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REACTION MECHANISMS
REACTION MECHANISMS A + B + C    ABC A + B    AB Which reaction do you think will proceed faster? Why? Reactions that require a  greater  number of particles to collide at the same time will  decrease  the chances of a successful reaction to occur.
REACTION MECHANISMS Of all possible chemical reactions, how many would require three particles colliding? Many reactions take place through multiple two-collision steps at a time, especially when more than two reactants are involved. Overall:  4 HBr + O 2     2 H 2 O + 2 Br 2 Step 1:  HBr + O 2     HOOBr Step 2:  HOOBr + HBr    2 HOBr Step 3:  (HOBr + HBr    H 2 O + Br 2 ) x2
REACTION MECHANISMS Each step of the mechanism is known as an  elementary process . The complete series of elementary processes is known as the  reaction mechanism  of a chemical reaction. You are not expected to come up with elementary processes!!
REACTION MECHANISMS If each elementary process occurs at different rates, how fast is the overall reaction? Step 1:  HBr + O 2     HOOBr Step 2:  HOOBr + HBr    2 HOBr Step 3:  (HOBr + HBr    H 2 O + Br 2 ) x2 slow fast fast The overall reaction can only be  as fast as the   SLOWEST  elementary process. So the rate of the reaction ( r =k[HBr] x [O 2 ] y ) is the same as the rate of the slowest step. This step is called the  rate-determining step
REACTION MECHANISMS 4 HBr + O 2     2 H 2 O + 2 Br 2 Potential energy diagram Potential energy Reaction coordinate Reactants Products E a Δ H HBr + O 2 HOOBr 2 HOBr 2H 2 O + 2Br 2 3 peaks , therefore  3 steps  in the reaction mechanism
REACTION MECHANISMS ,[object Object],[object Object],[object Object]
REACTION MECHANISMS CH 2 O 2(aq)     CO (g)  + H 2 O (l) uncatalyzed catalyzed
REACTION MECHANISMS
REACTION MECHANISMS Rate Law for Elementary Processes ,[object Object],[object Object],[object Object]
REACTION MECHANISMS Rate Law for Elementary Processes EXAMPLE 1 ,[object Object],[object Object],[object Object],rate = k[NO 2 Cl] rate = k[NO 2 Cl][Cl] Elementary processes
REACTION MECHANISMS Rate Law for Elementary Processes EXAMPLE 2 rate = k[NO 2 ] 2 rate = k[NO 3 ] ,[object Object],[object Object],[object Object],Elementary processes
REACTION MECHANISMS Predicting Mechanisms ,[object Object],[object Object],[object Object]
REACTION MECHANISMS Predicting Mechanisms EXAMPLE 1b ,[object Object],[object Object],[object Object],rate = k[NO 2 Cl] Experimentally-determined 1 st  order reaction rate = k[NO 2 Cl] (predicted) Since this mechanism yields a rate law that matches the experimental one, it should be correct. (slow) (fast)
REACTION MECHANISMS Predicting Mechanisms EXAMPLE 2b rate = k[NO 2 ] 2 Experimentally-determined 2 nd  order reaction rate = k[NO 2 ] 2 (predicted) Since this mechanism yields a rate law that matches the experimental one, it should be correct. ,[object Object],[object Object],[object Object],(slow) (fast)
REACTION MECHANISMS Predicting Mechanisms ,[object Object],[object Object],[object Object]
REACTION MECHANISMS Predicting Mechanisms The reaction of ozone, O 3 , with nitric oxide, NO, forms nitrogen dioxide and oxygen gas.  It is believed to be a one step mechanism to produce smog. Determine the rate law. NO + O 3     NO 2  + O 2 rate = k[NO][O 3 ]
REACTION MECHANISMS Predicting Mechanisms ,[object Object],[object Object],[object Object],[object Object],rate = k[N 2 O 5 ] 2 N 2 O 5     some reaction intermediates
REACTION MECHANISMS Predicting Mechanisms ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],rate = k[Y] 2 [Z] 2Y + Z    some product(s)
REACTION MECHANISMS

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Tang 04 rate mechanisms

  • 2. REACTION MECHANISMS A + B + C  ABC A + B  AB Which reaction do you think will proceed faster? Why? Reactions that require a greater number of particles to collide at the same time will decrease the chances of a successful reaction to occur.
  • 3. REACTION MECHANISMS Of all possible chemical reactions, how many would require three particles colliding? Many reactions take place through multiple two-collision steps at a time, especially when more than two reactants are involved. Overall: 4 HBr + O 2  2 H 2 O + 2 Br 2 Step 1: HBr + O 2  HOOBr Step 2: HOOBr + HBr  2 HOBr Step 3: (HOBr + HBr  H 2 O + Br 2 ) x2
  • 4. REACTION MECHANISMS Each step of the mechanism is known as an elementary process . The complete series of elementary processes is known as the reaction mechanism of a chemical reaction. You are not expected to come up with elementary processes!!
  • 5. REACTION MECHANISMS If each elementary process occurs at different rates, how fast is the overall reaction? Step 1: HBr + O 2  HOOBr Step 2: HOOBr + HBr  2 HOBr Step 3: (HOBr + HBr  H 2 O + Br 2 ) x2 slow fast fast The overall reaction can only be as fast as the SLOWEST elementary process. So the rate of the reaction ( r =k[HBr] x [O 2 ] y ) is the same as the rate of the slowest step. This step is called the rate-determining step
  • 6. REACTION MECHANISMS 4 HBr + O 2  2 H 2 O + 2 Br 2 Potential energy diagram Potential energy Reaction coordinate Reactants Products E a Δ H HBr + O 2 HOOBr 2 HOBr 2H 2 O + 2Br 2 3 peaks , therefore 3 steps in the reaction mechanism
  • 7.
  • 8. REACTION MECHANISMS CH 2 O 2(aq)  CO (g) + H 2 O (l) uncatalyzed catalyzed
  • 10.
  • 11.
  • 12.
  • 13.
  • 14.
  • 15.
  • 16.
  • 17. REACTION MECHANISMS Predicting Mechanisms The reaction of ozone, O 3 , with nitric oxide, NO, forms nitrogen dioxide and oxygen gas. It is believed to be a one step mechanism to produce smog. Determine the rate law. NO + O 3  NO 2 + O 2 rate = k[NO][O 3 ]
  • 18.
  • 19.