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Unit 1 - Reaction Kinetics


Chemistry 12

Introduction to Reaction Kinetics

CHEMICAL KINETICS deals with the empirical research of reaction times and changes in measurable properties. We can use this empirical knowledge to form theories to explain and predict rates of reaction.

Measuring Reaction Rates

Cu(s) + 4 HNO3(aq) Cu(NO3)2(aq) + 2 H2O(l) + 2 NO2(g) + heat pH Change Pressure Change


(in a closed system) BROWN gas (NO2(g)) released

REACTION RATES are usually obtained by measuring how a property changes per unit of time. Any property may be used as long as it is OBSERVABLE and MEASURABLE. Consider the reaction of Copper metal with Nitric acid to illustrate the various methods that can be employed to measure reaction rates:

An acid is used up, less acidic, pH increases

Mass Change
(in an open system) A gas is released, NOT due to the decreasing mass of Cu

Temperature Change
HEAT is released (exothermic reaction)

Cu(s) + 4 HNO3(aq) Cu(NO3)2(aq) + 2 H2O(l) + 2 NO2(g) + heat

Solution turned BLUE, concentration of Cu(NO3)2(aq) increases (Concentration Change)

Colour Change

To measure a rate, the change needs to be measured during a certain time period. Any unit of time may be used (minutes, seconds, hours, days, etc.) The general way to express a rate is as follows:

For Example:

Rate =

Recall:

property time
Rates are always expressed per unit of time!!!
g/sec, M/min, s-1

delta means: final initial Therefore: time = tfinal - tinitial

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If we were to plot the graph of property vs. time for any reaction, the rate would be represented by the slope of that graph. For Example: Consider two tangents drawn at different points on the graph. For most reactions, the concentration changes are faster at the beginning of the reaction and tend to decrease as time elapses.

Factors Affecting Reaction Rates


When making chocolate milk, does the powder dissolve faster in hot milk or cold milk? When Magnesium metal is placed in equal volumes of Hydrochloric acid, will the reaction be faster in 3.0 mol/L or 6.0 mol/L HCl(aq)?

Steeper slope = FASTER RATE

1 2

Several factors can affect the rate at which a reaction takes place.

Temperature:

Nature of the Reactants:

Reactant molecules posses more kinetic energy at higher temperatures. More energy means a greater number of successful collisions will occur per unit of time. Since the time required for the reaction to reach completion decreases, the rate of the reaction must increase.

Not all reactants are the same. Therefore, not all reactants will react the same way. 2 things to consider:

Chemical Properties: Some reactions are naturally fast (combustion of gasoline), and some are naturally slow (rusting of Iron). We can only change the rate of these reactions by a small degree by manipulating temperature, pressure, and concentration. Number and Types of Bonds Broken and Formed:

Pressure/Concentration: (same effect)

Increasing the pressure/concentration increases the number of reactant species in the solution. Having more of the reactant species present means that more will react per unit of time. More reactions per unit of time means a higher rate.

The number (one, two, three, etc.) and type of bond (single, double, triple) can dictate the speed of the reaction. The stronger the bond, and the more bonds involved, the slower the reaction

Surface Area and Phase:

Surface Area: Increasing the surface area has the same effect as increasing the concentration. The ability for the reactants to meet is greater because there are more sites for the reaction to take place. More available sites = faster reaction rates. Phase of the Reactants: HOMOGENEOUS REACTION: a reaction in which all the reactants are in the same phase. For example: two gasses, two substances dissolved in water, and two liquids that completely dissolve in each other (miscible)

HETEROGENEOUS REACTION: a reaction in which the reactants are present in different phases.

For example:

a solid and a liquid, a liquid and a gas, a solid and a gas, and two liquids that do not dissolve in each other (immiscible)

To summarize phase: FASTEST SLOWEST


AQUEOUS IONS > (GASES or LIQUIDS) > SOLIDS

Lots of mobility, force of attraction between ions.

Low mobility.

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Catalysts and Inhibitors:

Which type of reaction (homogeneous or heterogeneous) are not affected by changes in surface area?

