Armarego / Chai Purification of Laboratory Chemicals

6. Auflage 2009
ISBN: 978-0-08-087824-9
Verlag: Elsevier Science & Techn.
Format: EPUB
Kopierschutz: 6 - ePub Watermark

E-Book, Englisch, 760 Seiten

A best seller since 1966, Purification of Laboratory Chemicals keeps engineers, scientists, chemists, biochemists and students up to date with the purification of the chemical reagents with which they work, the processes for their purification, and guides readerd on critical safety and hazards for the safe handling of chemicals and processes.
The Sixth Edition is updated and provides expanded coverage of the latest chemical products and processing techniques, safety and hazards. The book has been reorganised and is now fully indexed by CAS Registry Numbers. Compounds are now grouped to make navigation easier and literature references for all substances and techniques have been added, and ambiguous alternate names and cross references have been removed.
* The only comprehensive chemical purification reference, a market leader since 1966, Amarego delivers essential information for research and industrial chemists, pharmacists and engineers: '... (it) will be the most commonly used reference book in any chemical or biochemical laboratory' (MDPI Journal)
* An essential lab practice and proceedures manual. Improves efficiency, results and safety by providing critical information for day-to-day lab and processing work. Improved, clear organization and new indexing delivers accurate, reliable information on processes and techniques of purification along with detailed physical properties.
* The Sixth Edition has been reorganised and is fully indexed by CAS Registry Numbers; compounds are now grouped to make navigation easier; literature references for all substances and techniques have been added; ambiguous alternate names and cross references removed; new chemical products and processing techniques are covered; hazards and safety remain central to the book.


Wilfred L. F. Armarego graduated BSc (Hons) in 1953 and PhD from the University of London in 1956 and came to Australia in that year. After two years at the Central Research Laboratories (ICIANZ) in Melbourne, where he worked on plant growth substances, and one year on potentially carcinogenic polycyclic aromatic hydrocarbons at the University of Melbourne as Senior Demonstrator in Organic Chemistry, he joined the Department of Medical Chemistry as a Research Fellow in 1960. He became a Fellow in 1963 and was awarded a DSc degree (London) in 1968. He was promoted to Senior Fellow in 1967 and began research work on the biochemistry and molecular biology of pteridine-requiring enzymes related to the inherited metabolic disease phenylketonuria and its variants. He was head of the Protein Biochemistry Group and Pteridine Biochemistry Laboratory until his retirement in 1996. He is now a visiting fellow at the John Curtin School of Medical Research, and member of the editorial boards of 'Medicinal Research Reviews' and 'Pteridines' journals.

Autoren/Hrsg.

Armarego, W. L. F.

