LEGAZPI CITY HIGH SCHOOL BITANO, LEGAZPI CITY

(CHEMICAL KIN ETICS )

MAYOR, Victor Laurence IMPERIAL, Daryann Mae LONCERAS, Mary Ann MOLLENO, Quencess NARVAEZ, Maria Yvonne IV SHAKESPEARE Submitted To: Ms. Michelle Musni Daniel Submitted By:

MULTIPLE CHOICE. Answer the following questions by UNDERLINING the letter of the correct answer. 1. The combustion of ethane (C2H6) is represented by the equation: 2C2H6(g) + 7O2(g) In this reaction: the rate of consumption of ethane is seven times faster than the rate of consumption of oxygen. b. CO2 is formed twice as fast as ethane is consumed. c. water is formed at a rate equal to two-thirds the rate of formation of CO2. d. the rate of consumption of oxygen equals the rate of consumption of water. The speed of a chemical reaction a. 4CO2(g) + 6H2O(l)

2.

a. is constant no matter what the temperature is. b. is independent of the amount of contact surface of a solid involved. c. between gases should in all cases be extremely rapid because the average kinetic energy of the molecules is great. d. between ions in aqueous solution is extremely rapid because there are no bonds that need to be broken. 3. For a reaction 2A + B 2C, with the rate equation: Rate = k[A]2[B] a. the order with respect to A is 1 and the order overall is 1. b. the order with respect to B is 2 and the order overall is 3. c. the order with respect to A is 2 and the order overall is 3. d. the order with respect to B is 2 and the order overall is 2. 4. Given the following data for this reaction: NH4+(aq) + NO2-(aq) EXPT 1 2 3 The rate law for the reaction is: a. Rate = k[NH4+][NO2-] b. Rate = k[NH4+]2[NO2-]2 c. Rate = k[NH4+]2[NO2-] d. Rate = k[NH4+][NO2-]2 e. none of the above [NH4+] 0.010 M 0.015 M 0.010 M N2(g) + 2H2O(l) [NO2-] 0.020 M 0.020 M 0.010 M RATE 0.020 M/s 0.030 M/s 0.005 M/s

5. What is the activation energy (in kJ) of a reaction whose rate constant increases by a factor of 100 upon increasing the temperature from 300 K to 360 K? a. 27 b. 35 c . 42 d. 69

6. A catalyst: a. actually participates in the reaction. b. changes the equilibrium concentration of the products. c .does not affect a reaction energy path. d. always decreases the rate for a reaction. 7. A possible mechanism for the reaction, 2A + B (1) A + A (2) A2 + A (3) A3 + B A2 A3 C + D, is: fast, equilibrium Slow

A + C + D Fast

According to the mechanism, the rate law will be: a. Rate = k[A]3 b. Rate = k[A][B] c. Rate = k[A]2[B] d. Rate = k[A] 8. Suppose the reaction: A + 2B AB2 occurs by the following mechanism: Step 1 Step 2 A+B AB + B AB Slow

AB2 Fast AB2

Overall A + 2B The rate law expression must be Rate = _________.

a. k[A] b. k[A][B]2 c. k[A][B] d. k[B]2 9. If reaction A has an activation energy of 250 kJ and reaction B has an activation energy of 100 kJ, which of the following statements must be correct? a. If reaction A is exothermic and reaction B is endothermic then reaction A is favored kinetically. b. At the same temperature the rate of reaction B is greater than the rate of reaction A. c. The energy of reaction A must be greater than the energy of reaction B. d. The rate of reaction A at 25 oC equals the rate of reaction B at 100 oC. 10. What are the units of k for the rate law: Rate = k[A][B]2, when the concentration unit is mol/L? a. s-1 b. s c. L mol-1 s-1 d. L2 mol-2 s-1 e. L2 s2 mol-2 11. Which statement is false? a. If a reaction is thermodynamically spontaneous it may occur rapidly. b. If a reaction is thermodynamically spontaneous it may occur slowly. c. Activation energy is a kinetic quantity rather than a thermodynamic quantity. d. If a reaction is thermodynamically spontaneous, it must have a low activation energy.

12. The half-life for a first-order reaction is 32 s. What was the original concentration if, after 2.0 min, the reactant concentration is 0.062 M? a. 0.84 M b .0.069 M c. 0.091 M d. 0.075 M 13. In the reaction A + 2 B 3 C + 4 D, the initial concentration of A was 0.0442 M after 12.7 min the concentration of A was 0.0325 M. What is the average rate of disappearance (M/s) of reactant B? a. 3.07-5 M/s b. 6.02-2 M/s c. 3.05-5 M/s d. 6.03-5 M/s 14. In the reaction A + 2 B 3 C + 4 D, the initial concentration of B was 0.0388 M after 17.1 min the concentration of B was 0.0199 M. What is the average rate of appearance (M/s) of reactant C? a. 2.63-5 M/s b.5.76 -5 M/s c. 2.76 -5 M/s d. 6.03-5 M/s 15. In the reaction A + 2 B 3 C + 4 D, the initial concentration of A was 0.0413 M after 16.4 min the concentration of A was 0.0235 M. What is the average rate of disappearance (M/s) of reactant B? a. 2.63-5 M/s b. 3.62-5 M/s c. 2.76 -5 M/s d. 6.03-5 M/s 16. In the reaction A + 2 B 3 C + 4 D, the initial concentration of B was 0.0352 M after 12.5 min the concentration of B was 0.0227 M. What is the average rate of disappearance (M/s) of reactant A? a. 2.63-5 M/s b. 3.62-5 M/s c. 8.33-6 M/s d. 6.03-5 M/s 17. In the reaction A + 2 B 3 C + 4 D, the initial concentration of B was 0.0388 M after 16.9 min the concentration of B was 0.0264 M. What is the average rate of appearance (M/s) of reactant C? a. 1.83-5 M/s b. 3.62-5 M/s c. 8.33-6 M/s d. 6.03-5 M/s 18. In the reaction A + 2 B 3 C + 4 D, the initial concentration of A was 0.0419 M after 15.2 min the concentration of A was 0.0267 M. What is the average rate of disappearance (M/s) of reactant B? a. 1.83-5 M/s b. 3.62-5 M/s c. 3.33-5 M/s d. 6.03-5 M/s

19. Calculate the concentration of N2O5 after 4.0 min starting with a concentration of 0.160 mol/L. a. 0.83 mol/L b. 3.62 mol/L c. 0.040 mol/L d. 0.063 mol/L 20. How long will it take for the concentration to drop from 0.160 to 0.080 M? a. 2.0 min b. 6.0 min c. 7.0 min d. 3.0 min 21. How much time is required for the concentration to drop from 0.160 to 0.100 mol/L? a. 2.0 min b. 1.3 min c. 7.0 min d. 3.0 min 22. If 4.00 g A is allowed to decompose for 40 min , the mass of A remaining undecomposed is found to be 0.80 g . Calculate the half-life of the reaction. a. 2.0 min b. 1.3 min c. 7.0 min d. 39.67 min 23. If 8.00 g A is allowed to decompose for 34 min, the mass of A remaining undecomposed is found to be 0.70 g. Calculate the half-life of the reaction. a. 2.0 min b. 22.28 min c. 7.0 min d. 39.67 min 24. If 9.00 g A is allowed to decompose for 24 min, the mass of A remaining undecomposed is found to be 0.50 g. Calculate the half-life of the reaction. a. 13.25 min b. 22.28 min c. 7.0 min d. 39.67 min 25. For the reaction

