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Experiments in Physical Chemistry Experiments in Physical Chemistry Wodx] Carl W. Garland Joseph W. Nibler David P. Shoemaker This…
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gar28420_fm_i-x ix ic Confirming Pages This book is designed for use in a junior-level laboratory course in physical chemistry. It is…
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ic Rev. Confirming Pages References 89 before the regression. Make plots of the residuals in both cases and use the 95 percent P and F…
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Confirming Pages ic 90 Chapter Ill Use of Computers gar28420_ch03_068-090.indd Sec5:90 9. 10. 11. 12. 13. 14. 15. 16. S. Flugge, Practical…
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& Rev. Confirming Pages EXPERIMENTS 1. Gas Thermometry 2. Joule-Thomson Effect 3. Heatcapacity Ratios for Gases EXPERIMENT 1 Gas…
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92 Chapter IV Gases gar28420_ch04_091-118.indd 92 Rey. Confirming Pages ic In the original centigrade scale of temperature the two fixed…
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ic Rev. Confirming Pages Exp. 1 Gas Thermometry 93 hand, since it was needed only for a few highly accurate measurements, it did not need…
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94 Chapter IV Gases gar28420_ch04_091-118.indd 94 Rey. Confirming Pages ic where T, is room temperature. The small region of large…
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ic Rev. Confirming Pages Exp. 1 Gas Thermometry 95 Stainless steel FIGURE 1 be ( hypodermic ) Gas thermometry apparatus. capillary tubing…
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96 Chapter IV Gases gar28420_ch04_091-118.indd 96 Rey. Confirming Pages ic several times to flush out residual air. When the bulb has been…
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ic Rev. Confirming Pages Exp. 1 Gas Thermometry 97 TABLE | Second virial coefficients (in cm* mol ') T,°C He Ar N, co, —250 ~0 —200 +10.4…
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98 Chapter IV Gases gar28420_ch04_091-118.indd 98 Rey. Confirming Pages ic SAFETY ISSUES The ballast bulb must be taped to prevent flying…
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X Preface gar28420_fm_i-x x Confirming Pages ic teaching staff. Emphasis is given to the reasons behind the design and procedure for each…
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ic Rev. Confirming Pages Exp. 2 Joule-Thomson Effect 99 and (2) the internal energy E is independent of volume. Accordingly, E is…
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100 Chapter IV Gases gar28420_ch04_091-118.indd 100 Rey. Confirming Pages ic For a process involving arbitrary infinitesimal changes in…
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ic Rev. Confirming Pages Exp. 2 Joule-Thomson Effect 101 Combination of these two equations yields (“) ~Vob, 1a (10) Dp which on…
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102 Chapter IV Gases gar28420_ch04_091-118.indd 102 Rey. Confirming Pages ic Other semiempirical equations of state can be used to predict…
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Rev. Confirming Pages Exp. 2 Joule-Thomson Effect = To I) Bourdon gauge ) cas outlet To purge valve outlet Insulation Polyethylene 30…
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104 Chapter IV Gases gar28420_ch04_091-118.indd 104 Rey. Confirming Pages ic should be clamped together and the copper leads should be…
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ic Rev. Confirming Pages Exp. 2 Joule-Thomson Effect 105 Waals and Beattie—Bridgeman constants given in Table 1. C 'p values for He, N>,…
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106 Chapter IV Gases gar28420_ch04_091-118.indd 106 Rey. Confirming Pages ic APPARATUS Insulated Joule-Thomson cell similar to that of Fig.…
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ic Rev. Confirming Pages Exp. 3 Heat-Capacity Ratios for Gases 107 The number of degrees of freedom for a molecule is the number of…
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108 Chapter IV Gases gar28420_ch04_091-118.indd 108 Rey. Confirming Pages ic Using classical statistical mechanics, one can derive the…
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& Confirming Pages Physical chemistry deals with the physical principles underlying the properties of chemical substances. Like other…
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ic Rev. Confirming Pages Exp. 3 Heat-Capacity Ratios for Gases 109 A. Adiabatic Expansion Method For the reversible adiabatic expansion of…
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110 Chapter IV Gases gar28420_ch04_091-118.indd 110 Rey. Confirming Pages Although in theoretical calculations of Cy we are concerned only…
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ic Rev. Confirming Pages Exp. 3 Heat-Capacity Ratios for Gases 111 from which we obtain (using the perfect-gas approximation in the small…
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112 Chapter IV Gases gar28420_ch04_091-118.indd 112 Rey. Confirming Pages ic The thermodynamic equations, Eqs. (4) to (13), apply only to…
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ic Rev. Confirming Pages Exp. 3 Heat-Capacity Ratios for Gases 113 EXPERIMENTAL The apparatus should be assembled as shown in Fig. 2. If…
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114 Chapter IV Gases gar28420_ch04_091-118.indd 114 Rey. Confirming Pages ic DISCUSSION Compare your experimental ratios with those…
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ic Rev. Confirming Pages Exp. 3. Heat-Capacity Ratios for Gases 115 Comparison of Eqs. (25) and (29) leads to pc? = Bs (30) and one can now…
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116 Chapter IV Gases FIGURE 3 Apparatus for measuring the speed of sound ina gas. The Kundt’s tube should be a glass tube ~150 cm long and…
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ic Rev. Confirming Pages Exp. 3 Heat-Capacity Ratios for Gases 117 If necessary, repeat the entire procedure for a given gas until…
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118 Chapter IV Gases gar28420_ch04_091-118.indd 118 Rey. Confirming Pages ic Thermostat bath, set at 25°C (unless each vessel has an…
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2 = Chapter! Introduction gar28420_ch01_001-028.indd 2 Confirming Pages ic will require modifications of the procedure. Finally, at the end…
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EXPERIMENTS 4. Viscosity of Gases 5. Diffusion of Gases . KINETIC THEORY OF TRANSPORT PHENOMENA ® In this section we shall be concerned…
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Rey. Confirming Pages ic 120 Chapter V Transport Properties of Gases gar28420_ch05_119-144.indd 120 where k is the Boltzmann constant, R is…
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ic Rev. Confirming Pages Kinetic Theory of Transport Phenomena 121 Combining Eq. (1) or Eq. (2) with Eq. (4), we obtain 2 Z= (= ) N 27M The…
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Rey. Confirming Pages ic 122 Chapter V Transport Properties of Gases gar28420_ch05_119-144.indd 122 where m is the mass of a molecule.…
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ic Rev. Confirming Pages Kinetic Theory of Transport Phenomena 123 and 5 (MRT)? 95 (MRT)? —— = 2,928 x 10° ~— "” ter?n, @& d (13) It should…
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Rey. Confirming Pages ic 124 Chapter V Transport Properties of Gases gar28420_ch05_119-144.indd 124 This simple expression, which is…
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ic Rev. Confirming Pages Kinetic Theory of Transport Phenomena 125 So far we have neglected the mass flow, if any, that is needed for the…
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Rey. Confirming Pages ic 126 Chapter V Transport Properties of Gases gar28420_ch05_119-144.indd 126 collisions did not take place at all.…
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ic Rev. Confirming Pages Kinetic Theory of Transport Phenomena 127 is the “reduced mass” of a system comprising a molecule of kind 1 and a…
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Rey. Confirming Pages ic 128 Chapter V Transport Properties of Gases FIGURE 1 Ideal plane-parallel laminar flow. gar28420_ch05_119-144.indd…
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ic Confirming Pages Organization of the Book 3 U and V respectively. Systeme International (SI) units, described in Appendix B, are used…
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ic Rev. Confirming Pages Exp. 4 Viscosity of Gases 129 10'° P, and the viscosity of glass (a supercooled liquid) is many powers of 10…
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Rey. Confirming Pages ic 130 Chapter V Transport Properties of Gases FIGURE 2 (a) Definition of variables. (b) Parabolic velocity…
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ic Rev. Confirming Pages Exp. 4 Viscosity of Gases 131 Dust cover FIGURE 3 Gas viscosity apparatus. Capillary Pressure gauge To gas supply…
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Rey. Confirming Pages ic 132 Chapter V Transport Properties of Gases gar28420_ch05_119-144.indd Sec2:132 On inverting and integrating, we…
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ic Rev. Confirming Pages Exp. 4 Viscosity of Gases 133 point divided by the volume rate of flow of fluid past this point). For flow through…
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Rey. Confirming Pages ic 134 Chapter V Transport Properties of Gases gar28420_ch05_119-144.indd Sec2:134 shear only when variations in mass…
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ic Rev. Confirming Pages Exp. 4 Viscosity of Gases 135 For each gas (including air), calculate the maximum value of the Reynolds number…
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Rey. Confirming Pages ic 136 Chapter V Transport Properties of Gases gar28420_ch05_119-144.indd Sec2:136 EXPERIMENT 5 Diffusion of Gases In…
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ic Rev. Confirming Pages Exp. 5 Diffusion of Gases 137 between the diffusion constants for the systems Kr—He and Kr—H, than for Kr—He and…
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Rey. Confirming Pages ic 138 Chapter V Transport Properties of Gases gar28420_ch05_119-144.indd Sec3:138 t=o: An =0 -LS=xSsL (8) Allt or =…
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4 Chapter! Introduction gar28420_ch01_001-028.indd Sec1:4 Confirming Pages ic the principles and devices used in measurement and control of…
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ic Rev. Confirming Pages Exp. 5 Diffusion of Gases 139 FIGURE 1 Loschmidt diffusion apparatus: (a) curves showing schematically the…
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Rey. Confirming Pages ic 140 Chapter V Transport Properties of Gases FIGURE 2 U tube for absorbing CO, gas. gar28420_ch05_119-144.indd…
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ic Rev. Confirming Pages Exp. 5 Diffusion of Gases 141 3. Considerable heat is evolved in the reaction of CO, with Ascarite II; a U tube…
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Rey. Confirming Pages ic 142 Chapter V Transport Properties of Gases PROCEDURE B In carrying out the experiment with the apparatus shown in…
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ic Rev. Confirming Pages Exp. 5 Diffusion of Gases 143 hasten the warming up of the coil). After about a minute, remove the beaker and dry…
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Rey. Confirming Pages ic 144 Chapter V Transport Properties of Gases gar28420_ch05_119-144.indd Sec3:144 and (3) any other defects that…
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Confirming Pages EXPERIMENTS 6. Heats of Combustion 7. Strain Energy of the Cyclopropane Ring 8. Heats of lonic Reaction PRINCIPLES OF…
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Rey. Confirming Pages ic 146 Chapter VI. Thermochemistry As we shall see, it is often unnecessary to carry out this step in actuality,…
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ic Rev. Confirming Pages Principles of Calorimetry 147 either step II or its inverse, whichever is endothermic. Since the work is…
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Confirming Pages 148 Chapter VI. Thermochemistry FIGURE 1 (a) Plot of temperature T versus time t for an ideal adiabatic calorimeter. (b)…
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ic Confirming Pages Execution of an Experiment 5 The design of the experiment will require a decision about the number of data points to be…
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ic Rev. Confirming Pages Principles of Calorimetry 149 scale has been used with an interrupted temperature axis in order to show clearly…
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Confirming Pages ic 150 Chapter VI Thermochemistry The following are the most important experimental approaches aimed at minimizing the…
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ic Rev. Confirming Pages Principles of Calorimetry 151 where t, is chosen so that the two shaded regions in Fig. 3b are of equal area. The…
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Confirming Pages ic 152 Chapter VI Thermochemistry gar28420_ch06_145-171.indd 152 EXPERIMENT 6 Heats of Combustion In this experiment a…
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® Rev. Confirming Pages o Exp. 6 Heats of Combustion 153 0 to 30°C jacket Precision FIGURE 1 thermometer thermometer Bomb calorimeter (Parr…
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Confirming Pages 154 Chapter VI Thermochemistry FIGURE 2 Parr single-valve bomb, shown in contact with bottom of calorimeter pail. One…
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ic Confirming Pages Exp. 6 Heats of Combustion 155 The bomb is expensive and must be handled carefully. In particular, be very careful not…
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Confirming Pages 156 Chapter VI Thermochemistry FIGURE 3 Control box containing electrical circuit for bomb calorimeter. FIGURE 4…
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ic Rev. Confirming Pages Exp. 6 Heats of Combustion 157 CALCULATIONS For each run, plot temperature versus time using an expanded,…
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Rey. Confirming Pages ic 158 Chapter VI Thermochemistry reader (can be replaced by either a resistance thermometer or a calibrated…
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6 Chapter! Introduction FIGURE 1 Optimal spacing of data points when the observed quantity varies rapidly in some regions and slowly in…
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ic Confirming Pages Exp. 7 Strain Energy of the Cyclopropane Ring 159 For all conventional chemical bonds, the B; values are positive; AHfg…
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Confirming Pages ic 160 Chapter VI Thermochemistry example of the kind of reaction that is useful for this purpose, we consider combustion…
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ic Confirming Pages Exp. 7 Strain Energy of the Cyclopropane Ring 161 due to strain. However, it may be expected that, since molecules I…
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Confirming Pages ic 162 Chapter VI Thermochemistry contain a small Teflon-covered stirring bar and should sit in a heating mantle on top of…
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ic Confirming Pages Exp. 7 Strain Energy of the Cyclopropane Ring 163 extraction of the first portion of NaHCO, solution to extract the…
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Confirming Pages ic 164 Chapter VI Thermochemistry methanol boils substantially lower than butanol, simple distillation may be used instead…
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ic Confirming Pages Exp. 7 Strain Energy of the Cyclopropane Ring 165 Esters. Introduce about 0.7 to 0.9 g of one of the esters into the…
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Rey. Confirming Pages ic 166 Chapter VI Thermochemistry gar28420_ch06_145-171.indd 166 The strain energy S may be calculated from the heats…
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ic Rev. Confirming Pages Exp. 8 Heats of lonic Reaction 167 GENERAL READING J. L. Oscarson and P. A. Izatt, “Calorimetry,” in B. W.…
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Confirming Pages 168 Chapter VI Thermochemistry FIGURE 1 Solution calorimeter. The precision mercury thermometer can be replaced by a…
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ic Confirming Pages Recording of Experimental Data 7 1. Determine the potential hazards and review the safety procedures appropriate for…
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ic Confirming Pages Exp. 8 Heats of lonic Reaction 169 FIGURE 2 Electrical heating circuit for solution calorimeter. The standard resistor…
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Confirming Pages ic 170 Chapter VI. Thermochemistry Check the electrical connections to the heating coil. Connect the T tube to a…
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ic Rev. Confirming Pages Exp. 8 Heats of lonic Reaction 171 similar values, one can simplify the determination of (1; - Ti) by choosing t,…
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172 gar28420_ch07_172-198.indd 172 Confirming Pages & EXPERIMENTS 9. Partial Molar Volume 10. Cryoscopic Determination of Molar Mass 11.…
