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HANDBOOK of DETERGENTS Part C: Analysis Copyright © 2005 by Marcel Dekker HANDBOOK of DETERGENTS Editor-in-Chief Uri Zoller Haifa University–Oranim Kiryat Tivon, Israel Part C: Analysis edited by Heinrich Waldhoff Henkel KGaA Düsseldorf, Germany Rüdiger Spilker Sasol Germany GmbH Marl, Germany MAR CEL DE KKE R Copyright © 2005 by Marcel Dekker N E W Y ORK Although great care has been taken to provide accurate and current information, neither the author(s) nor the publisher, nor anyone else associated with this publication, shall be liable for any loss, damage, or liability directly or indirectly caused or alleged to be caused by this book The material contained herein is not intended to provide specific advice or recommendations for any specific situation Trademark notice: Product or corporate names may be trademarks or registered trademarks and are used only for identification and explanation without intent to infringe Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress ISBN: 0-8247-0351-0 This book is printed on acid-free paper Headquarters Marcel Dekker 270 Madison Avenue, New York, NY 10016, U.S.A tel: 212-696-9000; fax: 212-685-4540 Distribution and Customer Service Marcel Dekker Cimarron Road, Monticello, New York 12701, U.S.A tel: 800-228-1160; fax: 845-796-1772 World Wide Web http://www.dekker.com The publisher offers discounts on this book when ordered in bulk quantities For more information, write to Special Sales/Professional Marketing at the headquarters address above Copyright n 2005 by Marcel Dekker All Rights Reserved Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage and retrieval system, without permission in writing from the publisher Current printing (last digit): 10 PRINTED IN THE UNITED STATES OF AMERICA Copyright © 2005 by Marcel Dekker Handbook Introduction The battle cry for sustainable development is persistent in all circles, gaining acceptance, worldwide, as the guiding rationale for activities or processes in the science–technology–environment–economy–society interfaces targeting improvement and growth Such activities are expected to result in higher standards of living, leading eventually to a better quality of life for our increasingly technology-dependent modern society Models of sustainable management are continually being developed and/or adapted and creatively applied, taking into consideration human needs versus wants on the one hand, and long- versus short-term benefits and tradeoffs on the other ‘‘Detergents’’ constitute a classic case study within this context: this is a multidimensional systemic enterprise, operating within complex sociopolitical/technoeconomical realities, locally and globally, reflecting in its development and contemporary ‘‘state-of-affairs’’ the changing dynamic equilibria and interrelationships between demands/needs, cost/benefits, gains/tradeoffs, and social preferences Interestingly, it is not surprising, despite the overall maturity of the consumer market, that detergents continue to advance more rapidly than population growth The soap and detergent industry has seen great change in recent years, responding to the shifts in consume preferences, environmental pressures, the availability and cost of raw materials and energy, demographic and social trends, and the overall economic and political situation worldwide Currently, detergent product design is examined against the unifying focus of delivering to the consumer performance and value, given the constraints of the economy, technological advancement, and environmental imperatives The annual 2–3% growth of the detergent industry and a higher growth in personal care products reflect impressive developments in formulation and application The detergent industry is thus expected to continue steady growth in the near future For the detergent industry, the last decade of the twentieth century has been one of transformation, evolution, and even some surprises (e.g., the increase of heavy-duty liquid detergents at the expense of powder detergent products) On both the supplier and consumer market sides (both remain intensely competitive), the detergent industry has undergone dramatic changes, with players expanding their offerings, restructuring divisions, or abandoning the markets altogether This has resulted in the consolidation iii Copyright © 2005 by Marcel Dekker iv Handbook Introduction of the market, especially in the last several years, and this trend appears to be gaining momentum The key concepts have been and still are innovation, consume preferences, needs, multipurpose products, cost/benefit, efficiency, emerging