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Chapter 14 Chemical  Kinetics John D. Bookstaver St. Charles Community College Cottleville, MO Chemistry, The Central Science , 11th edition Theodore L. Brown; H. Eugene LeMay, Jr.; and Bruce E. Bursten
Kinetics ,[object Object],[object Object]
Factors That Affect Reaction Rates ,[object Object],[object Object],[object Object]
Factors That Affect Reaction Rates ,[object Object],[object Object]
Factors That Affect Reaction Rates ,[object Object],[object Object]
Factors That Affect Reaction Rates ,[object Object],[object Object],[object Object]
Reaction Rates ,[object Object]
Reaction Rates  ,[object Object],C 4 H 9 Cl ( aq )  + H 2 O ( l )     C 4 H 9 OH ( aq )  + HCl ( aq )
Reaction Rates  ,[object Object],C 4 H 9 Cl ( aq )  + H 2 O ( l )     C 4 H 9 OH ( aq )  + HCl ( aq )   Average rate =  [C 4 H 9 Cl]  t
Reaction Rates  ,[object Object],[object Object],C 4 H 9 Cl ( aq )  + H 2 O ( l )     C 4 H 9 OH ( aq )  + HCl ( aq )
Reaction Rates  ,[object Object],[object Object],C 4 H 9 Cl ( aq )  + H 2 O ( l )     C 4 H 9 OH ( aq )  + HCl ( aq )
Reaction Rates  ,[object Object],[object Object],C 4 H 9 Cl ( aq )  + H 2 O ( l )     C 4 H 9 OH ( aq )  + HCl ( aq )
Reaction Rates and Stoichiometry  ,[object Object],[object Object],C 4 H 9 Cl ( aq )  + H 2 O ( l )     C 4 H 9 OH ( aq )  + HCl ( aq )   Rate = -  [C 4 H 9 Cl]  t =  [C 4 H 9 OH]  t
Reaction Rates and Stoichiometry ,[object Object],2 HI ( g )      H 2 ( g )  + I 2 ( g ) ,[object Object],Rate =  − 1 2  [HI]  t =  [I 2 ]  t
Reaction Rates and Stoichiometry ,[object Object],a A +  b B  c C +  d D Rate =  − 1 a  [A]  t =  − 1 b  [B]  t = 1 c  [C]  t 1 d  [D]  t =
Concentration and Rate ,[object Object]
Concentration and Rate ,[object Object],NH 4 + ( aq )  + NO 2 − ( aq ) N 2 ( g )  + 2 H 2 O ( l )
Concentration and Rate ,[object Object],NH 4 + ( aq )  + NO 2 − ( aq ) N 2 ( g )  + 2 H 2 O ( l )
Concentration and Rate ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],Therefore,
Rate Laws ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Rate Laws ,[object Object],[object Object],[object Object]
Integrated Rate Laws ,[object Object],Where [A] 0  is the initial concentration of A, and [A] t  is the concentration of A at some time,  t , during the course of the reaction. ln [A] t [A] 0 =  − k t
Integrated Rate Laws ,[object Object],ln [A] t   −  ln [A] 0  =  −   k t ln [A] t  =  −   k t + ln [A] 0 … which is in the form y   =  mx  +  b ln [A] t [A] 0 =  − k t
First-Order Processes ,[object Object],ln [A] t  =  - k t + ln [A] 0
First-Order Processes ,[object Object],CH 3 NC CH 3 CN
First-Order Processes ,[object Object],CH 3 NC CH 3 CN
First-Order Processes ,[object Object],[object Object],[object Object],[object Object]
Second-Order Processes ,[object Object],also in the form y   =  mx +  b 1 [A] t =  kt  + 1 [A] 0
Second-Order Processes ,[object Object],1 [A] t =  kt  + 1 [A] 0 1 [A]
Second-Order Processes The decomposition of NO 2  at 300 ° C is described by the equation and yields data comparable to this: NO 2   ( g ) NO  ( g )  +  O 2   ( g ) 0.00380 300.0 0.00481 200.0 0.00649 100.0 0.00787 50.0 0.01000 0.0 [NO 2 ],  M Time ( s ) 1 2
Second-Order Processes ,[object Object],[object Object],0.00380 0.00481 0.00649 0.00787 0.01000 [NO 2 ],  M − 5.573 − 5.337 − 5.038 − 4.845 − 4.610 ln [NO 2 ] 300.0 200.0 100.0 50.0 0.0 Time ( s )