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ic Confirming Pages Exp.9 Partial Molar Volume 173 Among intensive variables important in thermodynamics are partial molar quantities,…
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Rey. Confirming Pages ic 174 Chapter VII Solutions gar28420_ch07_172-198.indd 174 containing a pure solid substance (e.g., NaCl) in…
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ic Rev. Confirming Pages Exp.9 Partial Molar Volume 175 and nV) = 1000 cm3 (15) dy where d is the density of the solution and dp is the…
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Confirming Pages ic 176 Chapter VII Solutions gar28420_ch07_172-198.indd 176 EXPERIMENTAL Make up 200 mL of approximately 3.2 m (3.0 M)…
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ic Rev. Confirming Pages Exp.9 Partial Molar Volume 177 FIGURE 1 Pycnometers: (a) Ostwald—Sprengel type; (b) Weld (stopper) type; “Fiducial…
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Rey. Confirming Pages ic 178 Chapter Vil Solutions gar28420_ch07_172-198.indd 178 Calculate V, and V, for m = 0, 0.5, 1.0, 1.5, 2.0, and…
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8 Chapter! Introduction gar28420_ch01_001-028.indd Sec3:8 Confirming Pages ic so as to leave it legible and then write the correct number…
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ic Confirming Pages Exp. 10 Cryoscopic Determination of Molar Mass 179 EXPERIMENT 10 Cryoscopic Determination of Molar Mass When a…
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Rey. Confirming Pages ic 180 Chapter Vil Solutions gar28420_ch07_172-198.indd 180 containing solute at mole fraction X, the freezing point…
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ic Confirming Pages Exp. 10 Cryoscopic Determination of Molar Mass 181 not appear. Those assumptions, together with Raoult’s law, may be…
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Confirming Pages ic 182 Chapter Vil Solutions Let the right-hand side of Eq. (5) be called y, AH, RTIgT; and express e” in a Maclaurin…
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ic Confirming Pages Exp. 10 Cryoscopic Determination of Molar Mass 183 TABLE 1 Cyclohexane Water Molar mass (g) Mo 84.16 18.02 Celsius…
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Confirming Pages ic 184 Chapter Vil Solutions FIGURE 2 Apparatus for cryoscopic determination of molar mass. The cryoscopic mercury…
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ic Confirming Pages Exp. 10 Cryoscopic Determination of Molar Mass 185 T FIGURE 3 Schematic cooling curves: (a) and (c) show the cooling…
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Confirming Pages ic 186 Chapter Vil Solutions gar28420_ch07_172-198.indd 186 for your own use. During the experiment, take care to keep the…
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ic Rev. Confirming Pages Exp. 10 Cryoscopic Determination of Molar Mass 187 The inner tube is removed, the cyclohexane is melted as before,…
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Rey. Confirming Pages ic 188 Chapter VII Solutions gar28420_ch07_172-198.indd 188 EXPERIMENT 11 Freezing-Point Depression of Strong and…
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gar28420_fm_i-x i ic Rev. Confirming Pages EXPERIMENTS IN PHYSICAL CHEMISTRY EIGHTH EDITION CARL W. GARLAND JOSEPH W. NIBLER =DAVID P.…
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ic Confirming Pages Literature Work 9 Instrumental records—such as spectra, computer data plots, and printouts of computer files (see…
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ic Rev. Confirming Pages Exp. 11 Freezing-Point Depression of Strong and Weak Electrolytes 189 where ay is the activity of the solvent and…
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Rey. Confirming Pages ic 190 Chapter Vil Solutions TABLE 1 o values from Ref. 1 Ka 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 o 0.7588 0.7129…
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ic Confirming Pages Exp. 11 Freezing-Point Depression of Strong and Weak Electrolytes 191 FIGURE 1 Apparatus for measuring the freezing…
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Confirming Pages ic 192 Chapter VII Solutions gar28420_ch07_172-198.indd 192 withdraw a second aliquot. If these results are not consistent…
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ic Rev. Confirming Pages Exp. 12 Chemical Equilibrium in Solution 193 REFERENCES 1. F. H. MacDougall, Thermodynamics and Chemistry, 3d ed.,…
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Rey. Confirming Pages ic 194 Chapter VII Solutions gar28420_ch07_172-198.indd 194 of ions. For the I, species, it will be observed that the…
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ic Confirming Pages Exp. 12 Chemical Equilibrium in Solution 195 TABLE 1° CCl, layer Aqueous layer Aqueous Layer (use 20-mL pipette) (use…
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Confirming Pages ic 196 Chapter VII Solutions gar28420_ch07_172-198.indd 196 The purpose of taking a second sample after further…
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ic Confirming Pages Exp. 12 Chemical Equilibrium in Solution 197 I, in CCl, (50 mL) as shown in Table 1 (runs 4 to 6). The equilibration…
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Confirming Pages ic 198 Chapter VII Solutions gar28420_ch07_172-198.indd 198 250-mL Erlenmeyer flasks; 10-mL graduated cylinder; three…
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10 Chapter! Introduction gar28420_ch01_001-028.indd Sec4:10 Confirming Pages ic DATABASE AND ABSTRACT SEARCHES Of the many compilations of…
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& Rev. Confirming Pages EXPERIMENTS 13. Vapor Pressure of a Pure Liquid 14. Binary Liquid-Vapor Phase Diagram 15. Ordering in Nematic…
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Confirming Pages ic 200 Chapter Vill Phase Behavior gar28420_ch08_199-234.indd 200 THEORY We are concerned here with the equilibrium…
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ic Rev. Confirming Pages Exp. 13 Vapor Pressure of a Pure Liquid 201 FIGURE 1 1.00 pene rn The compressibility factor Z of saturated vapor…
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Confirming Pages ic 202 = Chapter Vill Phase Behavior gar28420_ch08_199-234.indd Sec1:202 TABLE 1 Average values, J K~' mol"! Compound…
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ic Confirming Pages Exp. 13 Vapor Pressure of a Pure Liquid 203 FIGURE 2 x Boiling-point apparatus. The mercury thermometer can f be…
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Confirming Pages ic 204 Chapter Vill Phase Behavior FIGURE 3 Isoteniscope. (a) Schematic diagram of the apparatus, which must be connected…
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ic Rev. Confirming Pages Exp. 13 Vapor Pressure of a Pure Liquid 205 Take readings at approximately 5°C intervals until the bath is at…
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Rev. Confirming Pages ic 206 Chapter Vill Phase Behavior gar28420_ch08_199-234.indd Sec1:206 Pm associated with the temperature T,, at…
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ic Rev. Confirming Pages Exp. 14 Binary Liquid-Vapor Phase Diagram 207 position; reflux condenser; electrical heating mantle; two long…
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Confirming Pages ic 208 Chapter Vill Phase Behavior gar28420_ch08_199-234.indd Sec2:208 THEORY For a system of two components (A and B), we…
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ic Confirming Pages Reports 11 properly reported. Such reports should be well organized and readable, so that anyone unfamiliar with the…
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ic Rev. Confirming Pages Exp. 14 Binary Liquid-Vapor Phase Diagram 209 or FIGURE 1 B Schematic three-dimensional vapor-liquid equilibrium…
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Confirming Pages ic 210 Chapter Vill Phase Behavior FIGURE 2 Schematic vapor-pressure and boiling-point diagrams . L for systems showing…
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ic Rev. Confirming Pages Exp. 14 Binary Liquid-Vapor Phase Diagram 211 FIGURE 3 Variation of liquid and vapor compositions during…
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Confirming Pages ic 212 Chapter Vill Phase Behavior Another property that could also be used is the density, which varies in a nonlinear…
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ic Rev. Confirming Pages Exp. 14 Binary Liquid-Vapor Phase Diagram 213 vapor or distillate). Take samples of about 2 mL in size. Turn on…
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Rev. Confirming Pages ic 214 Chapter Vill Phase Behavior gar28420_ch08_199-234.indd Sec2:214 described in Chapter XIX. (If the experiment…
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ic Rev. Confirming Pages Exp. 15 Ordering in Nematic Liquid Crystals 215 GENERAL READING R. J. Silbey, R. A. Alberty, and M. G. Bawendi,…
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Rev. Confirming Pages ic 216 Chapter Vill Phase Behavior FIGURE 2 — (a) Simplified sketches of ALAS lf I / \ \/ I] | | |! the isotropic…
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ic Confirming Pages Exp. 15 Ordering in Nematic Liquid Crystals 217 the orientational function of quadrupolar symmetry, the second Legendre…
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Rev. Confirming Pages ic 218 Chapter Vill Phase Behavior gar28420_ch08_199-234.indd Sec3:218 M is observed to develop as clusters of spins…
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12 = Chapter! Introduction gar28420_ch01_001-028.indd Sec5:12 Confirming Pages ic Except for general physical and numerical constants or…
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ic Confirming Pages Exp. 15 Ordering in Nematic Liquid Crystals 219 FIGURE 3 G-G, T>T, (@) G — G, asa function of (t > 0) 7 the order…
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Confirming Pages ic 220 = Chapter Vill Phase Behavior positive S values. The presence of this cubic term means that the N-I transition must…
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ic Rev. Confirming Pages Exp. 15 Ordering in Nematic Liquid Crystals 221 At T = OK, the nematic order would become perfect; i.e., S(0) = 1.…
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Rev. Confirming Pages ic 222 = Chapter Vill Phase Behavior gar28420_ch08_199-234.indd Sec3:222 This approximation is excellent (typical…
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© Confirming Pages Exp. 15 Ordering in Nematic Liquid Crystals 223 polyvinyl! alcohol film so the epoxy will bind directly to the glass.…
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Rev. Confirming Pages ic 224 Chapter Vill Phase Behavior gar28420_ch08_199-234.indd Sec3:224 using a clamp-rod assembly and submerged in…
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gar28420_ch08_199-234.indd Sec3:225 Rev. Confirming Pages Exp. 15 Ordering in Nematic Liquid Crystals sb Warming Cooling 7 35 4 34 _ 6 2 &…
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Rev. Confirming Pages ic 226 Chapter Vill Phase Behavior gar28420_ch08_199-234.indd Sec3:226 where ®, is a constant representing the…
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ic Rev. Confirming Pages Exp. 15 Ordering in Nematic Liquid Crystals 227 Since A is known and D is either given or measured in the…
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Rev. Confirming Pages ic 228 = Chapter Vill Phase Behavior gar28420_ch08_199-234.indd Sec3:228 APPARATUS A suitable sample cell as…
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ic Confirming Pages Sample Report 13 Any symbols used in a table should be defined previously in the text. In a column of numbers, align…
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ic Confirming Pages Exp. 16 Liquid-Vapor Coexistence Curve and the Critical Point 229 14. E. F. Gramsbergen and W. H. de Jeu, J. Chem. Soc.…
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Confirming Pages ic 230 = Chapter Vill Phase Behavior gar28420_ch08_199-234.indd Sec4:230 CO, gas contained in a known volume at a known…
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ic Rev. Confirming Pages Exp. 16 Liquid-Vapor Coexistence Curve and the Critical Point 231 Now check the temperature of the bath. If it is…
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Rev. Confirming Pages ic 232 = Chapter Vill Phase Behavior gar28420_ch08_199-234.indd Sec4:232 The liquid and vapor densities can be…
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ic Rev. Confirming Pages Exp. 16 Liquid-Vapor Coexistence Curve and the Critical Point 233 These equations reduce to two equations in two…
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Confirming Pages ic 234 Chapter Vill Phase Behavior gar28420_ch08_199-234.indd Sec4:234 T,. For temperatures below T,, the system separates…
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© Rev. Confirming Pages EXPERIMENTS 17. Conductance of Solutions 18. Temperature Dependence of emf 19. Activity Coefficients from Cell…
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Rev. Confirming Pages ic 236 Chapter IX Electrochemistry gar28420_ch09_235-253.indd 236 or ii_k RAR K= (2) where « is the conductivity with…
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ic Rev. Confirming Pages Exp. 17 Conductance of Solutions 237 to determine this limiting value from extrapolation of A values obtained with…
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Rev. Confirming Pages ic 238 Chapter IX Electrochemistry quantity A in Eq. (11) has the value 0.509 kg!” mol” and the quantity B is found…
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Confirming Pages ic 14 Chapter! Introduction DETERMINATION OF THE DENSITY OF CRYSTALLINE GERMANIUM Maria Smith Sept. 25, 2008 (Partner:…
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ic Rev. Confirming Pages Exp. 17 Conductance of Solutions 239 where Z is the impedance. Since the cell has both resistance and capacitance,…
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Confirming Pages ic 240 Chapter IX Electrochemistry gar28420_ch09_235-253.indd 240 This is, fortunately, the behavior observed for cells…
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ic Confirming Pages Exp. 17 Conductance of Solutions 241 signal with a small 1-kHz bridge signal superimposed. Do not attempt to balance…
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Confirming Pages ic 242 Chapter IX Electrochemistry gar28420_ch09_235-253.indd Sec3:242 solution, using about enough to fill the cell…
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ic Rev. Confirming Pages Exp. 17 Conductance of Solutions 243 Dilutions. The quality of your results depends on accurate dilutions and…
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Rev. Confirming Pages ic 244 Chapter IX Electrochemistry gar28420_ch09_235-253.indd Sec4:244 TABLE 1 Solution Ag at 25°C dA,/dT HCl 0.04262…
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ic Rev. Confirming Pages Exp. 18 Temperature Dependence of emf 245 REFERENCES 1. S.1. Smedley, The Interpretation of Ionic Conductivity in…
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Confirming Pages ic 246 Chapter IX Electrochemistry gar28420_ch09_235-253.indd Sec5:246 THEORY When the cell operates reversibly at…
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ic Confirming Pages Exp. 18 Temperature Dependence of emf 247 FIGURE 1 Cadmium amalgam cell. bath level CdSO, solution Cd plating on Pt…
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Confirming Pages ic 248 Chapter IX Electrochemistry gar28420_ch09_235-253.indd Sec6:248 DISCUSSION Explain why AG° is not equal to zero, as…
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ic Confirming Pages Sample Report 15 I. Introduction The purpose of this experiment is to measure the density of crystals of germanium.…
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ic Rev. Confirming Pages Exp. 19 Activity Coefficients from Cell Measurements 249 Cell (1) may conveniently be considered as a combination…
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Rev. Confirming Pages ic 250 Chapter IX Electrochemistry gar28420_ch09_235-253.indd Sec7:250 where p is in bar and c is in mol L~'.+ From…
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ic Rev. Confirming Pages Exp. 19 Activity Coefficients from Cell Measurements 251 values can then be compared with those predicted by a…
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Confirming Pages ic 252 = Chapter IX Electrochemistry gar28420_ch09_235-253.indd Sec8:252 solution and a small side hole near the top for…
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ic Rev. Confirming Pages Exp. 19 Activity Coefficients from Cell Measurements 253 coefficient by use of the Debye—Hiickel equation in the…
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254 gar28420_ch10_254-298.indd 254 Confirming Pages EXPERIMENTS 20. Method of Initial Rates: lodine Clock 21. NMR Study of a Reversible…
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ic Confirming Pages Exp. 20 Method of Initial Rates: lodine Clock 255 part of the information needed to formulate uniquely and completely…
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Confirming Pages ic 256 Chapter X Chemical Kinetics gar28420_ch10_254-298.indd 256 determine the exponents merely by determining the time…
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ic Rev. Confirming Pages Exp. 20 Method of Initial Rates: lodine Clock 257 A constant initial concentration of H;AsO; is used in a series…
