CHEMICAL KINTETICS

INTRODUCTION Chemical kinetics is dealing with the rate of reactions and their mechanism. Different substances react at different rates and it was observed that these reaction rates change if certain conditions are changed. Summarizing these observations we find that the rate of a reaction depends upon: The relativities of the reacting substances. Some reactions are inherently rapid, some are inherently slow, and some are completed in a second or a millisecond (very small activation energy), some requires hours, days even years before they are over (higher activation energy).Taking into account this inherent difference in speed, we say that some substances are very reactive, whereas others are relatively nonreactive, with respect to certain type of reactions. Since every reaction involves the breaking of old bonds and the formation of new ones, the reactivity of a particular substance must be related to the facility of difficulty with which specific bonds are broken or formed. It should be pointed out that reactions are generally not as simple and straightforward as the chemical equation itself. Thus, the reaction of hydrogen with bromine, giving hydrogen bromide, which is generally represented by the equation: H 2 + Br2 2 HBr is in fact a complex reaction, a reaction chain which involves the following separate steps: Br2 2 Br Br + H 2 HBr + H H + Br2 HBr + Br 2 Br Br2 (initiation) (propagation) (interruption)

In such a sequence of reactions the overall rate is determined by the rate of the slowest step in the sequence: this is referred as the rate determining step. In the rate determining step, the reactivities of the substances involved exert a major effect upon the rate of reaction. It is universally agreed that the first step in a reaction of the type M + N MN , is the formation of an activated complex of M and N. The activation energy is the energy required to form this complex [MN]:
M + N [ M .......N ] products

The activation energy for this reaction is the minimum energy possessed by the molecules, in order to be able to react when they collide. It is normally expressed in Joules per mole.

In Fig. 1 is presented the energy profile of a reaction: Total energy

B A

x y

MN

Course of the reaction Fig. 1 The energy profile of a reaction The activation energy required by M+N to react and form MN is represented by the distance xy. The ordinate distance, yz, represents the heat of reaction: M + N MN . The ordinate distance zx, represents the activation energy required to determine the decomposition of MN, according to the reaction: MN M + N . This profile shows that, the more stable the MN compound is, the greater its heat of formation and the activation energy will be. Since C represents a lower energy state and, hence it corresponds to a more stable energy state than A, the reaction: M + N MN , will proceed spontaneously, once M+N have been activate to the energy level B. The heat of reaction, yz, will provide the activation energy necessary to keep the reaction going. Every reaction has its own characteristics energy profile. The activated complex reacts to form the products. If this complex reacts in one step the reaction should be a simple one, and when this complex reacts in more steps, the process is a complex one. As examples: A Pr oducts (monomolecular ) Simple reactions:
A + B Pr oducts (biomolecular ) 2 A + B Pr oducts (three molecular )

Complex reactions: chain (like HBr formation) Consecutive ( A B C ) Temperature. Irrespective of the fact a reaction is inherently slow or rapid, its rate will increase if the temperature is raised and will decrease if the temperature is lowered. For many reactions, the rate will

double for every 10C increase in temperature. This factor is referred as temperature coefficient of reaction ( ) . Thus, many reactions have a temperature coefficient of about 2:

k T +10 kT

Before two molecules can react with each other, they must collide. The raise in temperature increases the speed of molecules and therefore the number of collisions per time until will increase too. We know that the kinetic energy of a molecule is: Ec = mc 2 2

where c is the mean square velocity of molecules. At the same time, the kinetic energy of molecules of a gas is directly proportional to its absolute temperature. It results that 10 degrees increase in temperature falls for short of doubling the total number of collisions, which means that the increase in the total number of collisions with temperature is an insignificantly small factor in the temperature effect on the reaction rate. The major factor is the shift in energy distribution curve (Fig. 2) which results in a large increase in the fraction of molecules that have energies sufficiently high so that they fall within the activation range, and hence react when they collide. Percent of molecules

A Lower temperature

B Higher temperatures

Kinetic energy

Fig. 2 Distribution of kinetic energies of molecules of a gas at two temperatures, A and B. At the higher temperature, B, the average kinetic energy is higher, the distribution range of energy is wider, and a greater percent of molecules have energies greater than certain value E.