markets, partnership–cooperation–collaboration–merging (locally, regionally, and globally), and technological advancements Although substantial gains and meaningful rapid changes with respect to the preceding concepts have been experienced by the surfactants/detergents markets, the same cannot be said for detergents/surfactant technology itself The $9-billion-plus detergent ingredients market has many entrenched workhorse products This may suggest that the supply of ‘‘solutions’’ to most cleaning ‘‘problems’’ confronted by consumers in view of the increasing global demand for a full range of synergistic, multifunctional detergent formulations having high performance and relatively low cost, and the need for compliance with environmentally oriented (green) regulation, may be based on modifications of existing technologies What does all this mean for the future of the detergent enterprise? How will advances in research and development affect future development in detergent production, formulation, applications, marketing, consumption, and relevant human behaviors as well as short- and long-term impacts on the quality of life and the environment? Since new findings and emerging technologies are generating new issues and questions, not everything that can be done should be done; that is, there should be more response to real needs rather than wants Are all the questions discussed above reflected in the available professional literature for those who are directly involved or interested engineers, scientists, technicians, developers, producers, formulators, managers, marketing people, regulators, and policy makers? After a thorough examination of the literature in this and/or related areas, I came to the conclusion that a comprehensive series was needed that focuses on the practical aspects of the topic and provides the detergent industry perspective to all those involved and interested The Handbook of Detergents is an up-to-date compilation of works written by experts each of whom is heavily engaged in his or her area of expertise, emphasizing the practical and guided by a common systemic approach The aim of this six-volume handbook (Properties, Environmental Impact, Analysis, Formulation, Applications, and Production) is to reflect the above and to provide readers who are interested in any aspect of detergents a state-of-the-art comprehensive treatise, written by expert practitioners (mainly from industry) in the field Thus, various aspects involved—raw materials, production, economics, properties, formulations, analysis and test methods, applications, marketing, environmental considerations, and related research problems—are dealt with, emphasizing the practical in a shift from the traditional or mostly theoretical focus of most of the related literature currently available The philosophy and rationale of the Handbook of Detergents series are reflected in its title, its plan, and the order of volumes and flow of the chapters (within each volume) The various chapters are not intended to be and should not necessarily be considered mutually exclusive or conclusive Some overlapping facilities the presentation of the same issue or topic from different perspective, emphasizing different points of view, thus enriching and complementing various perspective and value judgements There are many whose help, capability, and dedication made this project possible The volume editors, contributors, and reviewers are in the front line in this Copyright © 2005 by Marcel Dekker Handbook Introduction v project Many others deserve special thanks, including Mr Russell Dekker and Mr Joseph Stubenrauch, of Marcel Dekker, Inc., as well as my colleagues and friends in (or associated with) the detergent industry whose dedication and involvement certainly facilitated this work My hope is that the final result will complement the tremendous effort invested by all those who contributed; you the reader, will be the ultimate judge Uri Zoller Editor-in-Chief Copyright © 2005 by Marcel Dekker Preface The intention of this volume is to demonstrate the state of the art of strategies, methods, and techniques applied for the analytical deformulation of modern detergents These are defined as surface active agent containing formulations, used in household and industry in aqueous application solutions for the cleaning of textiles and hard surfaces The emphasis is on up-to-date techniques and methods that are proved effective and useful in daily work In order to impart to the reader, besides product analysis, a comprehensive view of all aspects of detergents, typical ingredients of modern products, testing