DeutschesFachbuch.de : Chemical Kinetics and Reaction Dynamics Von Santosh K. Upadhyay


Contents
	Preface				vii

	1.	Elementary			1
		1.1	Rate of Reaction		1
			1.1.1	Experimental Determination of Rate	2
		1.2	Rate Constant		3
		1.3	Order and Molecularity		4
		1.4	Rate Equations		6
			1.4.1	Integral Equations for n^thOrder Reaction of a Single Reactant	6
			1.4.2	Integral Equations for Reactions Involving More than One Reactants	7
		1.5	Half-life of a Reaction		8
		1.6	Zero Order Reactions		10
		1.7	First Order Reactions		12
		1.8	Radioactive Decay as a First Order Phenomenon		17
		1.9	Second Order Reactions		20
		1.10	Third Order Reactions		28
		1.11	Determination of Order of Reaction		30
			1.11.1	Integration Method	30
			1.11.2	Half-life Period Method	34
			1.11.3	Graphical Method	34
			1.11.4	Differential Method	35
			1.11.5	Ostwald Isolation Method	35
		1.12	Experimental Methods of Chemical Kinetics		39
			1.12.1	Conductometric Method	39
			1.12.2	Polarographic Technique	40
			1.12.3	Potentiometrie Method	41
			1.12.4	Optical Methods	42
			1.12.5	Refractometry	42
			1.12.6	Spectrophotometry	43
	Exercises				44

	2.	Temperature Effect on Reaction Rate			46
		2.1	Derivation of Arrhenius Equation		46
		2.2	Experimental Determination of Energy of Activation and Arrhenius Factor		48
		2.3	Potential Energy Surface		50
		2.4	Significance of Energy of Activation		51
	Exercises				53

	3.	Complex Reactions			55
		3.1	Reversible Reactions		55
			3.1.1	Reversible Reaction When Both the Opposing Processes are Second Order	57
		3.2	Parallel Reactions		59
			3.2.1	Determination of Rate Constants	59
		3.3	Consecutive Reactions		63
			3.3.1	Concentration-Time Relation	64
		3.4	Steady-State Treatment		66
		3.5	Chain Reactions		67
			3.5.1	Rate Determination	68
			3.5.2	Reaction between H₂and Br₂	69
			3.5.3	Chain Length	70
			3.5.4	Chain Transfer Reactions	70
			3.5.5	Branching Chain Explosions	70
			3.5.6	Kinetics of Branching Chain Explosion	71
			3.5.7	Free Radical Chains	72
			3.5.8	Chain Length and Activation Energy in Chain Reactions	75
	Exercises				76

	4.	Theories of Reaction Rate			79
		4.1	Equilibrium and Rate of Reaction		79
		4.2	Partition Functions and Statistical Mechanics of Chemical Equilibrium		80
		4.3	Partition Functions and Activated Complex		82
		4.4	Collision Theory		83
			4.4.1	Collision Frequency	84
			4.4.2	Energy Factor	86
			4.4.3	Orientation Factor	87
			4.4.4	Rate of Reaction	87
			4.4.5	Weakness of the Collision Theory	88
		4.5	Transition State Theory		89
			4.5.1	Thermodynamic Approach	91
			4.5.2	Partition Function Approach	93
			4.5.3	Comparison with Arrhenius Equation and Collision Theory	93
			4.5.4	Explanation for Steric Factor in Terms of Partition Function	94
			4.5.5	Reaction between Polyatomic Molecules	95
		4.6	Unimolecular Reactions and the Collision Theory		100
			4.6.1	Lindemann's Mechanism	100
			4.6.2	Hinshelwood Treatment	103
			4.6.3	Rice and Ramsperger, and Kassel (RRK) Treatment	105
			4.6.4	Marcus Treatment	106
			4.6.5	RRKM Theory	107
		4.7	Kinetic and Thermodynamic Control		109
		4.8	Hammond's Postulate		110
		4.9	Probing of the Transition State		111
	Exercises				113

	5.	Kinetics of Some Special Reactions			115
		5.1	Kinetics of Photochemical Reactions		115
			5.1.1	Grotthuss-Draper Law	115
			5.1.2	Einstein Law of Photochemical Equivalence	115
			5.1.3	Primary Process in Photochemical Reactions	116
			5.1.4	H₂-Br₂Reaction	118
			5.1.5	H₂and Cl₂Reaction	119
		5.2	Oscillatory Reactions		120
			5.2.1	Belousov-Zhabotinskii Reaction	122
		5.3	Kinetics of Polymerization		124
			5.3.1	Step Growth Polymerization	125
			5.3.2	Polycondensation Reactions (in Absence of the Catalyst)	125
			5.3.3	Acid Catalyzed Polycondensation Reaction	126
			5.3.4	Chain Growth Polymerization	127
			5.3.5	Kinetics of Free Radical Polymerization	127
			5.3.6	Cationic Polymerization	130
			5.3.7	Anionic Polymerization	131
			5.3.8	Co-polymerization	132
		5.4	Kinetics of Solid State Reactions		135
		5.5	Electron Transfer Reactions		139
			5.5.1	Outer Sphere Mechanism	139
			5.5.2	Inner Sphere Mechanism	140
	Exercises				141

