Boltzmanns Concepts of Reaction Rates Boltzmanns Concepts of Reaction Rates

B o l t z m a n n D

i s t r i b

r o

t r i c

r m

l l - B

l t z m

l o

i t Di e e s r i v a

t i E o nn es r g

i e

02/27/12

l l i s i o

M n

eN a u n m

F b r Ve e ri e ss c P o a s t hi t

Distribution of Air Particles Distribution of Air Particles

1.2 .10
5

9.6 .10

N u m b e r

P2( h1) Pa 7.2 .104 P3( h1) Pa P( h1) 4.8 .104 Pa

2.4 .10

0 0 5000

1 .10

h1 m

1.5 .10

2 .10

2.5 .10

Height

P.S. 5

Distribution of Molecular Energy Levels Distribution of Molecular Energy Levels

Ni g i E / kT = e Nj gj Boltzmann Equation

Where:

E = Ei Ej

&

e- E/kT = Boltzman Factor

If
E << kT E ~ kT E >> kT

Boltz. Factor
Close to 1 1/e = 0.368 About 0

Comment
Ratio of population is equal Upper level drops suddenly Zero upper level population

The Barometric Formulation The Barometric Formulation

The Barometric Formulation The Barometric Formulation

Calculate the pressure at mile high city (Denver, CO). [1 mile = 1610 m] Po = 101.325 kPa , T = 300. K . Assume 20.0 and 80.0 mole % of oxygen gas and nitrogen gas, respectively.

Molecular Temperature Molecular Temperature

Distribution Vibrational Rotational Electronic Measurement of Temp. in Hot Gases, Plasmas, Explosions Low Temp. in Interstellar Gases High Stellar Temp. of Atoms and Ions

The Kinetic Molecular Model for The Kinetic Molecular Model for Gases (( Postulates )) Gases Postulates
Gas consists of large number of small individual particles with negligible size Particles in constant random motion and collisions No forces exerted among each other Kinetic energy directly proportional to temperature in Kelvin
K = E 3 R T 2

K-M Model: Root-Mean-Square Speed K-M Model: Root-Mean-Square Speed

Maxwell-Boltzmann Distribution Maxwell-Boltzmann Distribution

M-B Equation gives distribution of molecules in terms of: Speed/Velocity, and Energy One-dimensional Velocity Distribution in the x-direction: [ 1Du-x ]

dN = N

1 mu x 2 / k T Ae 2

du x

dN = N
0.0025 0.002

1 mu x 2 / k T Ae 2

du x

Mcad

F1( u) m s F2( u) m s F3( u)

1 1 1

0.0015

0.001

m s 4 5 .10

0 1500 1500

1000

500

0 u m s
1

500

1000

1500 1500

MB Distribution: Normalization MB Distribution: Normalization

1D-x Maxwell-Boltzmann Distribution 1D-x Maxwell-Boltzmann Distribution

One-dimensional Velocity Distribution in the x-direction: [ 1Du-x ]

dN = N 1D u x

m 2 k T

1 mu x 2 / k T e 2

du x

One-dimensional Energy Distribution in the x-direction:

[ 1DE-x ]

dN = N 1D E x

1 1 x / k T x 2 e d x 4 k T

 dN = N 1D u x

m 2 k T

1 mu x 2 / k T e 2

du x

dN = N 1D E x

1 1 x 2 e x / k T d x 4 k T

3D Maxwell-Boltzmann Distribution 3D Maxwell-Boltzmann Distribution

3D Velocity Distribution: [ 3Du ] , Let: a = m/2kT

a au x 2 dN = e du x N 1D u x
a au y 2 dN = e du y N 1D u y

a au z 2 dN = e du z N 1D u z

Cartesian Coordinates:

dN a = N 3 D

3/ 2

a[u x 2 +u y 2 +u z 2 ]

du x du y du z

3D Maxwell-Boltzmann Distribution 3D Maxwell-Boltzmann Distribution

dN a = N 3 D
3/ 2

a[ u x 2 +u y 2 +u z 2 ]

du x du y du z

Re-shape box into sphere of same volume with radius u . V = (4/3) u3 with u2 = ux2 + uy2 + uz2

dV = dux duy duz = 4 u2 du

4 dN / N 3/ 2 2 au 2 a u e = du 3 D

3D Maxwell-Boltzmann Distribution 3D Maxwell-Boltzmann Distribution

Mcad

0.0035 0.003 F1( u) m s F2( u) 0.002 m s F3( u) m s 0.001

1 1 1

Low T

High T
0 0 500 1000 u m s
1

0 0 1500 2000 2500 2500

3D Maxwell-Boltzmann Distribution 3D Maxwell-Boltzmann Distribution

4 dN / N 3/ 2 2 au 2 = a u e du 3 D u
Conversion of Velocity-distribution to Energy-distribution: = m u2 ; d = mu du

