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ELECTROLYTES, EMF, AND CHEMICAL EQUILIBRIUM 8.115 8.4.1 Electrometric Measurement of pH The pH value is defined for an aqueous solution in an operational (arbitrary but reproducible) manner according to the Bates-Guggenheim convention: pHx pHs Ex Es 2.3026RT/F where R is the gas constant per mole, T is the temperature on the absolute scale, and F is the faraday. The pH x ofthe unknown medium is calculated from that ofan accepted standard (pH s ) and the measured difference in the emf (E) ofthe electrode combination when the standard solution is removed from the cell and replaced by the unknown. The double vertical line marks a liquid junction. Electrodes as fabricated exhibit variations in the reproducibility of the reference electrode, in the liquid-junction potential, and, with glass electrodes, in the asymmetry potential. These differences are all eliminated in the standardizing procedure with standard reference pH buffers. (See R. G. Bates, Determination of pH, Theory and Practice, Wiley, New York, 1964.) Electrode reversible Standard reference Salt bridge Reference to hydrogen ions buffer or unknown (KCl. 3.5M electrode solution or saturated) An electrometric pH-measurement system consists of(1) pH-responsive electrode, (2) reference electrode, and (3) potential-measuring device—some form of high-impedance electronic voltmeter for glass-electrode combinations and this or a potentiometer arrangement for other pH-responsive electrodes. Electronic pH meters are simply voltmeters with scale divisions in pH units which are equivalent to the values of2.3026RT/F (in mV) per pH unit. Values ofthis function at several temperatures are given in Table 8.22. There is no compensation incorporated in the meter for the changes in pH of the test solution as a function of temperature. Reliability of an indicator–reference electrode combination must be ascertained by standardization ofthe pH meter with one standard buffer and checking the pH response by immersing the combination in a second and different reference buffer. The temperature compensator on a pH meter varies the instrument definition ofa pH unit from 54.20 mV at 0C to perhaps 66.10 mV at 60C. This permits one to measure the pH ofthe sample (and reference buffer standard) at its actual temperature and thus avoid error due to dissociation equilibria and to junction potentials which have significant temperature coefficients. TABLE 8.22 In millivolts. Values of2.3026RT/F at Several Temperatures t C Value t C Value t C Value t C Value 0 54.197 25 59.157 50 64.118 80 70.070 5 55.189 30 60.149 55 65.110 85 71.062 10 56.181 35 61.141 60 66.102 90 72.054 15 57.173 38 61.737 65 67.094 95 73.046 18 57.767 40 62.133 70 68.086 100 74.038 20 58.165 45 63.126 75 69.078 Report ofthe National Academy ofSciences: National Research Council Committee ofFundamental Constants, 1963.
8.116 SECTION 8 8.5 INDICATORS TABLE 8.23 Indicators for Aqueous Acid-Base Titrations This table lists some selected indicators. The pH range or transition interval given in the third column may vary appreciably from one observer to another, and, in addition, it is affected by ionic strength, temperature, and illumination; consequently only approximate values can be given. They should be considered to refer to solutions having low ionic strengths and a temperature ofabout 25C. In the fourth column the pK a (log K a ) ofthe indicator as determined spectrophotometrically is listed. In the fifth column the wavelength of maximum absorption is given first for the acidic and then for the basic form of the indicator, and the same order is followed in giving the colors in the sixth column. The abbreviations used to describe the colors ofthe two forms ofthe indicator are as follows: B, blue G, green V, violet P, purple Y, yellow R, red O, orange O-Br, orange-brown C, colorless Indicator Chemical name pH range pK a max ,nm Color change Cresol red o-Cresolsulfonephthalein 0.2–1.8 R-Y (acid range) Cresol purple m-Cresolsulfonephthalein 1.2–2.8 1.51 533, — R-Y (acid range) Thymol blue Thymolsulfonephthalein 1.2–2.8 1.65 544, 430 R-Y (acid range) Tropeolin OO Diphenylamino-p-benzene 1.3–3.2 2.0 527, — R-Y sodium sulfonate 2,6-Dinitrophenol 2,6-Dinitrophenol 2.4–4.0 3.69 C-Y 2,4-Dinitrophenol 2,4-Dinitrophenol 2.5–4.3 3.90 C-Y Methyl yellow Dimethylaminoazobenzene 2.9–4.0 3.3 508, — R-Y Methyl orange Dimethylaminoazobenzene 3.1–4.4 3.40 522, 464 R-O sodium sulfonate Bromophenol blue Tetrabromophenolsulfonephthalein 3.0–4.6 3.85 436, 592 Y-BV Bromocresol green Tetrabromo-m-cresolsulfonephthalein 4.0–5.6 4.68 444, 617 Y-B Methyl red o-Carboxybenzeneazodimethylaniline 4.4–6.2 4.95 530, 427 R-Y Chlorophenol red Dichlorophenolsulfonephthalein 5.4–6.8 6.0 —, 573 Y-R Bromocresol purple Dibromo-o-cresolsulfonephthalein 5.2–6.8 6.3 433, 591 Y-P Bromophenol red Dibromophenolsulfonephthalein 5.2–6.8 —, 574 Y-R p-Nitrophenol p-Nitrophenol 5.3–7.6 7.15 320, 405 C-Y Bromothymol blue Dibromothymolsulfonephthalein 6.2–7.6 7.1 433, 617 Y-B Neutral red Aminodimethylaminotoluphenazonium 6.8–8.0 7.4 R-Y chloride Phenol red Phenolsulfonephthalein 6.4–8.0 7.9 433, 558 Y-R m-Nitrophenol m-Nitrophenol 6.4–8.8 8.3 —, 570 C-Y
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LANGE'S HANDBOOK OF CHEMISTRY John
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Grateful acknowledgment is hereby m
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PREFACE TO FIFTEENTH EDITION This n
