Practice of Kinetics (Comprehensive Chemical Kinetics, Volume 1)

More documents

Recommendations

Info

4 THE SOLID-SOLID INTERFACE 257Fig. 42. Block diagram of an apparatus for differential thermal analysis. Area inside the circleis enlarged to show details of the thermocouples and sample block. B, sample block; F, furnace;R, reference material; S, sample; HC, furnace heating current; Th, furnace thermocouple.characteristic of the reaction which has occurred. A block diagram to illustrate theessentials of a DTA apparatus is shown in Fig. 42.Two thermocouples pass through the sample block and into cavities whichcontain the sample and the inert reference material respectively. These thermocouplesare joined in opposition, so that the potential difference seen by theamplifier is a measure of the temperature difference (AT) between the sample andthe reference material. One of the thermocouples is used to measure the sampletemperature (T) directly. The output of both signals from the amplifier can bemeasured on a two pen recorder. It is usually necessary to control the furnacetemperature automatically to ensure a uniform rate of heating or cooling. Manydifferent types of commercial apparatus are available with various refinementsand convenience features334* 335.The major problem with DTA stems from the difficulty of obtaining a uniformtemperature throughout the sample. For this reason, there is rarely quantitativeagreement between the results of different workers. The peak shape and area on thethermogram are affected by non-uniformity of furnace temperature, rate of heating,sample geometry, particle size, and dilution with inert material. In many instances,the atmosphere above the sample also influences the reaction.All the factors mentioned above become more important in any attempt to makekinetic measurements for a solid state reaction. Ki~singer~~ has attempted touse the temperature of maximum reaction rate to derive reaction order by usingthe following expressiondx/dt = A(l -x)” exp (-E/RT)References pp. 270-278
258 EXPERIMENT A L METHODS F 0 R HE TE R 0 GENE 0 US RE ACT I0 NSn. 1800 850 900 960 mooShape index= S. 5Fig. 43. (a) Effect of order of reaction on plots of reaction rate against temperature for constantheating rate, frequency factor and activation energy. E/R = 20,000, In A = 16.0. From ref. 350.(b) Method of measuring reaction order from the shape index of DTA peak. Shape index S = u/b.From ref. 350.differentiating the above expression and setting it equal to zero givesE*lrn= [An(l-x)"-'exp (-E/RT)],where subscript m refers to conditions at peak temperature. 4 is the heating rate
Page 2:
COMPREHENSIVE CHEMICAL KINETICS
Page 5 and 6:
P.O.ELSEVIER PUBLISHING COMPANY335
Page 7 and 8:
Contributors to Volume 1L. BATTDepa
Page 9 and 10:
This Page Intentionally Left Blank
Page 11 and 12:
XCONTENTS4.3 Gas chromatography ...
Page 13:
XI1CONTENTS4.6 Magnetic measurement
Page 19:
4 EXPERIMENTAL METHODS FOR SLOW REA
Page 23 and 24:
8EXPERIMENTAL METHODS FOR SLOW REAC
