Rate of reaction The rate of a chemical reaction is defined as number of moles of reactant reacted per unit time per

unit volume, i.e., mol m 3 s 1 .

The rate of a homogeneous reaction is determined by the composition of the reaction mixture, the temperature and the pressure. The pressure can be determined from an equation of state together with the temperature and composition. Let us focus on a representative volume of reaction mass that has the following characteristics: (i) (ii) (iii) (iv) one single phase exists uniform in composition and temperature the reactor is spatially uniform the representative volume is the total volume

Consider the reaction

a A + b B cC + d D
Carried out in a batch reactor. The reactant and product are indicated by the capital letters and their respective stoichiometric coefficients are represented by corresponding lowercase letters.

A and B react at rates

rA = 1 dN A 1 dN B and rB = V dt V dt
1 dN D V dt

C and D are formed at rates

rC = 1 dN C V dt and rD =

N i (i = A, B , C , D ) represents the molar amount of one of the chemical species in the reaction (kmol), and t represents time.
Note: Depletion of reactant (A and B) due to reaction is represented by negative sign

whereas, formation of product (C and D) is represented by positive sign.

The following equalities exist between the different rates

1 dN A 1 dN B 1 dN C 1 dN D = = = a dt b dt c dt d dt

or

rA rB rC rD = = = a b c d

Each term of the above equality may be considered as the rate of the reaction. When the density remains constant, i.e., when the reaction volume does not vary

rA =

dC A dt

where C A (= N A V ) is the concentration of A in the reaction mixture. It is convenient to express the rate of reaction in terms of one of the reactants or products. Thus for example for the reaction

a A + b B cC + d D
rate of reaction ( rA ) is defined as the number of moles of A reacting (disappearing) per unit time per unit volume mol m 3 s 1

rA =

dC A dt

Other forms of expressions for reaction rate

In heterogeneous reaction systems, the rate of reaction is usually expressed measures other than volume, such as reaction surface area or the weight of the catalyst

(mol (kg catalyst )1 s 1 ), i.e.,

rA =

1 dN A W dt

Based on unit interfacial area in two-fluid systems or based on unit surface of solid in gas-solid systems

rA =

1 dN A S dt

Based on unit volume of solid in gas-solid systems

 rA = The rate constant

1 dN A Vs dt

Let us consider the reaction

a A + b B cC + d D
The rate of depletion of A is given by the rate law rA = dC A = k (C A ) (C B ) dt

where k, and are constants. The constant k is called the rate constant of the reaction or specific reaction rate. The rate constant is an experimentally determined quantity. The unit of rate constant is (time )1 (concentration )1 . Sometimes the rate constant is also called the velocity constant for the reaction. Order of reaction The order of a chemical reaction is the sum of the exponents of the concentration terms in the experimentally determined rate expression. The above reaction has overall order of

+ . The reaction is th order with respect to A and th order with respect to B. The
order of a reaction is an experimentally determined quantity. It can be positive, negative, fraction or an integer. Molecularity of a reaction The molecularity of a reaction refers to an elementary reaction only. It is the number of molecules involved in the reaction. An elementary reaction is complete in a single act of collision. A classic example is
H 2 + I 2 = 2 HI

The above reaction is bimolecular. Molecularity being a number, is always an integer.

Order and molecularity is the same only for an elementary reaction. For a non-elementary reaction, order and molecularity are not usually the same. For a multistep reaction, each elementary step has its own rate constant, order and molecularity. Consider the following reaction
H 2 + Br2 = 2 HBr

The mechanism of this reaction consist of five elementary reactions

1 Br2 2 Br
2 Br + H 2 HBr + H 3 H + Br2 HBr + Br 4 H + HBr H 2 + Br 5 2 Br Br2

Each of the above elementary reactions has its own rate constant, order and molecularity. Rate of reaction and stoichiometry Consider the reaction a A + b B cC + d D The rate of depletion of A is given by the rate law rA = k (C A ) (C B ) The parameters k, and are determined experimentally. In this rate law, the stoichiometric coefficients are already included in the rate constant. If we express the reaction as A+ b c d B C+ D a a a

the rate law will still be expressed as rA = k (C A ) (C B ) The representation of the reaction by different stoichiometry does not change the rate of the reaction.