As was pointed out before, only the molecules that collide and have also the required high energy will react. To increase the rate of reaction, we must increase the number of high energy collisions. A number of reactions which are known to involve collisions of two molecules and are called second order reactions have the temperature coefficients of about 2. As it was pointed out above, many reactions have temperature coefficients of about 2, so it follows that many ratedetermining reactions are second order ones, in other words, involve the collision of two molecules. The presence of a catalyst. A catalyst speeds up (or in some cases slows down) a reaction without apparently being changed. Although there is a great deal of speculations and questions about how a specific catalyst acts when it modifies the speed of a reaction, it seems a pretty well established fact that a catalyst cannot initiate a reaction. All it can do is to speed up a reaction that is already proceeding at a finite rate. It probably accomplishes this speed up because it provides a different, easier path or mechanism for the reaction to follow, corresponding to lower activation energy. The concentration of the reacting substances. Whether a reaction is inherently slow or inherently rapid, increasing in a reactant concentration will increase its speed. As the concentration means the quantity of substance per volume unit, increasing the number of molecules in a given volume means increasing their concentration and collision number. As a general rule, the rate of any reaction increases when the reactant concentration is increased. To determine the speed of a reaction, we measure the time required for a certain quantity of reactant to be used up, or for a certain quantity of product to be formed. The formation of hydrogen iodine is a typical second order reaction: the rate is in fact directly proportional to both hydrogen and iodine concentration. This proportionality relationship can be expressed in form of a mathematical relationship by introducing the proportionality constant k: rate = k [ H 2 ] [ I 2 ] Let us consider a chemical reaction expressed by the generalized equation:
' ' 1 A1 + 2 A2 + ........ = 1' A1' + 2 A2 + ...........

(1)

where i and 1 ' are the stoechiometric coefficients and Ai and Ai are the compounds participating in the reaction. The rate of a homogenous reaction with respect to the ith component is given by:

 1 dn v R ,i = i (2) V dt where ni is the mole number of the ith component. If the volume does not change during the reaction, the reaction rate may be written as follows: v R ,i = dci dt (3)

In equations (2) and (3) the sign + is assigned to reaction products, for each dni < 0, so that v R ,i > 0 . dt

dni > 0, and the dt

sign - to reactants for which

For a certain reacting system, the reaction rate is a function of concentrations of the compounds participating in the reaction and the temperature, i.e. v R = f ( ci , T ) . The concrete form of the function f ( ci , T ) depends on the reaction itself. For most reaction f ( ci , T ) is factorizable, that is, it may be expressed as a product of two functions one depending only on temperature and the other only on concentrations: f ( ci , T ) = f 1 ( T ) f 2 ( ci ) . The function f 1 ( T ) designated with the letter k is called the
rate constant. The function f 2 ( ci ) is a product of powers of concentration, f 2 ( ci ) = c1 1 c 2 2 ........ The

power at which the concentration are raised are called the partial order of reaction regarding the ith component. The reaction rate is written by means of the kinetic equation: (4) The kinetic parameters k and i may be obtained only through experimental measurements. The reaction orders values may be integers or fractions, sometimes they may be zero or negative. For simple reactions, the orders of reaction with respect to reactants have the same values as the stoechiometric coefficients. 1. THE DETERMINATION OF THE ORDER OF A REACTION In this work, we shall investigate the reaction between sodium thiosulfate Na2S2O3 and sulfuric acid, H2SO4 in aqueous solution. Na 2 S 2 O3 + H 2 SO4 Na 2 SO4 + SO2 + H 2 O + S (5) The reaction is easy to examine because colloid sulfur is obtained, which causes the solution to become opaque. The reaction rate with respect to sulfur is: vR = c s t (6)
v R = k c1 c 2
1 2

c3

.... c i ...

The quantity c s is a constant for a particular temperature; it corresponds to the concentration of sulfur which produces the precipitation. By dividing the equation (4) applied to the chemical reaction (5) by c s , the following kinetic equation is obtained: vR = 1 1 = kc 1 2 S 2O3 c 22 SO4 Na H t c S (7)

The influence of the concentration of sodium thiosulfate on the reaction rate is examined and the partial order of reaction with respect to this reactant is obtained. At constant temperature and constant sulfuric acid concentration, equation (7) becomes: v R' = where k =
SO k cHH22SO44

1 = k ' c 1 2 S 2O3 Na t

(8)

cs

is the apparent constant rate.