of application abilities detergent formulations, and the determination of detergent ingredients in environment, are outlined in separate chapters Furthermore, the basics of modern instrumental techniques with emphasis to application in the detergent analysis field are also described The scope and spectrum of methods and techniques applied in detergent analysis have changed significantly during the last decade Driving forces were the rapid progress in instrumental analysis which led to a far reaching replacement of classical labor-intensive manual procedures by modern, often computer aided instrumental techniques, and also changes in the product spectrum The former all purpose cleansers and detergents have largely been replaced by specialized products which contain new—even in very low concentrations—effective ingredients; these require for determination more sensitive and specific methods The field of detergent analysis can roughly be divided into two sectors: 1) quality control and 2) monitoring of the multi-billion dollar market It is of vital interest for the market participants to know exactly what is going on there Quality control analysis is characterized by the application of fixed, often standardized procedures and methods, which are designed in such a way, as to allow an operation with relatively simple equipment, by semi-skilled technicians Additionally big corporations use on-line or semi on-line systems for the fully automated determination of essential parameters, not normally described in literature because they are proprietary production facilities and are therefore subject to secrecy The analysis of unknown products from market sources, which is the main subject of this book, is due to the diversity and complexity of modern detergents, a very demanding task It requires much experience and product knowledge, but also the vii Copyright © 2005 by Marcel Dekker viii Preface availability of nearly the whole spectrum of the modern analysis techniques used, and, especially important, highly skilled staff Often no defined strategy can be given; the performing analyst has to decide with respect to the product type and the individual analytical task, how to approach and how detailed the characterization of the various ingredients must be done in order to obtain the required information Sometimes rough data about the concentration of the main raw material types are sufficient without any further determination of their exact structure But for a comprehensive analysis often the concentrations as well as the isomer and homologue distribution of ingredients has to be determined in great detail in order to allow an identification of the contained commercial raw material For new, so far unknown formulations or totally new raw materials, a final formula reconstruction at an acceptable price often is only possible in close cooperation of analysts, product developers, patent specialists, and marketing people In the scope of this volume it is not possible to describe the discussed analysis methods in great detail, but the basic features and experimental parameters for many essential procedures are outlined to a degree, such that an experienced analyst may be able to use them for exploratory work Nevertheless for a better understanding and/or use in daily routine the analyst should refer to the cited references Heinrich Waldho Ruădiger Spilker Copyright â 2005 by Marcel Dekker Analytical Techniques 62 63 64 65 66 67 641 Klug, H.P.; Alexander, L.E X-ray Diffraction Procedures for Polycrystalline and Amorphous Materials; Wiley: New York, 1974 McClune, W.F., Ed.; Powder Diffraction File (Organic and Inorganic); International Centre for Diffraction Data (ICDD): Newton Square, PA, 2003–2004; www.icdd.com Woodruff, D.P.; Delchar, T.A Modern Techniques of Surface Science; Cambridge University Press: Cambridge, 1988 Goodhew, P.J.; Humphreys, F.J Electron Microscopy and Analysis; Taylor and Francis: London, 1988 Briggs, D.; Seah, M.P., Eds Practical Surface Analysis by Auger and X-ray Photoelectron Spectroscopy; Wiley: New York, 1983 Wunderlich, B Thermal Analysis; Academic Press: San Diego, 1990 Copyright © 2005 by Marcel Dekker Future Trends In the years to come detergent analysis will of course be influenced by future types and composition of commercial detergent products Another interacting force will be the further development of analytical science, especially analytical instrumentation As far as it is predictable now, the tendency in detergent product development is leading towards more and more sophisticated detergent formulations New ingredients may be introduced, that provide