A CATALYST is a chemical that can be added in order to increase the rate of reaction (more to come later). After the reaction is complete, the same amount of catalyst will be present as was added in at the beginning, it is not consumed during the reaction.

An INHIBITOR is a chemical that can be added in order to slow a reaction down.

Homework

Reaction Rate Theory


Read: Pages 5 16 Do:

Molecules cannot react with one another at a distance. In order for there to be a reaction, molecules must collide with each other. The KINETIC MOLECULAR THEORY states this and several other important points.

#1 17 Study for quiz.

A chemical sample consists of particles (molecules, atoms, or ions). They act as small, hard spheres that collide and bounce off each other transferring energy among themselves during their collisions. An effective collision requires sufficient energy and correct positioning of the particles so that bonds can be broken, and new ones can be formed. Ineffective collisions result in the particles rebounding off each other unaltered in nature.

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When chemical reactions occur:


Enthalpy Changes in Chemical Reactions

bonds are broken and formed. phases may change. work may be done on or is done by the system. heat may be transferred into or out of the system.

ENTHALPY:

The total kinetic and potential energy of a system under constant pressure.

POTENTIAL ENERGY (PE):


A stored form of energy. Exists as a result of the objects position in space and as a sum of all the repulsive and attractive forces amongst the particles that make up the object. Directly related to the energy of the electrons in the chemical bonds and the number and type of atoms in the molecule.

To make all these changes in energy easier to keep track of, we can find the CHANGE IN ENTHALPY (H) of the open system at constant atmospheric pressure.

H = Hproducts Hreactants
Where: Hreactants = the combined enthalpies of all the reactants. Hproducts = the combined enthalpies of all the products.

KINETIC ENERGY (KE):

A form of energy related to the motion of a particle.

The Sign of H

Therefore:

Hproducts > Hreactants

or

H > 0

The sign of H can either be + or depending whether the reaction is ENDOTHERMIC or EXOTHERMIC.

The two ways to express this in a chemical equation are: 2 N2(g) + O2(g) + 164

Endothermic:

kJ 2 N2O(g) kJ

Energy is absorbed by a system from the Results in an increase in the potential energy of The products have more energy than the reactants. The loss of energy from the surroundings to the
system makes the surroundings feel cooler. the system. surroundings.

2 N2(g) + O2(g) 2 N2O(g) ; H = +164

In endothermic reactions, energy in the form of heat enters (+) the system. The energy term is on the reactants side of the equation. You are putting in energy to make the reaction happen.

Exothermic:

change in which energy is released from a system into the surroundings, resulting in a decrease in potential energy of the system. The products have less energy than the reactants.

In exothermic reactions, energy in the form of heat exits (-) the system. In this case, energy is on the products side of the equation. Energy in the form of heat is one of the products. Energy is being lost to the surroundings, thus making the surroundings feel warmer.

Therefore:

Hproducts < Hreactants

or

H < 0
kJ kJ

The two ways to express this in a chemical equation are: H2(g) + Cl2(g) 2 HCl(g) + 184

H2(g) + Cl2(g) 2 HCl(g) ; H = -184

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Homework

Kinetic Energy Distributions


Read:

The average kinetic energy of system is perceived as the temperature. Consider the reaction: C2H5OH(l) C2H4(g) + H2O(l)

Pages 17 - 25

Do:

#18 28

At room temperature (20C), the reaction occurs at an undetectable rate. At 200C, the reaction proceeds at a very slow rate. At 400C the reaction if fairly rapid.

Consider the kinetic energy distribution of molecules in a system:

If we change the temperature, as stated before, the KE distribution of the molecules changes:

Some molecules have a lot of kinetic energy, some have little. When we increase the temperature, we increase the average kinetic energy of the entire system.

Using the above graph:


@20oC:

@400oC:

The average kinetic energy is far below the minimum needed for the reaction to occur. Very few molecules have sufficient kinetic energy to react; therefore we have a very low reaction rate.

At this temperature, the most number of molecules have sufficient kinetic energy to react. Here we get the greatest reaction rate.