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Confirming Pages ic 258 Chapter X Chemical Kinetics gar28420_ch10_254-298.indd 258 Two or three runs should be made on each of the four…
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16 Chapter! Introduction gar28420_ch01_001-028.indd Sec6:16 Confirming Pages ic —“———— Capillary top <-—————- Ground-glass joint Fig. 1.…
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ic Confirming Pages Exp. 20 Method of Initial Rates: lodine Clock 259 2. IO; + Ht = HIO; (fast, to equil.) +H “=a (fast, to equil.) HIO, +…
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Rev. Confirming Pages ic 260 Chapter X Chemical Kinetics FIGURE 1 Schematic diagram of the “flowing clock” apparatus.…
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ic Rev. Confirming Pages Exp. 20 Method of Initial Rates: lodine Clock 261 TABLE 2 Reservoir 1, vol. in mL Reservoir 2, vol. in mL Run 4M…
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Confirming Pages ic 262 Chapter X Chemical Kinetics TABLE 3 Reservoir 1, vol. in mL Reservoir 2, vol. in mL 1M Run Buffer Phenol- Distilled…
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ic Confirming Pages Exp. 21 NMR Study of a Reversible Hydrolysis Reaction 263 EXPERIMENT 21 NMR Study of a Reversible Hydrolysis Reaction…
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Confirming Pages ic 264 Chapter X Chemical Kinetics gar28420_ch10_254-298.indd Sec1:264 Introducing an abbreviated notation for convenience…
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ic Rev. Confirming Pages Exp. 21 NMR Study of a Reversible Hydrolysis Reaction 265 Arrhenius plots of In k versus 1/T should yield a…
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Rev. Confirming Pages ic 266 Chapter X Chemical Kinetics FIGURE 1 Changes in the NMR spectrum for a two-site exchange system as a function…
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ic Confirming Pages Exp. 21 NMR Study of a Reversible Hydrolysis Reaction 267 Thus, for very small rate constants, the widths are dominated…
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Confirming Pages ic 268 Chapter X Chemical Kinetics gar28420_ch10_254-298.indd Sec1:268 The concentration of D,O is fixed at the same value…
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ic Confirming Pages Sample Report 17 Wi = Ws — Wo, (3) where W3 is the weight of the pycnometer plus sample plus water. If the density of…
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ic Rev. Confirming Pages Exp. 21 NMR Study of a Reversible Hydrolysis Reaction 269 sample temperature, the peaks will shift laterally…
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Rev. Confirming Pages ic 270 Chapter X Chemical Kinetics gar28420_ch10_254-298.indd Sec1:270 An effort should be made to evaluate the…
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ic Confirming Pages Exp. 22 Enzyme Kinetics: Inversion of Sucrose 271 REFERENCES 1. R. J. Silbey, R. A. Alberty, and M. G. Bawendi,…
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Rev. Confirming Pages ic 272 = Chapter X Chemical Kinetics FIGURE 1 Reaction velocity versus substrate concentration.…
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ic Confirming Pages Exp. 22 Enzyme Kinetics: Inversion of Sucrose 273 When (S) is very high, (S) >> K,,, the reaction becomes zero order…
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Confirming Pages ic 274 Chapter X Chemical Kinetics gar28420_ch10_254-298.indd Sec2:274 of the temperature dependence of the rates. This…
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ic Confirming Pages Exp. 22 Enzyme Kinetics: Inversion of Sucrose 275 possess significantly different visible absorption spectra,…
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Confirming Pages ic 276 Chapter X Chemical Kinetics gar28420_ch10_254-298.indd Sec2:276 7. Using a suitable spectrophotometer, determine…
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ic Confirming Pages Exp. 22 Enzyme Kinetics: Inversion of Sucrose 277 C-D. Progress of the Reaction with Time. For the second of the…
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Confirming Pages ic 278 Chapter X Chemical Kinetics gar28420_ch10_254-298.indd Sec2:278 5 min. Cool the reaction tube, and dilute by adding…
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18 Chapter! Introduction gar28420_ch01_001-028.indd Sec6:18 Confirming Pages ic III. Results The average values of the measured weights Wi,…
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ic Confirming Pages Exp. 22 Enzyme Kinetics: Inversion of Sucrose 279 One 1-mL graduated pipette, used for dispensing buffer solution and…
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Rev. Confirming Pages ic 280 chapter X Chemical Kinetics gar28420_ch10_254-298.indd Sec2:280 Run Enzyme, mL Water, mL Buffer, mL 0.3 M…
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ic Confirming Pages Exp. 22 Enzyme Kinetics: Inversion of Sucrose 281 up by weighing, nj may not be precisely equal to n; and it is…
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Rev. Confirming Pages ic 282 Chapter X Chemical Kinetics gar28420_ch10_254-298.indd Sec2:282 DISCUSSION A number of questions might be…
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ic Rev. Confirming Pages Exp. 23 Kinetics of the Decomposition of Benzenediazonium lon 283 I. Tinoco, Jr., K. Sauer, and J. C. Wang,…
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Rev. Confirming Pages ic 284 Chapter X Chemical Kinetics gar28420_ch10_254-298.indd Sec3:284 If the value of a rate constant is measured at…
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ic Confirming Pages Exp. 23 Kinetics of the Decomposition of Benzenediazonium lon 285 The diazonium salt that should be used in this…
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Confirming Pages ic 286 Chapter X Chemical Kinetics gar28420_ch10_254-298.indd Sec3:286 Take as many measurements as you reasonably can…
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ic Confirming Pages Exp. 24 Gas-Phase Kinetics 287 3. P. W. Atkins and J. de Paula, Physical Chemistry, 8th ed., p. 432, Freeman, New York…
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Rev. Confirming Pages ic 288 Chapter X Chemical Kinetics gar28420_ch10_254-298.indd Sec4:288 where A* is an activated A molecule with a…
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Rey. Confirming Pages ic The McGraw-Hill companies McGraw-Hill Higher Education EXPERIMENTS IN PHYSICAL CHEMISTRY, EIGHTH EDITION Published…
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ic Confirming Pages Sample Report 19 When Eq. (6) is applied to our results, we obtain for p* the following values: Sample I: 5.310 g cm?…
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ic Confirming Pages Exp. 24 Gas-Phase Kinetics 289 frequencies—namely, 10'° s~'. [A more realistic and sophisticated molecular model,'…
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Confirming Pages ic 290 Chapter X Chemical Kinetics gar28420_ch10_254-298.indd Sec4:290 compared with decomposition. At low pressures k,(A)…
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ic Confirming Pages Exp. 24 Gas-Phase Kinetics 291 to add small amounts of a compound that is known to provide relatively large concentra-…
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Rev. Confirming Pages ic 292 Chapter X Chemical Kinetics FIGURE 1 Apparatus for high- temperature gas-phase kinetics experiment. FIGURE 2…
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ic Confirming Pages Exp. 24 Gas-Phase Kinetics 293 For a first-order reaction, In [(A))/(A)] = kt; therefore 0. P 2p° —p Thus a plot of…
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Confirming Pages ic 294 Chapter X Chemical Kinetics gar28420_ch10_254-298.indd Sec4:294 of evaluating specific rate constants which…
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ic Confirming Pages Exp. 24 Gas-Phase Kinetics 295 temperature. If the temperature shows appreciable long-term drift (greater than +0.5…
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Confirming Pages ic 296 Chapter X Chemical Kinetics gar28420_ch10_254-298.indd Sec4:296 if possible do not regrease stopcocks just before a…
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ic Confirming Pages Exp. 24 Gas-Phase Kinetics 297 resulting values of the parameters differ much from the previous values? If so, use the…
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Confirming Pages ic 298 Chapter X Chemical Kinetics REFERENCES vt ee une 10. 11. 12. 13. 14, 15. 16. 17. S. W. Benson, The Foundations of…
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Confirming Pages ic 20 Chapter! Introduction value of Ap. With this simplification, the 95% confidence limit in p is given by (Ap)?/p? =…
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Rev. Confirming Pages EXPERIMENTS 25. Surface Tension of Solutions 26. Physical Adsorption of Gases EXPERIMENT 25 Surface Tension of…
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Rev. Confirming Pages ic 300 Chapter XI Surface Phenomena FIGURE 1 Schematic plot of Qy versus x. The shaded area is equal to Qy.…
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ic Rev. Confirming Pages Exp. 25 Surface Tension of Solutions 301 Surface Free Energy or Surface Tension. Under conditions of constant tem-…
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Rev. Confirming Pages ic 302 Chapter XI Surface Phenomena gar28420_ch11_299-317.indd 302 This can be rewritten as —tr(a) = l(a) ©) dce\ dV…
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ic Confirming Pages Exp. 25 Surface Tension of Solutions 303 FIGURE 2 Variation of the solute concentration near a free surface for the…
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Rev. Confirming Pages ic 304 Chapter XI Surface Phenomena FIGURE 3 Variation of ionic solute concentration near a free surface: (a)…
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ic Rev. Confirming Pages Exp. 25 Surface Tension of Solutions 305 FIGURE 4 Capillary rise h in a tube of radius r. 7 1 ri for the amount of…
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Confirming Pages ic 306 Chapter XI Surface Phenomena FIGURE 6 Apparatus for measuring surface tension by the method of capillary rise.…
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ic Rev. Confirming Pages Exp. 25 Surface Tension of Solutions 307 Repeat the above procedure with 0.8 M n-butanol solution, dilute to…
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Confirming Pages ic 308 Chapter XI Surface Phenomena gar28420_ch11_299-317.indd 308 SAFETY ISSUES If the capillary tube is cleaned with hot…
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ic Confirming Pages Sample Report 21 that the material examined may be somewhat inhomogeneous, yielding two samples of slightly different…
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ic Rev. Confirming Pages Exp. 26 Physical Adsorption of Gases 309 5 FIGURE 1 250) A typical isotherm for the physical adsorption of…
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Rev. Confirming Pages ic 310 = Chapter XI Surface Phenomena gar28420_ch11_299-317.indd 310 gas molecules to form each adsorbed layer is…
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ic Confirming Pages Exp. 26 Physical Adsorption of Gases 311 Although we shall not be concerned experimentally with measuring heats of…
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Confirming Pages 312 = Chapter XI Surface Phenomena an electrostatic balance may be used. In the volumetric method, the amount of…
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ic Rev. Confirming Pages Exp. 26 Physical Adsorption of Gases 313 the volume between fiducial marks (V, and V,) can be measured accurately…
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Rev. Confirming Pages ic 314 Chapter XI Surface Phenomena FIGURE 4 Detail drawing of the sample bulb, showing method of filling.…
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ic Confirming Pages Exp. 26 Physical Adsorption of Gases 315 fill bulb V,. Equation (11) is still applicable, but the value of the last…
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Confirming Pages ic 316 Chapter XI Surface Phenomena gar28420_ch11_299-317.indd 316 previously for obtaining the new equilibrium pressure…
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ic Confirming Pages Exp. 26 Physical Adsorption of Gases 317 APPARATUS Adsorption apparatus (Fig. 3), containing high-area sample, attached…
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318 gar28420_ch12_318-335.indd 318 Confirming Pages EXPERIMENTS 27. Intrinsic Viscosity: Chain Linkage in Polyvinyl Alcohol 28. Helix—Coil…
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22 = Chapter! Introduction gar28420_ch01_001-028.indd Sec6:22 Confirming Pages ic which could be explained by the presence of voids as…
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ic Rev. Confirming Pages Exp. 27 Intrinsic Viscosity: Chain Linkage in Polyvinyl Alcohol 319 that all monomer units go together “head to…
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Rev. Confirming Pages ic 320 Chapter XII_ Macromolecules FIGURE 1 Viscosimeter arrangement to be used if a glass-walled thermostat bath is…
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ic Rev. Confirming Pages Exp. 27 Intrinsic Viscosity: Chain Linkage in Polyvinyl Alcohol 321 viscosimeter of a type similar to that shown…
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Rev. Confirming Pages ic 322 = Chapter XII_ Macromolecules gar28420_ch12_318-335.indd Sec1:322 more than a few carbon atoms apart are…
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ic Rev. Confirming Pages Exp. 27 Intrinsic Viscosity: Chain Linkage in Polyvinyl Alcohol 323 Equation (7) also holds for a polydisperse…
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Rev. Confirming Pages ic 324 Chapter XII_ Macromolecules gar28420_ch12_318-335.indd Sec1:324 Determination of Frequency of Head-to-Head…
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ic Confirming Pages Exp. 27 Intrinsic Viscosity: Chain Linkage in Polyvinyl Alcohol 325 solution promptly and very thoroughly, for once the…
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Rev. Confirming Pages ic 326 Chapter XII_ Macromolecules gar28420_ch12_318-335.indd Sec1:326 for your calibration run, the density and…
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ic Confirming Pages Exp. 28 Helix-Coil Transition in Polypeptides 327 REFERENCES 1. P. J. Flory and F. S. Leutner, J. Polym. Sci. 3, 880…
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Rev. Confirming Pages ic 328 Chapter XII_ Macromolecules has a helical conformation when dissolved in ethylene dichloride at 25°C, but it…
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ic Confirming Pages Sample Report 23 References 1. N. Bauer and S. Z. Lewin, “Determination of Density”, in A. Weissberger and B. W.…
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ic Rev. Confirming Pages Exp. 28 Helix-Coil Transition in Polypeptides 329 As we shall see below, the solvent plays a crucial role in…
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Rev. Confirming Pages ic 330 Chapter XII_ Macromolecules gar28420_ch12_318-335.indd Sec2:330 or completely in the random-coil form. This…
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ic Rev. Confirming Pages Exp. 28 Helix-Coil Transition in Polypeptides 331 Recalling that AV is small so that AG = AA, we can make use of…
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Rev. Confirming Pages ic 332 Chapter XII_ Macromolecules FIGURE 3 Percentage of polypeptide in helix form, as a function of the parameter s…
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ic Rev. Confirming Pages Exp. 28 Helix-Coil Transition in Polypeptides 333 where [a]}, and [a], are the specific rotations of helix and…
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Rev. Confirming Pages ic 334 Chapter XII_ Macromolecules gar28420_ch12_318-335.indd Sec2:334 CALCULATIONS For each data point, calculate…
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ic Confirming Pages Exp. 28 Helix-Coil Transition in Polypeptides 335 REFERENCES 1. M. A. Stahmann (ed.), Polyamino Acids, Polypeptides and…
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336 gar28420_ch13_336-392.indd 336 Rev. Confirming Pages EXPERIMENTS 29. Dipole Moment of Polar Molecules in Solution 30. Dipole Moment of…
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ic Rev. Confirming Pages Exp. 29 Dipole Moment of Polar Molecules in Solution 337 the cell when the medium between the capacitor plates is…
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Rev. Confirming Pages ic 338 Chapter XIII Electric, Magnetic, and Optical Properties gar28420_ch13_336-392.indd 338 The moment of a…
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gar28420_ch01_001-028.indd Sec6:24 Confirming Pages 24 Chapter! Introduction Apyendiy A: Xam copy of dalle for Exp.'3 24 Mata, Sancth 1€…
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ic Rev. Confirming Pages Exp. 29 Dipole Moment of Polar Molecules in Solution 339 where the average is taken over all orientations in…
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Rev. Confirming Pages ic 340 Chapter XIII Electric, Magnetic, and Optical Properties gar28420_ch13_336-392.indd 340 distortion polarization…
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ic Rev. Confirming Pages Exp. 29 Dipole Moment of Polar Molecules in Solution 341 On substituting the numerical values of the physical…
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Rev. Confirming Pages ic 342 = Chapter XIII Electric, Magnetic, and Optical Properties FIGURE 1 "Stop" for closed Variable-capacitance…