What is the rate equation ? a. r = k[H][NO] b. r = k[H2]1[NO]2 c. r = k[H2]1[NO] d. r = k[H2]1[N]2

KEY TO CORRECTION
1. b. 2. d 3. c 4. d 5. d 6. a 7. a 8. c 9. b 10. d 11. d 12. a 13. a 14. c 15. b 16. c 17. a 18. c 19. c 20. a 21. b 22. d 23. b 24. a 25. b

Rate Law
is a mathematical equation that describes the progress of the reaction. In general, rate laws must be determined experimentally. Unless a reaction is an elementary reaction, it is not possible to predict the rate law from the overall chemical equation. There are two forms of a rate law for chemical kinetics: the differential rate law the integrated rate law The differential rate law relates the rate of reaction to the concentrations of the various species in the system. Differential rate laws can take on many different forms, especially for complicated chemical reactions. However, most chemical reactions obey one of three differential rate laws. Each rate law contains a constant, k, called the rate constant. The units for the rate constant depend upon the rate law, because the rate always has units of mole L-1 sec-1 and the concentration always has units of mole L-1. General Reaction:

aA + bB
the rate law takes t and it form :

cC +dD

rate= k[A]x[B]y
where: x and y are the numbers that must be determined experimentally and specify the relationships between the concentration of reactants A and B and the reaction rate.

ZERO-ORDER REACTION
For a zero-order reaction, the rate of reaction is a constant. When the limiting reactant is completely consumed, the reaction quickly stops.

DIFFERENTIAL RATE LAW:

rate = k[A]0

The rate constant, k, has units of mole L-1 sec-1. The rate of reaction is constant as the reaction progresses.

FIRST-ORDER REACTION
For a first-order reaction, the rate of reaction is directly proportional to the concentration of one of the reactants.

DIFFERENTIAL RATE LAW:

rate = k[A]1

The rate constant, k, has units of sec-1.T he rate of reaction is directly proportional to the concentration. As the reactant is consumed during the reaction, the concentration drops and so does the rate of reaction.

SECOND-ORDER REACTION
For a second-order reaction, the rate of reaction is directly proportional to the square of the concentration of one of the reactants.

DIFFERENTIAL RATE LAW:

rate = k[A]2

The rate constant, k, has units of L mole-1 sec-1. ). The rate of reaction increases with the square of the concentration. For this type of reaction, the rate of reaction decreases rapidly as the concentration of the reactant decreases.

EXAMPLE
1. For the reaction H2 + Br2 = 2 HBr The following mechanism has been proposed

SOLUTION: I II III Br2 Br + H2 H + Br2 k1 k2 k3 2 Br HBr + H HBr + Br (both directions are fast) (slow) (fast)

a. Derive the rate law that is consistent with this mechanism.

The factor 1/2 results from the 2 HBr formed every time, one in step II and one in step III. Since [Br] is not one of the reactants, its relationship with the concentration of the reactants must be sought. The rapid reaction in both direction of step i implies the following relationship, k1 [Br2] = k-1 [Br]2 or [Br] = ((k1/k-1) [Br2])(1/2) b. Substituting this in the rate expression results in, rate = k2 (k1/k-1)(1/2) [H2] [Br2](1/2) The overall reaction order is 3/2, 1 with respect to [H2] and 1/2 with respect to [Br2]. In an acid solution, the mechanism for the reaction. NH4+ + HNO2 will give you, I. HNO2 + H+ = H2O + NO+ (equilibrium, K1) II. NH4+ = NH3 + H+ (equilibrium, K2) III. NO+ NH3 NH3NO+ (slow, k3) IV. NH3NO+ H2O + H+ + N2 (fast, k4) c. Derive the rate law Neither NO+ nor NH3 is a reactant. You must express their concentrations in terms of [NH4+] and [HNO2] from elementary processes I and II. From I, [NO+] = K1 [HNO2] [H+] / [H2O] - - (5) From II, [NH3] = K2 [NH4+] / [H+] - - - - (6) d. Substituting (6) and (5) in (4) gives, [HNO2] [NH4+] = k [HNO2] [NH4+] where: k = K3 K1 K2 / [H2O] is the overall rate constant. N2 + 2 H2O + H+

SAMPLE EXERCISE:
Determine the rate law of the following reaction.. if you pass this exercise, you will now answer the next test which is the post test...

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

2SO42- (aq) + I3- (aq) Initial Rate (M/s) 2.2 x 10

-4

Experiment

[S2O8 ]

[I ]

0.08

0.034

0.08

0.017

1.1 x 10
-4

0.16

0.017

2.2 x 10
-4

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)

In many reactions, the rate of reaction changes as the reaction progresses. Initially the rate of reaction is relatively large, while at very long times the rate of reaction decreases to zero (at which point the reaction is complete). In order to characterize the kinetic behaviour of a reaction, it is desirable to determine how the rate of reaction varies as the reaction progresses. The rate of a reaction is the speed at which a reaction happens. If a reaction has a low rate, that means the molecules combine at a slower speed than a reaction with a high rate. Some reactions take hundreds, maybe even thousands of years while other can happen in less than one second. The rate of reaction depends on the type of molecules that are combining.

Reactions happen, no matter what. Chemicals are always combining or breaking down. The reactions happen over and over but not always at the same speed. A few things affect the overall speed of the reaction and the number of collisions that can occur.

CONCENTRATION: If there is more of a substance in a system, there is a greater chance that molecules will collide and speed up the rate of the reaction. If there is less of something, there will be fewer collisions and the reaction will probably happen at a slower speed. TEMPERATURE: When you raise the temperature of a system, the molecules bounce around a lot more (because they have more energy). When they bounce around more, they are more likely to collide. That fact means they are also more likely to combine. When you lower the temperature, the molecules are slower and collide less. That temperature drop lowers the rate of the reaction. PRESSURE: Pressure affects the rate of reaction, especially when you look at gases. When you increase the pressure, the molecules have less space in which they can move. That greater concentration of molecules increases the number of collisions. When you decrease the pressure, molecules don't hit each other as often. The lower pressure decreases the rate of reaction.

EXPERIMENTAL DATA FOR THE REACTION BETWEEN

Concentration of Phenolphthalein (M) 0.0050 0.0045 0.0040 0.0035 0.0030 0.0025 0.0020 0.0015 0.0010 0.00050 0.00025 0.00015 0.00010 Time (s)

0.0 10.5 22.3 35.7 51.1 69.3 91.6 120.4 160.9 230.3 299.6 350.7 391.2

Experiments such as the one that gave us the data in the above table are classified as measurements of chemical kinetics (from a Greek stem meaning "to move"). One of the goals of these experiments is to describe the rate of reaction the rate at which the reactants are transformed into the products of the reaction.

Rate
is often used to describe the change in a quantity that occurs per unit of time. The rate of inflation, for example, is the change in the average cost of a collection of standard items per year. The rate at which an object travels through space is the distance travelled per unit of time, such as miles per hour or kilometre per second. In chemical kinetics, the distance travelled is the change in the concentration of one of the components of the reaction. The rate of a reaction is therefore the change in the concentration of one of the reactants (X) that occurs during a given period of time t.

