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Kinetics Lesson 5 PE Diagrams Mechanisms Potential and Kinetic Energy Changes during a Collision Endothermic Reactants Activated Complex Products Potential and Kinetic Energy Changes during a Collision Endothermic Reactants Activated Complex Products Potential and Kinetic Energy Changes during a Collision Endothermic Reactants Activated Complex Products Potential and Kinetic Energy Changes during a Collision Endothermic Reactants Activated Complex Products Potential and Kinetic Energy Changes during a Collision Endothermic Reactants Potential Energy Activated Complex Products Potential and Kinetic Energy Changes during a Collision Endothermic Reactants Potential Energy Activated Complex Products Potential and Kinetic Energy Changes during a Collision Endothermic Reactants Activated Complex Products max Potential Energy low high Potential and Kinetic Energy Changes during a Collision Endothermic Reactants Activated Complex Products max Potential Energy low Kinetic Energy high Potential and Kinetic Energy Changes during a Collision Endothermic Reactants Activated Complex Products max Potential Energy high low Kinetic Energy high min low Potential and Kinetic Energy Changes during a Collision Endothermic Reactants Activated Complex Products max Potential Energy high low Uphill- endothermic! Kinetic Energy high min low Pick the slow and fast reaction Pick the slow and fast reaction Ea Ea Pick the slow and fast reaction Ea Ea Slow Fast- low Ea Reaction Mechanisms Consider the following reaction: 4 HBr(g) + O2(g) → 2H2O(g) + 2Br2(g) Watch Simulation- set both temperature and mass to the highest setting. Set red to 1 and blue to four and remove the barrier. How often do all five particles collide? There are five reactant particles. If there are three or more reactant particles they will not likely react in one step. They will react in a series of steps, which is a mechanism. Mechanism 1 . HBr(g) + O2(g) HBr(g) + HOOBr(g) → 2HOBr(g) +2HBr(g) → HOOBr(g) slow 2HOBr(g) → fast 2H2O(g)+ 2Br2(g) PE Reaction Path fast Mechanism 1 Cancel out identical formulas to get the overall equation. HBr(g) + O2(g) HBr(g) + HOOBr(g) → 2HOBr(g) +2HBr(g) → HOOBr(g) slow 2HOBr(g) → fast 2H2O(g)+ 2Br2(g) PE Reaction Path fast Mechanism 1 Cancel out identical formulas to get the overall equation. HBr(g) + O2(g) HBr(g) + HOOBr(g) → 2HOBr(g) +2HBr(g) → HOOBr(g) slow 2HOBr(g) → fast 2H2O(g)+ 2Br2(g) PE Reaction Path fast Mechanism 1 Cancel out identical formulas to get the overall equation. HBr(g) + O2(g) HBr(g) + HOOBr(g) → 2HOBr(g) +2HBr(g) → HOOBr(g) slow 2HOBr(g) → fast 2H2O(g)+ 2Br2(g) PE Reaction Path fast Mechanism 1 Intermediates are produced and then consumed and cross out from right (first) and left (second). HBr(g) + O2(g) → HOOBr(g) slow HBr(g) + HOOBr(g) → 2HOBr(g) +2HBr(g) 2HOBr(g) → fast 2H2O(g)+ 2Br2(g) PE Reaction Path fast Mechanism 1 What is left is the overall reaction. HBr(g) + O2(g) HBr(g) + HOOBr(g) → 2HOBr(g) +2HBr(g) → HOOBr(g) slow 2HOBr(g) → fast 2H2O(g)+ 2Br2(g) PE Reaction Path fast Mechanism 1 What is left is the overall reaction. HBr(g) + O2(g) HBr(g) + HOOBr(g) → 2HOBr(g) 4HBr(g) + → HOOBr(g) slow 2HOBr(g) fast +2HBr(g) → 2H2O(g)+ 2Br2(g) O2(g) → 2H2O(g)+ 2Br2(g) PE Reaction Path fast Mechanism 1 Step 1, which is the slow step, is called the rate determining step and has the highest activation energy. HBr(g) + O2(g) → HOOBr(g) slow HBr(g) + HOOBr(g) → 2HOBr(g) 4HBr(g) + 2HOBr(g) fast +2HBr(g) → 2H2O(g)+ 