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ic Rev. Confirming Pages Exp. 29 Dipole Moment of Polar Molecules in Solution 343 cell and a precision variable air capacitor is mixed with…
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Rev. Confirming Pages ic 344 Chapter XIII Electric, Magnetic, and Optical Properties FIGURE 2 A simple oscillator circuit for capacitance…
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ic Rev. Confirming Pages Exp. 29 Dipole Moment of Polar Molecules in Solution 345 CALCULATIONS For each solution studied, calculate « from…
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Rev. Confirming Pages ic 346 Chapter XIII Electric, Magnetic, and Optical Properties gar28420_ch13_336-392.indd 346 calculated for…
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ic Rev. Confirming Pages Exp. 30 Dipole Moment of HCI Molecules in the Gas Phase 347 10. S.R. Kurtz, O. T. Anderson, and B. R. Willeford…
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Rev. Confirming Pages ic 348 Chapter XIII Electric, Magnetic, and Optical Properties FIGURE 1 Schematic representation of the frequency…
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ic Confirming Pages Sample Report 25 Appendie B: Semple cable Pation far Exp. 13 The Com pita tien 4p fee Gemanin. annphe TE da pum Fare on…
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ic Rev. Confirming Pages Exp. 30 Dipole Moment of HCI Molecules in the Gas Phase 349 even the electrons are unable to respond to the…
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Rev. Confirming Pages ic 350 Chapter XIII Electric, Magnetic, and Optical Properties gar28420_ch13_336-392.indd 350 to the frequency…
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ic Rev. Confirming Pages Exp. 30 Dipole Moment of HCI Molecules in the Gas Phase 351 FIGURE 2 BNC connectors Suggested design for gas…
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Rev. Confirming Pages ic 352 Chapter XIII Electric, Magnetic, and Optical Properties gar28420_ch13_336-392.indd 352 Only C,,,; varies with…
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ic Rev. Confirming Pages Exp. 30 Dipole Moment of Polar Molecules in Solution 353 FIGURE 3 Gas-handling system for gas dielectric constant…
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Rev. Confirming Pages ic 354 Chapter XIII Electric, Magnetic, and Optical Properties gar28420_ch13_336-392.indd 354 valve and either pump…
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gar28420_ch13_336-392.indd 355 Rev. Confirming Pages Exp. 30 Dipole Moment of HCI Molecules in the Gas Phase He-Ne laser (0.5-1.0 mW) 50%…
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Rev. Confirming Pages ic 356 Chapter XIII Electric, Magnetic, and Optical Properties gar28420_ch13_336-392.indd 356 as the body of the cell…
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ic Rev. Confirming Pages Exp. 30 Dipole Moment of HCI Molecules in the Gas Phase 357 Here A, and A are the wavelengths of the light in the…
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Rev. Confirming Pages ic 358 Chapter XIII Electric, Magnetic, and Optical Properties gar28420_ch13_336-392.indd 358 field, the permanent…
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26 Chapter! Introduction gar28420_ch01_001-028.indd Sec6:26 Confirming Pages ic SPECIAL PROJECTS In order to become a creative and…
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ic Rev. Confirming Pages Exp. 30 Dipole Moment of HCI Molecules in the Gas Phase 359 from the transition moment from the ground state to…
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Rev. Confirming Pages ic 360 Chapter XIII Electric, Magnetic, and Optical Properties gar28420_ch13_336-392.indd 360 and readout meter;…
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ic Rev. Confirming Pages Exp. 31 Magnetic Susceptibility 361 GENERAL READING J. M. Pochan, J. J. Fitzgerald, and G. Williams, “Experimental…
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Rev. Confirming Pages ic 362 Chapter XIII Electric, Magnetic, and Optical Properties gar28420_ch13_336-392.indd 362 (where M is the molar…
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ic Rev. Confirming Pages Exp. 31 Magnetic Susceptibility 363 where S is the spin quantum number (equal to the sum of the individual…
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Rev. Confirming Pages ic 364 Chapter XIII Electric, Magnetic, and Optical Properties gar28420_ch13_336-392.indd 364 Transition-Metal…
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ic Rev. Confirming Pages Exp. 31 Magnetic Susceptibility 365 _—— +3, FIGURE a 5 Weak field, e.g., [Co(IDF,}*, and strong field, e.g.,…
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Rev. Confirming Pages ic 366 Chapter XIII Electric, Magnetic, and Optical Properties FIGURE 2 Gouy balance. Analytical balance suitably…
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ic Rev. Confirming Pages Exp. 31 Magnetic Susceptibility 367 In making a measurement, the “apparent weight” W is determined in the absence…
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Rev. Confirming Pages ic 368 Chapter XIII Electric, Magnetic, and Optical Properties gar28420_ch13_336-392.indd 368 A suitable analytical…
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ic Confirming Pages References 27 Polanyi dilute flame reaction; e.g., K + Br, EPR study of gas-phase hydrogen and deuterium atoms…
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ic Rev. Confirming Pages Exp. 31 Magnetic Susceptibility 369 the known density of water at this temperature, calculate the volume. Then…
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gar28420_ch13_336-392.indd 370 Rev. Confirming Pages ic 370 Chapter XIII Electric, Magnetic, and Optical Properties state of the free ion…
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ic Rev. Confirming Pages Exp. 32 NMR Determination of Paramagnetic Susceptibility 371 EXPERIMENT 32 NMR Determination of Paramagnetic…
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Rev. Confirming Pages ic 372 = Chapter XIII Electric, Magnetic, and Optical Properties FIGURE 1 Energy levels, allowed transitions, and…
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ic Rev. Confirming Pages Exp. 32 NMR Determination of Paramagnetic Susceptibility 373 Most organic compounds are not paramagnetic, and so…
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Rev. Confirming Pages ic 374 Chapter XIII Electric, Magnetic, and Optical Properties gar28420_ch13_336-392.indd 374 The third term is a…
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ic Rev. Confirming Pages Exp. 32 NMR Determination of Paramagnetic Susceptibility 375 As noted in Exp. 31, magnetic susceptibility…
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Rev. Confirming Pages ic 376 Chapter XIII Electric, Magnetic, and Optical Properties gar28420_ch13_336-392.indd 376 The latter is the…
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ic Rev. Confirming Pages Exp. 32 NMR Determination of Paramagnetic Susceptibility 377 in the spectrometer manual. This usually involves a…
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Rev. Confirming Pages ic 378 Chapter XIII Electric, Magnetic, and Optical Properties gar28420_ch13_336-392.indd 378 The structures of…
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Confirming Pages ic 28 Chapter! Introduction GENERAL READING Chemistry Writing Guide; available online at http://www.chem.orst.edu, which…
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ic Rev. Confirming Pages Exp. 33 Dynamic Light Scattering 379 5. E. W. Washburn (ed.), International Critical Tables, vol. Il, p. 28,…
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Rev. Confirming Pages ic 380 Chapter XIII Electric, Magnetic, and Optical Properties FIGURE 1 (a) Variation of a macroscopic property A(t),…
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ic Rev. Confirming Pages Exp. 33 Dynamic Light Scattering 381 Detector FIGURE 2 Ly Incident light with wave Polarizer vector kp is…
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Rev. Confirming Pages ic 382 Chapter XIII Electric, Magnetic, and Optical Properties gar28420_ch13_336-392.indd 382 where I” = 1/7 is the…
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ic Rev. Confirming Pages Exp. 33 Dynamic Light Scattering 383 a simpler and less-expensive apparatus and data collection procedure that is…
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Rev. Confirming Pages ic 384 Chapter XIII Electric, Magnetic, and Optical Properties gar28420_ch13_336-392.indd 384 background light. (This…
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ic Rev. Confirming Pages Exp. 33 Dynamic Light Scattering 385 EXPERIMENTAL Sample Preparation. The polystyrene spheres to be used should be…
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Rev. Confirming Pages ic 386 Chapter XIII Electric, Magnetic, and Optical Properties gar28420_ch13_336-392.indd 386 processed. An…
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® ® ©) Count evelDeter View Project File Edit Rev. Confirming Pages Exp. 33 Dynamic Light Scattering 387 =/05) x! olny] Continuous Samples…
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Rev. Confirming Pages ic 388 Chapter XIII Electric, Magnetic, and Optical Properties gar28420_ch13_336-392.indd 388 In part C the data in…
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gar28420_fm_i-x iil Confirming Pages Preface ix I. INTRODUCTION 1 Organization of the Book 2 Preparation for an Experiment 4 Execution of…
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The usual objective of performing an experiment in physical chemistry is to obtain one or more numerical results. Between the recording of…
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ic Rev. Confirming Pages Exp. 33 Dynamic Light Scattering 389 equipment and analysis are working properly; fit values for the parameter A…
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Rev. Confirming Pages ic 390 Chapter XIII Electric, Magnetic, and Optical Properties gar28420_ch13_336-392.indd 390 where T= | If(l)dl =…
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ic Rev. Confirming Pages Exp. 33 Dynamic Light Scattering 391 For the milk sample, make a rough estimate of the width of the distribution…
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Rev. Confirming Pages ic 392 Chapter XIII Electric, Magnetic, and Optical Properties gar28420_ch13_336-392.indd 392 REFERENCES 10. 11. 12…
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& Rev. Confirming Pages EXPERIMENTS 34. Absorption Spectrum of a Conjugated Dye 35. Raman Spectroscopy: Vibrational Spectrum of CCl, 36.…
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Rev. Confirming Pages ic 394 Chapter XIV Spectroscopy gar28420_ch14_393-499 394 THEORY The visible bands for polymethine dyes arise from…
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ic Rev. Confirming Pages Exp. 34 Absorption Spectrum of a Conjugated Dye 395 Since AE = hv = hc/A, where c is the speed of light and A is…
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Rev. Confirming Pages ic 396 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec1:396 discussed in Chapter XIX, and this material should be…
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ic Rev. Confirming Pages Exp. 34 Absorption Spectrum of a Conjugated Dye 397 Choose any one of the available dyes, and prepare 10 mL of a…
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Rev. Confirming Pages ic 398 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec1:398 iodide or 1,1’-diethyl-2,2'-cyanine iodide,…
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Confirming Pages ic 30 Chapter Il Treatment of Experimental Data gar28420_ch02_029-067.indd 30 y while varying x, then changes z to a new…
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ic Rev. Confirming Pages Exp. 35 Raman Spectroscopy: Vibrational Spectrum of CCl, 399 THEORY In Exp. 29, the effect of a static or…
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Rev. Confirming Pages ic 400 Chapter XIV Spectroscopy FIGURE 1 Energy levels and transition frequencies involved in Raman spectroscopy.…
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ic Rev. Confirming Pages Exp. 35 Raman Spectroscopy: Vibrational Spectrum of CCl, 401 of allowed transitions for both cases represents an…
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Rev. Confirming Pages ic 402 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec2:402 4?) = — (12) ma 3 \k 4nv3 = (2.)& 3 TWVy Ma P (13) Am…
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ic Rev. Confirming Pages Exp. 35 Raman Spectroscopy: Vibrational Spectrum of CCl, 403 If one expresses the frequencies in wavenumbers y…
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Rev. Confirming Pages ic 404 Chapter XIV Spectroscopy FIGURE 2 Polarization arrangements for Raman depolarization measurements.…
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ic Rev. Confirming Pages Exp. 35 Raman Spectroscopy: Vibrational Spectrum of CCl, 405 You will note some structure in the Stokes band near…
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Rev. Confirming Pages ic 406 Chapter XIV Spectroscopy with programs with visualization options, such as HyperChem, animated displays of the…
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ic Rev. Confirming Pages Exp. 36 Stimulated Raman Spectra of Benzene 407 EXPERIMENT 36 Stimulated Raman Spectra of Benzene In Exp. 35,…
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Rev. Confirming Pages ic 408 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec3:408 Yo Vsi Yo Yo | Vsi Vsi} Yo Yo |Ysi Yo |VAI Vin ky kin…
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ic Rev. Confirming Pages Precision of Calculations 31 PRECISION OF CALCULATIONS The rules given above for determining the number of…
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ic Rev. Confirming Pages Exp. 36 Stimulated Raman Spectra of Benzene 409 the fields of the second harmonic photons to give a laserlike beam…
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Rev. Confirming Pages ic 410 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec3:410 efficient, with greater than 10 percent conversion of…
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ic Rev. Confirming Pages Exp. 36 Stimulated Raman Spectra of Benzene 411 As for most molecules, Raman-active modes that retain the full…
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Rev. Confirming Pages ic 412 Chapter XIV Spectroscopy FIGURE 2 Experimental setup for the measurement of stimulated Raman spectra. The…
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ic Rev. Confirming Pages Exp. 36 Stimulated Raman Spectra of Benzene 413 manufacturer. A suitable grating with d = 1333.3 nm (750 lines per…
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Rev. Confirming Pages ic 414 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec3:414 With a photomultiplier detector, the measurement can…
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ic Rev. Confirming Pages Exp. 36 Stimulated Raman Spectra of Benzene 415 instructor has determined it is safe to remove them to make…
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Rev. Confirming Pages ic 416 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec3:416 EXPERIMENT 37 Vibrational-Rotational Spectra of HCI…
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ic Rev. Confirming Pages Exp. 37 Vibrational-Rotational Spectra of HCland Dc 417 with the levels expressed as term values T in cm! units…
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Rev. Confirming Pages ic 418 Chapter XIV Spectroscopy state (v" = 0) to J’ levels in the first excited vibrational state (v’ = 1). From the…
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Confirming Pages ic 32 = Chapter Il Treatment of Experimental Data gar28420_ch02_029-067.indd 32 The uncertainty in 0.132 is about 0.7…
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ic Rev. Confirming Pages Exp. 37 Vibrational-Rotational Spectra of HClandDcl| 419 FIGURE 3 P branch R branch Schematic vibrational- 6 5 4 5…
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Rev. Confirming Pages ic 420 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec12:420 A similar conclusion is reached if U(r) is taken to…
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ic Rev. Confirming Pages Exp. 37 Vibrational-Rotational Spectra of HClandDc|_ 421 EXPERIMENTAL A general description of infrared…
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Rev. Confirming Pages ic 422 Chapter XIV Spectroscopy FIGURE 5 Apparatus for preparing deuterium chloride. gar28420_ch14_393-499 Sec12:422…
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ic Rev. Confirming Pages Exp. 37 Vibrational-Rotational Spectra of HCland DCc| 423 cm! units to tenths of acm”! if possible. Then list the…
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Rev. Confirming Pages ic 424 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec12:424 APPARATUS Medium- or high-resolution infrared grating…
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ic Rev. Confirming Pages Exp. 38 Vibrational-Rotational Spectra of Acetylenes 425 and intensity patterns of the spectral transitions is…
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Rev. Confirming Pages ic 426 Chapter XIV Spectroscopy FIGURE 1 Vibrational energy levels and relevant infrared-active transitions for…