EXAMPLES:
Use the data in the above table to calculate the rate at which phenolphthalein reacts with the OH- ion during each of the following periods:

a. During the first time interval, when the phenolphthalein concentration falls from
0.0050 M to 0.0045 M.

b. Calculate the rate constant for the reaction between phenolphthalein and the OH- ion if the instantaneous rate of reaction is 2.5 x 10-5 mole per liter per second when the concentration of phenolphthalein is 0.0025 M. Rate = k (phenolphthalein) ( K= 0.010 s-1 c. Use the rate constant for the reaction between phenolphthalein and the OH- ion to calculate the initial instantaneous rate of reaction for the experimental data listed in the preceding table. Substituting the rate constant for the reaction from the preceding problem and the initial concentration of phenolphthalein into the rate law for this reaction gives the following: Rate = k(phenolphthalein) = (0.010 s-1)(0.0050 mol/L) = 5.0 x 10-5 (mol/L)/s) Because the rate of reaction is the change in the concentration of phenolphthalein divided by the time over which the change occurs, it is reported in units of moles per liter per second. Because the number of moles of phenolphthalein per liter is the molarity of this solution, the rate can also be reported in terms of the change in molarity per second: M/s )

1. The concentrations of N2O5 are 1.24e-2 and 0.93e-2 M at 600 and 1200 s after the reactants are mixed at the appropriate temperature. Evaluate the reaction rates for 2 N2O5 = 4 NO2 + O2 2. Write the rate expression for the following reaction: CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (g)

3. C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)

Calculate the average rate.

KEY TO CORRECTION
1.
(0.93 1.24)e-2 0.31e-2 M

Decomposition rate of N2O5 = =

1200 600 = 5.2e-6 M s-1. 600 s

rate of formation of NO2 = 1.02e-5 M s-1. rate of formation of O2 = 2.6e-6 M s-1.

2.

3.

= 1.9 X 10-4 M/s

STOICHIOMETRY OR REACTION STOICHIOMETRY

is different from composition stoichiometry and is the calculation of measurable quantitative relationships of the products with reactants in a balanced reaction. It can be used for calculating quantities such as the amount of products that can be produced with the given reactants and percent yield.

STOICHIOMETRY rests upon the law of mass conservation, the law of constant composition
and the law of multiple proportion. Chemical reactions combine in definite ratios of chemicals in general. As chemical reactions can neither create nor destroy matter, nor one element is transmuted into another, the amount of each element must be the same throughout the overall reaction. For example, the amount of element A on the reactant side must equal the amount of element A on the product side and vice-versa.

GAS STOICHIOMETRY is the quantitative relationship between reactants and products when
it is employed for reactions where the product is a gas. Gas stoichiometry applies when the gases produced are assumed to follow ideal gas laws for calculations, and the temperature, pressure, and volume of the gases are all known. Often, but not always, the STPs are taken as 0C and 1 bar and used as the conditions for gas stoichiometric calculations.

EXAMPLES:
glucose + ATP glucose-6-P + ADP 2lactate + 2ATP

glucose + 2ADP + 2 Pi In general:

aA + bB

pP

The stoichiometric coefficients are important in the context of this kinetic discussion, because they determine the order of reaction. This term describes how the rate of the reaction depends on the concentrations of the species involved. In general, the rate of a reaction, v, is described by an equation such as the following:

v = k[A]a[B]b[P]p

where: k = is the rate constant A and B = are reactants, P = is the product, with stoichiometric coefficients a, b, p, respectively. Then the overall order of reaction is given by the sum of the stoichiometric coefficients:

order of reaction = a + b + p + .....n

where: n = indicates the possible involvement of other species not included in the general mechanism above. However, use of the term "overall order of reaction" is a little muddled, because it is generally recognized as an empirical term, so that the value found by experiment might not correspond to that expected by applying the above general rule. Most frequently, for simple chemical processes, the order of reaction found experimentally turns out to be equal to the sum of the stoichiometric coefficients of the reactants. This is generally the case for reactions with a large Keq, starting from the condition of [P] = 0, since [P] will then be negligible during the time of measurement, and the reverse reaction will not be significant. Then, for the general reaction above:

v = k[A]a[B]b
If a and b are both 1, then the overall order of reaction will be 2nd-order (1 + 1 = 2). FOR MOST BIOCHEMICAL PROCESSES

Enzyme catalysis and the saturation effects resulting from this, determine that the steady-state reaction does not obey the simple rules. However, if the pre-steady-state kinetics are measured, in which the enzyme is considered as a reactant, then the simple rate laws pertain.

While the overall order of reaction is described as above, a second term is also often used, - the order of reaction with respect to a particular species. For example, in a reaction involving 2A, the reaction is said to be second-order in A. The order is given simply by the stoichiometric ratio. From this it can be seen that measurement of the order of reaction can provide a value for the coefficient if this is otherwise unknown. A useful protocol for

determining the order of reaction with respect to a particular component is to measure the concentration dependence of rate when all other reactants are in great excess. Under these circumstances, their concentrations will not vary significantly during the reaction, and the rate law revealed by experiment will give the order of reaction with respect to the tested component:

v = k[A]aexcess[B]b v = k'[B]b k' = k[A]aexcess

TRY THIS!

Consider the reaction: 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g) the rate of reaction expressed in terms of any of the reactants or products: rate of rxn = -1 [NH3] = - 1 [ O2] 4 t 5 t = 1 [NO] = 1 [H2O] 4 t 6 t

A RATE LAW (EQUATION) tells us how the rate of a reaction varies with reactant
concentration. But chemists also need an equation to show how reactant concentration changes with time. This equation would allow us to summarize experimental data, which is usually a reactant concentration versus time. A more useful mathematical relationship would show how a reactant concentration changes over a period of time. This provides a graphical method for determining rate laws.

CONCENTRATION AND CHEMICAL REACTION RATE

Chemical Reaction Rates

The reaction rates of chemical reactions are the amounts of a reactant reacted or the amount of a product formed per unit time, (moles per second). Often, the amount can be expressed in terms of concentrations.

units: g/s, mol/s, or %/s At certain conditions, the rates are functions of concentrations. Depending on the time interval between measurements, the rates are called.

AVERAGE RATE: rate measured between long time intervals. INSTANTANEOUS RATE: rate measured between very short interval INITIAL RATE: instantaneous rate at the beginning of an experiment However, a more realistic representation for a reaction rate is the change in concentration per unit time, either the decrease of concentration per unit time of a reactant or the increase of concentration per unit time of a product. In this case, the rate is expressed in Mol/(L sec).

Rate =

concentration change of a reactant or product time interval

Measuring Reaction Rate

To measure a reaction rate, we usually monitor either a product or a reactant for its change. Any physical characteristic related to the quantity or concentration of a product or reactant can be monitored. Some of the characteristics to be monitored are: change in pressure, change in color (spectroscopic measurement), temperature for exothermic or endothermic reaction, and presence of certain key substance, The change can be plotted on a graph, and from the graph, we can get the average rate or the instantaneous rate by either graphical method or using computer for the data analysis.

CONCENTRATION-TIME EQUATION( INTEGRATED RATE LAW)

Zero-Order Rate Law

Suppose we look at a simple generic zero order reaction of the reactant A to form products.

