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Krasnov k s Red Fizicheskaya Himiya Kniga 2 Elektrohimiya Hi
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ФИЗИЧЕСКАЯ
ХИМИЯ
В двух книгах
Под редакцией доктора химических наук, профессора К. С.Краснова,
Издание второе, переработанное и дополненное
Электрохимия
Химическая кинетика
и катализ
Москва «Высшая школа»
1995
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ББК24.5 Ф50 УДК 541.1
Издание выпущено в свет при содействии Комитета Российской Федерации по печати
К.С. Краснов, Н.К. Воробъев, И.Н. Годнев, В.Н. Васильева, В.П.Васильев, В.Л.Киселева, К.Н. Белоногое, В.П. Гостикин
Р е ц е н з е н т : Л.В.Пучков (зав. каф. физической химии Санкт-Петербургского технологического института)
Рекомендовано Государственным комитетом Российской Федерации по высшему образованию
в качестве учебника для студентов химико-технологических специальностей
и направления "Химическая технология и биотехнология" высших учебных заведений
Физическая химия. В 2 кн. Кн. 2. Электрохимия. Химическая ки- нетика и катализ: Учеб. для вузов/К.С.Краснов, Н.К. Воробьев, И.Н. Годнев и др.; Под ред. К.С.Краснова - 2-е изд., перераб. и доп. - М.: Высш.шк., 1995. - 319 с: ил.
ISBN 5-06-002914-Х
Учебник составлен в соответствии с программой по физической химии для хи мических специальностей и химико-технологических вузов и факультетов. Во вто-
рой части раздела курса физической химии электрохимия, химическая кинетика и катализ излагаются на основе представлений, развитых в первой части книги, -строение вещества и статистическая термодинамика. Второе издание (1-е 1982 г.) существенно переработано. Заново написан раздел "Катализ", в котором отражены также кинетика гетерогенных и диффузионных процессов, термодинамика адсорб-ции и вопросы реакционной способности.
ISBN 5-06-002914-Х (кн.2)
ISBN 5-06-002915-8
ББК24.5 541
© Коллектив авторов, 1995
Ф50
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ПРЕДИСЛОВИЕ
Во второй книге рассмотрены разделы физической химии: электро-химия, химическая кинетика и катализ. Материал учебника излагает-ся на основе представлений, изложенных в первой части книги, — строение вещества и статистическая термодинамика. Второе издание (1-е — 1982 г.) существенно переработано. Заново написан раздел "Катализ", в котором отражены также кинетика гетерогенных и диффузионных процессов, термодинамика адсорбции и вопросы реакционной способности.
Для удобства пользования учебником сохранена сквозная нумера-ция глав.
Учебник предназначен для студентов, но может быть интересен и для аспирантов, специализирующихся в области физической химии. Весь материал отражает современное состояние науки.
Авторы
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ОГЛАВЛЕНИЕ
Предисловие............................................................................................... 3
Раздел шестой. Электрохимия
Г л а в а 17. Растворы электролитов............................................................. 4
§ 17.1. Предмет электрохимии .................................................................... 4 § 17.2. Специфика растворов электролитов ........................................... 5 § 17.3. Электролитическая диссоциация в растворе.............................. 6 § 17.4. Средняя ионная активность и коэффициент активности . . . 10 § 17.5. Основные понятия электростатической теории сильных
электролитов Дебая и Хюккеля ..................................................... 13 § 17.6. Основные понятия теории ассоциации ионов.............................. 22 § 17.7. Термодинамические свойства ионов ........................................... 24 § 17.8. Термодинамика ионной сольватации ........................................... 28
Г л а в а 18. Неравновесные явления в электролитах. Электрическая проводимость электролитов .................................................................... 30
§ 18.1. Основные понятия. Законы Фарадея.......................................... 30 § 18.2. Движение ионов в электрическом поле. Числа переноса . . . . 32 § 18.3. Электрическая проводимость электролитов. Удельная
электрическая проводимость ............................................................ 37 § 18.4. Электрическая проводимость электролитов. Молярная
электрическая проводимость ............................................................ 39 § 18.5. Молярная электрическая проводимость ионов гидроксония
и гидроксида ....................................................................................... 43 § 18.6. Электрическая проводимость неводных растворов .................... 44 § 18.7. Электрическая проводимость твердых и расплавленных
электролитов ........................................................................................ 46 § 18.8. Кондуктометрия ............................................................................. 47
Г л а в а 19. Равновесные электродные процессы ......................................... 49
§ 19.1. Основные понятия ............................................................................ 49
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§ 19.2. ЭДС электрохимической системы. Электродный потенциал ............................................................................................ 51
§ 19.3. Возникновение скачка потенциала на границе раствор-металл .................................................................................. 53
§ 19.4. Диффузионный потенциал ............................................................ 55 § 19.5. Строение двойного электрического слоя на границе
раствор-металл .................................................................................. 56 § 19:6. Термодинамика обратимых электрохимических систем . . . . 60 § 19.7. Классификация обратимых электродов ...................................... 64 § 19.8. Электродные потенциалы в неводных растворах ...................... 74 § 19.9. Электрохимические цепи .............................................................. 75 § 19.10. Применение теории электрохимических систем к
изучению равновесия в растворах .................................................. 82 § 19.11. Потенциометрия ........................................................................... 85
Раздел седьмой. Кинетика химических реакций
Г л а в а 20. Законы химической кинетики .................................................. 93