additional benefit for the consumer even at low concentration levels The application of product is going to be made as comfortable as possible by tailored formulation Typical examples are automatic dishwasher agent tablets that contain—besides the cleansing agent—water softener and rinsing aids Classical commercial raw materials and raw material compounds will be further improved in order to achieve better performance or to enable the composition of highly effective products at lower costs The comprehensive analysis of these future detergents will require analysis techniques that are, on the one hand, sufficiently sensitive to detect low concentrated ingredients and, on the other hand, powerful enough to allow for a very detailed characterization of molecule structure In the field of analytical science instrumental techniques will be improved further Their operation will be more and more simplified by computer-based operation and data evaluation systems, that will make an application become a daily routine, even by semi-skilled technicians Highly sensitive and specific techniques, such as HPLC-MS and MALDI-TOF-SIMS, may become broadly available and routine tools Multidimensional NMR techniques may be used more often for direct, highly specific determination of ingredients without preseparation These future developments will lead to a further, nearly total substitution of classical labor intensive separation and determination procedures by automated instrumental techniques An additional driving force will be steady pressure to save costs by the reduction of expensive human labor But never forget: even in the future, deformulation of complex detergents cannot be achieved without the expertise of highly qualified and experienced technicians and analytical chemists In spite of huge progress made in fully automated multicomponent analysis of detergents in production control, the desire of many customers for an analysis robot, by which any detergent market product can deformulate within minutes, will remain a dream, at least in the foreseeable future 643 Copyright © 2005 by Marcel Dekker Index 5-Bromoindoxolan-h-D-cellubioside, 475 Abrasives, 77 Accelerated solvent extraction (ASE), 120–121 Acids in cleaners, 72 Active oxygen based bleaching agents analytical identification and determination, 443 determination scheme for liquid detergents, 446 determination scheme for powder detergents, 445 Active oxygen quantification by cerimetry, 448 by iodometry, 447 by manganometry, 472 Alcohol determination by GLC, 509–511 by HPLC, 510–511, 513 Alcohol insoluble components, 122 Alcohol soluble ingredients, 121 Aldehyde determination by HPLC, 518–520, 521 Alkali carbonates analysis scheme, 133–134 Alkali phosphate general analysis scheme, 134 Alkali silicates common types, 135 determination scheme, 135 Alkalis in cleaners, 75–76 Alkanolamide application of, 151 ethoxylated, 151, 156, 164 formula of, 151 infrared of, 156 Alkyl chain branching of, 271 unsaturation per, 308 Alkyl chain distribution by hydrolysis, 357 by methylation 357 by pyrolysis GC, 356, 357 Alkyl chain length separation of, 184, 333, 342 Alkyl groups number of, 333, 342 Alkyl imidazolium quats, 294 Alkylbenzene sulfonate desulfonation of, 266 by ultraviolet spectroscopy, 279 Alkylphenol, ethoxylated, 151, 154, 162 Alkylpolyglucoside, 153 Alkyltrimethylammonium quantitative determination by mass spectrometry, 318 All-purpose cleaners, 14 composition of, 15 Amine ethoxylate, formula, 153 Amine oxide, 351 determination with amine, 331 formula, 153 645 646 Ammonia determination by IC, 117 by titrimetry, 118 Amphoteric surfactants determination of, 323 in shampoo, 347 infrared spectra of, 306 separation of, 337, 346 by postchromatographic reaction, 350 by prechromatographic reaction, 350 separation procedure, 132 Amylase, 472 antiredeposition effect, 472 detection by PhadebasR tablets, 472 increased oxidation stability, 472 starch degradation by, 472 Amylase activity measurement assaying of, 477–478 by colorimetric methods, 478–480 Analysis of detergents analysis process for detergent, 474 general procedure, 102 initial measures, 103 Anionic surfactants, 130 capillary electrophoresis, migration behavior, 251 determination of, 262 toluidine method, 257 determination scheme, 130 hydrolysis of, 220, 258 in washing powder, characterization of, 279 indicators in TLC for, 220 separation of, 220 Antifoaming agents, 142 Antimicrobial agents, 63–65, 67–68 Antistatic agents, 294 APEO traces extraction of, 555 metabolite isolation, 555 Atomic absorption spectrometry (AAS), 114 Atomic emission spectrometry element determination by, 114 Automatic