A
Its Rate Law would be:

PRODUCT Rate = K[A]0 = K

You could write the rate law in the form;

Rate [ A ] k[ A ]o k t

Using calculus, we can derive the following relationship between [A] and time,

Here [A]t is the concentration of reactant A at time t, and [A]o is the initial concentration.

[ A]t kt [ A]o

1. Suppose that the decomposition of a compound A is zero order with a rate constant of 1.2 x 10-4 (mol/L.s). If the initial concentration of A is 1.00 mol/L, what is the concentration of A after 750 seconds?
SOLUTION:

The zero-order concentration-time equation for this reaction would be:

[ A]t kt [ A]o

Substituting the given information we obtain: [A]t = [-( 1.2 X 10 -4)(750) + (1.00)]mol/L [A]t = [- (0.09) + (1.00)]mol/L [A]t = 0.91 mol/L

First-Order Rate Law

Consider a general reaction such as:

A products
Suppose that this reaction has a first-order rate law Using calculus we can show that such a first-order rate law leads to the following relationship between

Rate

[A], the concentration of A and time. This equation is sometimes referred to as the integrated rate law.

[ A ] k[ A ] t

[ A]t ln - kt [ A]o
Here [A]t is the concentration of reactant A at time t, and [A]o is the initial concentration. The ratio [A]t/[A]o is the fraction of A remaining at time t.

rate
| / | /rate = k [A] | / |- -/- - - - - rate = k | / |/ |/_________________ 0 1 2 3 4 [A] For a first order reaction, the plot is a straight line (linear), as shown above, because

rate = k [A]

(a straight line)

NOTE!!
rate = k when [A] = 1.

Second-order rate law

We write the equation of the second-order rate law in this form.

Rate

[ A] k[ A]2 t

Using calculus, you get the following equation.

1 1 kt [ A]t [A]o
In this equation [A]t is the concentration of reactant A at time t, and [A]o is the initial concentration.

For a second order reaction, the plot is a branch of a prabola, because

rate = k [A]2
rate
| . | rate = k [A]2 | . (a branch of | a parabola) | . |-.-----| . |._________________ 0 1 2 3 4 [A]

We are already finished in discussing the three (3) orders of rate law. This following table will let you understand easier the Rate laws and the concentration-time equation.

RATE LAW AND ITS EQUATION: Rate Law Concentration-time equation

Zero-order

Rate=k[A]0

[ A]t kt [ A]o
First-order Rate = k[A]1

A]t ln [[ A ]o - kt
1 [ A]t 1 kt [A] o

Second-order

Rate = k[A]2

RATE LAWS AND ITS PLOT Differential rate law - d[A]/dt = k Plot of rate vs [A] horizontal line straight line with slope = k a branch of parabola

0th order first order second order

- d[A]/dt = k[A]

- d[A]/dt = [A]2

Temperature and Rate

Generally, as temperature increases, so does the reaction rate. This is because k is temperature dependent

COLLISION THEORY OF CHEMICAL KINETICS

In this topic, we expect the rate of a reaction to be directly proportional to the number of molecular collisions per second, or to the frequency of molecular collisions:

Rate

number of collisions S

This simple relationship explains the dependence of reaction rate on concentration. In Collision Model, molecules must collide with the correct orientation and with enough energy to cause bond breakage and formation.

COLLISION MODEL

The central idea of this model is that molecules must collide to react. The greater the number of collisions occurring per second, the greater the reaction rate.

It allows us to understand the effect of concentration on rate: As the concentration of reactant molecules increases, the number of collision increases, leading to an increase in reaction rate. It also allows us to understand the effect of temperature: We know from the kinetic molecular theory of gases that increasing the temperature increases molecular speeds.

COLLISION THEORY
It is intuitively appealing, but the relationship between rate and molecular collisions is more complicated than you might expect. It was first proposed independently by Max Trautzb and William Lewis to explain the rates of bimolecular reactions occurring in gaseous state.

IMPLICATIONS:
The reaction always occurs when an A and B molecule collide. Not all collisions lead to reaction.

CALCULATIONS:
Based on the kinetic molecular theory, it shows that at ordinary pressures, let say (1 atm) and temperature say, (298 K), there are about 1 x 1027 binary collisions in 1 mL of volume every second, in the gas phase. If every binary collision led to a product, then most reactions would be complete almost instantaneously. We find that the rate of reactions differ greatly. This means that, in many cases collisions alone do not guarantee that a reaction will take place. As molecules move faster, they collide more forcefully and more frequently, increasing reaction rates. For reaction to occur, though, more is required than simply a collision. For most reactions, only a tiny fraction of the collisions leads to reaction.

The colliding molecules must have a total kinetic energy equal to or greater than the activation energy (Ea), which is the minimum amount of energy, required to initiate a chemical reaction. When molecules collide, they form an activated complex (also called the transition state), a temporary species formed by the reactant molecules as a result of the collision before they form the product

In other words, there is a minimum amount of energy required for reaction: the activation energy, Ea.

Example :
Just as a ball cannot get over a hill if it does not roll up the hill with enough energy, a reaction cannot occur unless the molecules possess sufficient energy to get over the activation energy barrier.

ARRHENIUS EQUATION
The dependence of the rate constants of a reaction on temperature can be expressed by the following equation, known as the ARRHENIUS EQUATION. SVANTE ARRHENIUS noted that most reactions, the increase in rate with increasing temperature is non linear. He found that most reaction rate data obeyed an equation based on three factors: The fraction of molecules possessing an energy of Ea, or greater. The number of collisions occurring per second. The fraction of collisions that have the appropriate orientation.

SVANTE ARRHENIUS

FORMULA:

The equation shows that the rate constant b is directly proportional to A and, therefore, to the collision frequency. In addition, because of the minus sign associated with the Ea/ RT, the rate constant decreases with increasing activation energy and increases with increasing temperature. That equation can be expressed in a more useful form by taking the natural logarithm of both sides: ln k = ln Ae Ea / RT = ln A -

Or it can be arranged to a linear equation. ln k = ( )( ) + ln A

y =

In that equation., it has the form of a straight line; it predicts that a graph of ln k versus 1/T will be a line with a slope equal to Ea / R and a y intercept equal to ln A.

ARRHENIUS PLOT

Practice Problems
1.The rate constants for decomposition of acetaldehyde 2HI(g) H2(g) + I2(g) were measured at five different temperatures.The data are shown below. Plot ln k versus 1/T, and determine the activation energy (in kJ/mole) for the reaction. 2. 1. The gas reaction N2O5 2NO2 + 1/2O2 follows the Arrhenius equation k = Ae (-Ea/RT) where: R = 8.314J K-1 mol -1 and 1 calorie = 4.184J. At the temperature T=273K, k = 3.46 x 10-5 s-1 , whereas at T = 298K, k = 8.87 x 10-3 s-1. What is the value of the activation energy Ea in kcal/mol? 3. The reaction between bromate ions and bromide ions in acidic aqueous solution is BrO3-(aq) + 5Br- (aq) + 6H+ (aq) 3Br2(l) + 3H2O(l) using the data from 4 experiments shown below determine the orders of the rate of reaction for ll three reactants, the overall reaction order, and the value of the rate constant k. 4. The half-life of a radioisotope is found to be 4.55 minutes. If the decay follows first order kinetics, what percentage of isotope will remain after 2.00 hours? 5. For the reaction A + B C, the rate constant at 215 oC is 5.0 x10 -3 and the rate constant at 452oC is 1.2 x 10-1 . a) What is the activation energy in kJ/mol? b) What is the rate constant at 100oC.

the sequence of elementary steps that leads to product formation and comparable to the route of travel followed during a trip the overall chemical equation specifies only the origin and destination.