§ 20.1. Общие понятия и определения..................................................... 93 § 20.2. Скорость химической реакции..................................................... 95 § 20.3. Закон действующих масс и принцип независимости протека
ния реакций........................................................................................ 101 Г л а в а 21. Кинетика химических реакций в закрытых системах . . . . 105
§ 21.1. Односторонние реакции первого порядка.................................. 105 § 21.2. Односторонние реакции второго порядка ................................. 109 § 21.3. Односторонние реакции n-го порядка ....................................... 111 § 21.4. Методы определения порядка реакции ...................................... 112 § 21.5. Двусторонние реакции первого порядка .......................... 113 § 21.6. Двусторонние реакции второго порядка .................................... 116 § 21.7. Параллельные односторонние реакции...................................... 117 § 21.8. Односторонние последовательные реакции............................... 119 § 21.9. Метод квазистационарных концентраций .................................. 125
Г л а в а 22. Кинетика реакций в открытых системах.............................. 127
§ 22.1. Кинетика реакций в реакторе идеального смешения ............... 127
§ 22.2. Кинетика реакций в реакторе идеального вытеснения ............. 129
Г л а в а 23. Теория элементарною акта химического взаимодействия 133
§ 23.1. Элементарный химический акт ..................................................... 133 § 23.2. Теория активных соударений ....................................................... 137 § 23.3. Теория активированного комплекса .......................................... 141
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§ 23.4. Предэкспоненциальный множитель в уравнении Аррениуса по теории переходного состояния ................................ 154
§ 23.5. Симметрия МО и энергия активации химических реакций 159
Г л а в а 24. Кинетика реакций в растворах, цепные и фотохимические реакции ................................... .................................................................. 166
§ 24.1. Особенности кинетики реакций в растворах .............................. 166 § 24.2. Влияние среды на константу скорости реакции ......................... 170 § 24.3. Кинетика ионных реакций в растворах ........................................ 178 § 24.4. Цепные реакции .............................................................................. 181 § 24.5. Фотохимические реакции ............................................................... 189
Г л а в а 25. Кинетика электродных процессов ...............................: . . . . 196
§ 25.1. Скорость электрохимической реакции. Ток обмена ................. 196 § 25.2. Электродная поляризация ............................................................. 197 § 25.3. Диффузионное перенапряжение ................................................... 199 § 25.4. Электрохимическое перенапряжение ............................................ 205 § 25.5. Другие виды перенапряжения ...................................................... 210 § 25.б. Темнературно-кинетический метод определения природы
поляризации при электрохимических процессах .................... 211 § 25.7. Перенапряжение при электролитическом выделении
водорода ............................................................................................ 213 § 25.8. Электролиз. Напряжение разложения.......................................... 217 § 25.9. Поляризационные явления в химических источниках элект
рического тока ..................................................................................... 220 § 25.10. Электрохимическая коррозия металлов. Пассивность метал
лов. Методы защиты от коррозии ............................................... 222
Раздел восьмой. Катализ
Г л а в а 26. Принципы каталитического действия .................................... 228
§ 26.1. Основные понятия и определения ................................................ 228 § 26.2. Особенности кинетики каталитических реакций ...................... 232 § 26.3. Энергия активации каталитических реакций ........................... 237 § 26.4. Взаимодействие реагентов с катализатором и принцины ката
литического действия.................................................................. 241
Г л а в а 27. Гомогенный катализ .................................................................. . 245
§ 27.1. Кислотно-основный катализ .......................................................... 246 § 27.2. Окислительно-восстановительный катализ ................................ 255 § 27.3. Ферментативный катализ............................................................... 260
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§ 27.4. Автокатализ, ингибирование и периодические каталитичес кие реакции.................................................................... 266
§ 27.5. Применение в промышленности и перспективы развития гомогенного катализа ........................................................................ 271
Г л а в а 28. Гетерогенный катализ.............................................................. 273
§ 28.1. Структура поверхности гетерогенных катализаторов .............. 273 § 28.2. Адсорбция как стадия гетерогенно-каталитических реакций 277 § 28.3. Механизм гетерогенно-каталитических реакций ..................... 282 § 28.4. Кинетика гетерогенно-каталитических реакций на равнодос
тупной поверхности ...................................................................... 285 § 28.5. Макрокинетика гетерогенно-каталитических процессов . . . . 292 § 28.6. Применение гетерогенного катализа в промышленности . . . . 300
Литература........................................................................................................... 303 Приложение ........................................................................................................... 305 Предметный указатель ................................................................................... 312 Оглавление........................................................................................................... 316
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