Chai, Christina

Inhaltsverzeichnis

1;Front Cover;1
2;Purification of Laboratory Chemicals;4
3;Copyright Page;5
4;CONTENTS;6
5;Preface to the Sixth Edition;13
6;Preface to the First Edition;15
7;Preface to the Second Edition;15
8;Preface to the Third Edition;15
9;Preface to the Fourth Edition;16
10;Preface to the Fifth Edition;17
11;CHAPTER 1. COMMON PHYSICAL TECHNIQUES USED IN PURIFICATION;18
11.1;INTRODUCTION;18
11.2;THE QUESTION OF PURITY;18
11.3;SAFETY PRECAUTIONS ASSOCIATED WITH THE PURIFICATION OF LABORATORY CHEMICALS;21
11.4;METHODS OF PURIFICATION OF REAGENTS AND SOLVENTS;24
11.5;TABLES;51
11.5.1;TABLE 1. SOME COMMON IMMISCIBLE OR SLIGHTLY MISCIBLE PAIRS OF SOLVENTS;51
11.5.2;FIGURE 1. NOMOGRAM;52
11.5.3;TABLE 2A. PREDICTED EFFECT OF PRESSURE ON BOILING POINT;53
11.5.4;TABLE 2B. PREDICTED EFFECT OF PRESSURE ON BOILING POINT;54
11.5.5;TABLE 3. HEATING BATHS;55
11.5.6;TABLE 4. WHATMAN FILTER PAPERS;55
11.5.7;TABLE 5. MICRO FILTERS;56
11.5.8;TABLE 6. COMMON SOLVENTS USED IN RECRYSTALLISATION;57
11.5.9;TABLE 7. PAIRS OF MISCIBLE SOLVENTS;57
11.5.10;TABLE 8. MATERIALS FOR COOLING BATHS;58
11.5.11;TABLE 9. LIQUIDS FOR STATIONARY PHASES IN GAS CHROMATOGRAPHY;59
11.5.12;TABLE 10. METHODS OF VISUALISATION OF TLC SPOTS;59
11.5.13;TABLE 11. GRADED ADSORBENTS AND SOLVENTS;60
11.5.14;TABLE 12. REPRESENTATIVE ION-EXCHANGE RESINS;60
11.5.15;TABLE 13. MODIFIED FIBROUS CELLULOSES FOR ION-EXCHANGE;60
11.5.16;TABLE 14. BEAD FORM ION-EXCHANGE PACKAGINGS;61
11.5.17;TABLE 15. LIQUIDS FOR DRYING PISTOLS;61
11.5.18;TABLE 16. VAPOUR PRESSURES (mm Hg) OF SATURATED AQUEOUS SOLUTIONS IN EQUILIBRIUM WITH SOLID SALTS;62
11.5.19;TABLE 17. DRYING AGENTS FOR CLASSES OF COMPOUNDS;63
11.5.20;TABLE 18. STATIC DRYING FOR SELECTED LIQUIDS (25°C);63
11.5.21;TABLE 19. AQUEOUS BUFFERS;64
11.5.22;TABLE 20. SOLUBILITY COEFFICIENTS OF AIR AT 1atm IN WATER;65
11.5.23;TABLE 21. SOLUBILITY COEFFICIENTS OF O2 AT 1atm IN WATER;65
11.5.24;TABLE 22. BUNSEN COEFFICIENTS (ß) OF GASES AT 1atm IN ORGANIC SOLVENTS AT 20°C;65
11.5.25;TABLE 23. OSTWALD COEFFICIENTS (l)/L OF O2 AT 1atm IN AQUEOUS SOLUTIONS AT 25°C;66
11.5.26;TABLE 24. SOLUBILITIES OF HCl AND NH3 AT 760mm (g/100g OF SOLUTION);67
11.5.27;TABLE 25. BOILING POINTS OF SOME USEFUL GASES AT 760 mm;67
11.5.28;TABLE 26. PREFIXES FOR QUANTITIES;67
11.6;BIBLIOGRAPHY;68
12;CHAPTER 2. CHEMICAL METHODS USED IN PURIFICATION;78
12.1;GENERAL REMARKS;78
12.2;REMOVAL OF TRACES OF METALS FROM REAGENTS;78
12.3;USE OF METAL HYDRIDES;80
12.4;PURIFICATION via DERIVATIVES;81
12.5;GENERAL METHODS FOR THE PURIFICATION OF CLASSES OF COMPOUNDS;85
12.6;GENERAL PROCEDURES FOR THE PURIFICATION OF SOME CLASSES OF ORGANIC COMPOUNDS;86
12.7;BIBLIOGRAPHY;95
13;CHAPTER 3. THE FUTURE OF PURIFICATION;97
13.1;INTRODUCTION;97
13.2;ORGANOCATALYSIS;97
13.3;MICROWAVE TECHNOLOGIES;98
13.4;SOLID PHASE SYNTHESIS;98
13.5;ALTERNATIVE SOLVENTS;100
13.6;BIBLIOGRAPHY;102
14;CHAPTER 4. PURIFICATION OF ORGANIC CHEMICALS;105
14.1;INTRODUCTION;105
14.2;ALIPHATIC COMPOUNDS;106
14.3;ALICYCLIC COMPOUNDS;211
14.4;AROMATIC COMPOUNDS;240
14.5;HETEROCYCLIC COMPOUNDS;370
15;CHAPTER 5. PURIFICATION OF INORGANIC AND METAL-ORGANIC CHEMICALS (Including Organic compounds of B, Bi, P, Se, Si, and ammonium andmetal salts of organic acids);462
15.1;INTRODUCTION;462
15.2;INORGANIC COMPOUNDS;463
15.3;METAL-ORGANIC COMPOUNDS;522
16;CHAPTER 6. PURIFICATION OF BIOCHEMICALS AND RELATED PRODUCTS;594
16.1;INTRODUCTION;594
16.2;AMINO ACIDS and PEPTIDES;600
16.3;PROTEINS, ENZYMES, DNA and RNA;624
16.4;CAROTENOIDS;642
16.5;CARBOHYDRATES;648
16.6;STEROIDS;667
16.7;MISCELLANEOUS COMPOUNDS;679
17;GENERAL SUBJECT INDEX;726
18;CAS REGISTRY NUMBERS INDEX;734

