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Kinetics of liquid phase reactions

Diffusion Controlled and

Activation Controlled Reactions

Ernő Keszei
Eötvös Loránd University, Institute of Chemistry
 Historical overview

Author(s), year, journal Content

 Smoluchowski, 1917 Growth of colloid particles via

(Z. Phys. Chem. 92, 129) aggregation from homogeneous solution

 Debye, 1942 Any reactants,

(Trans. Electrochem. Soc. 82, 265) any interaction potentials

 Chandrasekhar, 1943 Applicability of the molecular

(Rev. Mod. Phys. 15, 1) description of diffusion

 Collins & Kimball, 1949 (For colloid particle growth:)

(J. Colloid Sci. 4, 425) singularity at t = 0 at r = rAB
(infinite reaction rate)
 Historical overview

Author(s), year, journal Content

 Noyes, 1961 First proper treatment at t = 0

(Prog. React. Kinet., 1, 129) (molecular description instead of a
continuum treatment)

 Wilemski & Fixman, 1973 Mathematical generalisation of the theory

(J. Chem. Phys. 58, 4009) and a critical overview of previous papers

 Green & Pilling, 1982 General stochastic description;

(J. Phys. Chem. 86, 1318) molecular level simulation

Starink, 2014 extended volume concept combined with

(Thermochimica Acta, 596, 109) soft impingement of diffusion fields
 Reactions in solution
vs. gas phase reactions

Property in solution in gas phase

Distance between adjacent molecules very small large

Translational motion hindered free

Encounter of reactant molecules not too frequent frequent

Separation of adjacent molecules hindered free

Energy transfer from product easy rare event

molecules with high energy
 Cage effect
Reactants A and B get together: encounter pair

Solvent shell around the encounter pair: solvent cage

Cage-effect: the solvent cage

hinders the separation easily absorbs

of reactant molecules excess energy of products

largely facilitates product formation

 Formal kinetic description
diffusion, k d reaction, k r
A+ B {AB} product(s)
diffusion, k – d

dA  dB
   k d A B  k  d AB
dt dt

dAB
 k d A B  k  d AB  k r AB
dt

dproduct 
 k r AB
dt
 Formal kinetic description
Consider {AB} as a QSS species and apply QSSA:

dAB
 k d A B  k  d AB  k r AB  0
dt
rearrange

AB  kd
AB
kd  kr

d product 
substitute  k r AB
dt

d product 
 kr
kd
AB  k AB k  kr
kd
dt kd  kr k d  k r
 Formal kinetics: limiting cases
kr kd
k
kr  kd k d  k r kr  kd and kr  kd

Diffusion controlled reaction Activation controlled reaction

kr kd kk k r kd k
k  r d  kd k  kr d
kd  kr kr k d  k r k d

k ≈ kd k ≈ kr kd
k–d
Diffusion controlled if: kd
Let K AB  the
— reaction occurs instantaneously kd
at every encounter equilibrium constant
— and/or high solvent viscosity of the encounter pair formation:
keeps reactant molecules close
k ≈ kr KAB
 Rate constants: orders of magnitude

Solvent: water at 25 ºC

— activation energy of diffusion: ~ 15 kJ/mol

(„large” activation energy of reactions: well above 20 – 30 kJ/mol)

— kd ~ 109 – 1010 dm3mol–1s–1

— k– d ~ 1010 – 1011 s–1 (as KAB ~ 10–1 dm3mol–1)

— kr >> k– d : if kr > 1012 s–1 (diffusion control)

— kr << k– d : if kr < 109 s–1 (activation control)

Conditions to solve the diffusion equation
Approximations in the differential equation of diffusion:

Both A and B are neutral (uncharged) molecules

B is in a large excess compared to A; i. e. [B] ≈ constant

As [A] is small compared to [B], thus

individual molecules of A can react independently

The radial distribution of B around a molecule A

can be substituted by the ensemble average over large volumes

As a consequence, the reaction system can be considered

as many independent spherically symmetrical „cells” with
a central molecule A surrounded by many molecules B
 Conditions to solve the diffusion equation
B
B
rAB : reaction radius
B
(A and B react immediately within this distance)
B A r B
[B] : bulk concentration of B
B B
at r  rAB: [B]r = 0 (inner boundary condition)

at r   : [B]r = [B] (outer boundary condition)

