Boltzmann’s Concepts of Reaction Rates

Boltzmann Distribution

Barometric Formulation

Maxwell-Boltzmann Distribution

Velocities Derivations Energies

Collision Numbers
6/20/2018
Mean Free Path Viscosities
 Distribution of Air Particles

1.2 10
5

9.6 10
4

N
u P2( h1)
Pa 7.2 104
m
P3( h1)
b Pa
e P( h1) 4.8 104
r Pa

2.4 10
4

0
1 10 1.5 10 2 10 2.5 10
4 4 4 4
0 5000
h1
m

Height
Mathcad & EXCEL P.S. 5
Perrin Experiment: Mathcad Calculation Picture File
 Distribution of Molecular Energy Levels

Ni g i  E / kT
 e Boltzmann Equation
Nj gj

Where: E = Ei – Ej & e-E/kT = Boltzman Factor

If Boltz. Factor Comment

E << kT Close to 1 Ratio of population is equal

E ~ kT 1/e = 0.368 Upper level drops suddenly

E >> kT About 0 Zero upper level population

(S14) The Barometric Formulation
(S14) The Barometric Formulation

Ni g
 i  e  E / kT Boltzmann Equation E = Ei – Ej
Nj gj
The Barometric Formulation – S11
 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

Distribution Measurement of

Temp. in Hot Gases,

Vibrational
Plasmas, Explosions
Low Temp. in Interstellar
Rotational
Gases
High Stellar Temp. of
Electronic
Atoms and Ions
 The Kinetic Molecular Model for
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
3
KE   R T
2
K-M Model: Root-Mean-Square Speed
 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 ]

1
dN  mu x 2 / k T
 A e 2  du x
N
 1
dN  mu x 2 / k T
 A e 2  du x Mcad
N
0.0025

0.002
F1( u)
1
m s
0.0015
F2( u)
1
m s
0.001
F3( u)
1
m s
5 10
4

0 0
1500 1000 500 0 500 1000 1500
 1500 u 1500
1
m s
MB Distribution: Normalization
Mcad

Integral Tables
 1D-x Maxwell-Boltzmann Distribution

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

1
 dN  m  mu x 2 / k T
   e 2  du x
 N 1D u x 2   k  T

One-dimensional Energy Distribution in the x-direction: [ 1DE-x ]

 dN  1 
1
 x / k T
    x 2  e  d x
 N 1D  E x 4   k  T
 1
 dN  m  mu x 2 / k T
   e 2  du x
 N 1D u x 2   k  T

 dN  1 1
     x 2  e  x / k T  d x


 N 1D  E x 4   k  T
 3D Maxwell-Boltzmann Distribution

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

 dN  a  au x 2
   e  du x
 N 1D u x 

 dN  a  au y 2  dN  a  au z 2
   e  du y    e  du z
 N 1D u y   N 1D u z 

Cartesian Coordinates:

3/ 2
 dN  a  a[u x 2  u y 2  u z 2 ]
    e  du x  du y  du z
 N  3D   
 3D Maxwell-Boltzmann Distribution
3/ 2
 dN  a  a[u x 2  u y 2  u z 2 ]
    e  du x  du y  du z
 N  3D   

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

 dN / N  4  au 2
    a u e
3/ 2 2
 du  3D 
 3D Maxwell-Boltzmann Distribution Mcad

0.0035
0.003 Low T
F1( u)
1
m s

F2( u) 0.002
1
m s

F3( u)
 1 0.001
m s
High T
0
0
0 500 1000 1500 2000 2500
0 u 2500
1
m s
 3D Maxwell-Boltzmann Distribution

 dN / N  4  au 2
    a u e
3/ 2 2
 du  3 D u 

Conversion of Velocity-distribution to Energy-distribution:

 = ½ m u2 ; d  = mu du

3/ 2 
 dN / N  2  1  
      1/ 2
e kT
 d  3D    kT 
 Velocity Values from M-B Distribution
 dN / N  4  au 2
    a u e
3/ 2 2
 du  3 D u 

• urms = root mean square velocity

• uavg = average velocity
• ump = most probable velocity

 dN 

( x ) average  x   
n n
 N x

Integral Tables
Velocity Value from M-B Distribution – S14

Integral Tables
Velocity Value from M-B Distribution – S14
• urms = root mean square velocity
 dN / N  4  au 2
    a u e
3/ 2 2
 du  3D 