dishwashing machine care products, 13 product composition, 12 rinsing aids, 13 Average alkyl chain length, NMR, 161 Average degree of condensation, 154 of ethoxylation by NMR, 168 Index [Average degree] of polymerization by NMR, 161 of propoxylation by NMR, 168 Bacillus subtilis, 471 Balance, hydrophilic/lipophilic, 149 Bathroom cleaners, typical composition of, 18 Bentonite, 408 Benzene sulfonate, 514 Biocides, multifunctional, 525, 526 biosensors, for cationic surfactants, 367 Bleach boosters, composition of, Bleach catalysts analysis of, 460 structure, 441 Bleach systems in dishwasher detergents, 62 in laundry detergents, 59–62 in toilet and hygiene cleaners, 62 Bleaching accelerators, 138–139 general determination scheme, 139 types/structure, 440–442 Bleaching agents, 138 active chlorine based types, 139 active oxygen based types, 138 reaction mechanisms, 441 stability of, 442 Bleaching systems, 439 identification of, 443 Boron trace analysis, 572–575 by electroanalysis, CE, 574–575 by photometry, 573–574 by spectrometry, 575 Brightening colors analysis of, 496–497 structures, types, 492–495 Bromcresol green in semiquantative rapid test, 373 Bromthymol blue in photometric determination, 323 in semiquantative rapid test, 373 Builder by GC/GC-NPD, 569–572 raw materials, 389 Capillary electrophoresis, 117 Car wash/care car polish, 32 car polish composition, 31 car shampoo composition, 30 Index [Car wash/care] prewash detergent composition, 30 windscreen cleaners, 33–34 Carbohydrates colorimetric tests for, 530 determination by 1H NMR, 530, 532 structure of, 531 Carbonate carbonate, 112 detection, 390 fluorescent-whitening agents, 112 oxidizing agents, 112 quantification, 116, 118, 391–393 urea, 112 CaroatR, 448–449 composition, 448 quantification, 449 Carpet cleaning after-treatment, 27 basic cleaning, 25 with cleaning powder, 25 stain removal, 24 steam-cleaning process, 26 Cationic surfactants application of, 291 by indirect UV detection, 364 infrared spectra, 306 modifier in capillary electrophoresis for, 365 separation procedure, 131 titration with tetraphenylborate, 324 types of, 291 Cellulase degradation of cellulose fibers, 472 detection by CMC test, 475 identification by coloration, 475 pigment removing by, 472 Cellulose/starch derivatives, 530–535 Chloride determination by IC, 116 titrimetric determination, 118 Cleaning agent, infrared of, 266 Cleavage of alkyl sulfate with hydroiodic acid, 245 with hydrogen bromide, 197 with hydrogen iodide, 196 with lithium aluminium hydride, 197 C-length distribution with hydroiodic acid of alkyl sulfates, 245, 283 CMC Trypan Blue, 475 647 Cobuilder, 389 (see also Complexing agents) Cocoamidopropylbetaine, 349 Colorants for detergents, 87 commercial types, 390 common types, 136–137, 138 general determination procedure, 136–137 Complexation behavior, 255 Complexing agents polymeric general analysis procedure, 138 types, 137 Complexing agents/dispersants, 57–58 Conditioner ion-spray mass spectrometric analysis in, 277 Conditioning hair rinse formulation of, 299 Conductivity detector for anionic surfactants, 232, 239 Cosmetic cleaners, composition of detergent bars, 42 hair shampoos, 44 shower gels, 43 toilet soap, 41 tooth paste, 45–46 Cosmetic product soaps in, 258 Cumene sulfonate, 513–514 Cyanuric acid, 461 DADHT, (see Diacetyldioxohexahydrotriazine) Dean Stark apparatus, 508 Degree of ethoxylation, 238, 239, 245, 246, 261, 271, 273, 283 of quaternization, 308 Derivatization acetate, 196 diazomethane, 243, 247 iodide-trifluoroacetic anhydride, 247 with methanol, 357 phenylisocyanate, 191 trimethyl orthoformate, 247 trimethylsilyl, 169, 193, 245 Desulfonation of anionic surfactants, 243 micro, 244 Detection conductivity, 219, 235, 239, 343 evaporative light scattering, 184, 219, 233, 343, 349 648 [Detection] indirect, 364 indirect conductivity, 235, 247 indirect photometric, 343, 353, 354 indirect ultraviolet, 235, 247, 254 negative ion, 278 photometric, 255 suppressed conductivity, 353 Detergent soaps in, 258 Detergent ingredients alkalinity of, 109 Detergent pellets sampling, 107 Detergent polymers, 56–57 determination, 397–401 polyasparaginic acid, 59 polycarboxylates, 59 Diaminostilbene brighteners functional groups, 488 Differentiation of surfactants by HPLC, 233 Dishwashing, 8–14 Dishwashing liquids, composition of, 11 Disinfectants, 374, 375, 377 (see also Antimicrobial agents) Disinfecting cleaners, example for, 299 Disintegration of laundry tablets, Distribution alkyl chain length, 189, 193, 239, 283, 314 ethylene oxide, 168, 190, 191, 192, 194, 222, 239 homologue, 249 Distyrolbiphenyl, 488 Dryer sheets, active material