2 dN / N = d 3 D

1 kT

3/ 2

1/ 2 e kT

Velocity Values from M-B Distribution Velocity Values from M-B Distribution

urms = root mean square velocity uavg = average velocity ump = most probable velocity

( x ) average

dN = x N x

Velocity Value from M-B Distribution Velocity Value from M-B Distribution
2 4 dN / N = a 3 / 2 u 2 e au du 3 D

urms = root mean square velocity

Velocity Value from M-B Distribution Velocity Value from M-B Distribution
2 4 dN / N = a 3 / 2 u 2 e au du 3 D

uavg = average velocity

Velocity Value from M-B Distribution Velocity Value from M-B Distribution
2 4 dN / N = a 3 / 2 u 2 e au du 3 D

ump = most probable velocity

Comparison of Velocity Values Comparison of Velocity Values

Ratio in terms of : urms
kT m

kT m

uavg
8 kT m

ump
kT m

1.73

1.60

1.41

Application to other Distribution Functions Application to other Distribution Functions

Collision Properties (( Ref: Barrow )) Collision Properties Ref: Barrow

ZI = collision frequency = number of collisions per molecule = mean free path = distance traveled between collisions ZII = collision rate = total number of collisions Main Concept => Treat molecules as hard-spheres

Collision Frequency (( ZII )) Collision Frequency Z

Interaction Volume ( VI ): ( d = interaction diameter )

VI = 2 d u avg where : u relative = 2 u avg

Define: N* = N/V = molecules per unit volume

Z I = (VI ) ( N *) Z I = 2 d 2 u avg N *
u avg = 8 k T 8 R T = m M

Mean Free Path (( )) Mean Free Path

u avg distance traveled per unit time = = # molecules it collides with in unit time ZI

1 2 d N *
2

Collision Rate (( ZIIII )) Collision Rate Z

1 = Z I N * 2

Z II

Double Counting Factor Double Counting Factor

1 2 2 Z II = d uavg ( N *) 2

Viscosity (( )) from Drag Effects Viscosity from Drag Effects

1 = u avg N * m 2
u avg m 2 2 d
2

1 2 d 2 N *

PL R T where : L = 6.022 10 23 mol 1 N* =

Kinetic-Molecular-Theory Gas Properties - Collision Parameters @ 25oC and 1 atm Collision diameter Species d / 10-10 m d / H2 He N2 O2 Ar CO2 HI 2.73 2.18 3.74 3.57 3.62 4.56 5.56 2.73 2.18 3.74 3.57 3.62 4.56 5.56 / 10-8 m 12.4 19.1 6.56 7.16 6.99 4.41 2.96 ZI / 109 s-1 14.3 6.6 7.2 6.2 5.7 8.6 7.5
ZII / 1034 m-3 s-1

Mean free path

Collision Frequency

Collision Rate

17.6 8.1 8.9 7.6 7.0 10.6 10.6

Boltzmanns Concepts of Reaction Rates Boltzmanns Concepts of Reaction Rates

B o l t z m a n n D i s t r i b u t i o

r o

t r i c

r m

l a

t i

l l - B

l t z m

l o

i t iD e e s r i v a

t i Eo

n se

r g

i e

l l i s i o

nM

Ne

au n m

F b r e Ve r ei s s cP oa st h i t i e
n

4 dN / N 3/ 2 2 au 2 a u e = du 3D

( x ) average

dN = x N x

Theories of Reaction Rates Theories of Reaction Rates

A r r h e n i u s C o n c e p t

l l i s

i o

CP

oa

lr l a i s m i o e Hn t e a T r r shd

e S o p r yh

r e

t e

t i a Tl

r E a - n s su i r t f i ao cTn e D S s

tT a r t e e a T t m h

ee on r t y

r t i t i o

t i o

i m

l e

cR u e l a

cr

t R i o e n a Ds c i t i f in f o u nS s s oi o l un t iC o o n n s t

M Q I s

u M o

n T t o p

i u u e n

m n E e

i n l l i n

e g t s

t i c

f f e

Arrhenius Concept
The Arrhenius Equation Arrhenius discovered most reaction-rate data obeyed the Arrhenius equation:

k=

Ea A e RT

Including natural phenomena such as: Chirp rates of crickets Creeping rates of ants

