Chapter 16 : Reaction Rates

Section 2 : How Can reaction Rates be Explained ? p. 586

OBJECTIVES


Write a rate law using experimental rateversus-concentration data from a chemical reaction. Explain the role of activation energy and collision orientation in a chemical reaction. Describe the effect that catalysts can have on reaction rate and how this effect occurs. Describe the role of enzymes as catalysts in living systems, and give examples
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KEY TERMS
rate law reaction mechanism order rate-determining step intermediate activation energy activated complex catalyst catalysis enzyme
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Kagan Structure Numbered Heads Together

Answer the following question: Explain the effect of increasing the concentration on the reaction Rate.

Rate Laws


Rate Law : The expression that describes the relationship between the reaction rate and the concentrations of reactants. reactants. By studying rate laws , the reaction mechanism can be guessed.

Reaction mechanism: the way in which a chemical reaction takes place , expressed in a series of chemical equations

Determining a General Rate Law Equation:

For a reaction that involves a single reactant :


 

Rate = K [ reactant ]n
The exponent n is called the order. K : is the rate constant. Order : A way of classifying chemical reactions depending on the number of molecules that enter into the reaction. Reaction orders must be found by experiment. experiment.

Rate Law For One Reactant

2HI(g 2HI(g)

H2(g I2(g H2(g) + I2(g).

4 = (2)n
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Kagan Structure Rally Coach

With your shoulder partner , answer Practice B page 587.

Practice B (p.587):

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Rate Laws for Several Reactants:

Example : Practice : The following data relate to the reaction A + B C find the order with respect to each reactant. Rate = K [ A ]n1 [ B ]n2

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1.

2.

3.

Find two experiments in which all but one reactants concentration is constant. Observe the relationship between concentration change and rate change to determine the order for that reactant. Repeat for other reactant (s).

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Select a trial where one reactant concentration is held constant SO THAT IT CANCELS; the ks will also cancel.
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A + B C Rate = K [ A ]n1 [ B ]n2 To determine reaction order with respect to A , choose 2 data points between which [B] is unchanged. (Rate )1 = ( [A] 1) n1 (Rate )3 ( [A] 3) n1 0.012 0.003 ( [B] 1 ) n2 ( [B] 3 ) n2

= ( 0.08 ) n1 ( 0.04 ) n1 4 = 2 n1 2 = 2 n1 n1 = 2

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To determine reaction order with respect to B, choose 2 data points between which [A] is unchanged . (Rate )1 = ( [A] 1 ) n1 ( [B]1 ) n2 (Rate )2 ( [A] 2) n1 ( [B] 2) n2


0.012 0.006 2 = n2 = Rate =

( 0.06 ) n2 ( 0.03 ) n2

2 n2 1 K [ A ]2 [ B ]1

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Determine the rate law and calculate the rate constant for the following reaction from the following data: 2SO42- (aq) + I3- (aq) S2O82- (aq) + 3I- (aq)
Experiment

[S2O8

2-]

[I-] 0.034 0.017 0.017

Initial Rate (M/s) 2.2 x 10-4 1.1 x 10-4 2.2 x 10-4

1 2 3

0.08 0.08 0.16

rate = k [S2O82-]x[I-]y y=1 x=1 rate = k [S2O82-][I-]

Double [I-], rate doubles (experiment 1 & 2) Double [S2O82-], rate doubles (experiment 2 & 3) 2.2 x 10-4 M/s rate k= = = 0.08/Ms 2-][I-] [S2O8 (0.08 M)(0.034 M)

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13.2

Kagan Structure Numbered Heads Together

Exp. # [NH4+]o [NO2]o 1 2 3 0.100 0.100 0.200 0.0050 0.0100 0.0100

Initial Rate (Ms-1) (M 1.35 x 10-7 2.70 x 10-7 5.40 x 10-7

Rate determining step : in a multi step chemical reaction is the step that has the lowest velocity.  Intermediate : a substance that forms in a middle stage of a reaction and is considered a stepping stone between reactants and products.

yIn the above reaction HOBr is considered as intermediate.

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 NO3 + CO NO2+ CO 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 NO + NO3 NO2 + CO2 NO + CO2

What is the equation for the overall reaction?

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13.5

Zero order


The change in concentration of reactant has no effect on the rate. These are not very common. General form of rate equation:

Rate = k
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First order


Doubling concentration of reactant doubles rate. General form of rate equation:

Rate = k [A]

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Second order
  

When concentration of reactant is doubled Rate is quadrupled ( increase 4 times) when concentration of reactant is tripled, the tripled, rate increases by a factor of 9 These are common, particularly in gas-phase gasreactions. General form of rate equation:

Rate = k [A]2
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Fractional orders are rare! Ex. rate = k[A] m[B] n

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Example 1


Rate = k[A] [B]

In this case, the order of reaction with respect to both A and B is 1. The overall order of reaction is 2 it is found by adding up the individual orders.
Note: Where the order is 1 with respect to one of the reactants, the "1" isn't written into the equation. [A] means [A]1.
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Kagan Structure Rally Coach

With your shoulder partner answer the Rally Coach sheet.

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Reaction Pathways and Activation Energy:

For two molecules to react they must collide violently to overcome the repulsion force between their electrons, Violent collisions happen only when the colliding molecules have large amount of energy. Only molecules with high kinetic energy are likely to react. The other molecules must wait until the collision give them enough kinetic energy. Activation energy ( Ea ) : The minimum energy required to start a chemical reaction.
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Example

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Activation Energy Diagrams Model Reaction Progress:

For two molecules to react they must have enough Kinetic Energy to change chemically. With a combined K.E equal to the activation energy , the molecules reach a state where there is a 50 : 50 chance of either returning to the initial state without reacting ,or react to produce products . This point is called Activation complex or transition state of the reaction.

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Reaction Pathways and Activation Energy:

Activation complex : a molecule in an unstable state intermediate to the reactants and the products in the chemical reaction.

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Not All Collisions Result in Reaction:

Collision between the reacting molecules is necessary but not enough (why?) because molecules must collide with enough (why?) energy to overcome the activation energy barrier also the collision must be with correct orientation.. Unless the collision brings the correct atoms close together and in the proper orientation , the molecules will not react , even if the activation energy is enough.

Collision between the reacting molecules must have two conditions to be successful 1. Molecules must collide with enough energy to overcome the activation energy barrier 2. Also the collision must be with correct orientation..

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Numbered Heads Together

Answer the following question/ State the conditions that makes collision between the reacting molecules successful

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Molecular Collisions

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Successful Collision:

y In the above reaction if a chlorine molecule Cl2 collides with the oxygen end of nitrogen monoxide NO the reaction will occur , y But if the chlorine molecule collide with the nitrogen end the 35 reaction will not occur.

Possible Collision Orientations for the Reaction of H2 and I2

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Catalysts Increase Reaction Rate:

Catalyst : a substance that changes the rate of the reaction without being consumed or changed. Catalysis : the acceleration of a chemical reaction by a catalyst.

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Example : the decomposition of hydrogen peroxide H2O2

Two catalysts can be used potassium iodide KI or manganese dioxide MnO2 . Catalysis :is widely used in chemical industry specially in petrochemicals to save enormous amount of energy.

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Catalysts Lower the Activation Energy: Energy:

How catalysis works? By making different pathway available between the reactants and the products with lower activation energy than uncatalyzed reaction. reaction.

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Example :The decomposition of hydrogen peroxide H2O2

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Enzymes Are Catalysts found In Nature:

Enzyme : a type of protein that speeds metabolic reactions in plants and animals without being permanently changed or destroyed.

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Section 2 Review Questions (p. 595):

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