for, 297, 298 Dye transfer inhibitors, 141 commercial types, 536 determination by pyrolysis GC/NSD, 536–537 Electrode ion sensitive, 259, 260 solvent-resistant, 261 Electroosmotic flow, 201 influence on, 249 Emulsifying agents amines as, 294 nonionic surfactants as, 149 Endo-1,4,h-glucanase, 475, 480 Environmental matrices internal standards, 552 Index Environmental samples preservation, 553 sampling of, 552 Enzyme class identification analysis process for detergents, 474 principles of, 473 Enzymes, 63–64, 140–141 basic analysis mechanism, 140 decomposition of, 106 Esterquats, 52 methylation of, 355 separation of, 343 Ethoxylate broad-range, 150 ELISA of, 207 ester ethoxylates, 152, 158, 166 narrow-range, 150 Ethylene oxide content, 154 by hydrobromic acid cleavage, 196 by hydrogen iodide cleavage, 196 Ethylene oxide homologues separation of, 222 Ethylene oxide/propylene oxide copolymer, 152, 158, 166 infrared of, 158 ratio of, 168 European detergent regulation, 54 Exchanger anion, 234, 235 cation, 245, 278 Extraction, 176 free polymeric acid, 436 hexane, 282 ion pair, 231 on-line, 231 photometric method, 324, 373 solid phase, 238 Fabric softeners ditallowdimethylammonium chloride in, 294 formulations, types of, 296 Fast atom bombardment, 166, 168, 171, 314 Fatty acid alkanolamide, 151, 155, 164 alkanolamide, infrared of, 155 ethoxylate, infrared of, 155 Floor shine emulsion, 24 self-glazing effect, 25 Flooring cleaners, 21 composition of, 22 Index Flow injection alizarin fluorine blue in, 206 of cationic surfactants, 362, 363 Fluorescent whitening agents, 80 (see also Optical brighteners) Fluorimetry of cationic surfactants, 363 Foam boosters amine oxides as, 295 Foam depressors, 516–517, 518 common types, 516 Foam stabilizers, 295 Foaming agent, 149 low-foaming, 150 Food trade/industry cleaners, 34–36 Formaldehyde, photometric determination, 518–519 Formula reconstruction, 142–144 Fraction anionic, 247 soap, 219 Fractionation of alkylbenzene sulfonate homologues, 235 of surfactant mixtures, 228 Fractioning of detergents, 119 by ion exchange methods, 126– 129 by liquid/liquid extraction, 124–125 by open column chromatography, 125–126 by solid/liquid extraction, 119–122 by solid-phase extraction, 123–124 Fragrance oils, 81–86 Fragrants, 142, 525–528 Furniture care products, 21 Furniture cleaning/care products composition of, 21 Fusion, alkali, 245 Geraniol, 526 Germ reducing cleaners, 71 Germ reduction, 69 Glass cleaners, 17–18 composition of, 20 Glycerol monostearate, infrared of, 157 Hand dishwashing detergents, 10 composition of, 11 Hard surface cleaning, 14–28 Hardener elimination by ion exchange, 389 by sequestering, 389 649 Headspace SPME principle of, 527 Heavy duty laundry detergents compositions, 3–5 extrudates, liquids, market shares, 2, powders, 1, tablets, Homologue distribution by Hofman degradation, 360, 361 HyamineR1622, 257, 258, 260 Hybride plate, 221 Hydrogen peroxide, 460–461 formation of, 441 Hydrolysis of alcohol ether sulfate, 283 of alcohol sulfate, 245 of esterquat, 357 with perchloric acid, 220 Hydrotropes, (see Solubilizers) ICP-OES, 114 Inorganic acids, 72 Inorganic builder general analysis procedure, 133–136 Institutional dishwashing, 27 Institutional hard surface cleaners, 37–38 Institutional laundry detergents, 36–37 Instrumental micro element analysis, 115 Ion chromatography, 115 cations, 117 inorganic anions, 116 mobile phase, 238–352 phosphate species, 117 Ion exchangers (IE) commercial types, 127 silica based, 126 typical IE column, 127 Ion pairing chromatography, 239 Ion selective electrode, 239 Ionization atmospheric pressure chemical, 266 chemical, 168, 314 chemical, atmospheric pressure, 168, 172 electron impact, 168, 314 ion spray, 318 matrix-assisted laser desorption, 266, 277, 314 Ion-pairing agents, 234, 238, 239, 278 650 IR/NMR sample assessment by, 110 Isocyanurates, 462 Kitchen cleaners Kjehldal method, 115 typical composition, 18 Kongo Red, 475 LAS, synthesis of, 48 Laundry aids, 6–8 Layered disilicates determination by XRD, 410 Layered silicates, 389 Leather cleaning/care, 28 Limonen, 525, 526 Lipase, 472 qualitative test, 476 triglyceride hydrolysis by, 473 Lipolytic activity quantification of, 481–482 Liquid detergent, ion-spray mass spectrometric analysis, 277 Liquid heavy-duty detergent, 150 components of, 150 Lotus effect, 28 Lovibond test for cationic surfactants, 373 Maintenance/care components, 88 fluorocarbon resins, 93–94 polymer dispersions, 90–91 silicones, 91–93 waxes, 88–90 Membrane suppressor, 239 Metal cleaning, 39–40 Microscopical sample check, 109 MnTACN, 441 Mobility, electrophoretic, 254, 364 Modified soda, 