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PREFACE TO FIFTEENTH EDITION ix inv
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xii PREFACE TO FOURTEENTH EDITION l
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PREFACE TO FIRST EDITION This book
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For the detailed contents of any se
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1.2 SECTION 1 is derived from the G
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1.4 SECTION 1 rather than methylide
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1.6 SECTION 1 Styrene Toluene Xylen
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1.8 SECTION 1 TABLE 1.2 Fused Polyc
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1.10 SECTION 1 1.1.1.6 Bridged Hydr
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1.12 SECTION 1 TABLE 1.4 Suffixes f
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1.14 SECTION 1 TABLE 1.5 Trivial Na
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1.16 SECTION 1 TABLE 1.6 Trivial Na
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1.18 SECTION 1 Selection of the pri
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1.20 SECTION 1 attached to one anot
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1.22 SECTION 1 When side chains of
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1.24 SECTION 1 heterocyclic structu
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1.26 SECTION 1 Bivalent radicals of
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1.28 SECTION 1 Complex linear polya
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1.30 SECTION 1 TABLE 1.11 Names of
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1.32 SECTION 1 hydroxyamino- to the
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1.34 SECTION 1 may be named (1) by
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1.36 SECTION 1 Examples are methyl
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1.38 SECTION 1 tuted acid, respecti
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1.40 SECTION 1 FIGURE 1.2 Newman pr
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1.42 SECTION 1 from the ring are kn
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1.44 SECTION 1 FIGURE 1.11 Two isom
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1.46 SECTION 1 Chiral Center. The c
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1.48 SECTION 1 FIGURE 1.15 Isomers
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1.50 SECTION 1 entries to bring tog
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1.52 SECTION 1 TABLE 1.13 Names and
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1.60 SECTION 1 TABLE 1.14 Empirical
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2.2 SECTION 2 2.3.6 Student’s Dis
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2.4 SECTION 2 TABLE 2.1 Fundamental
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2.6 SECTION 2 TABLE 2.1 Fundamental
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2.8 SECTION 2 TABLE 2.2 Physical an
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2.10 SECTION 2 TABLE 2.2 Physical a
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2.24 SECTION 2 TABLE 2.3 Mathematic
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2.26 SECTION 2 TABLE 2.6 Abbreviati
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2.36 SECTION 2 TABLE 2.7 Conversion
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2.54 SECTION 2 TABLE 2.8 Temperatur
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2.66 SECTION 2 2.1.1 Conversion of
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2.68 SECTION 2 Oleometer. A hydrome
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2.70 SECTION 2 Example 3. 25 1.2500
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2.72 SECTION 2 TABLE 2.9 Barometer
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2.74 SECTION 2 TABLE 2.9 Barometer
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2.76 SECTION 2 TABLE 2.10 Barometri
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2.78 SECTION 2 TABLE 2.12 Reduction
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2.80 SECTION 2 TABLE 2.12 Reduction
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2.82 SECTION 2 TABLE 2.13 Viscosity
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2.84 SECTION 2 TABLE 2.14 Conversio
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2.86 SECTION 2 TABLE 2.15 Hydromete
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2.88 SECTION 2 TABLE 2.17 Correctio
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2.90 SECTION 2 TABLE 2.18 Pressure
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2.96 SECTION 2 TABLE 2.20 Values of
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2.98 SECTION 2 TABLE 2.21 Transmitt
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2.100 SECTION 2 TABLE 2.21 Transmit
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2.102 SECTION 2 2.2 MATHEMATICAL TA
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2.104 SECTION 2 TABLE 2.23 Derivati
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2.106 SECTION 2 TABLE 2.24 Integral
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2.108 SECTION 2 TABLE 2.24 Integral
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2.110 SECTION 2 Regular Polygon of
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2.112 SECTION 2 A h[0.4(y y ) 1.