In conclusion

@200oC:

The increase in temperature has increased the average kinetic energy of the molecules. A higher percentage of molecules now have the minimal amount of kinetic energy to react so the reaction rate increases.

The increased reaction rate due to an increase in temperature is not due solely to increased collisions between molecules, but also to an increase in the number of molecules that have sufficient kinetic energy to react. !

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The Rule of Thumb for temperature/rate:

Activation Energy
Every reaction has some sort of barrier that molecules must pass before they can react. Imagine rolling a ball down a smooth track shaped as below

For a slow reaction, a temperature increase doubles the rate.

10oC

Molecules behave much in the same way:

Point B:

As the molecule slows down due to those repulsive forces, the KE it possesses begins to convert to PE. If the molecule can obtain enough PE by converting KE gained into PE, and adding it to the PE it already possesses, an ACTIVATED COMPLEX is formed.

Point C:

Point A:

Activated Complex:

As molecules begin to approach each other, the like charges of the electrons create repulsive forces which push the molecules apart.

The structure arrangement of particles representing the highest potential energy (changeover) point in a chemical reaction. Also called an intermediate particle

Activation Energy (Ea):

The minimum amount of energy required to change the reactants into the activated complex.

At this point, bonds are broken and new ones are formed.

The imaginative barrier that keeps reactions from occurring is due to the repulsive forces between the molecules, as well as the energy required to break the bonds between the atoms. The higher the hill, the more KE is needed for the reaction to occur, and the slower the reaction.

Point D:

The electrons in the outer shell of the new products begin to repel each other and the products push themselves apart. They lose their excess PE by changing it back into KE.

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How does this KE PE change work?

There are three possible cases that can occur when two molecules react with one another:

Consider the diagram below:

PE < Ea: Molecules do not posses sufficient KE to change to PE to reach the top of the PE hump. Molecules will come to a stop before they collide, and then repel away from each other. This is called an INNEFECTIVE COLLISION. PE = Ea: Molecules posses just enough KE to change to PE to reach the top of the PE hump. Molecules will approach each other and come to a stop. Since PE = Ea a reaction may occur, but they may also just move away without reacting. PE > Ea: Molecules have enough KE to change to PE, plus some excess KE left over. This scenario results in an EFFECTIVE COLLISION.

Considering case number three from before, there are two requirements for a successful reaction:
1. Sufficient KE as outlined in case 3.

insufficient KE = insufficient PE If the reactants are not correctly aligned, more energy is required for the reaction to take place.

2. Correct Alignment

The activation energy values given on potential energy diagrams refer to a scenario where there is perfect alignment. Anything other than perfect will increase the Ea significantly!

PE diagrams give a snapshot of what energy is needed for a reaction to take place. They can be read from left to right, or right to left. Reactants can form products and products can re-form reactants (REACTANTS PRODUCTS).
Keep in mind that activation energy is always ENDOTHERMIC!

Endothermic Reactions:

Energy is absorbed from the surroundings. From the direction of the arrow, we can see H > 0.

Consider a standard PE diagram:

Exothermic Reactions:

Energy is released to the surroundings. From the direction of the arrow, we can see H < 0.

Ea(f) = the Ea for the forward rxn. Ea(r) = the Ea for the reverse rxn.

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Memorizing equations sucks! By sketching a potential energy diagram and labeling the important parts, you can just figure out what information is needed for the question.

Homework
Read:

1. If H = -32 kJ and Ea(f) = 72 kJ, what is the value of Ea(r)? 2. Draw and label a PE diagram for the reaction: CO(g) + NO2(g) CO2(g) + NO(g) + 227 kJ in which Ea(f) = 135 kJ. Indicate on your diagram, the point at which the activated complex exists. 3. Draw and label a PE diagram showing the enthalpy change and activation energies for a reaction in which Ea(f) = 135 kJ and Ea(r) = 82 kJ

Pages 26 - 30

Do:

#29 45 Study for quiz. Prerequisite Assignment due next class. Study for exam.