	6.	Kinetics of Catalyzed Reactions			142
		6.1	Catalysis		142
			6.1.1	Positive Catalysis	142
			6.1.2	Negative Catalysis	143
			6.1.3	Auto Catalysis	143
			6.1.4	Induced Catalysis	144
			6.1.5	Promoters	144
			6.1.6	Poisons	144
		6.2	Theories of Catalysis		145
			6.2.1	Intermediate Compound Formation Theory	145
			6.2.2	Adsorption Theory	145
		6.3	Characteristics of Catalytic Reactions		146
		6.4	Mechanism of Catalysis		147
		6.5	Activation Energies of Catalyzed Reactions		149
		6.6	Acid Base Catalysis		150
		6.7	Enzyme Catalysis		152
			6.7.1	Influence of pH	154
		6.8	Heterogeneous Catalysis		156
		6.9	Micellar Catalysis		159
			6.9.1	Models for Micellar Catalysis	161
		6.10	Phase Transfer Catalysis		165
			6.10.1	General Mechanism	166
			6.10.2	Difference between Micellar and Phase Transfer-Catalyzed Reactions	167
		6.11	Kinetics of Inhibition		168
			6.11.1	Chain Reactions	168
			6.11.2	Enzyme Catalyzed Reactions	169
			6.11.3	Inhibition in Surface Reactions	172
	Exercises				173

	7.	Fast Reactions			175
		7.1	Introduction		175
		7.2	Flow Techniques		176
			7.2.1	Continuous Flow Method	177
			7.2.2	Accelerated Flow Method	178
			7.2.3	Stopped Flow Method	178
		7.3	Relaxation Method		179
		7.4	Shock Tubes		181
		7.5	Flash Photolysis		182
		7.6	ESR Spectroscopic Technique		183
		7.7	NMR Spectroscopic Techniques		183
	Exercises				184

	8.	Reactions in Solutions			185
		8.1	Introduction		185
		8.2	Theory of Absolute Reaction Rate		185
		8.3	Influence of Internal Pressure		187
		8.4	Influence of Solvation		187
		8.5	Reactions between Ions		187
		8.6	Entropy Change		189
		8.7	Influence of Ionic Strength (Salt Effect)		190
		8.8	Secondary Salt Effect		192
		8.9	Reactions between the Dipoles		193
		8.10	Kinetic Isotope Effect		195
		8.11	Solvent Isotope Effect		197
		8.12	Hemmett Equation		198
		8.13	Linear Free Energy Relationship		199
		8.14	The Taft Equation		200
		8.15	Compensation Effect		201
	Exercises				202

	9.	Reaction Dynamics			204
		9.1	Molecular Reaction Dynamics		204
		9.2	Microscopic-Macroscopic Relation		205
		9.3	Reaction Rate and Rate Constant		207
		9.4	Distribution of Velocities of Molecules		209
		9.5	Rate of Reaction for Collisions with a Distribution of Relative Speeds		209
		9.6	Collision Cross Sections		210
			9.6.1	Cross Section for Hard Sphere Model	210
			9.6.2	Collision between Reactive Hard Spheres	211
		9.7	Activation Energy		213
		9.8	Potential Energy Surface		216
			9.8.1	Features of Potential Energy Surface	219
			9.8.2	Ab initio Calculation of Potential Energy Surface	222
			9.8.3	Fitting of ab initio Potential Energy Surfaces	225
			9.8.4	Potential Energy Surfaces for Triatomic Systems	226
		9.9	Classical Trajectory Calculations		229
			9.9.1	Initial State Properties	230
			9.9.2	Final State Properties	232
			9.9.3	Calculation of Reaction Cross Section	232
		9.10	Potential Energy Surface and Classical Dynamics		234
		9.11	Disposal of Excess Energy		239
		9.12	Influence of Rotational Energy		240
		9.13	Experimental Chemical Dynamics		241
			9.13.1	Molecular Beam Technique	241
			9.13.2	Stripping and Rebound Mechanisms	243
			9.13.3	State-to-State Kinetics	244
			9.13.4	Suggested Readings	247
	Index				251