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2.114 SECTION 2 2.2.3.1 Signs of th
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2.116 SECTION 2 x2 x3 x4 x5 ln(1 x
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2.118 SECTION 2 2.3.2 Errors in Qua
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2.120 SECTION 2 The breadth or spre
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2.122 SECTION 2 TABLE 2.26b Areas U
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2.124 SECTION 2 The distribution of
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2.126 SECTION 2 Should there be mor
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2.128 SECTION 2 Example 10 Six samp
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2.130 SECTION 2 2.3.9 The F Statist
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TABLE 2.29 F Distribution (Continue
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2.134 SECTION 2 mathematical treatm
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2.136 SECTION 2 The confidence limi
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2.138 SECTION 2 situation where rel
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3.2 SECTION 3 The alphabetical orde
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3.4 SECTION 3 When it is required t
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3.6 SECTION 3 PO phosphoryl SeO sel
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3.8 SECTION 3 3.1.5 Acids 3.1.5.1 A
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3.10 SECTION 3 3.1.6.6 Multiplicati
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3.12 SECTION 3 3.2 PHYSICAL PROPERT
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TABLE 3.2 Physical Constants of Ino
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3.62 SECTION 3 TABLE 3.3 Synonyms a
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SECTION 4 PROPERTIES OF ATOMS, RADI
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4.3 Fermium Fm 100 [Rn] 5f 12 7s 2
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Silver (argentum) Ag 47 [Kr] 4d 10
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PROPERTIES OF ATOMS,RADICALS,AND BO
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PROPERTIES OF ATOMS, RADICALS, AND
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SECTION 5 PHYSICAL PROPERTIES 5.1 S
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PHYSICAL PROPERTIES 5.3 5.1 SOLUBIL
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TABLE 5.1 Solubility of Gases in Wa
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TABLE 5.1 Solubility of Gases in Wa
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TABLE 5.2 Solubilities of Inorganic
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formateBa(CHO 2 ) 2 26.2 28.0 29.9
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(III) sulfateCe 2 (SO 4 ) 3 ·9H 2
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iodidePbI 2 0.044 0.056 0.069 0.090
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Nickel sulfateNiSO 4 ·6H 2 O (pale
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Praseodymium bromatePr(BrO 3 ) 3 55
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formate NaCHO 2 43.9 62.5 81.2 102
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Uranyl nitrate UO 2 (NO 3 ) 2 98 10
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PHYSICAL PROPERTIES 5.25 TABLE 5.3
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PHYSICAL PROPERTIES 5.57 5.3 BOILIN
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TABLE 5.12 Ternary Azeotropic Mixtu
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TABLE 5.12 Ternary Azeotropic Mixtu
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PHYSICAL PROPERTIES 5.83 5.4 FREEZI
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PHYSICAL PROPERTIES 5.87 5.5 DENSIT
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PHYSICAL PROPERTIES 5.89 dt Dt P
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PHYSICAL PROPERTIES 5.135 5.6.1 Ref
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PHYSICAL PROPERTIES 5.137 where the
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PHYSICAL PROPERTIES 5.139 5.7 COMBU
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Temperature, C Substance 40 20 0 20
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PHYSICAL PROPERTIES 5.171 This equa
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SECTION 6 THERMODYNAMIC PROPERTIES
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THERMODYNAMICPROPERTIES 6.3 6.1.1.2
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THERMODYNAMICPROPERTIES 6.5 A gener
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THERMODYNAMICPROPERTIES 6.7 TABLE 6
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THERMODYNAMICPROPERTIES 6.9 TABLE 6