EXAMPLE
Let us consider the reaction between nitric oxide and oxygen. 2NO (g) + O2 (g) 2NO2 (g) We know that the products are not formed directly from the collision of two NO molecules with an O2 molecules because N2O2 is detected during the course of the equation. Let us assume that the reaction actually takes place via two elementary steps as follows: 2No(g) N2O2(g) N2O2(g) + O(2)2 NO2(g)
SOLUTION:

In the first elementary step, two NO molecules collide to form a N2O2 molecule. The event is followed by the reaction between N2O2 and O2 to give two molecules of NO2. The net chemical equation, which represents the overall change, is given by the number of the elementary step. Elementary Step: Elementary Step: Overall reaction: NO +NO N2O2 N2O2 + O2 2 NO2 2NO + N2O2 + O2 N2O2 + 2NO2

Species such as N2O2 are called intermediate because they appear in the mechanism of the reaction (that is, the elementary steps) but not in the overall balanced equation. Keep in mind that an intermediate is always formed in an early elementary step and consumed in a later elementary step. The molecularity of a reaction is the number of molecules reacting in an elementary step. These molecules maybe of the same or different types. Each of the elementary steps discussed above is called a bimolecular reaction, an elementary step that involves molecules. An example of a

unimolecular reaction, an elementary step in which only one reacting molecule participates, is the conversion cysopropane to propene. Very few termolecular reactions are reactions that involve the participation of three molecules in one elementary step also known because the simultaneous counter of three molecules is a far less event than bimolecular collision.

A mechanism for a reaction is a collection of elementary processes (also called elementary steps or elementary reactions) that explains how the overall reaction proceeds. An elementary step is proposed to give the reaction rate expression. The rate of an elementary step is always written according to the proposed equation. This practice is very different from the derivation of rate laws for an overall reaction.

When a molecule or ion decomposes by itself, such an elementary step is called a unimolecular step (or process). A unimolecular step is always a first order reaction. The following examples are given to illustrate this point: O3 = O2 + O, Rate = k [O3] or in general A = B + C + D, Rate = k [A] A* = X + Y, Rate = k [A*] A* represents an excited molecule.

A bimolecular process involves two reacting molecules or ions. The rates for these steps are 2nd order, and some examples are given to illustrate how you should give the rate expression. The simulation illustrates a bimolecular process. NO + O3 = NO2 +O2, Rate = k [NO] [O3] Cl + CH4 = HCl + CH3, Rate = k [Cl] [CH4] Ar + O3 = Ar + O3*, Rate = k [Ar] [O3] A + A = B + C, Rate = k [A]2 A + B = X + Y, Rate = k [A] [B]

Elementary processes are written to show how a chemical reaction progresses leading to an overall reaction. Such a collection is called a reaction mechanism. In a mechanism, elementary steps proceed at various speeds. The slowest step is the ratedetermining step. The order for that elementary process is the order of a reaction, but the concentrations of reactants in that step must be expressed in terms of the concentrations of the reactants.

A trimolecular process involves the collision of three molecules. For example:

O + O2 + N2 = O3 + N2, Rate = k [O] [O2] [N2] O + NO + N2 = NO2 + N2, Rate = k [O] [NO] [N2]

The N2 molecules in the above trimolecular elementary steps are involved with energy transfer. They can not be canceled. They are written in the equation to give an expression for the Rates. In general, trimolecular steps may be, A + A + A = products, Rate = k [A]3 A + A + B = products, Rate = k [A]2 [B] A + B + C = products, Rate = k [A] [B] [C] Three molecules collide at an instant is rare, but occasionally these are some of the ways reactions take place.

DERIVING RATE LAWS FROM REACTION MECHANISMS The following example illustrates how elementary steps are used to represent a reaction mechanism. In particular, a slow step in a mechanism determines the rate of a reaction. Problem 1 If the reaction 2 NO2 + F2 = 2 NO2F follows the mechanism, i. NO2 + F2 = NO2F + F (slow) ii. NO2 + F = NO2F (fast) Work out the rate law.

Solution
Since step i is the rate-determining step, the rate law is 1 d[NO2] - --- ------ = k [NO2] [F2] 2 dt

This example illustrates that the overall reaction equation has nothing to do with the order of the reaction. The elementary process in the rate-determining step determines the order. Other possible elementary steps in this reaction are: F + F -> F2 F + F2 -> F2 + F NO2F + F -> F + NO2F but they do not lead to the formation of products. To propose a mechanism requires the knowledge of chemistry to give plausible elementary processes. A freshman in chemistry will not be asked to propose mechanisms, but you will be asked to give the rate laws from a given mechanism

RATE LAWS AND ELEMENTARY STEPS

Knowing the elementary steps of a reaction enables us to deduce the rate law. Suppose we have the following elementary reaction: A products Because there is only one moleculespresent, this is a unimolecular reactions. It follows that the larger the number of A molecules present, the faster the rate of product formation. Thus the rate of a unimolecular reaction is directly proportional to the concentration of A, or first order in A: Rate = k [A] For a bimolecular elementary reaction nvolving A anf B molecules. A + B product The rate of product formation depends on how frequently A and B collide, which in turn depends on the concentration of A and B. Thus we can express the rate as: Rate = k[A][B] Similarly, for a bimolecular elementary reaction of the type A + A products 2A products The rate becomes Rate = k[A]2 When we study a reaction that has more than one elementary step, the rate law for the overall process is given by the rate-determining step, which is the slowest step in the sequence of steps leading to product formation.

Because there is only one molecule present, this is a unimolecular reaction. It follows that the larger the number of A molecules present, the faster the rate of product formation. Thus, the rate of a unimolecular reaction is directly proportional to the concentration of A, or is first order in A. rate = k[A] For a bimolecular elementary reaction involving A and B molecules, A + B product the rate of product formation depends on how frequently A and B collide, which in turn depends on the concentrations of A and B. Thus, we can expect the rate as, rate = k[A][B] Similarly, for a bimolecular elementary reaction of the type A + A products 2A products

the rate becomes rate = k[A]2

The proceeding examples show that the reaction order for each reactant in an elementary reaction is equal to its stoichiometric coefficient in the chemical equation for that step. In general, we cannot tell by merely looking at the overall balanced equation whether the reaction occurs as shown or in a series of steps. This determination is made in the laboratory. When we study a reaction that has more than one elementary step, the rate law for the overall process is given by the rate-determining step, which is the slowest step in the sequence of steps leading to product formation. An analogy for the rate-determining step is the flow of traffic along a narrow road. Assuming the cars cannot pass one another on the road, the rate at which the cars travel is governed by the slowestmoving car. Experimental studies of reaction mechanisms begin with the collection of data (rate measurements). Next, we analyze the data to determine the rate constant and order of the reaction, and we write the rate law. The elementary steps must satisfy two requirements: 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 as is determined experimentally.