Page 25 and 26:
Reaction Furnace CircuitI10 EXPERIM
Page 27 and 28:
12 EXPERIMENTAL METHODS FOR SLOW RE
Page 29 and 30:
Page 31 and 32:
Page 33 and 34:
Page 35 and 36:
Page 37 and 38:
22 EXPERIMENTAL METHOD§ FOR SLOW R
Page 39 and 40:
Page 41 and 42:
Page 43 and 44:
Page 45 and 46:
Page 47 and 48:
Page 49 and 50:
Page 51 and 52:
~~ ~36 EXPERIMENTAL METHODS FOR SLO
Page 53 and 54:
Page 55 and 56:
~~~ ~ i_~~~~ ._I _.-.~ -~-~~L~ -~TA
Page 57 and 58:
Page 59 and 60:
Page 61 and 62:
Page 63 and 64:
Page 65 and 66:
Page 67 and 68:
Page 69 and 70:
Page 71 and 72:
Page 73 and 74:
Page 75 and 76:
Page 77 and 78:
Page 79 and 80:
Page 81 and 82:
Page 83 and 84:
Page 85 and 86:
Page 87 and 88:
Page 89 and 90:
Page 91 and 92:
Page 93 and 94:
Page 95 and 96:
Page 97 and 98:
Page 99 and 100:
Page 101 and 102:
Page 103 and 104:
Page 105 and 106:
Page 107 and 108:
Page 109 and 110:
Page 111 and 112:
Page 113 and 114:
Page 115 and 116:
100 EXPERIMENTAL METHODS FOR SLOW R
Page 117 and 118:
Page 119 and 120:
Page 121 and 122:
Page 123 and 124:
Page 125 and 126:
Page 127 and 128:
Chapter 2Experimental Methods for t
Page 129 and 130:
114 EXPERIMENTAL METHODS FOR FAST R
Page 131 and 132:
Page 133 and 134:
Page 135 and 136:
Page 137 and 138:
Page 139 and 140:
;,124 EXPERIMENTAL METHODS FOR FAST
Page 141 and 142:
Page 143 and 144:
Page 145 and 146:
Page 147 and 148:
Page 149 and 150:
Page 151 and 152:
Page 153 and 154:
Page 155 and 156:
Page 157 and 158:
Page 159 and 160:
Page 161 and 162:
Page 163 and 164:
Page 165 and 166:
Page 167 and 168:
Page 169 and 170:
Page 171 and 172:
Page 173 and 174:
Page 175 and 176:
Page 177 and 178:
Page 179 and 180:
Page 181 and 182:
Page 183 and 184:
Page 185 and 186:
Page 187 and 188:
Page 189 and 190:
Page 191 and 192:
Page 193 and 194:
178 REFERENCES46 M. EIGEN AND L. DE
Page 195 and 196:
Chapter 3Experimental Methods for t
Page 197 and 198:
182 EXPERIMENTAL METHODS FOR HETERO
Page 199 and 200:
Page 201 and 202:
Page 203 and 204:
Page 205 and 206:
~~~ ._190 EXPERIMENTAL METHODS FOR
Page 207 and 208:
192 EXPERIMENT A L MET H 0 D S F 0
Page 209 and 210:
194 EXPERIMENT A L MET H o D s F o
Page 211 and 212:
Page 213 and 214:
Page 215 and 216:
Page 217 and 218:
202 EXPERIMENT A L MET H 0 D S F 0
Page 219 and 220:
Page 221 and 222: 206 EXPERXMENTAL METHODS FOR HETERO
Page 223 and 224: 208 EXPERIMENTAL METHODS FOR HETERO
Page 237 and 238: 222 EXPERIMENT A L METHODS F 0 R HE
Page 241 and 242: 226 EXPERIMENT A L MET H 0 D S F 0
Page 245 and 246: 230 EXPERIMENT A L METHOD s FOR HET
Page 251 and 252: 236 EXPERIMENT A L METHOD s FOR HE
Page 257 and 258: 242 EXPERIMENT A L ME TH 0 D S FOR
Page 263 and 264: 248 EXPERIMENT A L METHOD s F o R H
Page 269 and 270: 254 EXPERIMENTAL MET HODS FOR HETER
Page 271: 256 EXPERIMENTAL METHODS FOR HETERO
Page 281 and 282: 266 EXPERIMENT A L MET H o D s F o
Page 285 and 286: 270 EXPERIMENTAL MET HODS FOR HE TE
Page 289 and 290: 274 EXPERIMENT A L METHOD s FOR HE
Page 295 and 296: 280 DETECTION AND ESTIMATION OF INT
