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# Boltzmann’s Concepts of Reaction Rates Boltzmann’s Concepts of Reaction Rates

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Distribution of Air Particles Distribution of Air Particles
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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

325 kPa . [1 mile = 1610 m] Po = 101.The Barometric Formulation The Barometric Formulation • Calculate the pressure at mile high city (Denver. . CO).0 mole % of oxygen gas and nitrogen gas. respectively. T = 300. Assume 20.0 and 80. K .

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

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 − ⋅m⋅u x 2 / k ⋅T A⋅e 2 ⋅ du x .

dN = N 0.002 1 − ⋅m⋅u x 2 / k ⋅T A⋅e 2 ⋅ du x Mcad F1( u) m ⋅s F2( u) m ⋅s F3( u) −1 −1 −1 0.10 0 0 1500 − 1500 1000 500 0 u m⋅ s −1 500 1000 1500 1500 .001 m ⋅s 4 5 .0015 0.0025 0.

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 ⋅π ⋅ k ⋅ T 1 − ⋅m⋅u 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 − −ε x / k ⋅T ⋅ε x 2 ⋅ e ⋅ dε x 4 ⋅π ⋅ k ⋅ T .

 dN  =    N 1D −u x m 2 ⋅π ⋅ k ⋅ T 1 − ⋅m⋅u x 2 / k ⋅T ⋅e 2 ⋅ du x  dN  =    N 1D −E x 1 1 − ⋅ ε x 2 ⋅ e −ε x / k ⋅T ⋅ dε x 4 ⋅π ⋅ k ⋅ T .

Let: a = m/2kT a −au x 2  dN  = ⋅e ⋅ du x   π  N 1D −u x a −au y 2  dN  = ⋅e ⋅ du y   N 1D −u y π  a −au z 2  dN  = ⋅e ⋅ du z   π  N 1D −u z Cartesian Coordinates:  dN  a   =   N 3 D  π  3/ 2 ⋅e −a[u x 2 +u y 2 +u z 2 ] ⋅ du x ⋅ du y ⋅ du z .3D Maxwell-Boltzmann Distribution 3D Maxwell-Boltzmann Distribution 3D Velocity Distribution: [ 3Du ] .

3D Maxwell-Boltzmann Distribution 3D Maxwell-Boltzmann Distribution  dN  a   =   N 3 D  π  3/ 2 ⋅e −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) π u3 with u2 = ux2 + uy2 + uz2 dV = dux duy duz = 4 π u2 du 4  dN / N  3/ 2 2 − a⋅u 2 ⋅ a ⋅u ⋅e   = π  du  3 D .

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 Mcad 0.0035 0.

3D Maxwell-Boltzmann Distribution 3D Maxwell-Boltzmann Distribution 4  dN / N  3/ 2 2 − a⋅u 2 = ⋅ a ⋅u ⋅e   π  du  3 D −u Conversion of Velocity-distribution to Energy-distribution: ε = ½ m u2 . d ε = mu du 2  dN / N  =   π  dε  3 D − ε  1  ⋅   kT  3/ 2 ε − 1/ 2 ⋅ ε ⋅ 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 n  dN  = x ⋅   N x ∫ n .

Velocity Value from M-B Distribution Velocity Value from M-B Distribution 2 4  dN / N  = ⋅ a 3 / 2 ⋅ u 2 ⋅ e − a⋅u   du  3 D π  • 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 − a⋅u   du  3 D π  • 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 − a⋅u   du  3 D π  • ump = most probable velocity .

Comparison of Velocity Values Comparison of Velocity Values Ratio in terms of : urms kT m kT m uavg 8 kT ⋅ π m ump kT m 3⋅ 2⋅ 1.73 1.41 .60 1.

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 • λ = 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 ⋅ π ⋅ d ⋅ u avg where : u relative = 2 ⋅ u avg Define: N* = N/V = molecules per unit volume 2 Z I = (VI ) ⋅ ( N *) Z I = 2 ⋅ π ⋅ d 2 ⋅ u avg ⋅ N * u avg = 8 ⋅ k ⋅T 8 ⋅ R ⋅T = π ⋅m π ⋅M .

Mean Free Path (( λ )) Mean Free Path λ u avg distance traveled per unit time λ= = # molecules it collides with in unit time ZI λ= 1 2 ⋅π ⋅ 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 = ⋅ π ⋅ d ⋅ uavg ⋅ ( N *) 2 .

022 ⋅10 23 mol −1 N* = .Viscosity (( η )) from Drag Effects Viscosity η from Drag Effects 1 η = ⋅ u avg ⋅ N * ⋅m ⋅ λ 2 u avg ⋅ m 2 2 ⋅π ⋅ d 2 λ= 1 2 ⋅π ⋅ d 2 ⋅ N * η= P⋅L R ⋅T where : L = 6.

