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Physical chemistry from a different angle introducing chemical equilibrium, kinetics and electrochemistry by numerous experiments 1st ed 2016 edition {PRG} Physical chemistry from a different angle introducing chemical equilibrium, kinetics and electrochemistry by numerous experiments 1st ed 2016 edition {PRG} Physical chemistry from a different angle introducing chemical equilibrium, kinetics and electrochemistry by numerous experiments 1st ed 2016 edition {PRG} Physical chemistry from a different angle introducing chemical equilibrium, kinetics and electrochemistry by numerous experiments 1st ed 2016 edition {PRG} Physical chemistry from a different angle introducing chemical equilibrium, kinetics and electrochemistry by numerous experiments 1st ed 2016 edition {PRG}
Georg Job Regina Rüffler Physical Chemistry from a Different Angle Introducing Chemical Equilibrium, Kinetics and Electrochemistry by Numerous Experiments Physical Chemistry from a Different Angle ThiS is a FM Blank Page Georg Job Regina Ruăfer Physical Chemistry from a Different Angle Introducing Chemical Equilibrium, Kinetics and Electrochemistry by Numerous Experiments Georg Job Job Foundation Hamburg Germany Regina Ruăfer Job Foundation Hamburg Germany Translated by Robin Fuchs, GETS, Winterthur, Switzerland Hans U Fuchs, Zurich University of Applied Sciences at Winterthur, Switzerland Regina Ruăfer, Job Foundation, Hamburg, Germany Based on German edition “Physikalische Chemie”, ISBN 978-3-8351-0040-4, published by Springer Vieweg, 2011 Exercises are made available on the publisher’s web site: http://extras.springer.com/2015/978-3-319-15665-1 By courtesy of the Eduard-Job-Foundation for Thermo- and Matterdynamics ISBN 978-3-319-15665-1 ISBN 978-3-319-15666-8 DOI 10.1007/978-3-319-15666-8 (eBook) Library of Congress Control Number: 2015959701 Springer Cham Heidelberg New York Dordrecht London © Springer International Publishing Switzerland 2016 This work is subject to copyright All rights are reserved by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed The use of general descriptive names, registered names, trademarks, service marks, etc in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use The publisher, the authors and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication Neither the publisher nor the authors or the editors give a warranty, express or implied, with respect to the material contained herein or for any errors or omissions that may have been made Printed on acid-free paper Springer International Publishing AG Switzerland is part of Springer Science+Business Media (www.springer.com) Preface Experience has shown that two fundamental thermodynamic quantities are especially difficult to grasp: entropy and chemical potential—entropy S as quantity associated with temperature T and chemical potential μ as quantity associated with the amount of substance n The pair S and T is responsible for all kinds of heat effects, whereas the pair μ and n controls all the processes involving substances such as chemical reactions, phase transitions, or spreading in space It turns out that S and μ are compatible with a layperson’s conception In this book, a simpler approach to these central quantities—in addition to energy—is proposed for the first-year students The quantities are characterized by their typical and easily observable properties, i.e., by creating a kind of “wanted poster” for them This phenomenological description is supported by a direct measuring procedure, a method which has been common practice for the quantification of basic concepts such as length, time, or mass for a long time The proposed approach leads directly to practical results such as the prediction—based upon the chemical potential—of whether or not a reaction runs spontaneously Moreover, the chemical potential is key in dealing with physicochemical problems Based upon this central concept, it is possible to explore many other fields The dependence of the chemical potential upon temperature, pressure, and concentration is the “gateway” to the deduction of the mass action law, the calculation of equilibrium constants, solubilities, and many other data, the construction of phase