Integral Tables
Velocity Value from M-B Distribution S14 • uavg = average velocity

 dN / N  4  au 2
    a u e
3/ 2 2
 du  3D 

 dN 

( x n ) average  x n   
 N x
Integral Tables
Velocity Value from M-B Distribution S14 • ump = most probable velocity

 dN / N  4  au 2
    a u e
3/ 2 2
 du  3D 
 Comparison of Velocity Values

Ratio in terms of : kT
m

urms uavg ump

kT 8 kT kT
3  2
m  m m

1.73 1.60 1.41

 Application to other Distribution Functions
3/ 2 
 dN  2  1  
       1/ 2  e kT
 d
 N 3 D    kT 

 dN 

( x n ) average  x n   
 N x
 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 ( ZI )

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

VI  2    d  u avg
2

where : u relative  2  u avg

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

Z I  (VI )  ( N *)
8  k T 8  R T
u avg  
 m  M
Z I  2    d 2  u avg  N *
 Mean Free Path (  )

distance traveled per unit time u avg

 
# molecules it collides with in unit time ZI

1

2   d  N *
2
 Collision Rate ( ZII )

1
Z II  Z I  N *  
2

Double Counting Factor

1
Z II     d  uavg  ( N *)
2 2

2
 Viscosity (  ) from Drag Effects

1
   uavg  N * m  
2
1

u avg  m 2   d 2  N *

2 2   d 2

PL
N* 
R T
where : L  6.022 10 23 mol 1
Kinetic-Molecular-Theory Gas Properties - Collision Parameters
@ 25oC and 1 atm

Mean Collision Collision

Collision diameter
free path Frequency Rate
Species

d / 10-10 m d / Å  / 10-8 m ZI / 109 s-1 ZII / 1034 m-3 s-1

H2 2.73 2.73 12.4 14.3 17.6

He 2.18 2.18 19.1 6.6 8.1
N2 3.74 3.74 6.56 7.2 8.9
O2 3.57 3.57 7.16 6.2 7.6
Ar 3.62 3.62 6.99 5.7 7.0
CO2 4.56 4.56 4.41 8.6 10.6
HI 5.56 5.56 2.96 7.5 10.6
 Boltzmann’s Concepts of Reaction Rates
Boltzmann Distribution

Barometric Formulation

Maxwell-Boltzmann Distribution

Velocities Derivations Energies

Collision Numbers Mean Free Path Viscosities

 dN / N  4  dN 

 au 2
    a u e ( x ) average  x  
3/ 2 2

n n
 du  3D   N x
 Theories of Reaction Rates
Arrhenius Concept

Collision Parameters Collision Theory Hard Sphere Diameters

Potential E-surfaces Transition State Theory TD Treatment of TST

Partition Functions

Unimolecular Reactions Reactions in Solutions Diffusion Controlled

Muonium Kinetics

QM Tunnelling

Isotope Effects
 Arrhenius Concept
The Arrhenius Equation
• Arrhenius discovered most reaction-rate data obeyed the
Arrhenius equation:
Ea

k A  e RT

• Including natural phenomena such as:

• Chirp rates of crickets
• Creeping rates of ants
 Extended Arrhenius Equation

E'

k a  T  e RT
m

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
A  a  e T
m m
Ea  E'm  R  T
Reaction Progress
 Collision Theory

Main Concept: Rate Determining Step requires Bimolecular

Encounter (i.e. collision)

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

ZII (from simple Fraction of molecules with E > Ea :

hard sphere collision e-Ea/RT (Maxwell-Boltzmann
properties) Distribution)
Fraction of molecules with E > Ea :
e-Ea/RT (Maxwell-Boltzmann
Distribution)
 Collision Theory: collision rate ( ZII )
1
Z II   ( N *)2    d 2  v [ v  vavg ]
2
8  k T 8  R T
v 
 m  M

For A-B collisions: AB , vAB

m A  mB
Reduced Mass   AB 
m A  mB

8  k T
Relative Velocity  v AB 
   AB
 Collision Diameter

d A  dB
d AB 
2

Number per Unit Volume

nA  L N A nB  L N B
N A*   NB*  
V V V V
 Collision Theory: collision rate ( ZII )