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THERMODYNAMICPROPERTIES 6.11 TABLE
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THERMODYNAMIC PROPERTIES 6.21 TABLE
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THERMODYNAMIC PROPERTIES 6.101 TABL
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THERMODYNAMIC PROPERTIES 6.143 The
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SECTION 7 SPECTROSCOPY 7.1 X-RAY ME
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SPECTROSCOPY 7.3 TABLE 7.1 Waveleng
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SPECTROSCOPY 7.9 TABLE 7.3 Critical
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SPECTROSCOPY 7.11 TABLE 7.4 X-Ray E
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SPECTROSCOPY 7.13 Emission line K 1
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SPECTROSCOPY 7.15 TABLE 7.7 Analyzi
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SPECTROSCOPY 7.17 TABLE 7.8 Mass Ab
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SPECTROSCOPY 7.19 TABLE 7.9 Electro
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SPECTROSCOPY 7.21 TABLE 7.11 Absorp
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SPECTROSCOPY 7.23 TABLE 7.13 Solven
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SPECTROSCOPY 7.25 7.3 FLUORESCENCE
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SPECTROSCOPY 7.27 TABLE 7.16 Fluore
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SPECTROSCOPY 7.29 TABLE 7.18 Detect
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SPECTROSCOPY 7.35 TABLE 7.19 Sensit
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SPECTROSCOPY 7.37 TABLE 7.19 Sensit
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SPECTROSCOPY 7.39 In terms of m ,
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SPECTROSCOPY 7.41 The ionization co
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SPECTROSCOPY 7.67 TABLE 7.28 Infrar
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7.69
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SPECTROSCOPY 7.71 7.6 RAMAN SPECTRO
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SPECTROSCOPY 7.73 TABLE 7.30 Raman
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SPECTROSCOPY 7.89 7.7 NUCLEAR MAGNE
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SPECTROSCOPY 7.91 TABLE 7.41 Nuclea
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SPECTROSCOPY 7.93 TABLE 7.42 Proton
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SPECTROSCOPY 7.95 TABLE 7.44 Estima
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SPECTROSCOPY 7.97 TABLE 7.46 Proton
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SPECTROSCOPY 7.99 TABLE 7.48 Solven
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SPECTROSCOPY 7.101 TABLE 7.49 Carbo
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SPECTROSCOPY 7.103 TABLE 7.51 Effec
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SPECTROSCOPY 7.107 TABLE 7.56 One-B
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SPECTROSCOPY 7.113 TABLE 7.63 Nitro
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SPECTROSCOPY 7.115 TABLE 7.64 Nitro
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SPECTROSCOPY 7.117 TABLE 7.69 Fluor
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SPECTROSCOPY 7.119 TABLE 7.72 Silic
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SPECTROSCOPY 7.121 TABLE 7.73 Phosp
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SPECTROSCOPY 7.123 TABLE 7.74 Phosp
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SPECTROSCOPY 7.125 when z 3 and y
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SPECTROSCOPY 7.127 Masses 19 and 31
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SPECTROSCOPY 7.129 TABLE 7.76 Conde
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SECTION 8 ELECTROLYTES, ELECTROMOTI
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ELECTROLYTES, EMF, AND CHEMICAL EQU
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TABLE 8.7 Proton Transfer Reactions
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TABLE 8.7 Proton Transfer Reactions
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KCl 127.3 124.4 122.4 115.8 112.0 1
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NaIO 3 75.2 72.6 70.9 64.4 60.5 1
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9.2 SECTION 9 9.1 LINEAR FREE ENERG
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9.4 SECTION 9 TABLE 9.1 Hammett and
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9.6 SECTION 9 TABLE 9.1 Hammett and
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9.8 SECTION 9 TABLE 9.3 pK a and Rh
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10.2 SECTION 10 10.4.6 Polyacrylate
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10.4 SECTION 10 10.2 ADDITIVES TO P
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10.6 SECTION 10 injection molding.