Measuring the rate of a reaction

Formulating the rate law

Postulating a reasonable reaction mechanism

Remember that for a proposed reaction scheme, we must be able to detect the presence of any intermediate formed in one or more elementary steps. The decomposition of hydrogen peroxide and the formation of hydrogen sulfide from molecular hydrogen and molecular iodine illustrate the elucidation of reaction mechanisms by experimental studies.

Hydrogen Peroxide Decomposition

The decomposition of hydrogen peroxide is facilitated by iodine ions. The overall reaction is 2H2O2(aq) 2H2O(l) + 02(g) By experiment, the rate law is found to be Rate = k[H2O2][I-] Thus the reaction is first order with respect to both H202 and I- . You can see that H202 decomposition does not occur in a single elementary step corresponding to the overall balanced equation. If it did, the reaction would be second order in H202 (as a result of collision of two H202 molecules).

We can account for the observed rate law by assuming that the reaction takes place in two separate elementary steps each of which is bimolecular. Step 1: Step 2: H2O2 + I- H2O + IOH2O2 + I- H2O + O2 + I-

If we further assume that step 1 is the rate-determining step, then the rate of the reaction can be determined from the first step alone. Rate = k[H2O2][I-] Where k1 =k. Note that the IO- ion is an intermediate because it does not appear in the overall balanced equation. Although the I- ion also does not appear in the overall equation, Although the

I- ion also does not appear in the overall equation, I- differs from IO- in that the former is present at the start of the reaction and its completion.

THE HYDROGEN IODIDE REACTION

A common reaction mechanism is one that involves at least two elementary steps, the first of which is very rapid in both the forward and reverse directions compared with the second step. An example is the rate reaction between molecular hydrogen and molecular iodine to produce hydrogen iodide. H2(g) + I2(g) 2HI(g) Experimentally, the rate law is found to be Rate= k[H2][I2] For many years it was thought the reaction occurred just as written, that is a bimolecular involving a hydrogen molecule and an iodine molecule. However in the 1960s chemist found that the actual mechanism is more complicated. A two step mechanism was proposed Step 1: I2 2I Step 2: H2 + 2I 2HI Where: k1, k- 1 and k2 are the rate constants for the reactions. The I atom are the intermediate in this reaction. When the reaction begins, there are very few I atoms present. But as dissolves, the concentration of I2 decreases while of I increases, Therefore, the forward rate of step 1 decreases and the reverse rate increases. Soon the two rates become equal and a chemical equilibrium is established. Because the elementary reactions in step 1 are much faster than the one in step 2, equilibrium is reached before any significant reaction with hydrogen occurs and it persists throughout the reaction. K1[[I2] = k-1 [I]2 [I]2 = [I2]

The rate of the reaction is given by the slow, rate determining step, which is step 2 Rate= k2[H2][I]2 Substituting the expression for [I]2 into this rate law, we obtain Rate= [ ][ ]

= k[H2][I2] Where k = k1k2/k-1, as you can see, this two step mechanism also gives the correct rate law for the reaction. This agreement along with the observation of intermediate atoms provides strong evidence than the mechanism is correct. Finally we note that not all reactions have a single rate determining step. A reaction may have two or more comparably slow steps. The kinetic analysis of such reactions is generally more involved.

It is a substance that increases the rate of a chemical reaction without itself being command. The catalyst may react to form an intermediate, but it is regenerated in a subsequent step of the reaction.

NOTE!!
The total energies of the reactants (A and B) and those of the products (C and D) are unaffected by the catalyst; the only difference between the two is a lowering of the activation energy from Ea to Ea-1. Because the activation energy for the reverse reaction also lowered, a catalyst enhances the rates of the reverse and forward reactions equally. A sample of sugar exposed to oxygen in the air can last for centuries. In your body, however, sugar exposed to oxygen is consumed in a few seconds. What accounts for this difference? Its because of the action of CATALYSTS. A CATALYST is a substance that speeds up reaction. It does not appear in the overall chemical equation as either a reactant or a product because the reaction mechanism of a catalyzed reaction involves one step in which the catalyst is consumed and one step in which it is regenerated. It exists before a reaction occurs and can be recovered and reused after the reaction is complete. Catalysis act in one or more steps at a reaction by covering the activation energy. Therefore a catalyst creates a different pathway from reactants to products-one that requires less energy.

The diagram above shows how a catalyst changes the energy. Let us assume that the following reaction has a certain rate constant k and activation energy Ea. A+BC+D In the presence of a catalyst, however the rate constant is k (called the catalytic rate constant) By the definition of a catalyst, Ratecatalyzed rate uncatalyzed There are three (3) general types of catalysiS HETEROGENEOUS CATALYSIS HOMOGENOUS CATALYSIS

ENZYME.

HETEROGENEOUS CATALYSIS In heterogeneous catalysis, the surface of the solid catalyst is usually the site of the reaction. Heterogeneous catalysis is usually solid and gaseous or liquid reactants. The reactants and the catalyst are in different phase.

In heterogeneous catalysis, reactants adsorbed onto surface (onto active sites). It weakens bonds. Bring molecules closer

More favourable orientation. The reactants diffuse to the catalyst surface and adsorb onto it by the formation of chemical bonds. After reaction, the products desorbed from the surface and diffuse. There are particular examples of heterogeneous catalysis that are needed in an industrial scale. The Haber Synthesis of Ammonia In 1905, Fritz Haber discovered that an iron together with a few percent of oxides of potassium and aluminum catalyze the reaction of hydrogen with nitrogen to yield ammonia at about 500C. This process is known as the Haber process. The Manufacture of Nitric Acid

Nitric acid is one of the most vital inorganic acids. It is used in the production of fertilizers, dyes, drugs, and explosives. The main industrial method of producing nitric acid is the Ostwald process. The preliminary materials, ammonia and molecular oxygen, is heated in the presence of a platinum-rhodium catalyst to about 800C. Catalytic Converters. At elevated temperatures inside a running cars engine, nitrogen and oxygen
gases react to form nitric oxide. When released into the atmosphere, NO rapidly combines with O2 to form NO2. Nitrogen dioxide and other gases emitted by an automobile, such as carbon monoxide (CO) and various unburned hydrocarbons, make automobile exhaust a major source of air pollution.