diagrams, and so on It is simple to expand the concept to colligative phenomena, diffusion processes, surface effects, electrochemical processes, etc Furthermore, the same tools allow us to solve problems even at the atomic and molecular level, which are usually treated by quantum statistical methods This approach allows us to eliminate many thermodynamic quantities that are traditionally used such as enthalpy H, Gibbs energy G, activity a, etc The usage of these quantities is not excluded but superfluous in most cases An optimized calculus results in short calculations, which are intuitively predictable and can be easily verified v vi Preface Because we choose in this book an approach to matter dynamics directly by using the chemical potential, application of the concept of entropy is limited to the description of heat effects Still, entropy retains its fundamental importance for this subject and is correspondingly discussed in detail The book discusses the principles of matter dynamics in three parts, • Basic concepts and chemical equilibria (statics), • Progression of transformations of substances in time (kinetics), • Interaction of chemical phenomena and electric fields (electrochemistry) and gives at the same time an overview of important areas of physical chemistry Because students often regard physical chemistry as very abstract and not useful for everyday life, theoretical considerations are linked to everyday experience and numerous demonstration experiments We address this book to undergraduate students in courses where physical chemistry is required in support but also to beginners in mainstream courses We have aimed to keep the needs of this audience always in mind with regard to both the selection and the representation of the materials Only elementary mathematical knowledge is necessary for understanding the basic ideas If more sophisticated mathematical tools are needed, detailed explanations are incorporated as background information (characterized by a smaller font size and indentation) The book also presents all the material required for introductory laboratory courses in physical chemistry Exercises are made available on the publisher’s web site A student manual with commented solutions is in preparation Detailed descriptions of a selection of demonstration experiments (partly with corresponding videos clips) can be found on our web site (www.job-foundation.org; see teaching materials); the collection will be continuously extended Further information to the topics of quantum statistics and the statistical approach to entropy, which would go beyond the scope of this book, can also be called up on the foundation’s home page Preface vii We would particularly like to thank Eduard J Job{, the founder of the Job Foundation, who always supported the goals of the foundation and the writing of the current book, with great personal commitment Because efficient application of thermodynamics played an important role in his work as an internationally successful entrepreneur in the field of fire prevention and protection, he was particularly interested in a simplified approach to thermodynamics allowing for faster and more successful learning We gratefully acknowledge the constant support and patience of the board of the Job foundation Additionally, we would like to thank the translators of the book, Robin Fuchs and Prof Hans U Fuchs, for their excellent collaboration, and Dr Steffen Pauly and Beate Siek at Springer for their advice and assistance Finally, we would like to express our gratitude to colleagues who gave their advice on the German edition and reviewed draft chapters of the English edition: Prof Friedrich Herrmann, Prof Guănter Jakob Lauth, Prof Friedhelm Radandt, and Dr Uzodinma Okoroanyanwu We would be very grateful for any contributions or suggestion for corrections by the readers Hamburg, Germany November 2014 Georg Job Regina Ruăfer ThiS is a FM Blank Page List of Used Symbols In the following, the more important of the used symbols are listed The number added in parentheses refers to the page where the quantity or term if necessary is described in detail Special characters as prefix (j, Δ, ΔR, Δs!l, ) were omitted when ordering the symbols alphabetically Greek letters