Extended Arrhenius Equation Extended Arrhenius Equation

E' m a T e RT

k=

where : m = 1, 1/2, - 3/2, - 2

A = a em T m Ea = E '+ m R T

Experimentally, m cannot be determined easily! Implication: both A & Ea vary quite slowly with temperature. On the other hand, rate constants vary quite dramatically with temperature,

Extended Arrhenius Equation Extended Arrhenius Equation

A = a e T
m m

Ea = E '+ m R T

Reaction Progress

Collision Theory Collision Theory

Main Concept: Rate Determining Step requires Bimolecular Encounter (i.e. collision)

Rxn Rate = (Collision Rate Factor) x (Activation Energy)

Z (from simple ZIIII (from simple hard sphere collision hard sphere collision properties) properties)

Fraction of molecules with E > Ea :: Fraction of molecules with E > Ea -E T a/R ee-Ea/RT (Maxwell-Boltzmann (Maxwell-Boltzmann Distribution) Distribution)

Fraction of molecules with E > Ea :: Fraction of molecules with E > Ea -E T a/R ee-Ea/RT (Maxwell-Boltzmann (Maxwell-Boltzmann Distribution) Distribution)

Collision Theory: collision rate (( ZIIII )) Collision Theory: collision rate Z

1 Z II = ( N *) 2 d 2 v 2
8 k T 8 R T v= = m M
For A-B collisions:
A B

[ v vavg ]

, vAB
m A mB = m A + mB 8 k T = AB

Reduced Mass > AB

Relative Velocity > v AB

Collision Diameter Collision Diameter

d AB d A + dB = 2

Number per Unit Volume Number per Unit Volume

nA L N A N A* = = V V nB L N B NB* = = V V

Collision Theory: collision rate (( ZIIII )) Collision Theory: collision rate Z

8kT m A
1/ 2

Z II ( AA) =

1 2

( N A *) d A

Z II ( AB ) = N A * N B * d AB v AB = N A * N B * d AB

8kT AB

1/ 2

Collision Theory: Rate Constant Calculations Collision Theory: Rate Constant Calculations
Ea Rate = ( Z II ) e RT

Collision Theory:

Kinetics:

Rate = (k 2 ' ) [ N A *] [ N B *]

Combining Collision Theory with Kinetics:

Z II k2 ' = ( N A *) ( N B *)

Ea e RT

Collision Theory: Rate Constant Calculations Collision Theory: Rate Constant Calculations
A-A Collisions
1/ 2

k2 ' =

1 2

d A
m2

8 k T m A
m s-1

E a e RT

per molecule

10 3 dm 3 6.022 10 23 molecule 1 m3 1 mol

k 2( A ) A

1 0 =

L 2

d A 2

8 k T m A

1/ 2

E a e R T

Units of k:

dm3 mol-1 s-1 M-1 s-1

Collision Theory: Rate Constant Calculations Collision Theory: Rate Constant Calculations
A-B Collisions

k 2 ( A ) =1 3 L d A 0 B B
Units of k:

8 k T A B

1/ 2

E a e RT

dm3 mol-1 s-1 M-1 s-1

d AB

d A + dB = 2

AB

m A mB = m A + mB

Collision Theory: Rate Constant Calculations Collision Theory: Rate Constant Calculations
Consider: 2 NOCl(g) 2NO(g) + Cl2(g) T = 600. K

Ea = 103 kJ/mol

dNOCl = 283 pm (hard-sphere diameter)

Calculate the second order rate constant.