Note:

If you express the definition of rate as rA = Then dC A = (ak )C A n = k C A n dt 1 dC A = kC A n a dt

The order n and the rate constant k (or k ) can be determined from a least-squares plot of
ln ( dC A dt ) vs. ln (C A ) , i.e., ln ( dC A dt ) = ln (k ) + n ln (C A )

Therefore, the stoichiometric coefficient is included in the rate constant when it is estimated from the experimental data. But take for example that the rate is already given in the form r = 0.8 C A1.6 for the reaction
2A B + C

One can interpret the rate as either or dC A = 0.8 C A1.6 dt 1 dC A = 0.8 C A1.6 2 dt

In the latter case, the rate of decrease in concentration of A with time is twice that of the first case. To avoid this ambiguity, we shall always assume that the stoichiometric coefficient is already included in the rate expression if the rate expression is already given, i.e., as per our convention rA = dC A = k C An dt

for the general reaction scheme a A + b B cC + d D

Homogeneous and heterogeneous reactions There are many ways of classifying chemical reactions. In chemical reaction engineering, probably the most useful scheme is the breakdown according to the number and types of phases involved, the big division being between the homogeneous and heterogeneous systems. A reaction is heterogeneous if it takes place in one phase alone. A reaction is heterogeneous if it requires the presence of at least two phases to proceed at the rate that it does. It is immaterial whether the reaction takes place in one, two or more phases, or at an interface, or whether the reactants and products are distributed among the phases or are all contained within a single phase. All that counts is that at least two phases are necessary for the reaction to proceed as it does. Examples of homogeneous reactions: Most gas and liquid phase reactions (including those having catalysts in liquid phase) Examples of heterogeneous reactions: Burning of coal, roasting of ores, attack of solids by acids, gas-liquid reactions, reduction of ore, ammonia synthesis, oxidation of ammonia to nitric acid, cracking of crude oil, oxidation of SO2 to SO3. Sometimes this classification is not clear-cut in many biological reactions and enzymesubstrate reactions. The enzymes act as catalysts for the manufacture of proteins. Since the enzymes themselves are proteins of colloidal dimensions (10 100), enzymecontaining solutions represent a gray region between homogeneous and heterogeneous systems. Another example is burning gas flame. Here large nonhomogeneity in composition and temperature can exist. Strictly then, we do not have a single phase, since a phase implies that uniform temperature, pressure and composition should exist throughout the phase. It depends upon how we prefer to treat these systems, and this in turn depends upon which description we think to be more useful. Effect of temperature on reaction rate Temperature has a profound influence on reaction rate. In homogeneous thermal reactions, for every ten-degree rise in temperature, the reaction rate is doubled or trebled.

The enhancement of reaction rate is found with reactions in gaseous as well as solution phases. Reaction in alcoholic solution: CH 3 I + C 2 H 5ONa CH 3OC2 H 5 Temp oC 0 6 12 24 30

( )

k 105 , lit mol 1 s 1 5.6 11.8 24.5 100 208

Arrhenius (1889) showed that the rate constant for a chemical process increases exponentially with temperature for a large number of reactions. A plot of ln(k ) with

(1 T ) gives a linear relation. He therefore suggested empirically the relation as

d ln k E = dT RT 2 or k = A e E RT

A is called frequency factor or pre-exponential factor. E is called the activation energy of the reaction. These two quantities have definite values for any given reaction. Consider a reversible reaction

k1
k2

The reaction takes place at temperature T. The rate constant for the forward reaction is k1 and that for the reverse reaction is k 2 . E ln(k1 ) = 1 + z1 RT E ln(k 2 ) = 2 + z 2 RT

k E E1 ln 1 = 2 + ( z1 z 2 ) k RT 2

E E1 ln(K ) = 2 + ( z1 z 2 ) RT E E1 E1 E2 d ln(K ) = 2 = dT RT 2 RT 2 d ln(K P ) H = dT RT 2

We know from Vant Hoffs equation that

where H is the heat of reaction at temperature T.