Distribution of [B]r between [B]r = 0 and [B]r = [B] : a smooth function

Concentration gradient: rAB  

Diffusive flux: rAB 
 The diffusion equation
Radial distribution of concentration of B around a central atom A:
zero from r = 0 to rAB , [B] at r = ∞, and
it is differentiable between the two.
dc
General diffusion flux: J x  D q
(1 dimension) dx
surface
concentration gradient
diffusion coefficient

For the spherically symmetric diffusion in the – r direction (←):

q  4 r 2 (the surface of a sphere)

 dBr
J  4  r 2 DAB (DAB = DA + DB : relative diffusion coefficient)
dr
 Solving the diffusion equation

 dBr
J  4  r DAB
2
readily provides the average radial concentration
dr

 B  



J
d r '   d B ' integration
B r  B  J
r
4  r '2 DAB B r
r
4  r DAB

 
At r = rAB , [B]r = 0, thus the flux J : J  4  r DAB B

As there is no production or consumption of B at r ≥ rAB ,

the flux should not depend on r.
 Solving the diffusion equation


J  4  r DAB B B r  B  J
Let us substitute into
4  r DAB

4  r DAB  rAB 
B r  B  J
 B  B  B1  
4  r DAB 4  r DAB  r 

Thus, the radial concentration profile is B r  B1  rAB 


 r 

B r 
 1 
rAB 

B  r 
 Radial concentration profile
B r 
 1 
rAB 
diffusion controlled reaction (a): 
B  r 

activation controlled reaction (b): B r  B

Pilling & Seakins 1995

 Diffusion controlled reaction rate
— the radial diffusion flux of molecules B is constant (around all A)
until rAB, where they immediately react
— the radial diffusion flux of B is the same around all A molecules

Thus, the reaction rate is the same as the rate of diffusion around all A’s:

v  J A  4  rAB DAB BA

The rate equation for the reaction: v  k BA

Comparing the two: k '  4 rABDAB

As the unit of DAB is m2s–1, the unit of k′ is m3s–1

The diffusion controlled rate constant k in dm3mol–1 s–1 unit:

k  1000  4 rABDAB N A
 DAB , the relative diffusion coefficient

How do we know DAB ? DAB  DA  DB

pure water solution of A

B A
pure water solution of B

Ionic species:  DAB ~ 2x10−9 m2s−1

k ~ 8x109 dm3mol−1s−1
 rAB ~ 0.5 nm

Rule of thumb: k > 109 dm3mol−1s−1 indicates diffusion control

 Typical diffusion controlled reactions
 Recombination (of radicals, atoms): small or zero activation energy

e. g. I + I I2 (in hexane: k = 1.3x1010 dm3mol−1s−1)

 Acid-base reactions

e. g. H+ + OH− H2O (in water: k = 4x1011 dm3mol−1s−1)

 Excitation quenching

hν biacetyl
e. g. naphtalene naphtalene* naphtalene + biacetyl*

(continuous excitation: k = 2.2x1010 dm3mol−1s−1)

 Diffusion controlled reactions of ions
 Brownian motion: can be simulated by discrete displacements
(„hopping”)

 If particles are charged (ions: r −2 potential dependence)

hopping is not completely random

 d B r 4  r 2 DAB Br dV (r )
J  4  r DAB
2

dr k BT dr

diffusion term migration term

 Diffusion controlled reactions of ions
 d B r 4  r 2 DAB Br dV (r )
J  4  r DAB
2

dr k BT dr
diffusion term migration term


Rearranged:
J
dr  d Br 
B r
dV (r )
4  r DAB
2
k BT

Solution of the linear differential equation:


  V (r )   
  V (r )  dr 
Br  exp   B 
J
r exp  kBT  r 2 
 k BT   4  DAB 
 Diffusion controlled reactions of ions
z A zBe2
Potential energy of the Coulomb interaction: V (r ) 
4 rc  0 r

Onsager (escape) radius: the distance where the

Coulomb interaction equals the average thermal energy: V (rc )  k BT

z A zBe2 z A zBe2
 k BT rc 
4 rc  0 r 4 rc  0 r k BT

Within the Onsager radius: attraction of oppositely charged ions

repulsion of ions both charged positively or negatively

rc
Comparing V(r) and rc : V (r )  k BT for Coulomb interaction
r
 Diffusion controlled reactions of ions
Solution for diffusion + migration:

 V (r )   
 V (r )  dr 
Br  exp   B 
J
r exp  kBT  2 
 k BT   4  DAB  r 
rc
Substitution of V (r )  k BT :
r

 rc    rc  dr 

Br  exp   B  J r exp  r  r 2 
 r  4  DAB

 rc 
 exp    1
 rc  dr  r 
r exp  r  r 2  rc
 Diffusion controlled reactions of ions
  rc  
  exp    1 
 rc   r  
Br  exp   B  J
 r  4  DAB rc 
 