2Br2(g) O2(g) → 2H2O(g)+ 2Br2(g) PE Reaction Path fast Mechanism 1 HBr(g) + O2(g) HBr(g) + HOOBr(g) → 2HOBr(g) 4HBr(g) + → HOOBr(g) slow 2HOBr(g) fast +2HBr(g) → 2H2O(g)+ 2Br2(g) O2(g) → 2H2O(g)+ 2Br2(g) A potential energy diagram for this reaction might look like this. PE Reaction Path fast Mechanism 1 HBr(g) + O2(g) HBr(g) + HOOBr(g) → 2HOBr(g) 4HBr(g) + → HOOBr(g) slow 2HOBr(g) fast +2HBr(g) → 2H2O(g)+ 2Br2(g) O2(g) → 2H2O(g)+ 2Br2(g) A potential energy diagram for this reaction might look like this. PE Reaction Path fast Mechanism 1 HBr(g) + O2(g) HBr(g) + HOOBr(g) → 2HOBr(g) 4HBr(g) + → HOOBr(g) slow 2HOBr(g) fast +2HBr(g) → 2H2O(g)+ 2Br2(g) O2(g) → 2H2O(g)+ 2Br2(g) highest A potential energy diagram for this Mechanism has three humps PE The slow step has the highest Ea fast Ea(rev) Ea Reaction Path The Rate Determining Step The slowest step in the reaction mechanism is called the ratedetermining step. It has the highest Ea. To increase the rate, you must increase the rate of this step. Increasing the rate of a fast step will not increase the rate of the overall reaction. Identifying a Catalyst in a Mechanism A catalyst is not consumed in the reaction. It is used in one step; it speeds up the reaction, and then is regenerated in a later step. A catalyst will cancel out but will be on the left side in an earlier step than on the right side. Identifying a Catalyst in a Mechanism A catalyst is not consumed in the reaction. It is used in one step; it speeds up the reaction, and then is regenerated in a later step. A catalyst will cancel out but will be on the left side in an earlier step than on the right side. C → → C Identifying a Catalyst in a Mechanism A catalyst is not consumed in the reaction. It is used in one step; it speeds up the reaction, and then is regenerated in a later step. A catalyst will cancel out but will be on the left side in an earlier step than on the right side. C → → C Identifying a Catalyst in a Mechanism A catalyst is not consumed in the reaction. It is used in one step; it speeds up the reaction, and then is regenerated in a later step. A catalyst will cancel out but will be on the left side in an earlier step than on the right side. C → → C An intermediate is produced and then consumed. It will be on the right side in an earlier step than on the left side. Identifying a Catalyst in a Mechanism A catalyst is not consumed in the reaction. It is used in one step; it speeds up the reaction, and then is regenerated in a later step. A catalyst will cancel out but will be on the left side in an earlier step than on the right side. C → → C An intermediate is produced and then consumed. It will be on the right side in an earlier step than on the left side. I → → I Identifying a Catalyst in a Mechanism A catalyst is not consumed in the reaction. It is used in one step; it speeds up the reaction, and then is regenerated in a later step. A catalyst will cancel out but will be on the left side in an earlier step than on the right side. C → → C An intermediate is produced and then consumed. It will be on the right side in an earlier step than on the left side. I → → I Mechanism 2 1. A + B → C 2. C + D → CD 3. CD + E → ABE Overall Equation: Catalyst: Intermediate: + D Mechanism 2 1. A + B → C 2. C + D → CD 3. CD + E → ABE Overall Equation: Catalyst: Intermediate: + D Mechanism 2 1. A + B → C 2. C + D → CD 3. CD + E → ABE Overall Equation: Catalyst: Intermediate: C + D Mechanism 2 1. A + B → C 2. C + D → CD 3. CD + E → ABE Overall Equation: Catalyst: Intermediate: C + D Mechanism 2 1. A + B → C 2. C + D → CD 3. CD + E → ABE C CD Overall Equation: Catalyst: Intermediate: + D Mechanism 2 1. A + B → C 2. C + D → CD 3. CD + E → ABE C CD Overall Equation: Catalyst: Intermediate: + D Mechanism 2 1. A + B → C 2. C + D → CD 3. CD + E → ABE Overall Equation: Catalyst: D Intermediate: C CD + D Mechanism 2 1. A + B → C 2. C + D → CD 3. CD + E → ABE Overall Equation: A + B + E → ABE Catalyst: D Intermediate: C CD + D Mechanism 3 Step 1 Step 2 Step 3 Br2 Br + OCl2 Br + Cl → 2Br → BrOCl + Cl → BrCl PE Reaction Path Overall Reaction: Intermediates: Mechanism 3 Step 1 Step 2 Step 3 Br2 Br + OCl2 Br + Cl → 2Br → BrOCl + Cl → BrCl PE Reaction Path Overall Reaction: Intermediates: Mechanism 3 Step 1 Step 2 Step 3 Br2 Br + OCl2 Br + Cl → 2Br → BrOCl + Cl → BrCl PE Reaction Path Overall Reaction: Intermediates: Br2 + OCl2 → BrOCl + BrCl Mechanism 3 Step 1 Step 2 Step 3 Br2 Br + OCl2 Br + Cl → 2Br → BrOCl + Cl → BrCl PE Reaction Path Overall Reaction: Br2 + OCl2 → BrOCl + BrCl Intermediates: Br Cl Mechanism 3 Step 1 Step 2 Step 3 Br2 Br + OCl2 Br + Cl → 2Br → BrOCl + Cl → BrCl PE 800 600 400 200 Reaction Path Overall Reaction: Br2 + OCl2 → BrOCl + BrCl Intermediates: Br ΔH = Ea (forward) = Ea (reverse) = The enthalpy of Br The enthalpy of BrCl Cl Mechanism 3 PE Step 1 Step 2 Step 3 Br2 Br + OCl2 Br + Cl → 2Br → BrOCl + Cl → BrCl 800 600 400 200 Reaction Path Overall Reaction: Br2 + OCl2 → BrOCl + BrCl Intermediates: Br ΔH = Ea (forward) = Ea (reverse) = The enthalpy of Br The enthalpy of BrCl Cl 200 kJ Mechanism 3 PE Step 1 Step 2 Step 3 Br2 Br + OCl2 Br + Cl → 2Br → BrOCl + Cl → BrCl 800 600 400 200 Reaction Path Overall Reaction: Br2 + OCl2 → BrOCl + BrCl Intermediates: Br ΔH = Ea (forward) = Ea (reverse) = The enthalpy of Br The enthalpy of BrCl Cl 200 kJ Mechanism 3 PE Step 1 Step 2 Step 3 Br2 Br + OCl2 Br + Cl → 2Br → BrOCl + Cl → BrCl 800 600 400 200 Reaction Path Overall Reaction: Br2 + OCl2 → BrOCl + BrCl Intermediates: Br ΔH = Ea (forward) = Ea (reverse) = The enthalpy of Br The enthalpy of BrCl Cl 200 kJ 600 kJ Mechanism 3 PE Step 1 Step 2 Step 3 Br2 Br + OCl2 Br + Cl → 2Br → BrOCl + Cl → BrCl 800 600 400 200 Reaction Path Overall Reaction: Br2 + OCl2 → BrOCl + BrCl Intermediates: Br ΔH = Ea (forward) = Ea (reverse) = The enthalpy of Br The enthalpy of BrCl Cl 200 kJ 600 kJ 400 kJ Mechanism 3 PE Step 1 Step 2 Step 3 Br2 Br + OCl2 Br + Cl → 2Br → BrOCl + Cl → BrCl 800 600 400 200 Reaction Path Overall Reaction: Br2 + OCl2 → BrOCl + BrCl Intermediates: Br ΔH = Ea (forward) = Ea (reverse) = The enthalpy of Br The enthalpy of BrCl Cl 200 kJ 600 kJ 400 kJ 300 kJ Mechanism 3 PE Step 1 Step 2 Step 3 Br2 Br + OCl2 Br + Cl → 2Br → BrOCl + Cl → BrCl 800 600 400 200 Reaction Path Overall Reaction: Br2 + OCl2 → BrOCl + BrCl Intermediates: Br ΔH = Ea (forward) = Ea (reverse) = The enthalpy of Br The enthalpy of BrCl Cl 200 kJ 600 kJ 400 kJ 300 kJ 400 kJ Mechanism 4 The following mechanism shows how chlorine-containing fluorocarbons destroy the ozone layer. Ozone is O3 and O 1. CFCl3 2. Cl 3. ClO → CFCl2 + + O3 → ClO + O2 + O → Cl + O2 Overall Reaction: Intermediates: Cl Mechanism 4 The following mechanism shows how chlorine-containing fluorocarbons destroy the ozone layer. Ozone is O3 and O 1. CFCl3 2. Cl 3. ClO → CFCl2 + + O3 → ClO + O2 + O → Cl + O2 Overall Reaction: Intermediates: Cl Mechanism 4 The following mechanism shows how chlorine-containing fluorocarbons destroy the ozone layer. Ozone is O3 and O 1. CFCl3 