Leseproben

CHAPTER 2 CHEMICAL METHODS USED IN PURIFICATION GENERAL REMARKS
Greater selectivity in purification can often be achieved by making use of differences in chemical properties between the substance to be purified and the contaminants. Unwanted metal ions may be removed by precipitation in the presence of a collector (see below). Sodium borohydride and other metal hydrides transform organic peroxides and carbonyl-containing impurities such as aldehydes and ketones in alcohols and ethers. Many classes of organic chemicals can be purified by conversion into suitable derivatives, followed by regeneration. This chapter describes relevant procedures. REMOVAL OF TRACES OF METALS FROM REAGENTS
METAL IMPURITIES
The presence of metal contaminants in reagents may sometimes affect the chemical or biochemical outcomes of an experiment. In these cases, it is necessary to purify the reagents used. Metal (and other) impurities can be determined qualitatively and quantitatively by atomic absorption spectroscopy (AAA), x-ray photoelectron spectroscopy (XPS), various mass spectrometric methods and/or inductively coupled plasma mass spectrometry (ICP-MS) (see Chapter 1, Question of Purity) and the required purification procedures can be formulated. Metal impurities in organic compounds are usually in the form of ionic salts or complexes with organic compounds and very rarely in the form of free metal. If they are present in the latter form then they can be removed by crystallising the organic compound (whereby the insoluble metal can be removed by filtration), or by distillation in which case the metal remains behind with the residue in the distilling flask. If the impurities are in the ionic or complex forms, then extraction of the organic compound in a suitable organic solvent with aqueous acidic or alkaline solutions will reduce their concentration to acceptable levels. When the metal impurities are present in inorganic compounds as in metals or metal salts, then advantage of the differences in chemical properties should be taken. Properties of the impurities like the solubility, the solubility product (product of the metal ion and the counter-ion concentrations), the stability constants of the metal complexes with organic complexing agents and their solubilities in organic solvents should be considered. Alternatively the impurities can be masked by the addition of complexing agents which could lower the concentration of the metal ion impurities to such low levels that they would not interfere with the main compound (see complexation below). Specific procedures and examples are provided below. DISTILLATION
Reagents such as water, ammonia, hydrochloric acid, nitric acid, perchloric acid, and sulfuric acid can be purified via distillation (preferably under reduced pressure and particularly with perchloric acid) using an all-glass still. Isothermal distillation is convenient for ammonia: a beaker containing concentrated ammonia is placed alongside a beaker of distilled water for several days in an empty desiccator so that some of the ammonia distils over into the water. The redistilled ammonia should be kept in polyethylene or paraffin-waxed bottles. Hydrochloric acid can be purified in the same way. To ensure the absence of metal contaminants from some salts (e.g. ammonium acetate), it may be more expedient to synthesise the salts using distilled components rather than to attempt to purify the salts themselves. SCAVENGER RESINS AND OTHER SUPPORTS
There is now an extensive range of supported reactants that use resins, silica, carbons etc, to clean up reactions prior to final purification and is gaining favour in the laboratory. [See section on “Scavenger Resins” in Chapter 3, at the ends of the sections on “Preparation of other adsorbents”, “FPLC” and “HPLC”.] USE OF ION-EXCHANGE RESINS
Application of ion-exchange columns has greatly facilitated the removal of heavy metal ions such as Cu2+, Zn2+ and Pb2+ from aqueous solutions of many reagents. Thus, sodium salts and sodium hydroxide can be purified by passage through a column of a cation-exchange resin in its sodium form, prepared by washing the resin with 0.1M aqueous NaOH then washing with water until the pH of the effluent is ~7. Similarly, for acids, a resin in its H+ form [prepared by washing the column with 0.1M aqueous mineral acid (HCl, H2SO4) followed by thorough washing with water until the effluent has pH ~7 is used]. In some cases, where metals form anionic complexes, they can be removed by passage through an anion-exchange resin. Iron in hydrochloric acid solution can be removed in this way. Ion-exchange resins are also useful for demineralising biochemical preparations such as proteins. Removal of metal ions from protein solutions