H = E1 E2

Therefore, the heat of reaction of a process is the energies of activation of the two opposing changes.
Note: The Vant Hoff isochore is given by

d ln(K C ) U = dT RT 2 where U is the energy change at constant volume, i.e., heat-change at constant volume.
Temperature dependence of chemical reaction

The rate of a chemical reaction is given by

b rA = k C a C B A

The rate of reaction changes with temperature because k changes with temperature. The quantitative relation is given by the Arrhenius equation

k = k 0 e E a RT
Since the activation energy is always (well, almost!) a positive quantity, k always increases with temperature. This should mean that for every reaction an increase in temperature increases the rate. Excluded from this are enzyme-mediated reactions; the rate of these will fall with increasing temperature beyond the optimum for the enzyme since the enzyme gets cooked.

For a very small number of reactions, all involving NO, the rate of reaction falls with an increase in temperature. This implies negative activation energy. The reason for this apparent peculiarity is that although the rate constant k does indeed increase with increasing temperature, the mechanism is such that another constant, the equilibrium constant for one of the mechanistic steps, is also involved in the rate equation. This falls with increasing temperature. The reaction of nitrogen monoxide (nitric oxide, nitrogen (II) oxide) with oxygen is:
2 NO (g ) + O2 ( g ) 2 NO2 ( g )

The probability of a termolecular reaction, where the three species collide simultaneously with the correct energy and the correct orientation in a single step, is very small. The suggested mechanism for the oxidation of NO with O2 involves an initial dimerization in an equilibrium reaction, followed by reaction of the dimer with the oxygen: 2 NO ( g ) ( NO )2 ( g ) (1) (2)

(NO )2 (g ) + O2 (g ) 2 NO2 (g )

The following discussion depends on two things: firstly that the rate of attainment of the equilibrium (1) is very fast compared with reaction (2), and secondly that reaction (2) is the rate limiting step. Consider the equilibrium reaction (1). From usual equilibrium considerations

Kc =

C( NO )
2 C NO

2 C( NO ) = K c C NO 2

For the rate limiting step (2) we can write

2 2 rate = k C( NO ) CO2 = (k K c ) C NO CO2 = k C NO CO2
2

This is the rate equation quoted. In this rate equation, both k and K c are temperature dependent. The constant k increases with increasing temperature. The variation of K c with changing temperature depends on the thermicity of the equilibrium producing the dimer

(NO )2 .

The reaction: 2 NO ( g ) ( NO )2 ( g ) involves bond formation and is

9

therefore exothermic. For equilibrium where the reaction from left to right is exothermic,
K c decreases with an increase in temperature. So, k rises with temperature increase, but K c falls. In this reaction k increases less than the fall in K c , so that the overall value

( k = k Kc )
positive.

also falls with an increase in temperature. So, does the reaction rate. The

activation energy is only apparently negative. For the rate-limiting step it is, as is usual,

The reaction of OH with olefins shows negative temperature dependence. It is possible that the activation energies are small or close to zero, and the pre-exponential factor is dependent on temperature. The formation of an intermediate adduct has also been suggested to explain these facts.
Significance of activation energy

According to Arrhenius theory, the molecules must acquire a certain energy before they would undergo chemical transformation. This means that before the chemical reaction can occur, the molecule or molecules involved must be raised to a higher energy level, i.e., the molecules must be in an energy-rich or activated state before they can react. This is illustrated in the following diagrams.

The average energy of the reactant is represented by E A and that of the resultant by E B . But even if E A > E B , the reactant will not be straight way transformed into the product

B. There is a minimum energy level for the reaction E x to which the reactant molecule
must be raised in order to enable it to undergo the chemical change. The excess or additional energy

(E x E A ) ,

which the reactant must acquire in order to undergo

10

transformation, is the activation energy E1 . Molecules having energy E x or above, are said to be in activated state. Such molecules are only fit for chemical reaction. This idea of the activated state (or activated complex formed from the reactants) has been qualitatively presented in the above figures by plotting the energy of the system in relation to the reaction co-ordinate. The reaction co-ordinate is a measure of the approach of the reactant molecules towards transformation. As the reactant molecules come together, their structural orientations, their internal vibrations, their internuclear distances change, and even they may make a transient association. The reaction co-ordinate is a measure of these physical variations that necessarily involve energy-changes of the system. It does not depend on a single internuclear distances and structural variations during the transformation into product molecules. It is not possible to give any quantitative value for the reaction co-ordinate. It merely gives a qualitative description of the conversion of reactants into products. After the chemical transformation, the products will have the average energy E B . Hence an amount of energy (E x E B = E2 ) will be given out. If E2 > E1 , the reaction is evidently exothermic, whereas, if E2 < E1 , the reaction is endothermic. Moreover, if the reverse reaction B A is followed, the molecules of B must reach the level E x by acquiring energy E2 and thus be activated to be transformed into the A molecules. Then, on reaction, the excess energy E1 will be given up by the activated species. This concept that the molecules must possess the activation energy before they can undergo the chemical change has now been universally accepted for all reactions. It is now necessary to find out how the activation of the molecules is realized and how the molecules behave during the transformation. In other words, a probe into the molecular mechanism or the detailed way by which the reactant molecules are converted into