CLASSES OF THE HETEROGENEOUS CATALYST

REACTANT PHASE Solid + Gas

EXAMPLE Ammonia synthesis from N2+H2 over iron catalysts

Solid + Solution Immiscible liquid phase NATURE OF HETEROGENEOUS CATALYSIS Large surface area Spread thinly over ceramic honeycomb

Hydrogen of fatty acids with Nickel Hydro formulation at propane

Note: Some substances may block active sites (they adsorb and will not come off) that can ruin catalyst. Example: S in Haber process Pb in catalytic convertors EXAMPLE OF HETEROGENEOUS CATALYSIS The oxidation of hydrocarbons to water and carbon dioxide. This process can occur with any of the hydrocarbons, but most commonly is performed with petrol or diesel. Ammonia synthesis (Haber-Bosch process) The reduction of nitrogen monoxide back to nitrogen. 2NO(g) + 2CO(g) N2(g) + 2CO2(g) Catalytic converters are often needs in automobiles. The oxidation of carbon monoxide Carbon dioxide. 2CO(g) + O2(g) Hydrogen production by steam reforming. 2CO2(g) to

Exercise

Find the words that are related to Heterogeneous Catalysis.

n X A D S O R B E d L o f

h i C A M E L A L i O s r

A a t H E R E S A f U t i

L D b r L A M Y B f A w t

r A M e i H Y K S u L a z

e R I Z r c L O U s B l h

d Y K s X p a T J e E d a

u A E o J V r c O M R p b

c N E l A I J o i J T r e

t N R i M C O X c d Q o r

i A E d E s o r b E D c L

O S N T S J A N D I S E A

n H Z A B g A S E O U S B

Y V O N N E M A R I A s S

KEY TO CORRECTION n X A D S O R B E d L o f h i C A M E L A L i O s r A a t H E R E S A f U t i L D b r L A M Y B f A w t r A M e i H Y K S u L a e R I Z r c L O U s B l d Y K s X p a T J e E d u A E o J V r c O M R p c N E l A I J o i J T r t N R i M C O X c d Q o i A E d E s o r b E D c o S N T S J A N D I s e A N H Z A B g A S E O U S B Y V O N N E M A R I A s S

z h a b e r L HOMOGENEOUS CATALYSIS

In Homogeneous Catalysis, catalyst reacts with a reactant to form intermediate. Intermediate reacts to form product faster than the original reactant (and regenerates catalyst). Most examples of it involve reactions in solution with catalyst in solution.

Example: Acid catalyst X+Y product 1. X + H+ 2. HX+ + Y HX+ products + H+

Acid and base catalyses are the most important types of homogeneous catalysis in liquid solution. Homogeneous catalysis can also take place in the gas phase. A familiar example of catalyzed gas-phase reactions is the lead chamber process, which for many years was the primary method of manufacturing sulfuric acid. In Homogeneous catalysis the reactions can be often carried out under atmospheric conditions, thus redacting production cost and minimizing the decomposition of products at high temperature. For a particular type of reaction, it can be designed to function selectively.

Example: Transition metal catalyst works by metal varying oxidation state. Mn2+ 2 MnO4- + 16 H+ + 5 C2O42-

2 Mn2+ + 8 H2O + 10 CO2

The reaction is catalysed by one of the products (Mn2+) this is called autocatalysis.

ADVANTAGE of HOMOGENEOUS CATALYSIS

The reactions can often be carried out under atmospheric conditions, as a result it reduce the production costs and minimize the decomposition of products at high temperatures. Can be designed to function selectively for a particular type of reaction. Cost less than the precious metals.

Homogenous VS Heterogeneous Catalysts

A catalyst in the same phase (gases and solutions) as the reactants is a homogeneous catalyst. It effective, but recovery is difficult. When the catalyst is in a different phase than reactants (and products), the process involve heterogeneous catalysis. Chemisorptions, absorption, and adsorption cause reactions to take place via different pathways. Platinum is often used to catalyze hydrogenation Catalytic converters reduce CO and NO emission

PRE-TEST IN HETEROGENEOUS CATALYSIS 1. When the catalyst in a different phase than reactants and products the process involve is __________________. a. Enzyme catalysis b. Heterogeneous catalysis

c.

Homogeneous catalysis

d. Catalysis 2. The following are the reasons why heterogeneous catalysis reactant adsorbed onto surface EXEPT ONE. a. To weaken bonds b. bring molecules closer c. Can be regulated d. more favourable orientation. 3. The main industrial method of producing nitric acid is _________________. a. Ostwald Process b. Haber process c. Chamber process d. None of this 4. _________________ is one of the most vital inorganic acids. a. Nitrogen oxide b. H2O c. Carbon oxide d. Nitric acid 5. ______________discover the Haber Process. a. Albert Einstein b. Isaac Newton c. Fritz Haber d. France Haber 6. The reactants diffuse to the catalyst surface and adsorb onto it by the formation of chemical bonds. After reaction, the products_____________.

Bring molecules closer 7. There are particular examples of heterogeneous catalysis that are needed in an industrial scale EXCEPT. a. The Haber Synthesis of Ammonia b. The biological catalysts for biological systems c. The Manufacture of Nitric Acid d. Catalytic Converters 8. Heterogeneous catalysis is usually _______________.

a. b. c. d.

Desorbed from the surface and diffuse Weaken bond Adsorb chemical bond

All of the above 9. Nitric acid is used in the production of __________________

a. b. c. d. a. b. c. d.

Solid Gaseous Liquid

Medicine Explosives Machine

Food 10. What happen when the substance block active sites?

a. Adsorb and will not come off b. Can ruin catalyst. c. Both a and b d. B only
PRE TEST IN HOMOGENEOUS CATALYSIS 1. ___________________ are the most important types of homogeneous catalysis in liquid solution.

a. Liquid catalysis b. Gaseous catalysis c. Acid and base catalysis d. All of the above 2. ___________ Catalyst reacts with a reactant to form intermediate. a. Enzyme catalysis b. Heterogeneous catalysis c. Homogeneous catalysis d. Catalysis 3. Intermediate reacts to form product______________________.

both a and b 4. Homogeneous catalysis can also take place in the______________.

a. b. c. d. a. b. c. d.

faster than the original reactant and regenerates catalyst a only

Gas phase Solution phase Reactant phase

None of this 5. A familiar example of catalyzed gas-phase reactions is the_________. a. Ostwald Process b. Haber process c. Lead Chamber process d. None of this 6. In Homogeneous catalysis the reactions can be often carried out under___________. a. Same condition b. Atmospheric condition c. Sulphuric condition 7. d. Nitric condition What happens when the reactions is carried? a. redacting production cost b. minimizing the decomposition of products c. a only 8. d. both a and b The following are the advantages of homogeneous catalysis EXCEPT 1. a. The reactions can often be carried out under atmospheric conditions, as a result it reduce the production costs and minimize the decomposition of products at high temperatures. b. Can be designed to function selectively for a particular type of reaction.

c. Cost less than the precious metals. d. bring molecules closer 9. Platinum is often used to__________. a. CO and NO emission b. Catalyze hydrogenation c. Reduce oxidation number d. All of the above 10. Catalytic converters reduce______________. a. CO and NO emission b. Catalyze hydrogenation c. Reduce oxidation number d. All of the above PRE TEST IN ENZYME CATALYSIS FILL IN THE BLANKS 1. ______________Biological catalysts that promote and speed up chemical reactions without themselves being altered (consumed) in the process. 2. They determine the patterns of transformations for chemicals, as well as forms of__________. 3. They often have a metal coordinated to the_____. 4. Molecules catalyzed by enzymes are called_____________. 5. Enzyme is biological macromolecules that_______. 6. Many enzymes bring about_____________. 7-9. _____________,____________,______________, are characterization of enzymes that are important for understanding the nature of life. 10. An enzyme provides an _______________for the conversion of the substrates to the products.

Alternative pathway

purification

physicochemical

Energy in the living organisms Enzyme Isolation Enormous rate acceleration

Key to correction

O and N sites

substrate

Molecules catalyzed

Catalyzed chemical reaction

1. 2. 3. 4. 5. 6.