Substituting [B]r = 0 at r = rAB , we get:

 rc   rc 
 exp    1 exp    1
 rc   rAB   rAB 
B exp    J
; 
1
 rAB  4  DAB rc rc reff

 
Expressig J and calculating k  J B : k  4  reff DAB
 Diffusion controlled reactions of ions
Rate of diffusion controlled ion-ion reactions: k  4 reff DAB
rc
Effective reaction radius: reff 
(for pure Coulomb interactions)  rc 
exp    1
 rAB 
Dependence of reff on solvent permittivity; rAB= 0.5 nm, │zA│ = │zB│= 1

reff / nm
Solvent εr rc / nm zA = zB zA = − zB
Water 78,5 0,7 0,2 0,9
Methanol 32,6 1,7 0,06 1,8
Ethanol 24,3 2,3 0,02 2,3
Dietil-ethter 4,27 13 10−10 13
Hexane 1,89 29 10−24 29
 Time-dependent rate constants
Up to now, there was a stationary concentration gradient.

Initiating the reaction from a precursor of A by pulse radiolysis, a

laser pulse, T-jump or P-jump, the initial distribution of the
molecules is homogeneous; i. e., [B]r = constant, independent of r,
even if r < rAB .
In this case, the onset of reaction involves close partners first, thus
the concentration profile will change until the stationary profile
would form.
The time-dependent concentration profile can be calculated using
Fick’s 2nd law:

 B  r
 DAB 2 B r
t
 Time-dependent rate constants
The Laplace operator (  or  2 ) for a sphere can be given as:

 2
2  1     1 2
  2 
2
 2  sin    2 2
r r  r r sin      r sin   2

2
d 2 d
For an isotropic sphere: 2  
d r2 r dr

B r  d 2 B r 2 d B  
The time-dependent equation:  DAB   r 
t  dr 2
r d r 
 

Boundary conditions (as before): B B  r

and B
AB
0
 Time-dependent rate constants
 d Br
The flux J  4 r DAB
2
depends on the radius !
dr
The concentration profile is time-dependent
the rate constant is also time-dependent
The concentration profile will ″smoothen″
until the stationary profile is achieved, when the
diffusion flux inwards at r = rAB is equal to the reaction rate.

Solution for the time-dependent concentration profile:

error function:
 r  r  rAB 
Br  B 1  erfc 
AB  2


 
z2
erfc ( x)  e dz
 r  4 DAB t   x
 Time-dependent rate constants
Solution for the time-dependent flux:

 d Br  
 B 
J r  rAB   4  rAB DAB
rAB
2
 4  r DAB 1 
2

dr
AB
 4 DAB t 
r  rAB  

 r  r  rAB 
Relations used to get the solution: Br  B 1  erfc 
AB 

 r  4 DABt 
 x2
d 2e
erfc ( x)  
dx 

erfc (0)  1
 Time-dependent rate constants
Reaction rate:
  
v  J r  rAB A  4 rAB DAB 1   BA  k AB
rAB
  DAB t 
 

Rate constant:  rAB 

k (t )  4  rAB DAB 1  
  DAB t 
 

• problem : at t  0 : k  

• Solution: at short times, continuum description is not valid;

(we should use molecular description below ~ 1ps)
Time-dependent rate constants
t  0s
109 s
108 s
107 s
t 

Br  1
rAB  r  rAB
erfc 


B r  4D t
 AB


DAB  109 m 2s 1
rAB  0.5 nm

Pilling & Seakins 1995

From diffusion control to activation control
Former inner boundary condition: at r  rAB : Br  0
advantage: simplifies the maths; no need to deal with conditions within rAB
disadvantage: applicable only for diffusion control

Let us use a more general inner boundary condition

it should be applicable for:
• diffusion controlled
• activation controlled reactions
• and mixed control

A suitable modification: B  rAB  0

Let us reformulate the problem using this latter boundary condition.

