Introduction of Chemical Kinetics

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Scope of Chemical Kinetics

Chemical Kinetics deals with the rates of chemical reactions and with how the rates depend on factors such as concentration and temperature. Such studies are important in providing essential evidence as to the mechanisms of chemical processes

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Macroscopic and Microscopic Kinetics

Macroscopic kinetics describes the branch of kinetics, which results relate to the behavior of a very large group of molecules in thermal equilibrium. Microscopic kinetics is to investigate the molecules in well-defined states, which will provide information about the dynamic of both reactive and unreactive collisions. (crossed molecular beams).
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Kinetics covers many areas

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Definition of rate
For reaction rate of A + 3B 2 Z d [ A] d [ B] B = dt dt d[Z ] rate of formation Z = dt considering Volume change during the reaction 1 d [ B] 1 dnB 1 d [ B] [ B] dV nB = [ B] V ; dnB = Vd [ B] + [ B]dV = B = = = + 3V dt 3 dt 3V dt 3 3 dt consumption A = rate of reaction =

1 3

Z
2

n A nB nZ n = = = 2 1 3 1 d rate of reaction = rate of conversion V dt Empirical rate equation Extent of reaction =

d dt

= k[ A]n [ B]m

reaction order

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Analysis of results-differential
Order with respect to concentration, true order. Order with respect to time
For reaction A Z dC = A = kC A n ; ln = ln k + n ln C A dt However , the reaction may be reversible A Z
k 1 k1

dC Z 0 = k1 (C A C Z ) k 1C Z dt

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Analysis of results-integration
First order reactions dx 0 = k (Ca x); dt int egration AZ dx = kdt 0 Ca x with int itial condition t = 0 x = 0 dx Ca0 x = kdt

0 Ca ln( 0 ) = kt Ca x

0 0 or ln(Ca x) = ln Ca + kt

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Half Life
Half-life (t1/2): the time required for the concentration of a particular reactant to reach a value that is half-way between its initial and final values.
first order reaction C ln( ) = kt1/ 2 C C /2 ln 2 t1/ 2 = kA For sec ond order reaction 1 t1/ 2 = kC 0 For third order reaction 3 t1/ 2 = 2k (C 0 ) 2 For

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Second-order reaction
Second order reactions 2 A Z dx dx 0 2 = k (Ca x) ; = kdt 0 2 (Ca x) dt int egration dx (Ca0 x) 2 = kdt or with int itial condition t = 0 x = 0

1 1 0 = kt 0 Ca x Ca

x = kt x x Ca (Ca x)

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Properties of Umass Boston

Measurement methods-Flow system

Static system Vs flow system Flow system

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Stop flow for fast reaction

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Relaxation method
The method differs from conventional kinetic methods, the system is initially at equilibrium, when the condition suddenly changes the system will become non-equilibrium and relaxes to new equilibrium.
For let first order a0 = sum of reaction A Z
k 1 k1

concentration of Z

A Z

x = concentration of dx = k1 (a0 x) k 1 x dt at final equilibrum k1 (a0 xe ) k 1 xe = 0

xe = [ Z ]e

dx d ( x xe ) dx = = = k1 (a0 x) k 1 x dt dt dt combine the last two equations dx = k1 ( xe x) k 1 ( xe x) = (k1 + k 1 )x dt int egration with conditon when t = 0 x = (x) 0 ln[ (x) 0 ] = ( k k + k 1 )t x (x) 0 = e called x 1 = k1 + k 1 relaxation time

The time correspondes to ln[ (x) 0 ] = 1 = ( k k + k 1 ) ; x

at equilibrium K =

k1 ; both k1 , k 2 k 1

can be det er min ed

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Shock tube method (t1/2=10-3-10-6)

Diaphragm Driver gas with high pressure

Mixture of reactants at low pressure (about 0.001 atm)

The rupture of the membrane will create a narrow shock front travels along the tube at supersonic speed. As the shock front passes through each element of volume there is considerable temperature rise to 1000-10000 K at 1s.
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Flash photolysis (t1/2=10-6)