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ic Rev. Confirming Pages Exp. 38 Vibrational-Rotational Spectra of Acetylenes 427 frequency v;. The precise combination is obtained by…
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Rev. Confirming Pages ic 428 chapter XIV Spectroscopy gar28420_ch14_393-499 Sec4:428 and the equivalent pair ,, “, are of symmetries =; and…
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ic Confirming Pages Numerical Methods 33 functions f(x) are difficult to integrate analytically, and the roots of some equations are dif-…
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ic Rev. Confirming Pages Exp. 38 Vibrational-Rotational Spectra of Acetylenes 429 The normal modes are combinations of r, R, and 6…
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Rev. Confirming Pages ic 430 Chapter XIV Spectroscopy Dy 600 cm 700cm FIGURE 2 Aah 800 cm 900 cm7 1300 cm =1400cm_ 1500 cm~ 3200 cm 3600…
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ic Rev. Confirming Pages Exp. 38 Vibrational-Rotational Spectra of Acetylenes 431 Intensities and Statistical Weights. The absolute…
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Rev. Confirming Pages ic 432 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec4:432 TABLE 2 Infrared regions to be scanned for acetylenes…
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ic Rev. Confirming Pages Exp. 38 Vibrational-Rotational Spectra of Acetylenes 433 FIGURE 3 Pressure Apparatus for the synthesis of gauge…
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Rev. Confirming Pages ic 434 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec4:434 acetylenes owing to overlap with combination and…
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ic Rev. Confirming Pages Exp. 38 Vibrational-Rotational Spectra of Acetylenes 435 solution of Eqs. (7a) and (7b) for both isotopic species.…
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Rev. Confirming Pages ic 436 Chapter XIV Spectroscopy Round-bottom flask (250 mL) with septum port; syringe; 5 mL D,O (99+ percent);…
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ic Rev. Confirming Pages Exp. 39 Absorption and Emission Spectra of 437 resolution and extensive rotational structure® at very high…
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Rev. Confirming Pages ic 438 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec5:438 energy, E,, is the vibrational energy, and E, is the…
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Confirming Pages ic 34 = Chapter Il Treatment of Experimental Data gar28420_ch02_029-067.indd Sec1:34 extrapolations, interpolations, and…
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ic Rev. Confirming Pages Exp. 39 Absorption and Emission Spectra of 439 The energy D, to dissociate from the v = 0 level is smaller than D,…
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Rev. Confirming Pages ic 440 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec5:440 This is a general equation for the transition…
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ic Rev. Confirming Pages Exp. 39 Absorption and Emission Spectra of 441 FIGURE 2 A portion of the medium- resolution spectrum of the…
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Rev. Confirming Pages ic 442 Chapter XIV Spectroscopy FIGURE 3 I, transitions excited within the gain curve of a doubled Nd:YAG laser at…
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ic Rev. Confirming Pages Exp. 39 Absorption and Emission Spectra of 443 The cell is prepared by adding several crystals of I,, after which…
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Rev. Confirming Pages ic 444 Chapter XIV Spectroscopy gar28420_ch14_393-499.indd Sec5:444 Emission Spectrum. The emission spectrum should…
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ic Rev. Confirming Pages Exp. 39 Absorption and Emission Spectra of 445 to calculate a ground-state potential-energy curve for comparison…
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Rev. Confirming Pages ic 446 Chapter XIV Spectroscopy 8. J. Tellinghuisen, J. Chem. Educ. 58, 438 (1981). 9. See G. Herzberg, Vol. I, op.…
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ic Rev. Confirming Pages Exp. 40 Fluorescence Lifetime and Quenching in|, Vapour 447 TABLE 1 I, atlas line no.” Wavenumber Assignment 1109…
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Rev. Confirming Pages ic 448 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec6:448 It is found that the lifetimes change as v’ and J’…
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ic Rev. Confirming Pages Graphs and Graphical Methods 35 1. Design an Overall Layout. In planning the overall dimensions of the plot,…
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ic Rev. Confirming Pages Exp. 40 EXPERIMENTAL The pulsed laser beam in this experiment is of high power and can cause eye damage. Read the…
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Rev. Confirming Pages ic 450 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec6:450 50 ©. at the oscilloscope to ensure fast time…
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ic Rev. Confirming Pages Exp. 40 Fluorescence Lifetime and Quenching in|, Vapour 451 term on the right-hand side of Eq. (4) will be…
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Rev. Confirming Pages ic 452 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec6:452 TABLE 2 Molecular properties of some collision…
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ic Rev. Confirming Pages Exp. 40 Fluorescence Lifetime and Quenching in|, Vapour 453 Theoretical Calculations. The program Gaussian can be…
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Rev. Confirming Pages ic 454 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec6:454 9. G.E. Busch, R. T. Mahoney, R. I. Morse, and K. R.…
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ic Rev. Confirming Pages Exp. 41 Electron Spin Resonance Spectroscopy 455 angular momenta for each electron. Since spin is a vector…
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Rev. Confirming Pages ic 456 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec7:456 To chemists, the principal aspect of interest in…
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ic Rev. Confirming Pages Exp. 41 Electron Spin Resonance Spectroscopy 457 3.75 FIGURE 2 gauss Proton hyperfine splitting j pattern in the…
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Rev. Confirming Pages ic 458 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec7:458 dy = 0.0529 nm equal to the Bohr radius. The resultant…
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Confirming Pages ic 36 Chapter Il Treatment of Experimental Data them greater visibility. If it is desired to draw a straight line “by eye”…
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ic Rev. Confirming Pages Exp. 41 Electron Spin Resonance Spectroscopy 459 FIGURE 3 Crvetal Schematic diagram of an detector ESR…
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Rev. Confirming Pages ic 460 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec7:460 Prepare 5 to 10 mL of concentrated solution (1 M or…
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ic Rev. Confirming Pages Exp. 41 Electron Spin Resonance Spectroscopy 461 by a simple linear combination of the constants. After you have a…
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Rev. Confirming Pages 462 Chapter XIV Spectroscopy These equations have a nontrivial solution only if the corresponding secular determinant…
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ic Rev. Confirming Pages Exp. 41 Electron Spin Resonance Spectroscopy 463 Since a and f are negative, negative values X; correspond to…
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Rev. Confirming Pages ic 464 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec7:464 TABLE 2 Hiickel molecular-orbital calculations for…
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ic Rev. Confirming Pages Exp. 41 Electron Spin Resonance Spectroscopy 465 TABLE 3 Calculated Hiickel molecular-orbital spin densities for…
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Rev. Confirming Pages ic 466 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec7:466 7. H.M. McConnell, J. Chem. Phys. 24, 764 (1956). 8.…
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Rev. Confirming Pages Exp. 42 NMR Determination of Keto-Enol Equilibrium Constants where B,,. is the magnetic induction (“local field”) at…
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Rev. Confirming Pages ic 468 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec8:468 TABLE 1 Typical proton chemical shifts 5 CH; protons…
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ic Confirming Pages Graphs and Graphical Methods 37 FIGURE 2 A graphical method of determining the limit of error ina slope. GRAPHICAL…
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ic Rev. Confirming Pages Exp. 42 NMR Determination of Keto-Enol Equilibrium Constants 469 CH spin FIGURE 2 Energy levels, transitions, and…
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Rev. Confirming Pages ic 470 Chapter XIV Spectroscopy FIGURE 3 NMR spectrum of highly purified ethanol obtained at 100 MHz.…
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ic Rev. Confirming Pages Exp. 42 NMR Determination of Keto-Enol Equilibrium Constants 471 FIGURE 4 f } , 4 14 | t t tf 4 { Illustration of…
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Rev. Confirming Pages ic 472 = Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec8:472 that distinct NMR spectra are obtained for both…
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ic Rev. Confirming Pages Exp. 42 NMR Determination of Keto-Enol Equilibrium Constants 473 For FT-NMR instruments that require a deuterated…
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Rev. Confirming Pages ic 474 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec8:474 Further aspects of this equilibrium that could be…
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ic Rev. Confirming Pages Exp. 43 NMR Study of Gas-Phase DCI-HBr Isotopic Exchange Reaction 475 EXPERIMENT 43 NMR Study of Gas-Phase DCI-HBr…
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Rev. Confirming Pages ic 476 Chapter XIV Spectroscopy FIGURE 1 Potential-energy diagram relevant to the DCI-HBr exchange reaction. The v =…
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ic Rev. Confirming Pages Exp. 43 NMR Study of Gas-Phase DCI-HBr Isotopic Exchange Reaction 477 TABLE 1 Molecular parameters (cm~')?…
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Rev. Confirming Pages ic 478 Chapter XIV Spectroscopy FIGURE 2 (a) Magnetic-moment distribution at the start of the nuclear induction…
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Confirming Pages ic 38 Chapter Il_ Treatment of Experimental Data gar28420_ch02_029-067.indd 38 2. The viscosity 7 of pure ethanol in…
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ic Rev. Confirming Pages Exp. 43. NMR Study of Gas-Phase DCI-HBr Isotopic Exchange Reaction 7/2 pulse, after which the M vector is aligned…
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Rev. Confirming Pages ic 480 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec9:480 exchange processes (T>) and by the residual magnetic…
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ic Rev. Confirming Pages Exp. 43 NMR Study of Gas-Phase DCI-HBr Isotopic Exchange Reaction 481 FIGURE 4 Apparatus for small-scale Pressure…
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Rev. Confirming Pages ic 482 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec9:482 To fill the valved NMR cell to | bar, it is necessary…
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ic Rev. Confirming Pages Exp. 43 NMR Study of Gas-Phase DCI-HBr Isotopic Exchange Reaction 483 of the rotational partition function…
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Rev. Confirming Pages ic 484 Chapter XIV Spectroscopy FIGURE 1 Pumping-emission cycle for a typical four-level laser. gar28420_ch14_393-499…
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ic Rev. Confirming Pages Exp. 44 Solid-State Lasers: Radiative Properties of Ruby Crystals 485 FIGURE 2 is Energy-level diagram for the…
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Rev. Confirming Pages ic 486 Chapter XIV Spectroscopy FIGURE 3 Energy-level diagram for the Cr°*:A1,0, ruby system. gar28420_ch14_393-499…
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ic Rev. Confirming Pages Exp. 44 Solid-State Lasers: Radiative Properties of Ruby Crystals 487 spins are unpaired, but pairing of two of…
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Rev. Confirming Pages ic 488 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec10:488 Following excitation at 532 nm into the *T, state at…
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iv Contents gar28420_fm_i-x iv Confirming Pages ic Ill. USE OF COMPUTERS 68 Word Processors 68 Spreadsheets 69 Symbolic Mathematics…
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ic Confirming Pages Errors 39 output, corresponding to +1 in the final digit, is smaller than the differences expected between different…
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ic Rev. Confirming Pages Exp. 44 Solid-State Lasers: Radiative Properties of Ruby Crystals 489 occurs at temperatures above about 200°C,…
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Rev. Confirming Pages ic 490 Chapter XIV Spectroscopy FIGURE 5 Ruby sample holder and experimental arrangement for radiative-lifetime…
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ic Rev. Confirming Pages Exp. 44 Solid-State Lasers: Radiative Properties of Ruby Crystals 491 slightly and transfer the data to a…
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Rev. Confirming Pages ic 492 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec10:492 APPARATUS Nd:YAG laser with second-harmonic output of…
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ic Rev. Confirming Pages Exp. 45 Spectroscopic Properties of CdSe Nanocrystals 493 FIGURE 1 (a) The wurtzite crystal structure of bulk…
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Rev. Confirming Pages ic 494 Chapter XIV Spectroscopy FIGURE 2 Schematic parabolic band structure for CdSe, which has a band gap E, of 1.75…
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ic Rev. Confirming Pages Exp. 45 Spectroscopic Properties of CdSe Nanocrystals 495 indicated in Fig. 2. Thus, the fundamental (n = 1)…
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Rev. Confirming Pages ic 496 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec11:496 Equations (6) and (7) predict a transition whose…
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ic Rev. Confirming Pages Exp. 45 Spectroscopic Properties of CdSe Nanocrystals 497 well-defined maximum at the n = 1 exciton peak. Thus,…
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Rev. Confirming Pages ic 498 Chapter XIV Spectroscopy gar28420_ch14_393-499 Sec11:498 and then do a least-squares fit of the left-hand side…
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Confirming Pages ic 40 Chapter Il Treatment of Experimental Data gar28420_ch02_029-067.indd Sec2:40 The difference between a factor of N —…
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ic Rev. Confirming Pages Exp. 45 Spectroscopic Properties of CdSe Nanocrystals (www.evidenttech.com), Nanomaterials and Nanofabrication…
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500 gar28420_ch15_500-537.indd 500 Confirming Pages & EXPERIMENTS 46. Determination of Crystal Structure by X-Ray Diffraction 47. Lattice…
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ic Confirming Pages Exp. 46 Determination of Crystal Structure by X-Ray Diffraction 501 A crystal may for some purposes be described in…
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502 Chapter XV Solids FIGURE 2 Cubic unit cells: P, primitive; I, body-centered; F, face- centered. gar28420_ch15_500-537.indd Sec1:502…
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ic Rev. Confirming Pages Exp. 46 Determination of Crystal Structure by X-Ray Diffraction 503 Bragg Reflections. Let us now determine the…
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504 Chapter XV Solids gar28420_ch15_500-537.indd Sec1:504 Confirming Pages ic planes. If, however, there is a very large (or “infinite”)…
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ic Confirming Pages Exp. 46 Determination of Crystal Structure by X-Ray Diffraction 505 For a face-centered lattice F, some of the lattice…
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506 Chapter XV Solids gar28420_ch15_500-537.indd Sec1:506 Confirming Pages TABLE 1 Possible values of M? for cubic lattices hkl M P, Ve M2…
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ic Confirming Pages Exp. 46 Determination of Crystal Structure by X-Ray Diffraction 507 I hkl M P, M2 mM we/.2 F, 444 6.9282 48 48 24 48…
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508 Chapter XV Solids gar28420_ch15_500-537.indd Sec1:508 Confirming Pages ic symmetry, though the number of possible choices may not be…
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ic Confirming Pages Errors 41 “A” on the experiment). Persons of the highest character may not be altogether immune from this tendency,…
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ic Confirming Pages Exp. 46 Determination of Crystal Structure by X-Ray Diffraction 509 The diffraction pattern of a powdered material can…
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510 Chapter XV_ Solids gar28420_ch15_500-537.indd Sec1:510 Confirming Pages crystallographic planes. The direction of the diffracted rays…