B C A D C A

7. B 8. D 9. B 10. C
KEY TO CORECTION 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. C C D A C B D D B A

KEY TO CORRECTION (Enzyme catalysis) M A D G J U Y T R S Q P Z F A G D S D F S F P F R E U N C A T A L Y Z E D O N T E H R G D A S Q E S P O T U U K O G J G D D S O R R M A R I M J K V U Z R M A D S A P U O L Y P S T O N G B D A J F L J T E I U S U B S T R A T E S K O S I F E F H L O U S C P N R T D O P W F A B C C U A A I F D F A J H V X N X L T O E N Z Y M E A T G Y F E N B I O L O G I C A L F S

ENZYME CATALYSIS
Enzymes: Biological catalysts that promote and speed up chemical reactions without themselves being altered (consumed) in the process. They determine the patterns of transformations for chemicals, as well as forms of energy in the living organisms. Enzymes are long protein molecules that fold into balls. They often have a metal coordinated to the O and N sites.

Molecules catalyzed by enzymes are called substrates. They are held by various sites (together called the active site) of the enzyme molecules and just before and during the reaction. After having reacted, the products P1 & P2 are released. Enzyme + Substrate ES ES (activated complex) P1 + P2 + E

Enzymes are biological catalysts for biological systems.

The mathematical treatment of enzyme kinetics is quite complex, even when we know the basic steps involved in the reaction. A simplified scheme is given by the following elementary steps:

where E, S, and P represent enzyme, substrate, and product, and ES is the enzyme substrate intermediate. Enzyme is biological macromolecules that catalyzed chemical reactions. Enzyme show high specificities compound that differ only slightly from the natural substrate are often not acted upon. Activity of many enzymes can be finely tuned, allowing the metabolism proceed at a rate optimal for the well being of the organism. Many enzymes bring about enormous rate acceleration. The rate remains the same even though the substrate concentration increases.

General Properties of Enzymes Increased reaction rates sometimes 106 to 1012 increase (Enzymes do not change G just the reaction rates.)

Milder reaction conditions Great reaction specificity Can be regulated

The kinetics of the enzyme-catalyzed reaction was found to be rather different from those of a typical chemical reaction. The rate is proportional to the concentration of the reactant in a typical chemical reaction. Enzymes however showed saturation kinetics: formation of ES complex was hypothesized (1902).

Enzymes are central to every biochemical process (Hofmeister, 1901): life is short and thus has to be catalyzed. Isolation, purification and physicochemical characterization of enzymes would be important for understanding the nature of life. Without catalysis, the chemical reactions needed to sustain life could not occur on a useful time scale. An enzyme provides an alternative pathway for the conversion of the substrates to the products. The strained reaction more closely resembles the transition state and interactions that preferentially bind to the transition state will have faster rates.

kN S P kE ES EP

kN for uncatalyzed reaction and kE for catalyzed reaction

EXERCISE

M A D G J U Y T R S Q P Z

F A G D S D F S F P F R E

U N C A T A L Y Z E D O N

T E H R G D A S Q E S P O

T U U K O G J G D D S O R

R M A R I M J K V U Z R M

A D S A P U O L Y P S T O

N G B D A J F L J T E I U

S U B S T R A T E S K O S

I F E F H L O U S C P N R

T D O P W F A B C C U A A

I F D F A J H V X N X L T

O E N Z Y M E A T G Y F E

N B I O L O G I C A L F S

If you have answered all the test correctly, you may now answer the last post test of this discussion.

Post-test in Heterogeneous catalysis

1. What is heterogeneous catalysis? 2. Why does in heterogeneous catalysis, reactants adsorbed onto surface? 3. Give the different classes of heterogeneous catalysis. 4. Give the nature of heterogeneous catalysis. 5. The reactants diffuse to the catalyst surface and adsorb onto it by the formation of chemical bonds, after reaction what happens? 6. What is the main industrial method of producing nitric acid? 7. Who discover the Haber Process? 8. What are does particular examples in heterogeneous catalysis that are needed in industrial scale. 9. What is the most important inorganic acids? 10. What is the use of nitric acid? Post-test in Homogeneous catalysis What is homogeneous catalysis? Give example of catalyzed gas-phase reactions. What happens when the reactions is carried out under atmospheric conditions? Give some advantage of homogeneous catalysis. What are the causes for the reactions to take place via different pathways What are the difference between heterogeneous catalysis and homogeneous catalysis? Give example of homogeneous catalysis. What are the most important types of homogeneous catalysis in liquid solution?

1. 2. 3. 4. 5. 6. 7. 8.

9. In what condition does the reaction can often be carried out under? 10. What happen when the reaction carried out? Post-test in Enzyme catalysis 1. 2. 3. 4. 5. 6. 7. WHAT IS ENZYME? What does it determine? What is substrate? What are the general properties of enzyme? What does enzyme show/ What does other enzyme brings? What are those characterizations of enzyme that are important for understanding the nature of life? 8. What does an enzyme provides? 9. What happen to the substrate concentration increases? 10. How does the activity of enzyme can be finely tuned?

KEY TO CORRECTION

1. 3. 4. 5. 6. 7. 8. 9.

The catalyst is in a different phase than reactant and products. (1)Solid + Gas, (2)Solid + Solution, (3)Immiscible liquid phase *Large surface area *Spread thinly over ceramic honeycomb The products desorbed from the surface and diffuse. Ostwald Process Fritz Haber The Haber Synthesis of Ammonia, The Manufacture of Nitric Acid, and Catalytic converter. Nitric acid Key to Correction 1. 3. 4. (a)The reactions can often be carried out under atmospheric conditions, as a result it reduce the production costs and minimize the decomposition of products at high temperatures. (b)Can be designed to function selectively for a particular type of reaction. (c)Cost less than the precious metals. Chemisorptions, absorption, and adsorption. It effective, but recovery is difficult. When the catalyst is in a different phase than reactants (and products), the process involve heterogeneous catalysis. 7. 8. 9. Transition metal catalyst works by metal varying oxidation state. Acid and base catalysis Under atmospheric conditions. temperature. Key to Correction A catalyst in the same phase (gases and solutions) as the reactants is a homogeneous catalyst. Redacting production cost and minimizing the decomposition of products at high temperature. 2. lead chamber process

2. To weaken bonds, bring molecules closer and more favourable orientation.

10. It is used in the production of fertilizers, dyes, drugs, and explosives.

5.

6. A catalyst in the same phase (gases and solutions) as the reactants is a homogeneous catalyst.

10. Redaction production cost and minimizing the decomposition of products at high

1.

Biological catalysts that promote and speed up chemical reactions without themselves being altered (consumed) in the process.

2. The patterns of transformations for chemicals, as well as forms of energy in the living organisms . Enzymes are long protein molecules that fold into balls. 3. Molecules catalyzed by enzymes. 4. General Properties of Enzymes 5. 6. 7. 8. 9. Increased reaction rates sometimes 106 to 1012 increase (Enzymes do not change G just the reaction rates.) Milder reaction conditions Great reaction specificity Can be regulated High specificities compound that differ only slightly from the natural substrate are often not acted upon. Many enzymes bring about enormous rate acceleration. Isolation, purification and physicochemical. Alternative pathway for the conversion of the substrates to the products. The rate remains the same even though the substrate concentration increases.

10. By allowing the metabolism proceeds at a rate optimal for the well being of the organism.