Reaction Mechanisms

The chances of the twenty three particles coming together, such as the reaction above, are ZERO! This leads us to conclude that complex reactions cannot go in a single step; most chemical reactions must occur as a sequence of individual steps.

Reaction Mechanism:

the individual steps during the progress of a reaction.

A collision between two particles lasts for a very short time period. The chances of having more than two particles colliding in space with enough energy to react and with the correct orientation is very low. Consider this: 5 C2O4-2 + 2 MNO4- + 16 H+ 10 CO2 + 2 Mn2+ + 8 H2O

Consider the following example: 4 HBr + O2 2 H2O + 2 Br2

The preceding reaction is broken down into a series of three steps: Step 1: HBr + O2 HOOBr (slow)

There are a couple of important things to remember when talking about reaction mechanisms:

Step 2:

HOOBr + HBr 2 HOBr

(fast)

Step 3:

2HOBr + 2HBr 2H2O + 2Br2

(fast)
The overall reaction is comprised of these three steps put together.

The slowest step in the reaction is called the RATE DETERMINING STEP. Just remember it as the bottle neck. The reaction can become instantly frozen. This happens because HOOBr is produced very slowly and HOBr is consumed very fast. Thus the concentration of these reagents cannot build up. To determine the overall equation for the reaction, add up all the steps in the reaction and then cross out any species that appear on both sides of the final equation. For Example: Step 1: HBr + O2 HOOBr Step 2: Step 3: Overall: HOOBr + HBr 2 HOBr 2 HOBr + 2 HBr 2H2O + 2Br2 4 HBr + O2 2 H2O + 2 Br2

Overall:

4 HBr + O2 2 H2O + 2 Br2

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Substances such as HOOBr and HOBr which are formed during the reaction, but react immediately and are not present at the end of the reaction are called REACTION INTERMIDIATES.

What if we have to find a missing step? For Example:


The suggested equation: Overall: CFCl3 + O3 + O CFCl2 + Cl + 2O2

To find the activated complex in a reaction, add up all the atoms involved in that step:
For Example: Step 2

has a three step mechanism. If the proposed 1st and 3rd steps are: Step 1: CFCl3 CFCl2 + Cl ??? ClO + O Cl + O2

HOOBr + HBr 2 HOBr Activated Complex: H2O2Br2

Step 2: Step 3:

What is the 2nd step in the proposed reaction?

The PE diagram for this type of reaction gets a little more complicated. Each step has its own activated complex and activation energy. Since there are three steps, there will be three humps in the PE diagram.

We can find the activation energy for each step. For Example:

Consider step 2 for the above reaction:

Homework

The Effects of Catalysts

Read: Pages 30 - 36

Catalyst:
A substance that speeds up a reaction rate by providing an overall reaction with an alternative mechanism having lower activation energy.

Do: #46 - 55

Catalysts provide an alternative pathway by inserting different intermediate steps and lowering the activation energy for the reaction to occur. H is not changed, but the energy hump is lowered, therefore, the reaction rate INCREASES.

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By lowering the energy hump for the forward reaction, we have also lowered it for the reverse reaction. Since a greater fraction of product molecules will have sufficient KE to form the activated complex, the reverse reaction rate increases also.

For Example:

Consider the decomposition of Formic acid which occurs at a very slow rate at room temperature:

As soon we acidify the solution with Sulfuric acid, it begins to bubble.

Some important things to remember about catalysts:

Your lab write-up


The catalyst is an active participant in a reaction which is regenerated in a later step of the reaction mechanism. H for the overall reaction is the same for both the catalyzed and un-catalyzed reaction; only the intermediate reactions differ. All intermediates and catalysts cancel out when the individual steps are added up to get the overall reaction.

Labs are to be done in a coiled book. Leave the first page blank for a table of contents. All labs are written in BLUE or BLACK ink. Underlining is done in RED. Numeric calculations in the Analysis/Questions section may be done in PENCIL.

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What should it look like?

Homework

Read: Experiment 1 Measuring Reaction Rate Using Volume of Gas Produced Do:

#56 63 Assignment due next class.

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