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ic Confirming Pages Exp. 46 Determination of Crystal Structure by X-Ray Diffraction 511 the actual values of the wavelengths should then be…
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512 Chapter XV Solids FIGURE 7 Philips powder camera (shown with cover not in place). gar28420_ch15_500-537.indd Sec1:512 Confirming Pages…
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ic Confirming Pages Exp. 46 Determination of Crystal Structure by X-Ray Diffraction 513 dimensions of the collimating system. Typical…
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514 Chapter XV_ Solids gar28420_ch15_500-537.indd Sec1:514 Confirming Pages ic be used if at all possible, even if they are broad and…
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ic Rev. Confirming Pages Exp. 47 Lattice Energy of Solid Argon 515 REFERENCES 1. C. Giacovazzo (ed.), Fundamentals of Crystallography,…
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516 Chapter XV_ Solids Rey. Confirming Pages TABLE 1 Second virial coefficient of argon‘ (B in units cm? mol"') T(K) B dB/dT T(K) B dBldT…
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ic Confirming Pages Exp. 47 Lattice Energy of Solid Argon 517 of on for the solid and liquid phases and the experimental enthalpy of fusion…
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518 Chapter XV_ Solids FIGURE 1 Lennard-Jones potential U(r) as a function of interatomic distance r. The characteristic parameters ¢ and o…
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Confirming Pages ic 42 Chapter Il Treatment of Experimental Data gar28420_ch02_029-067.indd Sec2:42 executing the experiment. If the…
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ic Confirming Pages Exp. 47 Lattice Energy of Solid Argon 519 where d is the distance between nearest neighbors. Note that almost all the…
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Confirming Pages ic 520 Chapter XV Solids FIGURE 2 Filling port. Low-temperature vapor- pressure apparatus. (Metal parts to be well tinned…
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gar28420_ch15_500-537.indd Sec2:521 Confirming Pages Exp. 47 Lattice Energy of Solid Argon To high-capacity pump To To pressure gauge…
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522 Chapter XV Solids gar28420_ch15_500-537.indd Sec2:522 Confirming Pages ic Warning: A closed system containing a liquid with a normal…
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ic Confirming Pages Exp. 48 Statistical Thermodynamics of lodine Sublimation 523 SAFETY ISSUES Gas cylinders must be chained securely to…
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524 Chapter XV Solids gar28420_ch15_500-537.indd Sec3:524 Confirming Pages ic temperatures, are obtained from optical absorption…
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ic Confirming Pages Exp. 48 Statistical Thermodynamics of lodine Sublimation 525 In order to evaluate the canonical partition function Q…
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526 Chapter XV Solids gar28420_ch15_500-537.indd Sec3:526 Confirming Pages ic The translational partition function is given by” QmmkT \*?…
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ic Confirming Pages Exp. 48 Statistical Thermodynamics of lodine Sublimation 527 vibrational state.t Accordingly the energy of the…
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528 Chapter XV Solids FIGURE 1 The crystal structure of 1,(s).° The primitive unit cell, outlined in heavy lines, contains two molecules,…
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ic Confirming Pages Statistical Treatment of Random Errors 43 It should be noted that only one value in a series may be discarded in this…
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ic Rev. Confirming Pages Exp. 48 Statistical Thermodynamics of lodine Sublimation 529 where A; is the instantaneous amplitude of a…
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530 Chapter XV Solids gar28420_ch15_500-537.indd Sec3:530 Rey. Confirming Pages ic TABLE 1 Discrete (representative) phonon frequencies in…
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ic Rev. Confirming Pages Exp. 48 Statistical Thermodynamics of lodine Sublimation 531 Equilibrium Between Crystal and Gas. On substituting…
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532 Chapter XV Solids gar28420_ch15_500-537.indd Sec3:532 Confirming Pages ic EXPERIMENTAL The determination of the vapor pressure of solid…
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ic Confirming Pages Exp. 48 Statistical Thermodynamics of lodine Sublimation 533 FIGURE 3 Absorbance of I,(g), in equilibrium with the…
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534 Chapter XV Solids FIGURE 4 Suggested design for water-jacketed Pyrex spectrophotometer cell containing iodine. The recommended material…
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ic Rev. Confirming Pages Exp. 48 Statistical Thermodynamics of lodine Sublimation 535 TABLE 2 Molar absorption coefficients of iodine vapor…
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536 Chapter XV Solids gar28420_ch15_500-537.indd Sec3:536 Confirming Pages ic DISCUSSION Of the two methods of determining AE» with Eq.…
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ic Confirming Pages Exp. 48 Statistical Thermodynamics of lodine Sublimation 537 P. W. Atkins and J. de Paula, op. cit., pp. 596-597. C.…
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538 gar28420_ch16_538-556.indd 538 Confirming Pa; The rapid development of solid-state electronic devices in the last two decades has had a…
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Rey. Confirming Pages 44 Chapter Il Treatment of Experimental Data FIGURE 3 A typical distribution of errors. The bar graph represents the…
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gar28420_ch16_538-556.indd Sec8:539 Rev. Confirming Pages Connection LL tL * — a Fuse Resistor Resistor Capacitor Capacitor Capacitor…
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Rey. Confirming Pages ic 540 Chapter XVI Electronic Devices and Measurements FIGURE 2 Resistor code for ordinary (two-digit) and precision…
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ic Confirming Pages Circuit Elements 541 FIGURE 3 Typical labeling schemes for common capacitors. (a) and (b) are ceramic capacitors of 150…
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Confirming Pages ic 542 Chapter XVI Electronic Devices and Measurements gar28420_ch16_538-556.indd Sec2:542 Inductors, sometimes termed…
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ic Rev. Confirming Pages Operational Amplifiers 543 FIGURE 4 Simplified schematic of an LF351 BiFET integrated circuit operational…
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Rey. Confirming Pages ic 544 Chapter XVI_ Electronic Devices and Measurements FIGURE 5 Representation of an operational amplifier.…
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ic Confirming Pages Operational Amplifiers 545 Switch FIGURE 6 Some circuit configurations Vo=V; c with operational amplifiers. i vi R “…
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Confirming Pages ic 546 Chapter XVI _ Electronic Devices and Measurements gar28420_ch16_538-556.indd Sec2:546 flows into the inverting…
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ic Rev. Confirming Pages Analog-to-Digital Conversion 547 in | FIGURE 7 Thermocouple amplification using an instrumentation amplifier. 2R…
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Rey. Confirming Pages ic 548 Chapter XVI_ Electronic Devices and Measurements FIGURE 8 Dual-slope type A/D converter. For calibration,…
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ic Rev. Confirming Pages Statistical Treatment of Random Errors 45 If the true value x and thus the errors e, themselves are known, o can…
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ic Confirming Pages Analog-to-Digital Conversion 549 is thus determined by the accuracy and stability of the reference source. Resolution…
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Rey. Confirming Pages ic 550 Chapter XVI Electronic Devices and Measurements FIGURE 10 Block diagram of a digital multimeter (DMM).…
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Confirming Pages for example the averaging meter gives a value that is high by 11.1 percent for a square wave and low by 3.8 percent for a…
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Rey. Confirming Pages ic 552 Chapter XVI _ Electronic Devices and Measurements FIGURE 12 Schematic diagram of a simple slide-wire…
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ic Confirming Pages Potentiometer Circuits 553 The adjustment of the current through the slide-wire is accomplished by connecting a source…
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Confirming Pages ic 554 Chapter XVI_ Electronic Devices and Measurements vw FIGURE 14 Operational amplifier circuit to deliver current at a…
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ic Rev. Confirming Pages Wheatstone Bridge Circuits 555 voltage source is an oscillator, operating usually at 1 kHz (or any convenient…
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Rey. Confirming Pages ic 556 Chapter XVI_ Electronic Devices and Measurements gar28420_ch16_538-556.indd Sec7:556 Equation (19) is the…
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Confirming Pages Temperature is one of the most important variables in physical chemistry. In this chapter we are concerned with the…
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Confirming Pages ic 558 Chapter XVII Temperature gar28420_ch17_557-586.indd 558 TABLE 1 Fixed points of the International Temperature Scale…
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Rey. Confirming Pages ic 46 Chapter II Treatment of Experimental Data FIGURE 4 The integrated probability P for a normal error…
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ic Confirming Pages Temperature Scales 559 TABLE 2 Unofficial list of secondary reference points To (KK) Substance Kind* 63.152 N, Triple…
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Confirming Pages ic 560 Chapter XVII Temperature gar28420_ch17_557-586.indd Sec1:560 4. Range Above 1234.93 K. Above the freezing point of…
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ic Rev. Confirming Pages Triple-Point and Ice-Point Cell 561 range but rise to +80 mK at 350°C because an extrapolation beyond the fitted…
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Confirming Pages ic 562 Chapter XVII Temperature gar28420_ch17_557-586.indd Sec2:562 of practical thermometers. The ice point refers to an…
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ic Confirming Pages Thermometers 563 an outer glass shell. The enclosed-scale type is preferable for thermometers with extremely fine…
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Rey. Confirming Pages ic 564 Chapter XVII Temperature FIGURE 2 Schematic diagram of a two- junction thermocouple setup.…
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ic Rev. Confirming Pages Thermometers 565 the thermoelectric potential difference AV is measured between the ends of two wires of the same…
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Confirming Pages ic 566 Chapter XVII Temperature gar28420_ch17_557-586.indd Sec3:566 TABLE 3. Thermocouple characteristics Useful wees “1…
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ic Confirming Pages Thermometers 567 at lower temperatures after cycling above 760°C. A Chromel—Constantan (type E) thermo- couple is…
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Rey. Confirming Pages ic 568 Chapter XVII Temperature gar28420_ch17_557-586.indd Sec3:568 as high as 1425°C. Bare wires and Alundum tubes…
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ic Rev. Confirming Pages Statistical Treatment of Random Errors 47 of the measurements for which we use the quantity S, the estimated…
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ic Confirming Pages Thermometers 569 at minimizing errors due to heat conduction and radiation and maximizing stability and calibration…
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Rey. Confirming Pages ic 570 Chapter XVII_ Temperature FIGURE 4 Measurement of a four-lead PRT with a three-terminal Wheatstone bridge. The…
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ic Confirming Pages Thermometers 571 For a PRT with R, = 100 Q, a temperature resolution of +1 mK requires that R, be measured with a…
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Rey. Confirming Pages ic 572 Chapter XVII Temperature FIGURE 6 Resistance versus temperature characteristics for several typical…
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ic Confirming Pages Thermometers 573 TABLE 4 Comparison of performance characteristics for thermocouples, platinum resistance thermometers…
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Rey. Confirming Pages ic 574 Chapter XVII Temperature points given in Tables 1 and 2. Since thermistors are often used between 0°C and…
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ic Confirming Pages Thermometers 575 The optical pyrometer is essentially a photometer that measures the radiation inten- sity in a given…
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Confirming Pages ic 576 Chapter XVII Temperature gar28420_ch17_557-586.indd Sec3:576 inexpensive and sensitive, but they are subject to…
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ic Confirming Pages Temperature Control 577 There are two basic methods of achieving a constant temperature:”° 1. Phase equilibrium is…
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Confirming Pages ic 578 Chapter XVII Temperature gar28420_ch17_557-586.indd Sec4:578 TABLE 5 Materials suitable for low-temperature slush…
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Rey. Confirming Pages ic 48 Chapter Il Treatment of Experimental Data gar28420_ch02_029-067.indd Sec3:48 as the probability distribution…
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ic Rev. Confirming Pages Temperature Control 579 As in any system employing feedback to maintain a steady-state condition, certain design…
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Rey. Confirming Pages ic 580 Chapter XVII_ Temperature FIGURE 9 PB =25K Heater power output W from a proportional controller Wax as a…
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ic Confirming Pages Temperature Control 581 Slant EnnEEEEE EEE 1 FIGURE 12 | Schematic diagram of a | temperature-controlled | block at a…
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Confirming Pages ic 582 Chapter XVII Temperature gar28420_ch17_557-586.indd Sec4:582 Commercial Controllers. There is a large variety of…
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ic Confirming Pages Temperature Control 583 Thermometers. The sensor probe should be placed in the bath in a central location removed from…
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Confirming Pages ic 584 Chapter XVII Temperature gar28420_ch17_557-586.indd Sec4:584 also needed. Many of the low-temperature units…
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ic Confirming Pages metal container. After assembly, the furnace is slowly heated to slightly above 1000°C to set the cement. A cover plug…
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Confirming Pages ic 586 Chapter XVII_ Temperature gar28420_ch17_557-586.indd Sec5:586 19. A. Benjaminson and F. Rowland, “The Development…
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This chapter includes discussions of various topics of importance in the practice of han- dling gases at low pressures. Major emphasis is…
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Confirming Pages ic 588 Chapter XVIII Vacuum Techniques gar28420_ch18_587-600 Sec4:588 of about 10° Torr; however, there are special types…
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gar28420_fm_i-x v Confirming Pages Xi. SURFACE PHENOMENA 299 25. Surface Tension of Solutions 299 26. Physical Adsorption of Gases 308 XII.…
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gar28420_ch02_029-067.indd Sec3:49 Rev. Confirming Pages Statistical Treatment of Random Errors P(t) K norm “Critical” values of t for a…
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ic Confirming Pages Pumps 589 Gas intake FIGURE 1 Schematic diagram of a rotary oil pump similar to the Welch Duo-Seal; based on the Gaede…
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590 Chapter XVIII Vacuu FIGURE 2 Roots blower. gar28420_ch18_587-600 Sec1:590 Confirming Pages ic m Techniques resultant contamination of…
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ic Confirming Pages Pumps 591 contains the gas being pumped as a minority component; the very slight pressure differ- ence against which…
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Confirming Pages ic 592 Chapter XVIII Vacuum Techniques gar28420_ch18_587-600 Sec1:592 TABLE 1 Diffusion pump oils Vapor pressure at Name…
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ic Confirming Pages Pumps 593 To vacuum FIGURE 4 manifold Schematic drawing of a multistage, water-cooled, all- metal oil diffusion pump.…
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Confirming Pages ic 594 Chapter XVIII Vacuum Techniques gar28420_ch18_587-600 Sec1:594 The components of air are chemisorbed on the fresh…
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ic Confirming Pages TABLE 2 Operational range of various vacuum gauges (in Torr) Bourdon gauge 1—1000 Mercury manometer 1—1000 Oil…