in alphabetical order: Αα Ββ Γγ Δδ Εε Ζζ Ηη Θθϑ Iι Kκ Λλ Mμ Νv Ξξ Οo Ππ Ρρ Σσς Ττ Υυ Φφ Χχ Ψψ Ωω Roman A, B, C, jA, jB, Ad a, ja Bs C c, jc d, jd E e, eÀ e F g, jg J l, jl M M Me m, jm Ox Substance A, B, C, Dissolved in A, in B, (240) Acid (188) Amorphous (19) (also subscripted or superscripted) Base (188) Catalyst (462) Crystalline (19) (also subscripted or superscripted) Dissolved (19) (also subscripted or superscripted) Enzyme (466) Electron(s) (7, 553) (also subscripted) Eutectic (367) (also subscripted or superscripted) Foreign substance (320) Gaseous (19) (also subscripted or superscripted) Ion, unspecific (533) Liquid (19) (also subscripted or superscripted) Mixture (homogeneous) (346) Mixture (heterogeneous) (348) Metal, unspecific (533) Metallic (conducting electrons) (553) (also subscripted or superscripted) Oxidizing agent (537) ix Appendix Substance FÀ FH F2 Fe Fe Fe Fe2+ Fe3+ Fe(OH)2 Fe(OH)3 FeS FeSO4 FeS2 Fe2O3 Fe3O4 Ga Ga Ge Ge H H+ H2 He Hg Hg Hg2+ HgCl2 HgI2 HgI2 HgO HgO HgS HgS Hg2 2ỵ Hg2Cl2 Hf Hf I I IH I2 I2 I2 627 Phase w g g g l s, α, cubic w w s s s s s, pyrite s, hematite s, magnetite g s g s g w g g g l w s s, red s, yellow s, red s, yellow s, black s, red w s g s g w g g l s μ (kG) À278.79 À275.40 0.00 368.32 5.34 0.00 À78.90 À4.70 À496.98 À708.98 À101.97 À824.89 À166.90 À741.04 À1,017.48 233.74 0.00 333.68 0.00 203.28 0.00 0.00 0.00 32.46 0.00 164.40 À183.44 À101.70 À101.15 À58.54 À58.41 À47.70 À50.60 153.52 À209.33 579.62 0.00 70.17 À51.57 1.70 19.32 3.32 0.00 α (G KÀ1) Refs +13.80 [2] À173.78 [1] À202.79 [1] À180.49 [1] À35.55 [5] À27.28 [1] 137.70 [2] 315.90 [2] À88.00 [3] À105.00 [1] À60.32 [3] À120.96 [1] À52.93 [2] À87.40 [1] À145.27 [1] À169.04 [1] À40.73 [1] À167.90 [3] À31.09 [1] À114.72 [1] 0.00 [2] À130.68 [1] À126.15 [1] À174.97 [1] À75.90 [1] 32.20 [2] À144.49 [1] À180.00 [2] À186.29 [7] À70.29 [2] À71.10 [2] À88.30 [2] À82.40 [2] À84.50 [2] À192.54 [1] À186.90 [1] À43.56 [1] À180.78 [1] À111.30 [2] À206.59 [1] À260.68 [1] À150.36 [5] À116.14 [1] (continued) 628 Substance I2 In In Ir Ir K K K+ KBr KCl KF KI KOH K2O K2SO4 Kr La La Li Li Li+ LiH LiH Mg Mg Mg2+ MgCO3 MgCl2 MgO MgS MgSO4 Mn Mn Mn2+ MnO2 MnO4 Mo Mo N NH3 NH3 NH3 NH4 ỵ Appendix Phase w g s g s g s w s s s s s s s g g s g s w g s g s w s s s s s g s w s w g s g g l w w μ (kG) 16.40 206.08 0.00 622.87 0.00 60.48 0.00 À283.27 À380.07 À408.76 À538.93 À324.32 À379.46 À321.17 À1,319.59 0.00 392.59 0.00 126.66 0.00 À293.31 116.47 À68.63 115.98 0.00 À454.80 À1,012.21 À594.77 À569.31 À343.70 À1,174.48 238.50 0.00 À228.10 À465.08 À447.20 611.88 0.00 455.55 À16.45 À10.16 À26.59 À79.31 α (G KÀ1) À137.20 À173.78 À57.65 À193.58 À35.51 À160.34 À64.68 À102.50 À95.92 À82.56 À66.55 À106.05 À81.25 À96.00 À175.54 À164.09 À182.38 À56.90 À138.77 À29.12 À13.40 À170.91 À20.60 À148.65 À32.67 +138.10 À65.09 À89.62 À26.95 À50.33 À91.60 À173.70 À32.22 73.60 À53.05 À191.20 À181.95 À28.56 À153.30 À192.45 À103.90 À111.30 À113.40 Refs [2] [1] [1] [1] [1] [1] [1] [2] [1] [1] [1] [1] [1] [1] [1] [1] [1] [1] [2] [1] [2] [1] [1] [1] [1] [2] [1] [1] [1] [1] [1] [2] [1] [2] [1] [2] [1] [1] [1] [2] [7] [2] [2] (continued) Appendix Substance NH4Cl NO NOCl NO2 NO3 À NO3H NO3H N2 N2H4 N2H4O3 N2O N2O4 N2O4 N2O5 N2O5 N3H N3H Na Na Na+ NaBr NaCl NaI NaOH NaSO4H Na2O Na2SO4 Nb Nb Ne Ni Ni Ni2+ NiCl2 NiO NiSO4 O OD2 OD2 OD2 OHÀ OH2 629 Phase s g g g w g l g l s, ammonium nitrate g g l g s g l g s w s s s s s s s g s g g s w s s s g g l s w g μ (kG) À203.09 87.59 67.11 52.31 À108.74 À73.69 À80.71 0.00 149.34 À183.76 104.20 97.89 97.54 115.10 113.90 328.10 327.30 76.96 0.00 À261.91 À349.09 À384.07 À286.41 À379.65 À992.80 À379.18 À1,270.02 678.42 0.00 0.00 384.50 0.00 À45.60 À258.65 À211.59 À759.70 231.74 À234.54 À243.40 À242.89 À157.24 À228.58 α (G KÀ1) Refs À94.86 [1] À210.74 [1] À261.58 [1] À240.17 [1] À146.40 [2] À266.88 [1] À155.60 [2] À191.61 [1] À121.21 [2] À150.81 [1] À219.85 [2] À304.29 [2] À209.20 [2] À355.70 [2] À178.20 [2] À238.97 [2] À140.60 [2] À153.72 [1] À51.30 [1] À59.00 [2] À86.93 [1] À72.12 [1] À98.56 [1] À64.43 [1] À113.00 [2] À75.04 [1] À149.58 [1] À186.27 [1] À36.27 [1] À146.33 [1] À182.19 [2] À29.80 [1] 128.90 [2] À98.10 [1] À38.07 [1] À92.00 [2] À161.06 [1] À198.34 [3] À75.94 [3] À50.59 [7] 10.75 [2] À188.83 [1] (continued) 630 Substance OH2 OH2 OH3 þ O2 O2 O2H2 O2H2 O2H2 O3 Os Os P P P PCl3 PCl3 PCl5 PH3 PO4 3À PO4 H2À PO4 H2À PO4H3 PO4H3 P4O10 P4O10 Pb Pb Pb Pb2+ PbCO3 PbI2 PbI2 PbO PbO PbO2 PbS PbSO4 Pd Pd Pt Pt Appendix Phase l s w g w g l w g g s g s, red s, white g l g g w μ (kG) À237.14 À236.55 À237.14 0.00 16.40 À105.45 À120.42 À134.03 163.29 740.31 0.00 280.09 À12.02 0.00 À269.61 À274.04 À305.00 13.55 À1,018.70 α (G KÀ1) À69.95 À44.81 À69.95 À205.15 À110.9 À233.00 À109.62 À143.90 À239.01 À192.58 À32.64 À163.20 À22.85 À41.09 À311.68 À218.49 À364.58 À210.31 222.00 w w l w g s g l s w s s s s, yellow s, red s s s g s g s À1,089.15 À1,130.28 À1,123.60 À1,018.70 À2,671.28 À2,724.15 162.23 2.22 0.00 À24.43 À625.41 À173.57 À173.57 À188.68 À188.92 À215.39 À97.77 À816.20 338.028 0.00 520.05 0.00 33.50 [2] À90.40 [2] À150.78 [5] 222.00 [2] À402.09 [1] À231.00 [1] À175.37 [1] À71.71 [5] À64.80 [1] À10.50 [2] À130.96 [1] À174.84 [1] À174.84 [1] À68.70 [1] À67.84 [1] À71.80 [1] À91.20 [1] À148.49 [1] À167.06 [3] À37.82 [1] À192.41 [1] À41.63 [1] (continued) Refs [1] [7] [1] [1] [2] [1] [1] [2] [1] [1] [1] [1] [1] [1] [5] [1] [2] [3] [2] Appendix Substance Re Re Rh Rh Ru Ru S S S S2À SF6 SHÀ SH2 SH2 SO2 SO3 SO3 2À SO3 HÀ SO3H2 SO4 2À SO4 HÀ SO4H2 SO4H2 S2Cl2 Sb Sb Sc Sc Se Se Si Si SiCl4 SiO2 SiO2 Sn Sn Sn2+ Sn4+ SnO SnO2 Sr Sr 631 Phase g s g s g s g s, α, rhombic s, β, monoclinic w μ (kG) 729.42 0.00 509.01 0.00 604.92 0.00 236.70 0.00 0.07 85.80 α (G KÀ1) À118.93 À36.48 À185.83 À31.56 À186.51 À28.61 À167.83 À32.07 À33.03 +14.60 Refs [1] [1] [1] [1] [1] [1] [1] [1] [5] [2] g w g w g g w À1,115.42 12.08 À33.44 À27.83 À300.12 À371.01 À486.50 À291.67 À62.80 À205.80 À121.00 À248.21 À256.77 29.00 [1] [2] [1] [2] [1] [1] [2] w w w À527.78 À537.81 À744.53 À139.70 À232.20 À20.10 [2] [2] [2] w À755.91 À131.80 [2] l w g g s g s g s g s g s, α, cristobalite s, α, quartz g s, β, white w w s s g s À689.92 À738.79 À28.66 227.00 0.00 335.92 0.00 197.41 0.00 405.53 0.00 À622.39 À855.43 À856.29 266.22 0.00 À27.2 +1.9 À251.91 À515.82 128.02 0.00 À156.90 [1] [7] À327.22 [1] À180.27 [1] À45.52 [1] À174.79 [1] À34.64 [1] À176.73 [1] À42.00 [1] À168.00 [1] À18.81 [1] À331.45 [1] À42.68 [2] À41.46 [1] À168.49 [1] À51.18 [1] 17.0 [2] [7] À57.17 [1] À49.01 [1] À164.64 [1] À55.69 [1] (continued) 632 Substance Te Te Ti Ti TiCl4 TiO4 Tl Tl U U V V W W Xe Zn Zn Zn2+ ZnCO3 ZnCl2 ZnI2 ZnO ZnS ZnSO4 Zr Zr Appendix Phase g s g s l s, rutile g s g s g s g s g g s w s s s s s, zinc blende s g s μ (kG) 169.65 0.00 429.12 0.00 À737.20 À888.77 146.22 0.00 490.40 0.00 472.19 0.00 809.11 0.00 0.00 94.81 0.00 À147.06 À731.45 À370.32 À209.26 À320.37 À198.52 À871.45 556.91 0.00 α (G KÀ1) À182.71 À49.22 À180.30 À30.72 À252.34 À50.62 À181.00 À64.30 À199.79 À50.20 À182.30 À30.89 À174.00 À32.62 À169.58 À161.00 À41.63 112.1 À82.43 À111.50 À161.50 À43.16 À58.66 À110.50 À181.34 À39.18 Refs [1] [1] [1] [1] [2] [1] [1] [1] [1] [1] [1] [1] [1] [1] [1] [1] [1] [2] [1] [1] [3] [1] [1] [3] [1] [1] Index A Absolute entropy, determination, 73 Absolute temperature, 69, 273 Absolute zero (point), 273 Accumulator, 567 Acid, 188 Acid-base indicator, 215 Acid-base pair, 188 strong, 193 weak, 195 Acid-base reaction, 189 Acid-base titration, 206 Acidity constant, 198 Activated complex, 445 Activation, 446 Activation energy, 440 Activation entropy, 450 Activation threshold, 448 Active site (of an enzyme), 461 Activity, 601 chemical, 599 Activity coefficient, 599, 602 Adsorbate, 392 Adsorbent, 392 Adsorption on liquid surfaces, 390 on solid surfaces, 392 Adsorption chromatography, 398 Adsorption equilibrium, 394 Adsorption isotherm, 393 Adsorptive, 392 Affinity, 108 Alkaline battery, 566 Allotropy, 311 Amorphous, 20 Amount of substance, 14 Amphoteric, 192 Anion, 499 Anode, 499 Antiderivative, 611, 614 Arrhenius activation energy, 440 Arrhenius diagram, 441 Arrhenius equation, 440 August vapor pressure formula, 306 Autocatalysis, 456 Avogadro constant, 15 Avogadro’s principle, 275 Azeotrope, 376 B Barometric formula, 293 Base, 188 Basic stoichiometric equation, 27 Basic substance, Basic value chemical drive, 159 chemical potential, 156 molar entropy, 231 molar volume, 224 Battery primary, 565 secondary, 567 Bimolecular reaction, 420 Biocatalyst, 461 Boiling point, 75, 