2. Cl 3. ClO → CFCl2 + + O3 → ClO + O2 + O → Cl + O2 Overall Reaction: Intermediates: Cl CFCl3 + O3 + O → CFCl2 + 2O2 + Cl Mechanism 4 The following mechanism shows how chlorine-containing fluorocarbons destroy the ozone layer. Ozone is O3 and O 1. CFCl3 2. Cl 3. ClO → CFCl2 + + O3 → ClO + O2 + O → Cl + O2 Cl Overall Reaction: CFCl3 + O3 + O → CFCl2 Intermediates: Cl ClO + 2O2+ Cl Determine the Missing Step of the Mechanism Mechanism 5 Overall: A + B → C C + D → B + AD A + D + E → ADE Determine the Missing Step of the Mechanism Mechanism 5 Overall: A + B → C C + D → B + AD A + D + E → ADE Determine the Missing Step of the Mechanism Mechanism 5 Overall: A + B → C C + D → B + AD A + D + E → ADE Put in step 3 so that you get the overall reaction Determine the Missing Step of the Mechanism Mechanism 5 A + B → C C + D → B + AD + D + E → ADE AD Overall: A Put in AD to cancel Determine the Missing Step of the Mechanism Mechanism 5 Overall: A + B → C C + D → B + AD AD + A + E → ADE Put in AD to cancel → D + Determine the Missing Step of the Mechanism Mechanism 5 Overall: Put in E A + B → C C + D → B + AD AD + E → A + D + E → ADE Determine the Missing Step of the Mechanism Mechanism 5 Overall: Put in ADE A + B → C C + D → B AD + E → ADE A + D + E + AD → ADE Determine the Missing Step of the Mechanism Mechanism 6 Overall: C + D → CD CD + E → ABE + D A + B + E → ABE Determine the Missing Step of the Mechanism Mechanism 6 Overall: C + D → CD CD + E → ABE + D A + B + E → ABE Determine the Missing Step of the Mechanism Mechanism 6 Overall: C + D → CD CD + E → ABE + D A + B + E → ABE Determine the Missing Step of the Mechanism Mechanism 6 Overall: C + D → CD CD + E → ABE + D A + B + E → ABE Determine the Missing Step of the Mechanism Mechanism 6 Overall: → C C + D → CD CD + E → ABE + D A + B + E → ABE Determine the Missing Step of the Mechanism Mechanism 6 Overall: → C C + D → CD CD + E → ABE + D A + B + E → ABE Determine the Missing Step of the Mechanism Mechanism 6 Overall: A + B → C C + D → CD CD + E → ABE + A + B + E → D ABE Determine the Missing Step of the Mechanism Mechanism 7 Overall: CFCl3 → CFCl2 + ClO O + → O + CFCl3 + O3 → Cl Cl + O2 CFCl2 + 2O2 + Cl Determine the Missing Step of the Mechanism Mechanism 7 Overall: CFCl3 → CFCl2 + ClO O + → O + CFCl3 + O3 → Cl Cl + O2 CFCl2 + 2O2 + Cl Determine the Missing Step of the Mechanism Mechanism 7 CFCl3 → CFCl2 + Cl Cl ClO Overall: + O → O + CFCl3 + O3 → Cl + O2 CFCl2 + 2O2 + Cl Determine the Missing Step of the Mechanism Mechanism 7 CFCl3 → CFCl2 + Cl Cl ClO Overall: + O → O + CFCl3 + O3 → Cl + O2 CFCl2 + 2O2 + Cl Determine the Missing Step of the Mechanism Mechanism 7 CFCl3 → Cl ClO Overall: + + CFCl2 + Cl O3 O → O + CFCl3 + O3 → Cl + O2 CFCl2 + 2O2 + Cl Determine the Missing Step of the Mechanism Mechanism 7 CFCl3 → Overall: CFCl2 + Cl + O3 → ClO + O Cl ClO + → Cl O + CFCl3 + O3 → O2 + O2 CFCl2 + 2O2 + Cl Determine the Missing Step of the Mechanism Mechanism 7 CFCl3 → Overall: CFCl2 + Cl + O3 → ClO + O Cl ClO + → Cl O + CFCl3 + O3 → O2 + O2 CFCl2 + 2O2 + Cl Determine the Missing Step of the Mechanism Mechanism 7 CFCl3 → Overall: CFCl2 + Cl + O3 → ClO + O Cl ClO + → Cl O + CFCl3 + O3 → O2 + O2 CFCl2 + 2O2 + Cl Determine the Missing Step of the Mechanism Mechanism 7 CFCl3 → Overall: CFCl2 + Cl + O3 → ClO + O Cl ClO + → Cl O + CFCl3 + O3 → O2 + O2 CFCl2 + 2O2 + Cl Determine the Missing Step of the Mechanism Mechanism 7 CFCl3 → Overall: CFCl2 + Cl + O3 → ClO + O Cl ClO + → Cl O + CFCl3 + O3 → O2 + O2 CFCl2 + 2O2 + Cl