Chemical Kinetics

1. Chemical Kinetics Chapter 14

2. 2NO (g) + O2 (g) 2NO2 (g) Elementary step: NO + NO N2O2 + Elementary step: N2O2 + O2 2NO2 Overall reaction: 2NO + O2 2NO2 Reaction Mechanisms The overall progress of a chemical reaction can be represented at the molecular level by a series of simple elementary steps or elementary reactions The sequence of elementary steps that leads to product formation is the reaction mechanism. N2O2 is detected during the reaction!

3. Elementary step: NO + NO N2O2 + Elementary step: N2O2 + O2 2NO2 Overall reaction: 2NO + O2 2NO2 Intermediates - species that appear in a reaction mechanism but notin the overall balanced equation An intermediate is always formed in an early elementary step and consumed in a later elementary step. • Molecularity of a reaction - the number of molecules reacting in an elementary step. • Unimolecular reaction – elementary step with 1 molecule • Bimolecular reaction – elementary step with 2 molecules • Termolecular reaction – elementary step with 3 molecules

4. Unimolecular reaction Bimolecular reaction Bimolecular reaction A + B products A + A products A products Rate Laws and Elementary Steps rate = k [A] rate = k [A][B] rate = k [A]2 • Writing plausible reaction mechanisms: • The sum of the elementary steps must give the overall balanced equation for the reaction. • The rate-determining step should predict the same rate law that is determined experimentally. Rate-determining step - the sloweststep in the sequence of steps leading to product formation.

5. The experimental rate law for the reaction between NO2 and CO to produce NO and CO2 is rate = k[NO2]2. The reaction is believed to occur via two steps: Step 1: Step 2: NO2 + NO2 NO + NO3 NO2+ CO NO + CO2 NO3 + CO NO2 + CO2 What is the equation for the overall reaction? What is the intermediate? NO3 What can you say about the relative rates of steps 1 and 2? rate = k[NO2]2 is the rate law for step 1 so step 1 must be slower than step 2

6. uncatalyzed catalyzed Ea k ' Ea< Ea Catalyst- a substance that increases the rate of a chemical reaction without itself being consumed k = A •exp( -Ea/RT ) Fig 14.17 ratecatalyzed > rateuncatalyzed

7. Heterogeneous catalysis- the reactants and the catalysts are in different phases. • Haber synthesis of ammonia • Ostwald process for the production of nitric acid • Catalytic converters Homogeneous catalysis - reactants and the catalysts are dispersed in a single phase, usually liquid. • Acid catalysis • Base catalysis

8. Fe/Al2O3/K2O N2 (g) + 3H2 (g) 2NH3 (g) catalyst Haber Process Fig 14.18

9. 4NH3(g) + 5O2(g) 4NO (g) + 6H2O (g) 2NO (g) + O2(g) 2NO2(g) 2NO2(g) + H2O (l) HNO2(aq) + HNO3(aq) Hot Pt wire over NH3 solution Pt-Rh catalysts used in Ostwald process Ostwald Process for Making Nitirc Acid Pt catalyst Fig on pg 438 Fig 14.19

10. catalytic CO + Unburned Hydrocarbons + O2 CO2 + H2O converter catalytic 2NO + 2NO2 2N2 + 3O2 converter Fig 14.20 Catalytic Converters Fig 14.21 Platinum, palladium, rhodium

11. Enzyme Catalysis Fig 14.22 Fig 14.23 glucose hexokinase

12. enzyme catalyzed uncatalyzed Δ[P] rate = Δt Basic reaction steps in enzyme catalysis E + S ⇌ ES (fast) ES → P + E (slow) k Fig 14.24 rate = k [ES]

13. Fig 14.25 Plot of rate of product formation vs substrate concentration Zero order First order rate k [S]