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Confirming Pages ic 596 Chapter XVIII Vacuum Techniques FIGURE 5 Design for a closed- tube laboratory mercury manometer. The capillary…
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ic Confirming Pages Pressure Gauges 597 A third class of pressure-measuring devices is based on the change in resistance of thick-film…
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Confirming Pages ic 598 Chapter XVIII_ Vacuum Techniques gar28420_ch18_587-600 Sec2:598 However, most ionization gauges are thermionic…
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Rey. Confirming Pages ic 50 Chapter II Treatment of Experimental Data gar28420_ch02_029-067.indd Sec3:50 TABLE 4 Factors for small-sample…
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ic Confirming Pages References 599 inside by an electron multiplier arrangement or outside by a vacuum-tube electrometer or by both.…
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Confirming Pages ic 600 Chapter XVIII_ Vacuum Techniques GENERAL READING R. P. Benedict, Fundamentals of Temperature, Pressure, and Flow…
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Confirming Pages This chapter consists of brief descriptions and discussions of certain devices and instru- ments that are commonly used in…
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Confirming Pages ic 602 Chapter XIX _ Instruments FIGURE 1 A single-pan mechanical analytical balance. gar28420_ch19_601-638 602 Fulcrum…
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ic Rev. Confirming Pages Balances 603 Nuil FIGURE 2 detector Simplified electromagnetic servo system for an electronic balance. Error ¥…
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Confirming Pages ic 604 Chapter XIX_ Instruments gar28420_ch19_601-638 Sec1:604 In top-loading versions of the electronic balance, the…
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ic Confirming Pages Oscilloscopes 605 The most common source of error in weighings, especially with two-pan balances, is due to inaccurate…
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Rev. Confirming Pages ic 606 Chapter XIX_ Instruments FIGURE 4 Detailed sketch of a Fortin barometer. Uncorrected reading shown is 79.02…
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ic Rev. Confirming Pages All oscilloscopes have an internal sawtooth waveform generator to produce this linear time-base sweep. In recent…
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Rev. Confirming Pages ic 608 Chapter XIX_ Instruments FIGURE 6 Lissajous figures: (a) several simple figures, with the ratios fy:fy…
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ic Confirming Pages Statistical Treatment of Random Errors 51 one of the marks of a good experimentalist. It would be very difficult to…
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ic Rev. Confirming Pages PH Meters 609 TABLE 1 Half-cell potentials of calomel reference electrodes KCI Conc Potential at 25°C, V 0.1.N…
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Rev. Confirming Pages ic 610 Chapter XIX_ Instruments gar28420_ch19_601-638 Sec3:610 Glass Electrode.'? The glass electrode is usually a…
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ic Rev. Confirming Pages Polarimeters 611 POLARIMETERS The polarimeter (Fig. 8) is an instrument for measuring the optical rotation…
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Confirming Pages ic 612 Chapter XIX_ Instruments gar28420_ch19_601-638 Sec4:612 Although laboratory polarimeters generally use Nicol prisms…
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ic Confirming Pages Refractometers 613 wall is prevented by molecules of some organic compound (i.e., ethanol) that is present as a “quench…
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Rev. Confirming Pages ic 614 Chapter XIX_ Instruments FIGURE 9 Reflection and refraction at an interface: (€) bm < Perit (D) bm = Bexic ©)…
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ic Rev. Confirming Pages Refractometers 615 FIGURE 10 Field of Essential features of an view . . immersion refractometer. The behavior of…
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Rev. Confirming Pages ic 616 Chapter XIX_ Instruments FIGURE 11 Schematic diagram of an Abbe refractometer. Scale - reading Lo eyepiece…
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ic Confirming Pages Signal-Averaging Devices 617 5. Rotate the prism until the boundary between the light and dark fields appears in the…
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Confirming Pages ic 618 Chapter XIX_ Instruments gar28420_ch19_601-638 Sec6:618 only a narrow bandwidth of the input at a specified…
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Rey. Confirming Pages ic 52 Chapter II Treatment of Experimental Data gar28420_ch02_029-067.indd Sec3:52 As results are prepared for…
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ic Rev. Confirming Pages Spectroscopic Components 619 Type of FIGURE 12 Type of transition spectroscopy The electromagnetic resulting from…
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Rev. Confirming Pages 620 Chapter XIX_ Instruments 0184.91 9 280.35 +365.02 piss 26 22 O08 73 : 306 33 ae! © 226. . 0737.83 ° 6302.15 +…
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ic Rev. Confirming Pages Spectroscopic Components 621 1 FIGURE 14 200-watt mercury lamp Typical output spectra of E some discharge and…
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Rev. Confirming Pages ic 622 Chapter XIX Instruments FIGURE 15 Schematic diagram of a simple prism spectrograph. Short wavelengths are…
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ic Confirming Pages Spectroscopic Components 623 FIGURE 16 G Refractive indexes for a0 —____ various optical materials. ow Figure from Ref.…
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Confirming Pages ic 624 Chapter XIX_ Instruments FIGURE 17 Cross section of a reflection grating with groove spacing d and blaze angle 69.…
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gar28420_ch19_601-638 Sec7:625 Absolute sensitivity, mA W' 100 80 60 40 0.1 100 © Rev. Confirming Pages Spectroscopic Components 625 100;-…
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Confirming Pages ic 626 Chapter XIX_ Instruments gar28420_ch19_601-638 Sec7:626 index modulations within a thin layer of material…
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ic Confirming Pages Spectroscopic Components 627 FIGURE 20 Typical connections for Photocathode a photomultiplier tube. Secondary emission…
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Confirming Pages ic 628 Chapter XIX_ Instruments FIGURE 21 Cross section of a p-n photodiode (a) and potential energy diagram or the…
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ic Confirming Pages Propagation of Errors 53 quantity x is established, the sign and magnitude of €(x) is known, and Eq. (37) can be used…
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ic Confirming Pages Spectroscopic Components 629 Detector arrays of up to 4000 silicon diodes are commercially available and are used in…
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Confirming Pages ic 630 Chapter XIX_ Instruments FIGURE 23 Typical detectivity D* values for various thermal detectors assuming total…
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ic Confirming Pages Spectroscopic Instruments 631 sensitivity and is especially useful in the far-IR (see Fig. 23). Bolometer detectors…
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Confirming Pages ic 632 Chapter XIX_ Instruments FIGURE 24 Examples of single-beam spectrophotometers. (a) Spectronic 20 (available as…
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ic Rev. Confirming Pages Spectroscopic Instruments 633 Entrance FIGURE 25 slit Optical diagram of Varian- Cary models 219 and 2000 series…
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Confirming Pages ic 634 Chapter XIX_ Instruments gar28420_ch19_601-638 Sec8:634 holographically produced filters that reduce the Rayleigh…
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ic Rev. Confirming Pages Spectroscopic Instruments 635 Stationary mirror FIGURE 27 M, Schematic diagram of a Michelson interferometer. The…
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Rev. Confirming Pages ic 636 Chapter XIX_ Instruments FIGURE 29 Typical optical diagram of the Mattson series of FTIR instruments. Courtesy…
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ic Confirming Pages References 637 experimenter, who is operating the start and stop buttons manually. Reaction times vary greatly from one…
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Confirming Pages ic 638 Chapter XIX_ Instruments gar28420_ch19_601-638 Sec9:638 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30.…
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Confirming Pages ic 54 Chapter Il Treatment of Experimental Data gar28420_ch02_029-067.indd Sec4:54 manner, we may resort to the following…
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Physical chemistry laboratory work involves many manual arts, techniques, and proce- dures in addition to those described in earlier…
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Rey. Confirming Pages ic 640 Chapter XX Miscellaneous Procedures FIGURE 1 Typical volumetric glassware: (a) volumetric flask, (b) transfer…
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ic Confirming Pages Volumetric Procedures 641 drainage and then withdrawn after again touching the tip to the wall of the receiving vessel…
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Confirming Pages ic 642 Chapter XX Miscellaneous Procedures gar28420_ch20_639-662.indd Sec1:642 TABLE 1 Capacity tolerances of precision…
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ic Confirming Pages Volumetric Procedures 643 in handling also required) and alcoholic KOH. Clean glassware is usually allowed to drain if…
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Confirming Pages ic 644 Chapter XX Miscellaneous Procedures gar28420_ch20_639-662.indd Sec1:644 throughout the volume. This should be…
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ic Confirming Pages Gas-Handling Procedures 645 convenient and desirable to obtain gases commercially in steel cylinders. These cylin- ders…
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Rey. Confirming Pages ic 646 Chapter XX Miscellaneous Procedures gar28420_ch20_639-662.indd Sec2:646 Do not allow a cylinder to be emptied…
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ic Confirming Pages Gas-Handling Procedures TABLE 2 Common drying agents Agent (Trade name) Hydrated form Comments Mg(ClO,)» Mg(ClO,), -…
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Confirming Pages ic 648 Chapter XX Miscellaneous Procedures gar28420_ch20_639-662.indd Sec2:648 TABLE 3_ Flow meters for liquids and gases…
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ic Confirming Pages Propagation of Errors 55 provided that A, B, ... are independent. If the quantities A, B, etc., are not independent…
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ic Rev. Confirming Pages Gas-Handling Procedures 649 Length of FIGURE 2 capillary tubing A typical flow manometer. Gas flow Colored organic…
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Confirming Pages ic 650 Chapter XX Miscellaneous Procedures gar28420_ch20_639-662.indd Sec2:650 usually a thin diaphragm with a strain…
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ic Confirming Pages Electrodes for Electrochemical Cells 651 necessary with a hydrogen electrode, but good ventilation is important; there…
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Confirming Pages ic 652 Chapter XX Miscellaneous Procedures gar28420_ch20_639-662.indd Sec3:652 per liter. Use a 4.5-V battery connected in…
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ic Confirming Pages Materials for Construction 653 TABLE 5 Mechanical properties of metals Young’s modulus of elasticity Tensile strength…
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Confirming Pages ic 654 Chapter XX Miscellaneous Procedures gar28420_ch20_639-662.indd Sec4:654 cast. Aluminum is seldom plated; it can be…
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ic Confirming Pages Materials for Construction 655 permeable to it and may be mechanically damaged by exposure to it. These metals easily…
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Confirming Pages 656 Chapter XX Miscellaneous Procedures tysue.ns yeorueysout qual} Ja0o wysuans poos UONITY MOT Jeorueypaut “AYATISISAI…
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ic Confirming Pages Materials for Construction 657 Saran (Dow polyvinylidene dichloride) is a tough, chemically resistant plastic avail-…
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Confirming Pages ic 658 Chapter XX Miscellaneous Procedures gar28420_ch20_639-662.indd Sec4:658 Most of the materials that we have…
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Rey. Confirming Pages ic 56 Chapter II Treatment of Experimental Data gar28420_ch02_029-067.indd Sec4:56 treatment of uncertainties, but…
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ic Confirming Pages Solders and Adhesives 659 Hard soldering, or silver soldering, requires the use of a hand torch and a soldering paste…
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Rey. Confirming Pages ic 660 Chapter XX Miscellaneous Procedures FIGURE 3 Typical Swagelok compression fitting. gar28420_ch20_639-662.indd…
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ic Rev. Confirming Pages Shopwork 661 TABLE 7 Recommended materials for Swagelok fittings Tubing Threaded body Front ferrule Rear ferrule…
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Confirming Pages ic 662 Chapter XX Miscellaneous Procedures gar28420_ch20_639-662.indd Sec6:662 REFERENCES 10. 11. 12. 13. D. A. Skoog, D.…
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Confirming Pages Among the most common computational operations in experimental science is the fitting of experimental data to a…
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Confirming Pages ic 664 Chapter XXI_ Least-Squares Fitting Procedures gar28420_ch21_663-686 664 We will not undertake to present here a…
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ic Confirming Pages Foundations of Least Squares 665 The least-squares criterion of best fit depends upon the concept known as maximum…
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Confirming Pages ic 666 Chapter XXI_ Least-Squares Fitting Procedures and use this form in what follows on the assumption that true weights…
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ic Rev. Confirming Pages Foundations of Least Squares 667 Equations (12), constituting a set of n simultaneous linear equations in n…
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Confirming Pages ic 668 Chapter XXI_Least-Squares Fitting Procedures where 6;, is the Kronecker delta (equal to unity when j = k and equal…
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ic Rev. Confirming Pages Propagation of Errors 57 One would report this result as [a] = 152.61+0.23 deg dm'(g cm“)?! or 1.5261 + 0.0023 deg…
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ic Rev. Confirming Pages Weights 669 is the determinant |A| of the matrix Zw, wx _ f iXi oo) A (: wx, > x) ) (If unit weights are employed,…
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Confirming Pages 670 Chapter XXI_Least-Squares Fitting Procedures Example of a Weighted Least-Squares Regression Raman intensity I as a…
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ic Confirming Pages Rejection of Discordant Data 671 calculation. Alternatively, the 07 may be averaged in blocks of data, having in each…
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Rev. Confirming Pages ic 672 Chapter XXI_ Least-Squares Fitting Procedures gar28420_ch21_663-686 Sec3:672 For values of m no larger than…
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ic Rev. Confirming Pages Goodness of Fit 673 Analogous to Eq. (II-5), there is the following expression for the variance of an observation…
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Rey. Confirming Pages ic 674 Chapter XXI_ Least-Squares Fitting Procedures gar28420_ch21_663-686.indd Sec4:674 TABLE 1 Limiting values of…
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ic Confirming Pages Goodness of Fit 675 fit to a data set with m = 32 and n = 2, let us assume that x? calculated with Eq. (31b) has the…
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Confirming Pages ic 676 Chapter XXI_ Least-Squares Fitting Procedures gar28420_ch21_663-686 Sec4:676 with a central block of positive…
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ic Confirming Pages Comparison of Models 677 x21 /xX22 does not require a priori knowledge of the o; values and true weights. If good…
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Confirming Pages ic 678 Chapter XXI_Least-Squares Fitting Procedures gar28420_ch21_663-686 Sec5:678 More detailed comparison of two models…
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Rey. Confirming Pages ic 58 Chapter II Treatment of Experimental Data gar28420_ch02_029-067.indd Sec4:58 differentiation of this equation…
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ic Confirming Pages Uncertainties in the Parameters 679 For the trivial one-parameter case in which the parameter to be determined is the…
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Rev. Confirming Pages ic 680 Chapter XXI_Least-Squares Fitting Procedures gar28420_ch21_663-686 Sec6:680 Eq. (31b), using in each case the…
