uncharged species.
Stripping ("re-extraction", "back-extraction", or "scrubbing") involves bringing the
element from the organic extract back into the aqueous phase.
The extraction efficiency, i.e., the degree of transfer of the species from the aqueous to
the organic phase, is defined in terms of the distribution- (or extraction-) coefficient, (D).
The quantity D is the ratio of total concentration (i.e., the concentration of all the existing
forms) of the element in the organic phase (Ec0) to the total concentration in the aqueous
phase (ECw) in the aqueous phase, at equilibrium
ZC o
The extraction efficiency (%E) is also expressed as the extraction percent
100D
%E =
D+(Vw/Vo)
where D is the distribution coefficient, and Vw and Vo are the volumes of the aqueous and the
organic phases, respectively.