using polystyrene-based resins, however, may lead to protein denaturation. This difficulty may be avoided by using a weakly acidic cation exchanger such as Bio-Rex 70. Heavy metal contamination of pH buffers can be removed by passage of the solutions through a Chelex X-100 column. For example when a solution of 0.02M HEPES [4-(2-Hydroxyethyl)piperazine-1-ethanesulfonic acid] containing 0.2M KCl (1L, pH 7.5) alone or with calmodulin, is passed through a column of Chelex X-100 (~60g) in the K+ form, the level of Ca2+ ions falls to less than 2 x 10-7 M as shown by atomic absorption spectroscopy. Such solutions should be stored in polyethylene containers that have been washed with boiling deionised water (5minutes) and rinsed several times with deionised water. TES [N,N,N',N'-Tetraethylsulfamide] and TRIS [Tris-(hydroxymethyl)aminomethane] have been similarly decontaminated from metal ions. Water, with very low concentrations of ionic impurities (and approaching conductivity standards), is very readily obtained by percolation through alternate columns of cation- and anion-exchange resins, or through a mixed-bed resin, and many commercial devices are available for this purpose. For some applications, this method is unsatisfactory because the final deionised water may contain traces of organic material after passage through the columns. However, organic matter can be removed by using yet another special column in series for this purpose (see Milli Q water preparation, Millipore Corpn., ). PRECIPITATION
In removing traces of impurities by precipitation, it is necessary to include a material to act as a collector of the precipitated substance so as to facilitate its removal by filtration or decantation. The following are a few examples: Removal of lead contaminants
Aqueous hydrofluoric acid can be freed from lead by adding 1mL of 10% strontium chloride per 100mL of acid, lead being co-precipitated as lead fluoride with the strontium fluoride. If the hydrofluoric acid is decanted from the precipitate and the process repeated, the final lead content in the acid is less than 0.003ppm. Similarly, lead can be precipitated from a nearly saturated sodium carbonate solution by adding 10% strontium chloride dropwise (1-2mL per 100mL) followed by filtration. (If the sodium carbonate is required as a solid, the solution can be evaporated to dryness in a platinum dish.) Removal of lead from potassium chloride uses precipitation as lead sulfide by bubbling H2S, followed, after filtration, by evaporation and recrystallisation of the potassium chloride. Removal of iron contaminants
Iron contaminants have been removed from potassium thiocyanate solutions by adding a slight excess of an aluminium salt, then precipitating aluminum and iron as their hydroxides by adding a few drops of ammonia. Iron is also carried down on the hydrated manganese dioxide precipitate formed in cadmium chloride or cadmium sulfate solutions by adding 0.5% aqueous potassium permanganate (0.5mL per 100mL of solution), sufficient ammonia to give a slight precipitate, and 1mL of ethanol. The solution is heated to boiling to coagulate the precipitate, then filtered. Ferrous ion can be removed from copper solutions by adding some hydrogen peroxide to the solution to oxidise the iron, followed by precipitation of ferric hydroxide by adding a small amount of sodium hydroxide. Removal of other metal contaminants
Traces of calcium can be removed from solutions of sodium salts by precipitation at pH 9.5-10 as the 8-hydroxyquinolinate. The excess 8-hydroxyquinoline acts as a collector and is extracted out with an organic solvent. EXTRACTION
In some cases, a simple solvent extraction is sufficient to remove a particular impurity. For example, traces of gallium can be removed from titanous chloride in hydrochloric acid by extraction with diisopropyl ether. Similarly, ferric chloride can be removed from aluminium chloride solutions containing hydrochloric acid by extraction with diethyl ether. Usually, however, it is necessary to extract an undesired metal with an organic solvent in the presence of a suitable complexing agent such as dithizone (diphenylthiocarbazone) or sodium diethyl dithiocarbamate. When the former is used, weakly alkaline solutions of the substance containing the metal impurity are extracted with dithizone in chloroform (at about 25mg/L of chloroform) or carbon tetrachloride until the colour of some fresh dithizone solution remains unchanged after shaking. Dithizone complexes metals more strongly in weakly alkaline solutions. Excess dithizone in the aqueous medium is removed by extracting with the pure solvent (chloroform or carbon tetrachloride), the last traces of which, in turn, are removed by aeration. This method...