Second-Order Processes ,[object Object],[object Object],0.00380 0.00481 0.00649 0.00787 0.01000 [NO 2 ],  M 263 208 154 127 100 1/[NO 2 ] 300.0 200.0 100.0 50.0 0.0 Time ( s ) 1 [NO 2 ]
Half-Life ,[object Object],[object Object],[object Object]
Half-Life ,[object Object],ln 0.5 =  − kt 1/2 − 0.693 =  − kt 1/2 NOTE: For a first-order process, then, the half-life  does not  depend on [A] 0 . 0.5 [A] 0 [A] 0 ln =  − kt 1/2 =  t 1/2 0.693 k
Half-Life ,[object Object],1 0.5 [A] 0 =  kt 1/2  +  1 [A] 0 2 [A] 0 =  kt 1/2  +  1 [A] 0 2  −  1 [A] 0 =  kt 1/2 1 [A] 0 = =  t 1/2 1 k [A] 0
Temperature and Rate ,[object Object],[object Object]
The Collision Model ,[object Object],[object Object]
The Collision Model ,[object Object]
Activation Energy ,[object Object],[object Object]
Reaction Coordinate Diagrams ,[object Object]
Reaction Coordinate Diagrams ,[object Object],[object Object],[object Object],[object Object]
Maxwell – Boltzmann Distributions ,[object Object],[object Object]
Maxwell – Boltzmann Distributions ,[object Object],[object Object]
Maxwell – Boltzmann Distributions ,[object Object],[object Object]
Maxwell – Boltzmann Distributions ,[object Object],[object Object],f  =  e - E a RT
Arrhenius Equation ,[object Object],[object Object],[object Object],- E a RT
Arrhenius Equation ,[object Object],[object Object],y   =  m  x   +   b Therefore, if  k  is determined experimentally at several temperatures,  E a   can be calculated from the slope of a plot of ln  k  vs.  . 1 T E a R 1 T
Reaction Mechanisms ,[object Object]
Reaction Mechanisms ,[object Object],[object Object]
Reaction Mechanisms ,[object Object]
Multistep Mechanisms ,[object Object],[object Object]
Slow Initial Step ,[object Object],[object Object],[object Object],[object Object],NO 2   ( g )  + CO  ( g )     NO  ( g )  + CO 2   ( g )
Slow Initial Step ,[object Object],[object Object],[object Object],[object Object],[object Object]
Fast Initial Step ,[object Object],[object Object],[object Object],2 NO  ( g )  + Br 2   ( g )     2 NOBr  ( g )
Fast Initial Step ,[object Object],Step 2:  NOBr 2  + NO    2 NOBr  (slow) Step 1 includes the forward  and  reverse reactions. Step 1:  NO + Br 2 NOBr 2   (fast)
Fast Initial Step ,[object Object],[object Object],[object Object],[object Object]
Fast Initial Step ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Fast Initial Step ,[object Object],[object Object],[object Object],k 1 k − 1 [NO] [Br 2 ] = [NOBr 2 ]
Fast Initial Step ,[object Object],=  k  [NO] 2  [Br 2 ] k 2 k 1 k − 1 Rate = [NO] [Br 2 ] [NO]
Catalysts ,[object Object],[object Object]
Catalysts ,[object Object]
Enzymes ,[object Object],[object Object]

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AP Chemistry Chapter 14 Outline

  • 1. Chapter 14 Chemical Kinetics John D. Bookstaver St. Charles Community College Cottleville, MO Chemistry, The Central Science , 11th edition Theodore L. Brown; H. Eugene LeMay, Jr.; and Bruce E. Bursten
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  • 30. Second-Order Processes The decomposition of NO 2 at 300 ° C is described by the equation and yields data comparable to this: NO 2 ( g ) NO ( g ) + O 2 ( g ) 0.00380 300.0 0.00481 200.0 0.00649 100.0 0.00787 50.0 0.01000 0.0 [NO 2 ], M Time ( s ) 1 2
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