11

products is necessary. Attempts in the elucidation of the mechanism led to two theories, e.g., (i) the collision theory and (ii) the transition state theory.
Theories of reaction rate

The collision theory: The collision theory is based on the concept that the reaction occurs
when the reactant molecules, say A and B, come very close to each other or collide. The collision between the reactant molecules is thus the first step in the process of a chemical transformation. The rate of reaction will naturally be proportional to the number of collisions per unit time between the reactant molecules. Every collision will not necessarily lead to reaction. During the collisions, some of the molecules acquire large amount of energy and those molecules, which would have energy greater than the activation energy are capable of undergoing transformation. It can be at least qualitatively visualized that the high energy at the moment of impact will be available to effect the necessary rearrangement of the atoms in the molecule leading to the reaction. Those collisions only, which raise the molecules to the activation energy level, are effective in causing chemical change. This can be tested easily in gaseous reactions where we can estimate the number of collisions. In fact this theory has been found to be satisfactory to explain many bimolecular gaseous reactions. We have attributed finite size to the molecules. If the diameter of the molecule is , then whenever the distance between the center of a selected molecule and the center of any other molecule is less than , there will be a collision.

The sphere of radius surrounding a molecule into which the center of no other molecule can penetrate may be called the sphere of influence of the molecule, or the effective volume.

12

Now suppose that there are n molecules present per m3 in a single gas (A) moving with an average velocity ca m s 1 . Due to incessant random motion, there will be an enormous number of collisions. Let us find out the number of binary collisions occurring in every

m3 of the gas. Consider the following figure.

A selected molecule P will collide with the molecule Q when the distance between their centers is . Imagine a sphere of radius around the center of P. Any other molecule whose center would come within this sphere will obviously collide with the given molecule P. Since the molecule travels a distance ca meter in one second, the volume of the colliding space that would be swept away by it in one second is 2 ca m3. If all other molecules were stationary, the number of molecules with which the selected molecule P will collide is 2 ca n . But the other molecules are not stationary, they are also in motion. It is therefore necessary to consider their relative motion. Two molecules may come to a head-on collision from opposite directions or may suffer a grazing collision moving in the same direction or may collide at an angle. As all angles of collision from 0 180o are possible, the average may be accepted as a 90o collision.

13

The relative velocity will then be

2ca . We can thus say that the number of collisions

suffered by a molecule per second is Z = 2 2 ca n . The total number of collisions occurring per second in one m3 of the gas is given by

2 ca n 2 1 Z AA = n 2 2 ca n = 2 2
where the average velocity is given by ca = 8 RT M . The factor 1 2 is necessary as each collision involves two molecules. Otherwise each collision would be counted twice. If it is a mixture of two gases A and B, then the number of collisions per m3 per second is given by the expression Z AB = ( A + B )2 The above relations show that Z T . In a gaseous system, as a result of incessant collision, there is interchange of energy between the molecules. There would always be some molecules, governed by the distribution law, which would possess energy much larger than the average value. When molecules collide vigorously enough to reach an energy level higher than the activation energy level E x , the chemical change occurs. Considering the molecules as rigid spheres, the activation energy may be regarded as entirely translational. Now, the proportion of activated molecules having excess energy equal to activation energy or greater, at temperature T is given by the Boltzmann factor, e E RT (assuming translational energy along to degrees of freedom).

RT n A n B where is the reduced mass. 2

n No. of activated molecules = = e E RT n0 Total number of molecules

If Z denotes the number of collisions per m3 per second, the number of effective collisions in which activated molecules will be involved will be given by Z e E RT . Hence, the rate of transformation per m3 per unit time is

dn = Z e E RT dt

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The collision number, Z, is obtained using molecular diameter from the viscosity data. The activation energy is determined from reaction rate measurements at different temperatures. Thus the reaction rate can be theoretically calculated from the above equation and then compared with experimental value from kinetic measurements to test the theory. The results are found to be satisfactory for many gas-reactions and some reactions in solution especially when the reacting molecules are simple. In reactions involving complex molecules, the observed reaction rates are markedly different from those calculated with the above equation.