136, 305 raising, 147, 331 standard, 305 © Springer International Publishing Switzerland 2016 G Job, R Ruăfer, Physical Chemistry from a Different Angle, DOI 10.1007/978-3-319-15666-8 633 634 Boiling point curve, 371, 372 Boiling point diagram, 372 Boiling pressure curve, 303 Boltzmann’s distribution law, 293 Boltzmann constant, 278 Bonding energy, 495 Bonding strength, 494 Boyle–Mariotte’s law, 272 Brownian motion, 56 Buffer, 210 Buffer capacity, 210 C Calomel electrode, 559 Calorimeter, 66, 246 Capillary action, 388 Capillary active, 390 Capillary pressure, 385 Carnot (unit), 71 Catalysis, 455 enzymatic, 456, 461 heterogeneous, 456, 467 homogeneous, 456 mechanism, 457 microheterogeneous, 456 Catalyst, 455 Catalyst poison, 457 Catalytic efficiency, 466 Cathode, 499 Cation, 499 Cell primary, 565 secondary, 567 Cell constant, 518 Cell voltage (reversible), 562 measurement, 570 Celsius temperature, 70 Chain reaction, 437 Charge, 16 Charge number, 495 Charles’s law, 273 Chemical drive, 108 basic value, 159 concentration dependence, 159 pressure coefficient, 141, 263 pressure dependence, 140 temperature coefficient, 131, 260 temperature dependence, 130 Chemical drive, determination calorimetric, 245 chemical (mass action law), 170 electrochemical, 564 Index Chemical engine, 236 Chemical potential, 93, 596 average (heterogeneous mixture), 346 average (homogeneous mixture), 344 basic characteristics, 96 basic value, 156 concentration coefficient, 155 concentration dependence, 154 prediction of transformations, 107 pressure coefficient, 140, 262 ideal gas, 148, 276 pressure dependence, 140 reference level, 100 standard value, 103 temperature coefficient, 131, 259 temperature dependence, 130 Chemisorption, 392 Chromatography adsorption, 398 partition, 182 Cohesion pressure, 296 Colligative properties, 320, 332 Collision frequency, 442 Collision theory, 442 Colloid, 16 Composite reaction, 413, 425 Compressibility, 267 ideal gas, 276 Concentration mass, 18 molar, 17 Condensation, 300 Conductance, 505 Conduction entropy, 89, 485 Conductivity entropy, 486 electric, 505 concentration dependence, 507 (molar) ionic, 506 measurement, 518 limiting molar, 506 molar, 506 thermal, 486 Conductometric cell, 518 Conductometric titration, 519 Conode, 359 Consecutive reaction, 433 Conservation of energy, 38 Contact angle, 385 Contact potential difference, 524 Content formula, Content number, Index Conversion, 28 degree, 163 extent, 27 Conversion density, 163 Conversion formula, 25 Conversion number, 26 Conversion rate, 405 Conversion rate density, 407 measurement, 409 flow method, 412 relaxation method, 413 temperature dependence, 439 Cooling curve, 367 Coupling, 249 chemical-chemical (n-n), 263 in the opposite direction, 254 in the same direction, 254 mechanical-chemical (V-n), 262 mechanical-thermal (V-S), 255 thermal-chemical (S-n), 259 Coverage, fractional, 394 Covolume, 296 Critical micelle concentration, 391 Critical point, 302 Critical pressure, 302 Critical solution point lower, 360 upper, 359 Critical temperature, 302 Cryoscopic constant, 332 Crystalline, 20 Cubic expansion coefficient, 255 ideal gas, 276 Current, electric, 499, 503 Cyclic process, 255 D Dalton’s law, 171 Daniell cell, 560 Deca potential, 157 Decomposition pressure, 150, 175 Decomposition temperature, 138 Degree of dissociation, 509 Degree of freedom, 281 Degree of protonation, 201 Derivative, 611 Desorption, 394 Dew point curve, 371, 373 Distillation, 373 Differential coefficient, 610 conversion, 267 partial, 613 635 Diffusion, 316, 474 Diffusion coefficient, 476 temperature dependence, 477 Diffusion-controlled reaction, 471, 479 Diffusion force, 317 Diffusion voltage, 542 Dipole, electric, 495 Displacement coefficient, 263 Dissociation degree, 509 electrolytic, 493 Distribution equilibrium, 181 Donnan equation, 546 Double layer, electric, 525, 528 Drive, chemical See Chemical drive Dynamic equilibrium, 165, 395, 428 E Ebullioscopic constant, 332 Efficiency, 86 Einstein–Smoluchowski equation, 476 Electric charge, 16 Electric conductivity, 505 Electric current, 499, 503 Electric double layer, 525, 528 Electric field, 497 Electric mobility, 500 Electric potential, 497 Electric resistance, 505 Electrochemical potential, 523 Electrochemical