Chapter 11.

Rate of Reaction

1. Meaning of Reaction Rate

Reaction:   →   

 ∆    ∆   ∆   ∆  
Rate:   
∆ ∆ ∆ ∆

Measurement Of Rate:

1. rate=-(slope of tangent) (Figure 11.2)

2. Change in pressure

3. Etc...


Ex)      →         
 

<Example 11.1>
2. Reaction Rate and Concentration

§ Reaction caused by collision between molecules

=> High concentration-> Faster collision-> Faster reaction

§ Rate expression

1) Involving one reactant

 →P r

     (k: rate constant, m: order of reaction)

*Knowing the order of reaction

-Cannot be determined theoretically

=>Determined through experiment

-Different mixture ready-> Rate calculated

     
Using   !
    

Ex)    ,    

2) Involving more than one reactant

   →

     ×   (k: rate constant, m, n: order of reaction)

Overall order of reaction: m+n

*Knowing the order of reaction

-Cannot be determined theoretically

=>Determined through two experiment

-Different mixture ready-> Rate calculated

      ×      
Using       !
     ×     

Ex)
 
   
<Example11.2>

<Example 11.3>
3. Reactant Concentration and Time


#Half-Time: Time consumed when [A]-> [A]

1) Zero-Order Reaction

Reaction: → P r Rate:        (k:  · min   )

Equation:       

   
Half-time:      Ex)    →           
  
 
  

 
∴   


2) First-Order Reaction

Reaction:  → P r

Rate:          (k: min   )

Equation: ln    ln    

ln    ln    

 
ln   
 

Half-time: ln  

ln
∴  


(Half time is fixed)


Ex)       →       


<Example 11.5>
 3) Second-Order Reaction

Reaction: P r

Rate:     

(k:   · min   )

 
Equation:   
   

 
Half-time:     
   

  
 
 
∴   · 
  

 
Ex)    →           
 

<Example 11.4>

<Example 11.6>
4. Models For Reaction Rate

*Collision Model

Collision -> Reaction

★Not every collision lead to reaction

Reason: 1. Molecule must be properly oriented

2. Kinetic energy of molecule is not enough

=>Energy should be large enough to break the bond

#Activation Energy( ): Minimum energy required for effective collision

★k(rate constant)= ×  × 

p: steric factor, account orientation of colliding molecule

Z: collision frequency, account number of collision in unit time

f: fraction of collisions in which the energy of molecule is greater than  

  
->   (R: gas constant, T: temperature,   : Activation Energy)

*Transition-State Model

#Activated complex: intermediate species

#Transition state: intermediate state of

system between

reactant and product

Advantage: Can determine why   <∆ 

5. Reaction Rate and Temperature

*Arrhenius Equation




  × ×



    ×        

ln 양변에 취하면 

∴ ln  ln            ·  


y-intercept
ln

slope




ln  ln  
 

ln  ln   
 
   

   
∴ ln       
   

<Example 11.8>
6. Catalysis

#Catalyst: substance that increase rate of reaction without being consumed

(Lower activation energy)

1) Heterogeneous Catalysis

#Heterogeneous catalyst: one that is different phase from reactant

 
Ex1)           
 

Ex2) Catalytic converter of an automobile

  
                            
 

           

Problem: Catalyst can be easily poisoned

2) Homogeneous Catalysis

#Homogeneous catalyst: one that is same phase as reactant

   
Ex)               

               →        

               →             

 3) Enzyme

#Enzyme: protein molecule that speed up the reaction

-Advantage: Very effective at increasing rate

-Drawback: Easily influenced by temperature


Ex1)             


Ex2)                     

7. Reaction Mechanism

-description of steps which reaction occurs

-may differ by the environment the reaction takes place

*Elementary step

-individual steps that constitute reaction mechanism


 →        


 →      


 →       

=>    × 

*Slow step

-slow-step: rate-determining

   → 
 Overall Rate=
   → 
 Rate of Step2
   →


 →

=>1. Overall rate < Rate of the slowest step

2. Rate ≃ Rate of the slowest step (If the step is by far the slowest)

3. Slowest step is step with highest activation energy

 *Deducing Rate expression

1. Find the slowest step

2. Find the rate expression of that step

3. Equate the rate expression to overall reaction

*Elimination of Intermediate

★Step before the slowest step is thought to be in equilbrum


        
 

        

   →

            

 ′    

         

   
  
 

This is substituted to original reaction

    

∴    
 

<Example 11.9>