Applying the logarithm to the eq (8) we get:

lg

1 = lg k + n Na2 S2O3 lg c Na2 S2O3 t

(9)

INSTRUCTIONS Put in 12 test-tubes the amount of solution indicated in the table below: a H2O [mL] 0 1 2 3 4 5 b Na2S2O3 [mL] 6 5 4 3 2 1 c H2SO4 [mL] 6 6 6 6 6 6 crel lg Crel

No. tube. 1 2 3 4 5 6

No. tube 7 8 9 10 11 12

t, [s]

lg

1 t

v=1/t [s-1] v1= v2= v3= v4= v5= v6=

Mix the contents of test tubes 1 and 6, stir the solution obtained in this way and measure the time between the mixing and the apparition of sulfur colloids (the solution becomes milky). Do the same thing with the pairs of test tubes 2-8, 3-9, 4-10, 5-11 and 6-12, measuring the corresponding times, t .

RESULTS AND CALCULUS

Fill the table using the relative concentration of sodium thiosulfate given by equation (9):
rel c Na S O =
2 3

c Na S O
2 2

0 Na 2 S 2 O3

V Na S O
2 2 2 2 3 2

V Na S O + V H O + V H

(9)
2 SO 4

Calculate the reaction rate for each reaction Plot the dependence t = f ( c rel ) , and the dependence of reaction rate function Na2S2O3 solution concentrations Plot the dependence ln
1 rel = f ln c Na S O . The slope of this straight line is 1 t
2 2 3

(see equation 8) while the origin ordinate represent the apparent constant rate k RESULTS INTERPRETATION: It will be observed if the reaction is a simple or complex one, and fast or slow reaction

2. DETERMINATION OF THE ACTIVATION ENERGY In this work, we shall investigate the reaction between sodium tiosulfate, Na2S2O3, and sulfuric acid, H2SO4 in aqueous solution. Na 2 S 2 O3 + H 2 SO4 Na 2 SO4 + SO2 + H 2 O + S

(5)

This reaction is easy to examine, because colloid sulfur is obtained, which causes the solution to become opaque. The reaction rate, with respect to sulfur is v r = c s / t . The quantity c s is constant at the same temperature, corresponding to the concentration of sulfur which produces the
precipitation. By dividing eq. v R = k c1 c 2 c 3 .... c i ... , applied to the chemical reaction (5),
1 2 3 i

with c s , the following kinetic equation is obtained:

' vR =

1 1 = kc 1 2 S 2O3 c 22 SO4 Na H t c s

(6)

The influence of temperature on the reaction rate is examined. In equation (6) only the rate constant k is depending on temperature, according to the equation of Arrhenius: E k = A exp a (7) RT where A is a constant called preexponentiaal factor and Ea is another constant for a certain reaction, called activation energy. For constant concentration, equation (6) and (7) yield: 1 E = k exp a (8) t RT By means of this equation, the activation energy may be calculated if the reaction rate at vR = several temperatures is measured. INSTRUCTIONS Put in five test-tubes 4 ml of solution of Na2S2O3 in each and in another five test tubes 4 ml of solution of H2SO4. The test tubes are immersed together with a thermometer in a beaker, half filled with water. The beaker is put on asbestos gauze and heated on a gas burner. The solution from a test tube containing Na2S2O3 is poured into another test tube containing H2SO4 solution. This mixture is stirred and the time laps t until the solution grows opaque are measured. The experiment is repeated at temperatures higher by 10, 20, 30 and 40C respectively. The results are noted in the table below:

Na2S2O3 V Na2 S 2O3 Nr. Eprubet 1 2 3 4 5 [mL] 4 4 4 4 4

H2SO4 Nr. Eprubet 6 7 8 9 10 V H 2 SO4 [mL] 4 4 4 4 4

Temperature t T 1/T [C] 10 17 24 38 45 [K] [K]

ln [t]

v=

1 t

[s-1] v1 = v2 = v3 = v4 = v5 =

RESULTS AND CALCULUS

Calculate the reaction rate vI Plot the dependence of the reaction time function of temperature and the dependence of rate function of temperature Plot the dependence ln t = f (1 / T ) From the equation: E ln t = ln k + a R 1 T

it may be seen that the slope of this dependence is Ea/R. The activation energy is to be determined, knowing R = 8,31 J/mol K (R = 1.987 cal/mol K). From the origin ordinate the apparent rate constant will be calculate. RESULTS INTERPRETATION: Depending on the value of the activation energy it will be established if the reaction is thermal activated (tens of thousands calories)