1/ 2
1  8kT 
Z II ( AA)   ( N A *)    d A
2 2
  
2    mA 

1/ 2
 8kT 
Z II ( AB)  N A * N B *   d AB  v AB  N A * N B *   d AB
2 2
  
    AB 
Collision Theory: Rate Constant Calculations

  Ea 
Collision Theory: Rate  ( Z II )   e RT 
 
 

Kinetics: Rate  (k 2 ' )  [ N A *] [ N B *]

Combining Collision Theory with Kinetics:

Ea
Z II 
k2 '  e RT
( N A *)  ( N B *)
Collision Theory: Rate Constant Calculations

A-A Collisions
1/ 2 Ea
1  8  k T  
k2 '    d A 2

  m 
 e RT
2  A 
m2 m s-1 per molecule
 10 3 dm3   6.022 10 23 molecule 
  
 1 m3   1 mol 
   

1/ 2 Ea
10  L
3
 8  k T  
k 2( AA)    d A 2

  m 
 e RT
2  A 

Units of k: dm3 mol-1 s-1  M-1 s-1

 Collision Theory: Rate Constant Calculations

A-B Collisions
1/ 2 Ea
 8  k T  
k 2( AB)  10  L    d AB
3 2

  
 e RT
 AB 

Units of k: dm3 mol-1 s-1  M-1 s-1

d A  dB m A  mB
d AB   AB 
2 m A  mB
 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 k2 / M s-1 Reaction Ea / kJ mol -1

atom-1/atom-2 atom-1 + atom-2-CO2- ---> atom-1-atom-2 + CO2-
1 1.20E+08 H + HCO2- ---> H2 + CO2-
0.5 2.30E+07 H + DCO2- ---> HD + CO2-
0.11 3.40E+06 Mu + HCO2- ---> MuH + CO2- 33
- -
0.056 9.90E+05 Mu + DCO2 ---> MuD + CO2 39

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 0.60 0.80 1.00
mass ratio
 Transition State Theory

Concept: Activated Complex or Transition State ( ‡ )

3D Potential Energy Surface
Saddle point

H2 + D2  2 HD

H H H H H H
H2 + D2     2 HD
D D D D D D

Activated Complex or Transition State ( ‡ )

 Potential Energy Surfaces

Consider: D + H2  DH + H
D
r1  r1= dH-D

r2 = dH-H
r2
HA HB

Most favorable at:  = 0o , 180o

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

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

Smoluchowski (1917): D = diffusion coefficient

kdiff  4    d AB  L  ( DA  DB )

k T a = radius;
D
6     a  = viscosity

8  R T
k diff 
3 
Diffusion Controlled (Aqueous) Reaction s

Diff-paper
viscosity 

3 1 1 3 1 1
 25C  0.8904 10 kg  m s  95C  0.2975 10 kg  m s

8R T T1  ( 25  273.15)  K
k 1 1
3  R  8.3145 J mol K
T2  ( 95  273.15)  K

8 R T1 8 R T2
k25C  k95C 
3  25C 3  95C

9 1 1 10 1 1
k25C  7.42  10 L mol s k95C  2.74  10 L mol s

 Ea
R T 3
Arrhenius Equation: k Ae kJ  10  J

R T1 T2  k25C 

Ea   ln   4 1 1
T2  T1 Ea  1.7  10 J mol Ea  17 kJ mol
 k95C 

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

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
 Boltzmann’s Concepts of Reaction Rates
Boltzmann Distribution

Barometric Formulation

Maxwell-Boltzmann Distribution

Velocities Derivations Energies

Collision Numbers Mean Free Path Viscosities

 dN / N  4  dN 

 au 2
    a u e ( x ) average  x  
3/ 2 2

n n
 du  3D   N x
 Theories of Reaction Rates
Arrhenius Concept

Collision Parameters Collision Theory Hard Sphere Diameters

Potential E-surfaces Transition State Theory TD Treatment of TST

Partition Functions

Unimolecular Reactions Reactions in Solutions Diffusion Controlled

Muonium Kinetics

QM Tunnelling 8  R T
k diff 
Isotope Effects 3 
1/ 2
 8  k T  
Ea
k 2 ( AB )  10 3  L    d AB   e
2 R T
  
 AB 