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ic Confirming Pages Sample Least-Squares Calculation 681 necessary to smooth the observed variances over the entire data set (see Sample…
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Confirming Pages 682 Chapter XXI_Least-Squares Fitting Procedures oro'l = "PS 9081 = Ys e801 = Ps wove = YS 2X0007'0 — 'XOS8'T — 8IDIZ =…
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ic Confirming Pages Sample Least-Squares Calculation 683 FIGURE 2 Plot of experimental points and leas squares lines: (a) straight-line fit…
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Confirming Pages ic 684 Chapter XXI_ Least-Squares Fitting Procedures gar28420_ch21_663-686 Sec7:684 Examination of the fit of the straight…
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ic Confirming Pages References 685 Coda. Now it can be told: The “experimental” y, values in Table 2 were actually generated from known…
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Confirming Pages ic 686 Chapter XXI_Least-Squares Fitting Procedures gar28420_ch21_663-686 Sec8:686 2. 3. 4. 10 . A. I. Khinchin,…
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Confirming Pages Listed below are the most common meanings of those symbols that occur frequently in this book; special usages of these…
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Confirming Pages ic 688 Appendix A Glossary of Symbols gar28420_app_687-720.indd 688 i) ° EC AACT ROMA HooNaw> VZ22 of NN =ES GUY DD & iw…
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Confirming Pages ic vi Contents XVIII. VACUUM TECHNIQUES 587 Introduction 587 Pumps 587 Pressure Gauges 594 Safety Considerations 599 XIX.…
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ic Rev. Confirming Pages Case History of an Error Evaluation 59 (instead of being neglected altogether). Then, we obtain from Eq. (42) A(T)…
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gar28420_app_687-720.indd 689 ic Confirming Pages Faraday constant Rydberg constant Thermal-expansion coefficient, degree of dissociation,…
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690 gar28420_app_687-720.indd 690 The International System of Units (SI, for Systéme International) is based on seven dimen- sionally…
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Confirming Pages International System of Units and Concentration Units There are also SI derived units with special names and symbols; some…
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Confirming Pages ic 692 Appendix B International System of Units and Concentration Units Note that the symbols for SI units and derived…
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& Confirming Pages Given below is a short reminder list of basic safety principles and specific warnings about hazards that can occur in a…
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694 Appendix Safety gar28420_app_687-720.indd 694 Confirming Pages ic assembling an electrical circuit. Remember that metal fixtures of all…
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ic Confirming Pages Safety 695 particularly hazardous substances. No strongly carcinogenic or strongly teratogenic sub- stances are used in…
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696 Appendix ¢ Safety gar28420_app_687-720.indd 696 Confirming Pages ic thoroughly bathing the eyeball. The eyelids should be lifted away…
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ic Confirming Pages Safety 697 the trap) and air at a total pressure of 1 atm has an oxygen partial pressure of 179 Torr. Thus, if an…
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698 Appendix ¢ Safety gar28420_app_687-720.indd 698 Confirming Pages ic is in terms of energy intensity (J cm~’) per flash and is more…
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Rey. Confirming Pages ic 60 Chapter Il Treatment of Experimental Data gar28420_ch02_029-067.indd Sec5:60 in Table 3 under the P = 0.95…
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ic Confirming Pages Sources of Safety Information 699 Safety Equipment. Safety glasses or goggles have been mentioned in this appen- dix…
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700 Appendix ¢ Safety gar28420_app_687-720.indd 700 Confirming Pages ic L. H. Keith and D. B. Walters (eds.), Compendium of Safety Data…
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Confirming Pages It is convenient to distinguish between two types of literature search: one concerned with a broad area of research, a…
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702 Appendix D gar28420_app_687-720.indd 702 Confirming Pages ic Literature Work Chemical Reviews Chemical Society Reviews Reviews of…
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ic Confirming Pages Physical Properties of Substances 703 tables are being supplanted by computer databases, they are still of value,…
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704 Appendix D gar28420_app_687-720.indd 704 Confirming Pages ic Literature Work Thermodynamic Tables. NIST-JANAF Thermochemical Tables,…
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ic Confirming Pages Abstract Search 705 In addition to abstract searches, SciFinder Scholar allows browsing the table of contents for a…
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706 Appendix D gar28420_app_687-720.indd 706 Confirming Pages ic Literature Work a search from 1973 to the present of more than 3000…
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Confirming Pages Out of the hundreds of different research periodicals currently being published, those listed below describe research of…
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708 Appendix E gar28420_app_687-720.indd 708 Confirming Pages Research Journals Abbreviated title Full title J. Phys. Soc. Jpn. J. Polym…
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ic Rev. Confirming Pages Fundamental Limitations on Instrumental Precision 61 rather inconspicuous pump switch. Unfortunately, he had also…
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Confirming Pages A brief introduction to numerical methods for handling experimental data is given in Chapter II, and a detailed…
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Confirming Pages ic 710 Appendix F Numerical Methods of Analysis gar28420_app_687-720.indd 710 SERIES APPROXIMATIONS For many purposes it…
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ic Confirming Pages Differentiation 711 Here the coefficients to be determined are a, and b,. This function is periodic in x, with a period…
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Confirming Pages 712 Appendix F Numerical Methods of Analysis gar28420_app_687-720.indd 712 variable x to be evenly spaced. For…
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ic Confirming Pages Integration 713 On referring to the display shown in Eq. (8), we see that the successive differences enter- ing into…
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Confirming Pages ic 714 Appendix F Numerical Methods of Analysis gar28420_app_687-720.indd 714 Simpson’s Rules. There are better procedures…
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ic Confirming Pages Root Finding 715 ROOT FINDING If a functional form y = f(x) has been obtained, one may need to determine one or more…
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Confirming Pages ic 716 Appendix F Numerical Methods of Analysis Application of Eq. (19) for the false position method gives . x 2. + 4, x…
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ic Confirming Pages REFERENCES 1. W.H. . Press, S. A. Teukolsky, W. T. Vetterling, and B. P. Flannery, Numerical Recipes—the Art of…
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Confirming Pages The entries A in the table below are calculated from Eq. (X VIII-1) on the assumption that the barometer has a brass scale…
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Rey. Confirming Pages ic 62 Chapter Il Treatment of Experimental Data gar28420_ch02_029-067.indd Sec6:62 LIMITATIONS DUE TO THERMAL…
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Confirming Pages Scientific research is an important social process. As such, it is based on “social contracts” as guidelines, and perhaps…
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Confirming Pages ic 720 Appendix H Ethical Conduct in Physical Chemistry gar28420_app_687-720.indd 720 which they contributed. Plagiarism…
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ic Rev. Confirming Pages A Abbe refractometer, 615-617 Ab initio calculations, 82-84, 397, 405, 423, 435, 444-445, 453 Absorbance, 284,…
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Rey. Confirming Pages ic 722 index B Balances: analytical, 601-605 corrections and errors, 604—605 Gouy, 365-368 Ballast bulb, 95, 203…
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Clausius—Mossotti equation, 338 Cleaning solution, 642-643 Clock reactions, 254-262 Coexistence curve, 230-234 Coherent anti-Stokes Raman…
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Rey. Confirming Pages ic 724 index Deshielding effects in NMR, 467-468 Deslandres table, 453 Detailed balancing, 264 Detectors, 612-613,…
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Enzyme kinetics, 271-282 Michaelis—Menton mechanism of, 271-273 Enzyme solution: preparation of, 279 specific activity, 281 Epoxy resins,…
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Rey. Confirming Pages ic 726 index Gases: adsorption of, 308-317 degrees of freedom in, 107 diffusion of, 124-127, 135-144 effusion of,…
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Infrared spectrometers, 633-636 detectors, 629-630 gratings, 622-624 prisms, 622 sources, 618, 622 Infrared spectrum, 420-423, 424-435…
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Rey. Confirming Pages ic 728 index Lattice types, crystal, 505-507 Lattice vibrations, 527-530 LC circuit, frequency of, 342 Least-squares…
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ic Confirming Pages Fundamental Limitations on Instrumental Precision 63 of which are subject to severe practical limitations. Doubling the…
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pressure variation of boiling point, 97 van der Waals constants for, 01 virial coefficient for, 97 Nomenclature, 10 Normal equations,…
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Rey. Confirming Pages ic 730 Index Polymers, 318-335 statistically coiled, 322-323 (see also Macromolecules; Plastics) Polynomial, fitting…
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Resonance energy, 159 Reversible reaction, 263-270 Reynolds number, 132 Root-mean-square speed, 119 Rotation, specific, 332-333, 611-612…
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Rey. Confirming Pages ic 732 index Spreadsheets—cont. exercises, 88-89 functions, 71, 77, 680 graphs, 72-73 linear regressions, 73-75…
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Transitions, vibrational: combination and difference, 428 fundamental, 425-426 overtones, 427 Transmittance, 631 Transport properties,…
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Rey. Confirming Pages ic 734 index ac circuit, 238-241, 554-556, 608 de circuit, 553-555 Wiens law, 621 Word processors, 68-69 Work:…
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ic Rev. Confirming Pages gar28420_idx_721-742.indd 735 & 1/28/08 7:19:33 PM
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ic Rev. Confirming Pages gar28420_idx_721-742.indd 737 & 1/28/08 7:19:34 PM
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Confirming Pages ic 64 Chapter II Treatment of Experimental Data gar28420_ch02_029-067.indd Sec6:64 SUMMARY The principal equations in Part…
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ic Rev. Confirming Pages gar28420_idx_721-742.indd 739 & 1/28/08 7:19:34 PM
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ic Rev. Confirming Pages gar28420_idx_721-742.indd 741 & 1/28/08 7:19:34 PM
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Rey. Confirming Pages ic gar28420_idx_721-742.indd 742 & 1/28/08 7:19:34 PM
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PHYSICAL CONSTANTS AND CONVERSION FACTORS’ 1. Values of Some Fundamental Constants Speed of light in vacuum c 299792458 m s"! (defined)…
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gar28420_ep_001-003.indd 2 3. Energy Conversion Table Three unusual but convenient “energy” quantities are temperature (K) representing the…
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RELATIVE ATOMIC MASSES‘ Atomic Atomic Atomic Atomic Element Symbol No. mass Element Symbol No. mass Actinium Ac 89 227 Mendelevium Md 101…
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Experiments in Physical Chemistry Experiments in Physical Chemistry Wodx] Carl W. Garland Joseph W. Nibler David P. Shoemaker This…
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ic Rev. Confirming Pages Propagation of Random Errors. Let x, y, z, ... be independent, directly mea- sured quantities; let F be a result…
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Rey. Confirming Pages ic 66 Chapter II Treatment of Experimental Data gar28420_ch02_029-067.indd Sec8:66 REFERENCES 10. 11. 12. 13. P. R.…
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ic Confirming Pages General Reading 67 N. C. Giri, Introduction to Probability and Statistics, 2d ed., Dekker, New York (1993). R. W.…
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68 gar28420_ch03_068-090.indd 68 Confirming Pages In most fields of physical chemistry, the use of digital computers is considered…
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gar28420_fm_i-x vii Confirming Pages APPENDICES 687 A. Glossary of Symbols 687 B. International System of Units and Concentration Units 690…
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ic Confirming Pages Spreadsheets 69 Word and WordPerfect. Although these and other commercial word processors vary some- what in the…
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Confirming Pages 70 Chapter Ill Use of Computers FIGURE 1 An Excel spreadsheet comparing potential energy curves calculated for HCI for…
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ic Rev. Confirming Pages Spreadsheets 71 of selected areas to distinguish, for example, cells for input data from those for calculated…
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Confirming Pages ic 72 Chapter Ill Use of Computers gar28420_ch03_068-090.indd Sec1:72 The value of this is obtained with the indicated…
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gar28420_ch03_068-090.indd Sec1:73 Rev. Confirming Pages ® Ch GR ew rome Fount ok rw Ep =o x A B Cc D E F cif 1 Temperature Dependence of…
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Rey. Confirming Pages ic 74 Chapter Ill Use of Computers gar28420_ch03_068-090.indd Sec1:74 In these relations, m is the number of…
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ic Confirming Pages Spreadsheets 75 Note that S(b) is given directly below the constant b (i.e., the “X coefficient”) in the output of Fig.…
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Confirming Pages & 76 Chapter Ill Use of Computers FIGURE 3 A Lotus 1-2-3 spreadsheet showing multiple linear regression results for two…
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ic Confirming Pages Spreadsheets 77 inclusion of a centrifugal distortion term can be explored in fitting vibrational—rotational data for…
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Confirming Pages 78 Chapter Ill Use of Computers FIGURE 4 An Excel spreadsheet illustrating the use of the Solver tool for nonlinear…
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Confirming Pages ic I often say that when you can measure what you are speaking about, and express it in numbers, you know something about…
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ic Confirming Pages Symbolic Mathematics Programs 79 SYMBOLIC MATHEMATICS PROGRAMS In addition to spreadsheet programs, a number of other…
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Rey. Confirming Pages ic 80 Chapter Ill Use of Computers gar28420_ch03_068-090.indd Sec2:80 Symbolics menu commands. The resultant exact…
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& Confirming Pages Symbolic Mathematics Programs 81 1. Generation of unitless parameters for ground (X) and excited (B) states; FIGURE 6…
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Confirming Pages ic 82 Chapter Ill Use of Computers gar28420_ch03_068-090.indd Sec2:82 precision of all numerical quantities at a high…
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ic Confirming Pages Quantum Mechanical Programs 83 The notation HF chooses a Hartree-Fock self-consistent-field (SCF) level of calcula-…
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Confirming Pages ic 84 Chapter Ill Use of Computers gar28420_ch03_068-090.indd Sec3:84 specific example of such a project, with the basis…
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ic Confirming Pages Interfacing with Experiments 85 However, the whole of chemistry is much more than just small, noninteracting gas-phase…
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Confirming Pages ic 86 Chapter IIl_ Use of Computers FIGURE 7 Screen display of data collected with the LabPro measurement system.…
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ic Confirming Pages Interfacing with Experiments 87 sheath, and the photomultiplier signal shows the temperature effect on the optical…
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Rey. Confirming Pages ic 88 Chapter Ill Use of Computers gar28420_ch03_068-090.indd Sec4:88 text boxes, graphs, charts, etc. The Block…