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Properties of Umass Boston

Temperature Dependence for k

For reaction at equilibrium ln K c U 0 ( )p = (?) T RT 2 k1[ A][ B ] = k 1[Y ][ Z ]; ( [Y ][ Z ] k = Kc = 1 [ A][ B] k 1 Kc equilibrum cons tan t A+ B Y + Z
k 1 k1

d ln k1 d ln k 1 U 0 = = dT dT RT 2 d ln k1 E d ln k 1 E1 Then ; = 12 ; = 2 dT RT dT RT E / RT so k = Ae van' t Hoff ' s equation

while E1 E1 = U 0

Y+Z U U A+B

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Arrhenius Equation
Arrhenius pointed out that the magnitudes of the temperature effects on rates are usually much too large to be explicable on the basis of how temperature affects the molecular translational energies.

Transition species or

A + B A B * Y + Z A B * and the reaction rate [ A B * ]

AB* E-1 Y+Z U A+B

A + B is at equilibrium with

[ A B * ] [ A][ B]e E1 / RT ;

E1

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Arrhenius Equation
Arrhenius concluded that an equilibrium is established between normal and active reactant molecules and that this equilibrium shifts in the manner predicted by vant Hoffs equation. The Arrhenius equation was accepted because it provides an insight into how reactions proceed.
k = Ae Ea / RT or ln K = ln A or Ea RT

E ln K = a R ( 1 ) T where A : pre exp onential factor Ea : activation energy

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Arrhenius parameters
k = Ae Ea / RT or ln K = ln A Ea RT A : pre exp onential factor Ea : activation energy

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Accounting for the rate laws reaction mechanism

Elementary reaction: reactant molecules collide and exchange energy, atoms, or groups of atoms, or undergo other kind of change, and forming product molecules. H+Br2HBr+Br, d[Br2]/dt = k[H][Br2] Molecularity: the number of molecules coming together to react in an elementary reaction. For the above reaction molecularity is 2. Reaction order and molecularity: reaction order is an empirical quantity, and obrained from the experimental rate law; molecularity refers to an elementary reactoin proposed as individual step in a mechanism. One reaction may involve several elementary reactions.

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Consecutive elementary reactions

A ka I kb P d [ A] = k a [ A] dt [ A] = [ A]0 e kat d[I ] d[I ] = k a [ A] kb [ I ] + kb [ I ] = k a [ A]0 e kat dt dt solving the first order differential equation [ I ]0 = 0 ka [I ] = (e kat e kbt )[ A]0 kb k a k a e kb t kb e k a t [ P] = {1 + }[ A]0 kb k a d [ P] = kb [ I ] dt
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t d [ A] [ A]0 [ A] = 0 ka dt [ A]

and [ A] + [ I ] + [ P] = [ A]0

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Rate determine step

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Steady-state approximation
A ka I kb P k a << kb d[ I ] so k a [ A] kb [ I ] 0 0 dt k [ I ] ( a )[ A] kb d [ P] k = kb [ I ] kb ( a )[ A] = k a [ A] kb dt [ A] = [ A]0 e k at d [ P] = k a [ A]0 e k at dt

[P]

d [ P] = k a [ A]0 e ka t dt
0

[ P] = (1 e k at )[ A]0

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Pre-equilibria
A + B I kb P
' ka

ka

' when k a >> kb

but

not

' when kb >> k a

ka [I ] = ' K= [ A][ B] k a d [ P] = kb [ I ] = kb K [ A][ B] = k[ A][ B] dt k a kb where k = Kkb = ' ka

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Example 7
overall reaction 2 N 2O5 ( g ) 4 NO2 ( g ) + O2 ( g ) mechanism N 2O5 NO2 + NO5
' ka

ka

NO2 + NO3 NO2 + O2 + NO NO + N 2O5 NO2 + NO2 + NO2 NO and NO3

kb kc are int ermediates

d [ NO ] = kb [ NO2 ][ NO3 ] kc [ NO ][ N 2O5 ] 0 dt d [ NO3 ] ' = k a [ N 2O5 ] k a [ NO2 ][ NO3 ] kb [ NO2 ][ NO3 ] 0 dt d [ N 2O5 ] ' = k a [ N 2O5 ] + k a [ NO2 ][ NO3 ] kc [ NO ][ N 2O5 ] dt 2k k [ N O ] = a 'b 2 5 k a + kb

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