series, 556 Electrode, 499, 528, 538 calomel, 559 film, 540 gas, 538 glass, 545 hydrogen (gas), 538 standard (SHE), 549 metal-metal ion, 539 redox, 534 reference, 558 silver-silver chloride, 540, 558 Electrode potential See Redox potential Electrolysis, 565 Electrolyte true, 493 potential, 494 strong, 508 weak, 509 Electrolytic dissociation, 493 Electromotive force See Reversible cell voltage 636 Electron potential in metals, 524 of a redox pair, 532 Electroneutrality rule, 497 Elementary amount (of substance), 15 Elementary charge, 16, 495 Elementary reaction, 413 Eley-rideal mechanism, 469 Endothermic, 240 Endotropic, 233, 240 Energy, 31 burnt, 79 conservation, 38 free, 586 Gibbs, 591 Helmholtz, 589 internal, 576 kinetic, 43 potential, 46 Enthalpy, 583 molar, 594 Entropy, 49 absolute, 74 exchanged, 65, 80, 240 generated, 65, 79, 240 latent, 84, 241 macroscopic properties, 51 molar (see Molar entropy) zero-point, 63 Entropy capacity, 75, 253, 487 difference Cp À CV, 269 ideal gas, 276 ideal gas, 282 molar, 76 specific, 76, 487 Entropy conduction, 89, 485 Entropy conductivity, 486 Entropy conservation, 56 Entropy demand See Molar entropy Entropy flux, 485 Entropy generation, 57, 89 Entropy transfer, 62 Enzymatic catalysis, 456, 461 Enzyme, 456, 461 Equilibrium chemical, 99, 109, 166 distribution, 181 dynamic, 165, 395, 428 electrochemical, 525 heterogeneous, 175 homogeneous, 166, 174 Equilibrium composition, 169 Equilibrium constant, 167, 427 Index Equilibrium number, 167 temperature dependence, 182 Equilibrium reaction, 426 Equivalence point, 207 Euler’s number, 609 Eutectic mixture, 365 Exchanged entropy, 65, 80, 240 Excitation equation, 285 Exhaust-gas catalytic converter, 469 Exothermic, 240 Exotropic, 233, 240 Expansion coefficient, cubic See Cubic expansion coefficient Exponential function, 609 Extensive factor, 45 Extensive quantity, 24, 45 Extent of reaction, 27 Extra potential, 342 F Fahrenheit temperature, 70 Faraday constant, 500 Faraday’s law, 500 Fick’s law, 476 Field, electric, 497 Film electrode, 540 First law (of thermodynamics), 53 First-order reaction, 415 Flip rule, 257 Flow method, 412 Flux entropy, 485 matter, 475 Flux density, 475 Force, 32 Force-like quantity, 45, 253 Fourier’s law, 486 Fractional coverage, 394 Free energy, 586 Freezing point, 75 lowering, 146, 329 raising, 147 Frequency factor, 440 Friction inner, 482 Newton’s law, 482 outer, 482 Fuel cell, 569 hydrogen-oxygen, 569 polymer electrolyte membrane, 570 solid oxide, 570 Fugacity, 606 Index Fugacity coefficient, 606 Function derived, 611 exponential, 609 linear, 607 logarithmic, 607 G Galvani potential, 522 Galvani potential difference, 522 Galvanic cell (reversible), 120, 550 Galvanic half-cell, 538 Gas, 19 ideal, 274 Gas constant, general, 148, 275 Gas electrode, 538 Gas law, general, 275 Gaussian distribution, 289, 620 Gay-Lussac’s law, 273 General gas constant, 148, 275 General gas law, 275 Generated entropy, 65, 79, 240 Gibbs (unit), 101, 124 Gibbs (free) energy, 591 molar, 595 Gibbs-Helmholtz equation, 245 Glass electrode, 545 Gruăneisens rule, 221 H Half-life, 418, 421 Heat, 80, 574 Heat capacity, 253, 582, 585 molar, 76, 253 specific, 253 Heat conduction See Entropy conduction Heat effect, 237 Heat engine, 85 Heat pump, 85 Helmholtz (free) energy, 589 Henderson-Hasselbalch equation, 201 Henry’s law, 180 Heterogeneous, Heterogeneous catalysis, 456, 467 Heterogeneous mixture, 16, 335 chemical potential, 346 Heterogeneous reaction, 408 Histogram, 620 Hittorf method, 517 Homogeneous, Homogeneous catalysis, 456 637 Homogeneous mixture, 16, 335 chemical potential, 344 Homogeneous reaction, 408 Hooke’s law, 40 Hydration, 496 Hydrogen (gas) electrode, 538 standard (SHE), 549 Hydron, 188 Hydrophilic, 341 Hydrophobic, 341 I Ideal gas, 274 Ideal mixture, 339, 350 Indicator See Acid-base indicator Indirect mass action, 318 Induction period, 435 Inhibitor, 456 Integration, 614 Intensive factor, 45 Intensive quantity, 24, 45 Interface, 381 Interfacial tension, 382 Intermediate (of a reaction), 403 Internal energy, 576 Internal pressure, 296 Ion, Ionic conductivity, 506 Irreversible process, 58 Isobar, 273 Isomerism stereo, 162 structural, Isotherm, 272 Isotonic solution, 326 J Joule (unit), 32 K Kelvin (unit), 