393 Molecular mass, 308, 309 Molecular size, 184 Molybdenum blue method, 400 Motor vehicle cleaning, 38 N,N,NV,NV-tetraacetylethylenediamine, (see TAED) Nitriles based bleach activators, 441, 459–460 Nitro musk analysis by GC, 529 NOBS, (see Nonanoyloxybenzenesulfonate) Nonanoyloxybenzenesulfonate, 440 H-NMR spectrum, 456 Index [Nonanoyloxybenzenesulfonate] application fields, 455 determination, 455–457 hydrolysis, 455 perhydrolysis, 455 reaction mechanism, 455 structure of, 440, 455 Nonionic ingredients isolation of, 208 Nonionic surfactant cobalt thiocyanate method, 175 extraction of, 176 flow injection analysis of, 202 general separation procedure, 133 potassium picrate method, 176 CE separations of, 201 tetrathiocyanatocobaltate method, 176 titration iodometric, 178 ion-sensitive electrode, 179 with tetraphenylborate, 178, 179 Nonionic trace determination by CE, 563, 566 by GC, 561, 562, 564 by HPLC, 559 by IR-spectroscopy, 567–568 by MS, 566–567 by NMR, 568 by SFC, 563 Non-surfactant org components extraction of, 121 Nonylphenol in food, 565 in mussels, 565 NTA/EDTA trace analysis by LC, 569 by polarography, 568 Odor adsorbents, 27, 86 composition of, 28 o-Phosphate determination by colorimetry, 118 by IC, 116 Optical brighteners analytical separation techniques, 500–502 chemical properties, 495 definition, 487 detection methods, 498 extraction of, 498 fluorescence effect, 496 identification, 498, 502–503 Index [Optical brighteners] isomerization of, 496 quantification, 503–505 types/properties, 487–492 Optical whiteners, 140 Optode, 367 Organic acids, 73 Organic solvents, 508–512 common types, 510 determination by GLC, 509–510 determination by HPLC, 510–513 Orthophosphate determination, 399–403 PAG, (see Pentaacetylglucose) Paintwork care cleaner composition, 31 cleaning, 32 preservation/sealing, 32 PAP, (see Phthalimidoperoxycaproic acid) P-determination by classical methods, 114 by XRF, 113 Pentaacetylglucose, 441 Peracetic acid, 439, 449, 451, 462 Perborate, 439, 443 application fields, 444 identification, 444 quantification, 444 reaction mechanism, 444 monohydrate, solubility of, 444 tetrahydrate, solubility of, 444 Percarbonate, 449 application fields, 444 identification, 444 quantification, 444 structure, 444 Peroxycarboxylic acids, 462–469 analysis by LC, 466–468 determination by GLC, 464–465 electroanalysis, 469 spectrophotometric methods, 465–466 titrimetric determination, 462–464 Phosphate analysis by electroanalysis, CE, 574–575 by photometry, 573–574 by spectrometry, 575 Phosphate species analysis 31 P-NMR, 407 capillary isotachophoresis, 407 by HPLC/IC, 405 by TLC, 405–406 651 Phosphates identification/detection of, 396–397 types/properties, 396 Phosphoric acid esters by NMR, 273 Photometry of cationic surfactants, 362, 373 Phototrode, 264 Phthalimidoperoxycaproic acid, 457–459 Physical detergent characterization apparent density, 108 density, 108 particle size distribution, 108 pH-value, 107 viscosity, 108 Pigment colorants crosslink degree, 126 exchange capability, 126 polymeric resin based, 126 structures, 490–491 Poly-(styrene-divinyl benzene)-gel, 223, 228, 235 Post-column reaction, 239 Potassium determination, 394–395 identification/detection, 394 Potassium hydrogen sulfate, 448 Potassium monopersulfate, 448 Powder detergent ion-spray mass spectrometric analysis, 277 Preservatives, 66–68, 142, 517–525 activity range, 70 aldehydes, 518–519, 520, 521 benzoic acid based types, 520, 524 isothiazoline-3-on types, 518, 523 QAVs, 522, 525 sorbic acid, 520, 524 Proteases, 471 commercial types, 477 detection of, 472 identification in products, 477 identification on IEF-Gel, 478, 479 serin types, 476 Proteolytic activity quantification of, 482–483 Pyrolysis, 362 Qualitative tests boron-containing components, 112 Quarternary ammonium compounds differentiation of, 323 652 [Quarternary ammonium compounds] extraction photometric determination, 323 separation of, 345, 354 Radiotracer, 374, 376 Residue, determination of, 375 Sample divider conical, 106 rotating instrument, 107 Sampling of detergents of bulk material/packages, 104–105 of laboratory samples, 105–107 Separation of alcohol ether sulfate, 222 alkylbenzene sulfonate isomers, 252 anionics and cationics, CE, 367 diethanolamide, 183 different hydrophobic groups, 223 functional groups, 219 ionic surfactants, 228 ionic surfactants by ion-pair chromatography, 232 monoethanolamide, 183 polyethylene glycols, 182 soap, 258 sorbitan monolaurate, 183 sulfates and sulfonates, 240 surfactant classes, 333 surfactant mixtures, 230 surfactants, 350 Separation of detergent samples scheme, 534 Sequestering agents, 389 