PURIFICATION OF LABORATORY CHEMICALS

Wilfred L. F.Armarego Christina U Un Chai

COMMON PHYSICAL TECHNIQUES USED IN PURIFICATION INTRODUCTION THE QUESTION OF PURITY SOURCES OF IMPURITIES PRACTICES TO AVOID IMPURITIES Cleaning practice Sily lation of glassware and plasticware SAFETY PRECAUTIONS ASSOCIATED WITH THE PURIFICATION OF LABORATORY CHEMICALS SOME HAZARDS OF CHEMICAL MANIPULATION IN PURIFICATION AND RECOVERY OF RESIDUES Perchlorates and perchloric acid Peroxides Heavy -metal-containing explosives Strong acids Picric acid Reactive halides and anhydrides Salts and organic esters of some inorganic acids Sol vents

1
1 1 3 3 3 .4 4 5 5 5 5 6 6 6 6 6

METHODS

OF PURIFICATION EXTRACTION

OF REAGENTS

AND SOLVENTS

7 7 8 8 9 10 10 10 11 11

SOLVENT

AND DISTRIBUTION

DISTILLATION Techniques Distillation of liquid mixtures Types of distillation

The distilling flask Types of columns and packings Types of condensers Vacuum distillation Spinning-band distillation Steam distillation Azeotropic distillation Kugelrohr distillation Isopiestic or isothermal distillation
RECRYST ALLIS ATION Techniques

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12

13 13 14
14 14

Filtration
Solvents

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15

Choice of solvents Water Petroleum ethers Mixed solvents

Recrystallisation Zone refining from the melt

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17 17

CHROMATOGRAPHy Vapour phase chromatography Liquid chromatography

(GC or gas-liquid

chromatography)

Adsorption chromatography Thin layer chromatography (TLC) Paper chromatography Column chromatography Graded adsorbents and solvents Preparation and standardisation of alumina Preparation of other adsorbents Silica Diatomaceous earth Charcoal Cellulose Supelco products
Flash Chromatography (FC and HPFC) Paired- ion Chromatography (PIC) Ion-exchange Chromatography

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19 20 20 20
20 21 21 21 21 21 21 22 22 23

Ion-exchange Resins Ion-exchange celluloses and sephadex

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Sephadex Sepharose Cellex CM Cellex D Crystalline hydroxylapatite Gel filtration High performance liquid chromatography (HPLC) Other types of liquid chromatography Automated column chromatography ELECTROPHORESIS DRyING Removal of solvents Removal of water Intensity and capacity of common desiccants Suitability of individual desiccants Molecular sieves MISCELLANEOUS TECHNIQUES Freeze-pump-thaw and purging Vacuum lines, Schlenk and glovebox techniques PROPERTIES USEFUL IN PURIFICATION Ionisation constants - pK pK and temperature pK and solvent Sol ubilities of gases in liquids CHEMICAL AND BIOCHEMICAL SOURCES TABLES TABLE 1.

24 24 25 25 25 25 25 26 27 27 27 27 27 28 28 30 31 31 31 32 32 33 33 33 34 34

FIGURE 1. TABLE 2A. TABLE 2B. TABLE 3. TABLE 4. TABLE 5. TABLE 6. TABLE 7. TABLE 8. TABLE 9. TABLE TABLE TABLE TABLE TABLE 10. 11. 12. 13. 14.

SOME COMMON IMMISCIBLE OR SLIGHTLY MISCIBLE PAIRS OF SOLVENTS 34 NOMOGRAM 35 PREDICTED EFFECT OF PRESSURE ON BOILING POINT 36 PREDICTED EFFECT OF PRESSURE ON BOILING POINT 37 HEATING BATHS 38 WHA TMAN FILTER PAPERS 38 MICRO FILTERS 39 COMMON SOLVENTS USED IN RECRYSTALLISATION .40 PAIRS OF MISCIBLE SOLVENTS .40 MATERIALS FOR COOLING BATHS .41 LIQUIDS FOR STATIONARY PHASES IN GAS CHROMATOGRAPHy 42 METHODS OF VISUALISATION OF TLC SPOTS .42 GRADED ADSORBENTS AND SOLVENTS .43 REPRESENTATIVE ION-EXCHANGE RESINS .43 MODIFIED FIBROUS CELLULOSES FOR ION-EXCHANGE ...43 BEAD FORM ION-EXCHANGE PACKAGINGS .44

TABLE TABLE TABLE TABLE TABLE TABLE TABLE TABLE TABLE TABLE TABLE TABLE

15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26.