70 Kelvin’s equation, 388 Kinetic energy, 43 Kohlrausch’s law of independent migration of ions, 506 Kohlrausch’s square root law, 509 L Langmuir-Hinshelwood mechanism, 468 638 Langmuir isotherm, 394 Latent entropy, 84, 241 Law of equipartition (of energy), 281 Law of thermodynamics first, 53 second, 53, 58 third, 62 Lead-acid battery, 567 Le Chatelier-Braun’s principle, 264 Level equation, 201 Lever rule, 346 Limiting molar conductivity, 506 Lineweaver-Burke diagram, 465 Liquid, 19, 300 Liquidus curve, 363 Logarithmic function, 607 M Main coefficient, 253 Main effect, 253 Main equation, 250 Main quantity, 252 Mass, molar, 16 Mass action, 154 indirect, 318 Mass action equation, 156 Mass action law, 166, 605 applications, 172 Mass concentration, 18 Mass fraction, 17 Matter capacity, 183 Matter capacity density, 183 Matter flux, 475 Maxwell’s construction, 302 Maxwell’s relation, 255 Maxwell’s speed distribution, 291 Melting point, 75, 134, 308 standard, 308 Melting point diagram, 362 Melting pressure curve, 308 Membrane voltage, 545 Metal-metal ion electrode, 539 Metastable substance, 106 Metricization, Micelle, 391 critical concentration, 391 Michaelis constant, 462 Michaelis-Menten equation, 463 Michaelis-Menten kinetics, 461 Microheterogeneous catalysis, 456 Migration of ions, independent, 506 Migration velocity Index of uncharged particles, 472 of ions, 499 Milieu, 97 Miscibility diagram, 359 Miscibility gap, 352 Mixed crystal, 362 Mixed phase, 16 Mixture heterogeneous, 16, 335 homogeneous, 16, 335 ideal, 339, 350 of highly compatible substances, 341 of incompatible substances, 340 of indifferent substances, 340 of lowly compatible substances, 340 Mixing chemical drive, 349 molar entropy, 349 molar volume, 349 Mobility electric, 500 mechanical, 472 Modification, 20, 311 Mol (unit), 15 Molality, 18 Molar concentration, 17 Molar conductivity, 506 limiting, 506 Molar entropy, 72, 228 basic value, 231 of fusion, 75, 311 of mixing, 349 partial, 230 standard value, 72, 231 of vaporization, 75, 307 Molar mass, 16 determination, 332 Molar reaction entropy, 232 exchanged, 242 generated, 242 latent, 242 Molar reaction volume, 227 Molar volume, 220 basic value, 224 partial, 224 standard value, 221, 224 of mixing, 349 Molarity, 17 Molecularity (of reaction), 413 Mole fraction, 17 Momentum, 44, 279 Monomolecular reaction, 415 Monoprotic, 188 Index N Nernst’s distribution law, 182 Nernst’s equation, 530, 536, 554, 564 Newton’s law of friction, 482 Nickel-cadmium battery, 568 Nickel-metal hydride battery, 568 Normal distribution, 289, 620 O Ohmic resistance, 505 Ohm’s law, 489, 505 Opposing reaction, 426 Osmometry, 333 Osmosis, 321 Osmotic concentration, 325 Osmotic pressure, 322 Ostwald’s dilution law, 511 Oxidizing agent, oxidant, 531 P Parallel reaction, 430 Partial differential coefficient, 613 Partial molar entropy, 230 Partial molar volume, 224 Partial pressure, 171 Partition chromatography, 182 Phase mixed, 16 single, 16 Phase boundary, 308 Phase diagram, 308 Phase transition, 25 pressure, 143 temperature, 134 Photometry, 411 pH value, 199 Physisorption, 392 Pictet-Trouton’s rule, 233, 307 pK value, 198 Plate, theoretical, 376 Polymerization, 438 Polymorphism, 311 Polyprotic, 188 Position-like quantity, 46, 253 Potential chemical (see Chemical potential) electric, 497 electrochemical, 523 Potential diagram, 116, 183 Potential energy, 46 Potentiometric titration, 570 639 Potentiometry, 570 Pre-exponential factor, 440 Pressure, 41 capillary, 385 critical, 302 osmotic, 322 partial, 171 Pressure coefficient, relative, 269 Primary battery, 565 alkaline battery, 566 zinc-carbon dry battery, 565 zinc-manganese dioxide battery, 565 zinc-mercury oxide button cell, 566 Principle of mobile equilibrium, 264 Probability calculation, 619 Process quantity, 22, 576 Proticity, 188 Proton, 188 Proton acceptor, 188 Proton donor, 188 Proton potential, 190 Protonation equation, 202 degree, 201 Pseudo reaction order, 424 Q Quadratic degree of freedom, 281 Quantity extensive, 24 force-like, 45, 253 intensive, 24 position-like, 46, 253 substance-like, 24, 252 Quantum number, 15 R Raoult’s law, 327 Rate coefficient, 414 Rate constant See Rate coefficient Rate density See also Conversion rate density initial, 463 Rate