Example: Let us consider a bimolecular reaction in which a single species undergoes

decomposition such as
2 HI H 2 + I 2

Suppose, n = number of molecules of HI present per m3. The number of binary collisions per m3 per second (Z) is 1 2C a n 2 2

Z=

Hence the number of activated collisions in one m3 per second is 1 Activated collisions = Z e E RT = 2C a n 2 e E RT 2 = 1 8 RT 2 E RT RT E RT = 2 2 n 2 e 2 n e M M 2

This is indeed the rate of reaction. Then the rate of formation of H 2 (or I 2 ) will be
dn H 2 dt = 2 2 n 2

RT
M

e E RT

since every activated collision will lead to the transformation of two molecules of HI. On the other hand, the rate of disappearance of HI is given by
dn HI RT E RT = 4 2 n 2 e dt M

The second term (i.e., e E RT ) is more sensitive to the change in temperature than the first term (i.e.,

RT
M

). In a bimolecular reaction, the rate is expressed by

15

dc = kc 2 dt
1 dc c 2 dt

k =

Now, concentration (c) is given by

c=

n mol m 3 NA

where N A is the Avogadros number.

dc 1 = dn N A k=

and

1 c2

N A2 n2

1 dc 1 dc dn = c 2 dt c 2 dn dt 1 dc dn N A 2 1 2 2 RT E RT 4 n e = 2 dn dt 2 N M n A c

k=

k = 4 N A 2

RT
M

e E RT

Using = 0.35 10 9 m and E = 184096 J mol 1 , the value of k is estimated to be k = 5.03 10 10 m 3 mol 1 s 1 . The experimental value is 3.5 10 10 m 3 mol 1 s 1 .
Note:

N A = 6.023 10 23 mol 1

= 0.35 10 9 m
= 3.14159
R = 8.314 J mol 1 K 1 T = 556 K M = 0.128 kg mol 1 E = 184096 J mol 1

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The prediction of the value of the rate constant from the collision theory is satisfactory in many reactions. But there are a number of reactions for which the calculated values of k are much higher than those experimentally observed. Difficulties are especially encountered with reactions of complex and large molecules. To account for this, the theory has been modified to give

Rate = P Z e E RT
where P is called the probability or steric factor. It covers the disparity between the calculated and observed rates. Reactions have been found where the steric factor can be as low as 10 5 . For some reactions, it can be of the order of 10 2 . The anomaly is
explained by assuming that for a reaction to occur, as a result of collision, acquiring the activation energy is not enough. A suitable orientation of the colliding molecules is necessary. With large molecules, many collisions would take place where the vulnerable reactive parts would not be brought together although the molecules have high energy. In consequence, many such impacts of activated molecules
Note: The reacting molecules may acquire the activation energy from translational,

potential, vibrational, rotational, etc. In collision theory, the term e E RT was used in which two degrees of freedom are used. It is tacitly assumed that the energy concerned is the translational energy along the direction of impact. The whole of the kinetic energy is not involved, but the translational component in one direction only along the line of centers of the molecules at the moment of impact. The energy is expressed in terms of the square of the velocity component in the appropriate direction. Hence for the two molecules coming into impact, two degrees of freedom are involved. The proportion of molecules having attained this energy in the minimum, following Maxwell is given by

e E RT . On collision, the translational energy is transformed into the vibrational energy

to reach the initial level for dissociation of bonds. If other degrees of freedom were used, such as, vibrational, the number of activated molecules would have been much higher and the calculated value would far exceed the experimental.

17

Estimation of heat of reaction Problem: Estimate H for the reaction: C ( graphite ) + O2 ( g ) CO2 ( g ) . Solution:

Energy consumed:
C (graphite ) C ( g ) O2 2O

H = 171 kcal

H = 118 kcal

Total = 289 kcal

Energy liberated: 2 O = C = 2 173 = 346 kcal Resonance energy = 33 kcal Total = 379 kcal

Energy liberated = 90 kcal

H R = 90 kcal

18