LIQUIDS FOR DRYING PISTOLS VAPOUR PRESSURES (mm Hg) OF SATURATED AQUEOUS SOLUTIONS IN EQUILIBRIUM WITH SOLID SALTS DRYING AGENTS FOR CLASSES OF COMPOUNDS STATIC DRYING FOR SELECTED LIQUIDS (25C) AQUEOUS BUFFERS SOLUBILITY COEFFICIENTS OF AIR AT 1atm IN WATER SOLUBILITY COEFFICIENTS OF O2 AT 1atm IN WATER BUNSEN COEFFICIENTS (~) OF GASES AT 1atm IN ORGANIC SOLVENTS AT 20C OSTWALD COEFFICIENTS (l)/L OF O2 AT 1atm IN AQUEOUS SOLUTIONS AT 25C SOLUBILITIES OF HCI AND NH3AT 760mm (g/lOOg OF SOLUTION) BOILING POINTS OF SOME USEFUL GASES AT 760 mm PREFIXES FOR QUANTITIES

.44 .45 46 46 47 .48 48 48 .49 50 50 50 51

BIBLIOGRAPHy

CHEMICAL METHODS USED IN PURIFICATION GENERAL REMARKS REMOVAL OF TRACES OF METALS FROM REAGENTS METAL IMPURITIES DISTILLATION SCAVENGER RESINS AND OTHER SUPPORTS USE OF ION EXCHANGE RESINS PRECIPITATION Removal of lead contaminants Removal of iron contaminants Removal of other metal contaminants EXTRACTION COMPLEXATION USE OF METAL HYDRIDES LITHIUM ALUMINIUM HYDRIDE CALCIUM HyDRIDE SODIUM BOROHYDRIDE POTASSIUM BOROHYDRIDE PURIFICATION via DERIV ATIVES ALCOHOLS ALDEHYDES AMINES Picrates

61 61 61 61 61 62 62 62 62 62 63 63 63 63 63 63 63 64 64 64 65 65 65

Salts Double salts N- Acetyl derivatives N- Tosy I derivatives AROMATIC HyDROCARBONS Adducts Sulfonation CARBOXYLIC ACIDS 4-Bromophenacy I esters Alkyl esters Salts HYDRO PEROXIDES KETONES Bisulfite adduct Semicarbazones PHENOLS Benzoates Acetates PHOSPHATE AND PHOSPHONATE ESTERS MISCELLANEOUS GENERAL METHODS FOR THE PURIFICATION OF CLASSES OF COMPOUNDS PROCEDURES CRITERIA OF PURITY GENERAL PROCEDURES FOR THE PURIFICATION OF SOME CLASSES OF ORGANIC COMPOUNDS ACETALS ACIDS Carboxylic acids Sulfonic acids Sulfinic acids ACID CHLORIDES ALCOHOLS Monohydric alcohols , Polyhydric alcohols ALDEHYDES AMI DES AMINES AMINO ACIDS ANHYDRIDES CAROTENOIDS ESTERS ETHERS HALIDES HyDROCARBONS IMIDES IMINO COMPOUNDS KETONES MACROMOLECULES NITRILES

65 66 66 66 66 66 66 66 66 66 67 67 67 67 67 67 67 68 68 68 68 68 69 69 70 70 70 70 70 71 71 71 71 71 71 72 72 72 72 73 73 74 74 75 75 75 75 75

NITRO COMPOUNDS NUCLEIC ACIDS PHENOLS POLYPEPTIDES AND PROTEINS QUINONES SALTS With metal ions With organic cations With sodium alkane sulfonates SULFUR COMPOUNDS Disulfides Sulfones Sulfoxides Thioethers (sulfides) Thiols Thiolsulfonates (disulfoxides)

76 76 76 76 76 76 76 77 77 77 77 77 77 77 77 77

THE FUTURE OF PURIFICATION INTRODUCTION ORGANOCATAL YSIS MICROWAVE TECHNOLOGIES SOLID PHASE SyNTHESIS SOLID PHASE PEPTIDE SYNTHESIS (SPPS) SOLID PHASE DEOXYRIBONUCLEOTIDE SYNTHESIS POLYMER SUPPORTED REACTANTS SCAVENGER RESINS COMBINATORIAL CHEMISTRy ALTERNATIVE SOLVENTS SUPERCRITICAL FLUIDS IONIC LIQUIDS FLUOROUS CHEMISTRY BIBLIOGRAPHy

80 80 80 81 81 82 82 82 82 83 83 83 84 84 85

PURIFICATION OF ORGANIC CHEMICALS INTRODUCTION ALIPHATIC COMPOUNDS ALICYCLIC COMPOUNDS AROMATIC COMPOUNDS HETEROCYCLIC COMPOUNDS 88 89 194 223 353

PURIFICATION

OF

INORGANIC

AND

METAL ORGANIC

CHEMICALS

(Including Organic compounds of B, Bi, P, Se, Si, and ammonium and metal salts of organic acids)
INTRODUCTION INORGANIC COMPOUNDS METAL-ORGANIC COMPOUNDS 445 446 505

PURIFICATION OF BIOCHEMICALS

AND RELATED PRODUCTS 577 583 607 625 631 650 662

INTRODUCTION AMINO ACIDS and PEPTIDES PROTEINS, ENZYMES, DNA and RNA CAROTENOIDS CARBOHyDRATES STEROIDS MISCELLANEOUS COMPOUNDS (including biologically useful reagents, Low-molecular-weight bioactive substances, antibiotics, coenzymes, vitamins, lipids, phospholipids, nucleosides, nucleotides and polynucleotides)