From diffusion control to activation control
 d Br
Diffusion flux is same as before: J diff  4  r DAB
2

dr

Reactive flux (that of molecules B at a distance through a

spherical shell at rAB :

J react  k R BrAB

In a stationary state, the two fluxes should be equal:

 
J diff  J react  k R BrAB
From diffusion control to activation control
 d Br
Differential equation to solve: J  4  r DAB
2

dr

Solution: Br  B  J
4  r DAB

Boundary conditions:

present former


J diff  k R BrAB at r  rAB : Br  0
From diffusion control to activation control
Applying the boundary conditions:

now formerly

B 
Br
AB

kR
J  4  rAB DAB B
1
4  rAB DAB

Rate constant:

now formerly

4  rAB DABk R k  4 rABDAB

k
k R  4  rAB DAB
From diffusion control to activation control

Concentration dependence of the rate constant:

now formerly

 
 
   rAB 
Br  B 1  rAB
 Br  B1  
  4  rAB DAB    r 
 r 1   
  kR  
From diffusion control to activation control
Substitute 4 rABDAB  kd
Calculate the concentration at r = rAB :

Br 
B 
B
AB
kR kR
1 1
4  rAB DAB kd

Limiting cases:

k R  kd kR << kd

Br AB
0 Br AB
 B
Fast reaction compared to diffusion; Slow reaction compared to diffusion;
applicable inner boundary condition diffusion „fills up” B down to rAB
→ diffusion controlled reaction → activation controlled reaction
From diffusion control to activation control
 
 
DAB  109 m 2s 1
Concentration profile: Br  B 1  AB 
r 1
 r 1  kd 
  rAB  0.5 nm
 kr 
1,0

0,9
If kR ≈ kd, B molecules
react relatively fast
0,8 (but not immediately),
[B]r / [B]

kd / kR = 10 diffusion cannot deliver

0,7 kd / kR = 2
kd / kR = 0
enough B to the close
vicinity of A.
0,6

0,5 Adapted from

Pilling & Seakins 1995
0 2 4 6 8 10 12
r / nm
From diffusion control to activation control
Substitute kd into the rate expression:

4  rAB DAB k R kd k R
k 
k R  4  rAB DAB k R  kd

kR << kd kR is comparable to kd

k ≈ kR k < kR
pure activation control diffusion cannot completely
”fill up” B that is consumed
by the reaction

kR is the rate constant that would apply if the concentration of B

at rAB were always the same as the bulk concentration
 Diffusion controlled reactions
diffusion control: k  kd  4  rAB DAB ( DAB  DA  DB )
1 k BT
Stokes-Einstein equation: D
 a rs
hydrodynamic radius
of the diffusing species
constant

solvent viscosity

Values of the constant: • a = 6: the solvent is a continuum, the spherical

species is much greater than
the solvent molecules, and it ″slips”
• a = 4: same case but the spherical species ″sticks″
• a = 1: the diffusing (spherical) species’ size is
roughly the same as the solvent molecule
 Diffusion controlled reactions
rs depends on solvent-reactant interactions
rAB  rs
rAB depends on reactant-reactant interactions

 1 
k d  4  rAB DAB  4  rAB DA  DB   4  rAB
1 k BT  1 
r  
 a  s , A rs , B 
4 rAB k BT  1 1 
k d  4  rAB   
a r r 
 s , A s , B 

In case of missing information, usual approximations: rA  rs ,A

rB  rs ,B
If rA and rB are also equal: rAB  rA  rB

4 rABk BT  1 1  4(rA  rA )k BT  1 1  16 k BT
kd        
a r  a a
 s , A rs , B   rA rA 
 Diffusion controlled reactions

4 rABk BT  1 1  16 k BT
kd     kd 
a r r  a
 s , A s , B 
General case Special case; with rA = rB

kd ∝ 1 / η is always a good approximation

If rA = rB then kd does not depend on rAB
reason: increasing reaction radius also increases kd but decreases DAB

Solvent 103 / kg m–1s–1 Solvent 103 / kg m–1s–1

hexane 0.326 2-propanol 2.26

water 1.00 1,2-ethanediol 19.9

ethanol 1.20 1,2,3-propanetriol 1490

 Diffusion controlled reactions
Temperature dependence:

Increasing T decreases  both D and kd increas e

Ea

Arrhenius equation: kd  A e RT

Aqueous solutions: Ea ~ 15 kJ mol−1

A ~ 1012 dm3 mol−1s−1

Ea for diffusion originates from more complex phenomena than in a gas

including close-packedness and cooperative displacement

The pre-exponencial factor A is somewhat higher

than the collision number Z in a gas
 Acknowledgements

Figures marked as Pilling & Seakins 1995 are reproduced from

M. J. Pilling, P. W. Seakins: Reaction Kinetics, Oxford University Press, 1995

 END of the lecture
Diffusion Controlled and
Activation Controlled Reactions

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