law, 414 integrated, 417 Rate limiting step, 436 Reaction bimolecular, 420 composite, 425 consecutive, 433 diffusion-controlled, 471, 479 first-order, 415 640 Reaction (cont.) heterogeneous, 408 homogeneous, 408 monomolecular, 415 opposing, 426 parallel, 430 second-order, 419 zero-order, 423 Reaction coordinate, 453 Reaction entropy, molar See Molar reaction entropy Reaction equation See Conversion formula Reaction formula See Conversion formula Reaction mechanism, 405 Reaction order, 414 Reaction rate See Conversion rate Reaction resistance, 402, 448, 455 Reaction volume, molar See Molar reaction volume Redox electrode, 534 Redox pair, 531 Redox potential, 552 basic value, 554 Redox reaction, 531 Reducing agent, reductant, 531 Reductive capacity, 533 Reference electrode, 558 calomel electrode, 559 silver-silver chloride electrode, 558 standard hydrogen electrode, 549 Refrigerator, 65 Relaxation method, 413 Resistance electric, 505 ohmic, 505 reaction, 402, 448, 455 Resistivity, 505 Reversible cell voltage, 562 Reversible process, 57 Richards’s rule, 233 Root mean square speed, 282 S Salt bridge, 550 Salting-in effect, 264 Salting-out effect, 264 Saturation concentration, 177 Schwarz’ theorem, 593 Second law of thermodynamics, 53, 58 Secondary battery, 567 lead-acid battery, 567 nickel-cadmium battery, 568 Index nickel-metal hydride battery, 568 Second-order reaction, 419 Selectivity (of a catalyst), 460 Side coefficient, 254 Side effect, 254 Single-step reaction, 413 Silver-silver chloride electrode, 540, 558 Solid, 19 amorphous, 20 crystalline, 20 Solidus curve, 363 Solubility of gases, 180 of ionic solids, 176 Solubility product, 177 Solution, 16 saturated, 176 Solution point, critical See Critical solution point Solvation, 496 Specificity (of a catalyst), 460 Speed distribution, Maxwell, 291 Stable substance, 106 Standard conditions, 72, 102, 104 Standard value chemical drive, 109 chemical potential, 103 molar entropy, 72, 231 molar volume, 221, 224 State, 18 of aggregation, 19 State equation, 22 State quantity, 21 Steady-state approximation, 436 Steric factor, 444 Stoichiometric coefficient See Conversion number Stoichiometric equation, basic, 27 Stokes law, 484, 501 Sublimation point, 137 Sublimation pressure curve, 308 Substance, spreading, 313 Substance-like quantity, 24, 252 Substrate, 461 Supercritical fluid, 302 Surface, 381 measurement, 398 Surface energy, 383 Surface tension, 382 Surfactant, 390 Surroundings, 18 System, 18 Index T Temperature, 68 absolute, 69, 273 critical, 302 Theoretical plate, 376 Thermal analysis, 367 Thermal conductivity, 486 Thermal expansion, 60 Thermodynamic temperature, 69 Third law (of thermodynamics), 62 Tie-line, 359 Transformation (of substances), 25 Transition complex, 445 Transition pressure curve, 311 Transition state, 445 Transition state theory, 445 Transition substance, 446 Transport equation, 488 Transport number, 512 Transport phenomena, 471 Triple point, 309 Turnover number, 465 641 Van der Waals forces, 296 Van’t Hoff’s equation, 324 Vapor pressure, 176, 301 of small drops, 387 Vapor pressure curve, 303 Vapor pressure diagram, 369 Vapor pressure lowering, 326 Variable dependent, 607 independent, 607 Viscosity, 480 dynamic, 482 kinematic, 482 Voltage, 498 Volume, molar See Molar volume Volume demand See Molar volume W Wetting, 385 Wheatstone bridge circuit, 518 Work mechanical, 31, 575 pressure-volume, 575 U Unstable substance, 106 V Valence, 495 Van der Waals constants, 298 Van der Waals equation, 298 Z Zero point, absolute, 273 Zero-point entropy, 63 Zinc-carbon dry battery, 565 Zinc-manganese dioxide battery, 565 Zinc-mercury oxide button cell, 566 .. .Physical Chemistry from a Different Angle ThiS is a FM Blank Page Georg Job Regina Ruăfer Physical Chemistry from a Different Angle Introducing Chemical Equilibrium, Kinetics and Electrochemistry. .. necessary for understanding the basic ideas If more sophisticated mathematical tools are needed, detailed explanations are incorporated as background information (characterized by a smaller font... defects, to name a few) are exchanged, transported, or transformed As long as the necessary data are also available, they help in dealing with and calculating various types of problems such as • • •