Page 323 and 324:
308 DETECTION AND ESTIMATION OF INT
Page 325 and 326:
Page 327 and 328:
Page 329 and 330:
Page 331 and 332:
Page 333 and 334:
Page 335 and 336:
Page 337 and 338:
Page 339 and 340:
Page 341 and 342:
Page 343 and 344:
Page 345 and 346:
Page 347 and 348:
Page 349 and 350:
Page 351 and 352:
Page 353 and 354:
Page 355 and 356:
Page 357 and 358:
Page 359 and 360:
344 TREATMENT OF EXPERIMENTAL DATAf
Page 361 and 362:
346 TREATMENT OF EXPERIMENTAL DATAp
Page 363 and 364:
348 TREATMENT OF EXPERIMENTAL DATAg
Page 365 and 366:
350 TREATMENT OF EXPERIMENTAL DATAT
Page 367 and 368:
352 TREATMENT OF EXPERIMENTAL DATAW
Page 369 and 370:
354 TREATMENT OF EXPERIMENTAL DATA[
Page 371 and 372:
Page 373 and 374:
358 TREATMENT OF EXPERIMENTAL DATA(
Page 375 and 376:
Page 377 and 378:
362 TREATMENT OF EXPERIMENTAL DATAI
Page 379 and 380:
364 TREATMENT OF EXPERIMENTAL DATAv
Page 381 and 382:
366 TREATMENT OF EXPERIMENTAL DATAW
Page 383 and 384:
Page 385 and 386:
370 TREATMENT OF EXPERIMENTAL DATAc
Page 387 and 388:
372 TREATMENT OF EXPERIMENTAL DATAw
Page 389 and 390:
Page 391 and 392:
376 TREATMENT OF EXPERIMENTAL DATAF
Page 393 and 394:
Page 395 and 396:
380 TREATMENT OF EXPERIMENTAL DATAe
Page 397 and 398:
382 TREATMENT OF EXPERIMENTAL DATAa
Page 399 and 400:
384 TREATMENT OF EXPERIMENTAL DATAt
Page 401 and 402:
Page 403 and 404:
388 TREATMENT OF EXPERIMENTAL DATAs
Page 405 and 406:
390 TREATMENT OF EXPERIMENTAL DATAI
Page 407 and 408:
Page 409 and 410:
Page 411 and 412:
Page 413 and 414:
Page 415 and 416:
400 TREATMENT OF EXPERIMENTAL DATAF
Page 417 and 418:
Page 419 and 420:
404 TREATMENT OF EXPERIMENTAL DATA4
Page 421 and 422:
406 TREATMENT OF EXPERIMENTAL DATAe
Page 423 and 424:
408 TREATMENT OF EXPERIMENTAL DATAA
Page 425 and 426:
410 TREATMENT OF EXPERIMENTAL DATAs
Page 427 and 428:
41 2 TREATMENT OF EXPERIMENTAL DATA
Page 429 and 430:
~~414 TREATMENT OF EXPERIMENTAL DAT
Page 431 and 432:
Page 433 and 434:
41 8 TREATMENT OF EXPERIMENTAL DATA
Page 435 and 436:
420 TREATMENT OF EXPERIMENTAL DATAA
Page 437 and 438:
IndexAabsorption cross section, che
Page 439 and 440:
424 INDEXbenzyl chloride, matrix ph
Page 441 and 442:
426 INDEXchlorine (contdj—, react
Page 443 and 444:
428 INDEXdeuterium oxide, addition
Page 445 and 446:
430 INDEXentropy change, in radical
Page 447 and 448:
432 INDEXfrequency of oscillation,
Page 449 and 450:
434 INDEXhydrogen atoms (contdj—,
Page 451 and 452:
436 INDEXisotopes (contd.J—, use
Page 453 and 454:
438 INDEXmethyl radicals, chain ter
Page 455 and 456:
440 INDEXoctadiene, ESR determinati
Page 457 and 458:
442 INDEXphotoelectric measurement,
Page 459 and 460:
444 INDEXrad, definition of, 66radi
Page 461 and 462:
446 INDEXSchmidt number, and mass t
Page 463 and 464:
448 INDEXTtailing reducer, in gas c
Page 465:
450 INDEXviscosity, and diffusion c
show all

Practice of Kinetics (Comprehensive Chemical Kinetics, Volume 1)

You also want an ePaper? Increase the reach of your titles

Delete template?

Save as template?