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10.8 SECTION 10 10.3 FORMULAS AND K
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10.10 SECTION 10 Key properties of
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10.12 SECTION 10 10.3.8 Fluorocarbo
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10.14 SECTION 10 10.3.11 Phenolics
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10.16 SECTION 10 The resin has the
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10.18 SECTION 10 10.3.19 Polyuretha
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10.20 SECTION 10 10.3.22 Sulfones B
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TABLE 10.2 Properties of Commercial
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10.58 SECTION 10 10.4 FORMULAS AND
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10.60 SECTION 10 10.4.8 Polychlorop
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10.62 SECTION 10 Styrene-butadiene
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10.5 CHEMICAL RESISTANCE TABLE 10.4
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10.6 GAS PERMEABILITY TABLE 10.5 Ga
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TABLE 10.5 Gas Permeability Constan
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TABLE 10.7 Constants ofFats and Oil
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TABLE 10.8 Constants ofWaxes Wax Me
Page 1092:
SECTION 11 PRACTICAL LABORATORY INF
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11.4 SECTION 11 TABLE 11.2 Molecula
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11.6 SECTION 11 A saturated aqueous
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11.8 SECTION 11 TABLE 11.6 Relative
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11.10 SECTION 11 11.3 BOILING POINT
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11.12 SECTION 11 TABLE 11.8 Organic
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11.14 SECTION 11 TABLE 11.9 Molecul
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11.4 SEPARATION METHODS TABLE 11.11
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11.18 SECTION 11 TABLE 11.12 Solven
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11.20 SECTION 11 TABLE 11.12 Solven
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TABLE 11.13 McReynolds’ Constants
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TABLE 11.13 McReynolds’ Constants
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11.26 SECTION 11 11.4.1 McReynolds
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11.28 SECTION 11 11.4.2.2 Partition
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11.30 SECTION 11 FIGURE 11.2 Band a
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11.32 SECTION 11 11.4.3 Ion-Exchang
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11.34 SECTION 11 TABLE 11.16 Guide
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11.36 SECTION 11 TABLE 11.16 Guide
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11.38 SECTION 11 TABLE 11.18 Relati
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11.40 SECTION 11 distribution coeff
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11.42 SECTION 11 TABLE 11.19 Gravim
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11.68 SECTION 11 TABLE 11.20 Elemen
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11.70 SECTION 11 TABLE 11.22 Common
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11.72 SECTION 11 TABLE 11.25 Tolera
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11.74 SECTION 11 TABLE 11.26 Heatin
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11.76 SECTION 11 TABLE 11.28 Titrim
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11.84 SECTION 11 appears becomes le
Page 1177 and 1178:
11.86 SECTION 11 TABLE 11.29 Equati
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11.88 SECTION 11 TABLE 11.29 Equati
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11.90 SECTION 11 The more stable th
Page 1183 and 1184:
11.92 SECTION 11 11.6.6.2.5 Buffer
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11.94 SECTION 11 TABLE 11.30 Standa
Page 1187 and 1188:
TABLE 11.32 Properties and Applicat
Page 1189 and 1190:
11.98 SECTION 11 TABLE 11.36 Maskin
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11.100 SECTION 11 TABLE 11.37 Anion
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11.102 SECTION 11 TABLE 11.39 Amino
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11.104 SECTION 11 TABLE 11.44 Facto
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11.106 SECTION 11 11.7 LABORATORY S
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11.108 SECTION 11 TABLE 11.48 Stand
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11.110 SECTION 11 Alizarin yellow G
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11.112 SECTION 11 Bromchlorophenol
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11.114 SECTION 11 p-Ethoxychrysoidi
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11.116 SECTION 11 Mercurous nitrate
Page 1209 and 1210:
11.118 SECTION 11 Potassium carbona
Page 1211 and 1212:
11.120 SECTION 11 until the ammoniu
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11.122 SECTION 11 TABLE 11.49 TLV C
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Page 1221 and 1222:
11.130 SECTION 11 TABLE 11.50 Chemi
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Page 1227 and 1228:
Page 1229 and 1230:
11.138 SECTION 11 of water which is
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TABLE 11.55 Thermoelectric Values i
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TABLE 11.56 Type B Thermocouples: P
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TABLE 11.58 Type J Thermocouples: I
Page 1237 and 1238:
TABLE 11.60 Type N Thermocouples: N
Page 1239 and 1240:
TABLE 11.62 Type S Thermocouples: P
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11.150 SECTION 11 11.11 CORRECTION
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Index Terms Links 2 Acid-base indic
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Index Terms Links 4 Alkynes, nomenc
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Index Terms Links 6 Aurintricarboxy
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Index Terms Links 8 Boron-11 chemic
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Index Terms Links 10 Cellulose acet
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Index Terms Links 12 Collective ino
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Index Terms Links 14 Degree Fahrenh
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Index Terms Links 16 Electrical res
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Index Terms Links 18 Equivalent wei
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Index Terms Links 20 Fluorocarbon p
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Index Terms Links 22 Halogenated hy
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Index Terms Links 24 Impact strengt
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Index Terms Links 26 Kα 1 lines, m
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Index Terms Links 28 Melmine phenol
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Index Terms Links 30 Neon-neon bond
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Index Terms Links 32 One-tailed tes
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Index Terms Links 34 Physical chemi
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Index Terms Links 36 Polyolefin the
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Index Terms Links 38 Pyridine: bina
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Index Terms Links 40 Rho values: fo
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Index Terms Links 42 Single-bond ra
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Index Terms Links 44 Stereoisomers
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Index Terms Links 46 Tension, aqueo
Page 1289 and 1290:
Index Terms Links 48 Triethylenetet
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Index Terms Links 50 Water (Cont.)
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