Shampoo components in, 266, 267 dioctyl sulfosuccinate in, 235 formulation of, 301 ion-spray mass spectrometric analysis, 277 lauryl ether sulfate in, 239 Shoe polishes composition of, 29 Shower gel, formulation of, 301 Silicates determination methods for, 410–414 identification/detection, 409 types, 407–409 Soap, titration of, 258, 261 Soda, (see Sodium carbonate) Sodium aluminum silicate, 389 Index Sodium carbonate, 390 Sodium hydrogen carbonate identification of, 393 Sodium hypochlorite, 461 Sodium metasilicate identification by XRD, 409 Sodium sesquicarbonate, 390 Sodium tri[poly]phosphate test for, 396 Softener, 396 ion-spray mass spectrometric analysis, 277 Soil antiredeposition agents, 142, 528–536 Soil release agents, (see Soil antiredeposition agents) Soil repelling agents, (see Soil antiredeposition agents) Solubilizer, 53, 76, 149, 513–516 determination by HPLC, 513–514 UV-spectrometric determination, 514 Solvay process, 390 Solvents, 141, 507–513 Solvents in cleaners, 75 Sorbitan monostearate, 157 Soxhlet apparatus, 120 SPE Sorption materials, 123 Speciality detergents, Stain removers, 18 Sulfate determination by gravimetry, 118 by IC, 116 by titrimetry, 118 Summary formulation characteristics alcohol solubles/insoluble matter, 108 alkalinity, 108 solid/volatile content, 108 water solubles/insoluble matter, 108 Summary parameters surfactants BiAS, 556 cobalt thiocyanate, 175 DBAS, 556 MBAS, 555 Surface active agents colorimetric test for, 110–111 Surface tension, 255 Surfactant classes in cosmetics, 377 in toiletries, 377 separation of, 333, 336 Surfactant trace analysis DSDMAC by HPLC, 559 LAS by GC, 561–562 Index [Surfactant trace analysis] LAS by HPLC, 556–558 LAS by HPLC/MS, 558–559, 561–562 SAS by GC, 562 Surfactant trace extraction by liquid/liquid extraction, 554 by SFE, 555 by solid/liquid extraction, 555 by solvent sublation, 554 by SPE, 553 Surfactants categories, 47 commodity types, 46 differentiation of, by TLC, 221 esterquats, 52 hydrotropes, 53 IE separation according to Gabriel, 128 LAS, synthesis of, 48 polymeric types, 54 separation by ion exchange methods, 126–129 separation by SPE, 124 silicone surfactants, 53 specialty types, 50 specific properties of, 46 structure of anionics, 49 structure of nonionics/betaines, 51 TAED, 440, 449 application fields, 449 reaction mechanism, 449 TAED identification by 1H NMR, 452 by IR, 451 by TLC, 450–451 TAED quantification by GLC, 454 by HPLC, 453–454 by jodometry, 452–453 TAGU, 442, (see also Tetraacetylglycoluril) Terephthalic acid esters, 535–536 Terpinen-4-ol, 526 Terpinene, 526 Tertiary amine oxide, titration of, 330 Tetraacetylethylenediamine, (see TAED) Tetraacetylglycoluril, 442 Theoretical plate, 230 Thickeners, 78–79, 295 thickener action, 79 Titration acid/base of amphoterics, 329 653 [Titration] by double wavelength spectroscopy, 264 cerimetric, 448, 462 iodometric, 447, 458, 462 neutralization, 258 of turbidity, 263 one-phase turbidity, 264 potentiometric, 255, 259, 282, 327 precipitation, 259, 325, 328 turbidimetric, 331 two-phase, 179, 261, 282 of amphoteric surfactants, 327 of anionic surfactants, 255–257, 261–262 of cationic surfactants, 325, 327 in cleaning agents, 257 with ion sensitive electrodes, 259 Titration indicators 2,7-dichlorofluorescein, 258 bromophenol blue, 255, 264 dimidium bromide, 256, 258 disulfine blue, 256, 258, 323, 325, 328 methylene blue, 255 mixed, 258 Toilet bowl cleaner composition, 20 twin-tank system, 16–17, 19 Toluene sulfonate, 271, 513–514 Tooth paste, 230, 267 Total phosphorous content determination, 398–399, 401–404 Trace detection, 249 Trimethylsilylation for GC/MS, 169 for NMR, 161 Trona, 390 Trypsin, 471 Turbidimetry, 264 Two-dimensional correlation spectroscopy, 274 Ultracentrifugal mill, 10 Urea, 112, 513–514 UV Protection additives, 80 Visualization in TLC bromocresol green, 223 bromophenol blue, 332 dehydrothio-p-toluidine-7-sulfonic acid, 222 Dragendorff, 180, 182, 222, 223 eosine, 222 654 [Visualization in TLC] iodine vapor, 221 Leucomalachite green, 222 phosphomolybdic(VI)acid, 222 pinacryptol yellow, 221, 222, 281, 332 primuline, 222 thioflavine S, 222 Washing agent, 149 infrared of, 266 two-phase titration in, 257 Water determination, 507 by azeotropic distillation, 508 KF-method, 507 Water glasses, 407–408 Index X-ray diffraction component identification by, 112 X-ray fluorescence spectrometry, 113 X-ray photoelectron spectroscopy, 376 Xylene sulfonate, 513–514 ion-chromatography of, 239 Zeolite A, 390, 415 Zeolite builders systems function of, 55 Zeolite P, 415 Zeolite X, 415 Zeolites determination, 416–417 identification of, 415 properties, 414–415