http://www.ubc.ca/index.html
mass ratio atom-1/atom-2 1 0.5 0.11 0.056 k2 / M s-1 Reaction atom-1 + atom-2-CO2- ---> atom-1-atom-2 + CO21.20E+08 H + HCO2- ---> H2 + CO22.30E+07 H + DCO2- ---> HD + CO23.40E+06 Mu + HCO2- ---> MuH + CO29.90E+05 Mu + DCO2---> MuD + CO233 39 Ea / kJ mol-1

1.4E+08

Simple Collision Theory: Comparison of Muonium/Hydrogen/Deuterium Abstractions

1.2E+08

1.0E+08

8.0E+07 k / M-1 s-1

6.0E+07

4.0E+07

2.0E+07

0.0E+00 0.00 0.20 0.40 mass ratio 0.60 0.80 1.00

Transition State Theory Transition State Theory

Concept: () Activated Complex or Transition State 3D Potential Energy Surface Saddle point H2 + D2 2 HD H D H D H D H D H D H D

H2 + D2

2 HD

Activated Complex or Transition State ( )

Potential Energy Surfaces Potential Energy Surfaces

Consider: D r1 HA r2 r1= dH-D r2 = dH-H HB = 0o , 180o D + H2 DH + H

Most favorable at:

Calculate energy of interaction at different r1, r2 and . Get 3D Energy Map. Reaction coordinate = path of minimum energy leading from reactants to products.

Reactions in Solutions Reactions in Solutions

Compared to gaseous reactions, reactions in solutions require diffusion through the solvent molecules. The initial encounter frequencies should be substantially higher for gas collisions. However, in solutions, though initial encounters are lower, but once the reactants meet, they get trapped in solvent cages, and could have a great number of collisions before escaping the solvent cage.

Diffusion Controlled Solutions Diffusion Controlled Solutions

Smoluchowski (1917): D = diffusion coefficient

k diff = 4 d AB L ( D A + DB )
k T D= 6 a

a = radius; = viscosity

k diff

8 R T = 3

Diffusion Controlled (Aqueous) Reactions

viscosity
3

Diff-paper
kg m
1 1

25C := 0.8904 10 8R T 3

95C := 0.2975 10

kg m

1 1

R := 8.3145 J mol

T1 := ( 25 + 273.15) K T2 := ( 95 + 273.15) K

k25C :=

8 R T1 3 25C
9 1 1

k95C :=

8 R T2 3 95C k95C = 2.74 10

Ea 10

k25C = 7.42 10 L mol

L mol

1 1

Arrhenius Equation:

Ae

R T

kJ := 10 J

Ea :=

R T1 T2 T2 T1

ln

k25C k95C

Ea = 1.7 10 J mol

Ea = 17kJ mol

Therefore all aqueous solutions whose rate is determined by the diffusion of species should have an Activation Energy of about 17kJ/mol.

Quantum Mechanical Tunneling Quantum Mechanical Tunneling

2 L 2 m ( Ea E )

Ea Ea Prob. of Tunneling = 4 1 e E E

curvature in Arrhenius plots abnormal A-factors relative isotope effects low Ea

Boltzmanns Concepts of Reaction Rates Boltzmanns Concepts of Reaction Rates

B o l t z m a n n D i s t r i b u t i o

r o

t r i c

r m

l a

t i

l l - B

l t z m

l o

i t iD e e s r i v a

t i Eo

n se

r g

i e

l l i s i o

nM

Ne

au n m

F b r e Ve r ei s s cP oa st h i t i e
n

4 dN / N 3/ 2 2 au 2 a u e = du 3D

( x ) average

dN = x N x

Theories of Reaction Rates Theories of Reaction Rates

A r r h e n i u s C o n c e p t C o l l i s i o n CP oa rl l a i s m i o e Hn t e a T r r sh d e S o p r y h e r e D i a m e

t e

t i a Tl

rE a - ns

us

i r t f i a o c nT e D Ss

t T a r t ee a T t mh

ee on rt y o

r t i t i o

t i o

i m

l e

cR u e l a

rc

t R i o e n a sD c

ti i fi n of u nS s s o i o l u n t i C o on ns t r o

l l e

M Q I s

u M o

n T t o p

i u u e n

m n E e

i n l l i n

e g

t i c

f f e

k diff
t s

8 R T = 3

k 2 ( AB ) =1 3 L d AB 0

8 k T A B

1/ 2

E a R T