96 ZI / 109 s-1 14.73 2.56 λ / 10-8 m 12.0 10.57 3.74 3.6 8.9 7.6 .41 2.1 8.62 4.18 3.6 10.74 3.6 7.56 2.1 6.56 7.16 6.6 7.Collision Parameters @ 25oC and 1 atm Collision diameter Species d / 10-10 m d / Å H2 He N2 O2 Ar CO2 HI 2.3 6.4 19.2 6.73 2.7 8.99 4.62 4.56 5.57 3.56 5.5 ZII / 1034 m-3 s-1 Mean free path Collision Frequency Collision Rate 17.2 5.Kinetic-Molecular-Theory Gas Properties .6 7.18 3.

Boltzmann’s Concepts of Reaction Rates Boltzmann’s Concepts of Reaction Rates B o l t z m a n n D i s t r i b u t i o B a r o m e t r i c F o r m u l a t i M a x w e l l .B o l t z m a n n D i V e l o c i t iD e e s r i v a t i Eo n se r g i e s C o 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 s 4  dN / N  3/ 2 2 − a⋅u 2 ⋅a ⋅u ⋅e   = π  du  3D ( x ) average  dN  = x ⋅   N x ∫ n .

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 lr l a i s m i o e Hn t e a T r r shd e S o p r yh e r e D P o t e n 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 P a r t i t i o n F u n c t i o n s U n i m o 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 o n T t o p i u u e n m n E e K i n l l i n e g t s t i c s f f e c .

Arrhenius Concept The Arrhenius Equation • Arrhenius discovered most reaction-rate data obeyed the Arrhenius equation: k= Ea − A ⋅ e R⋅T • Including natural phenomena such as: • Chirp rates of crickets • Creeping rates of ants .

. ± 1/2. . .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. rate constants vary quite dramatically with temperature.3/2.Extended Arrhenius Equation Extended Arrhenius Equation E' − m a ⋅ T ⋅ e R⋅T k= where : m = 1. On the other hand.

Extended Arrhenius Equation Extended Arrhenius Equation A = a ⋅ e ⋅T m m Ea = E '+ m ⋅ R ⋅ T .

Reaction Progress .

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

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 ⋅ π ⋅ d 2 ⋅ v 2 8 ⋅ k ⋅T 8 ⋅ R ⋅T v= = π ⋅m π ⋅M For A-B collisions: µ A B [ v ≡ vavg ] . vAB m A ⋅ mB = m A + mB 8 ⋅ k ⋅T = π ⋅ µ AB Reduced Mass ≡ > µ 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  ⋅ π ⋅m   A   1/ 2 Z II ( AA) = 1 2 ⋅ ( N A *) ⋅ π ⋅ d A 2 2 Z II ( AB ) = N A * ⋅ N B * ⋅π ⋅ d AB ⋅ v AB = N A * ⋅ N B * ⋅π ⋅ d AB 2 2  8kT ⋅ π ⋅µ AB      1/ 2 .

Collision Theory: Rate Constant Calculations Collision Theory: Rate Constant Calculations  − Ea Rate = ( Z II ) ⋅  e R⋅T       Collision Theory: Kinetics: Rate = (k 2 ' ) ⋅ [ N A *] ⋅ [ N B *] Combining Collision Theory with Kinetics: Z II k2 ' = ( N A *) ⋅ ( N B *) Ea − ⋅ e R⋅T .

Collision Theory: Rate Constant Calculations Collision Theory: Rate Constant Calculations A-A Collisions 1/ 2 k2 ' = 1 2 ⋅π⋅d A m2 2 8 ⋅k ⋅T ⋅  π⋅m A  m s-1     E a − ⋅e R⋅T per molecule  10 3 dm 3   6.022 ⋅10 23 molecule   ⋅   1 m3    1 mol     k 2( A ) A 1 0 = 3 ⋅L 2 ⋅π⋅d A 2 8 ⋅k ⋅T ⋅  π⋅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 ⋅π⋅d A 0 B B Units of k: 2  8 ⋅k ⋅T ⋅ π⋅ µ A B      1/ 2 E a − ⋅e R⋅T dm3 mol-1 s-1 ≡ M-1 s-1 d AB d A + dB = 2 µ 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.

20E+08 H + HCO2.60 0.056 k2 / M s-1 Reaction atom-1 + atom-2-CO2.http://www.---> HD + CO23.html mass ratio atom-1/atom-2 1 0.0E+08 8.2E+08 1.---> atom-1-atom-2 + CO21.80 1.0E+07 4.0E+00 0.20 0.30E+07 H + DCO2.0E+07 k / M-1 s-1 6.11 0.4E+08 Simple Collision Theory: Comparison of Muonium/Hydrogen/Deuterium Abstractions 1.0E+07 2.---> MuH + CO29.00 0.ca/index.5 0.---> H2 + CO22.40E+06 Mu + HCO2.0E+07 0.90E+05 Mu + DCO2---> MuD + CO233 39 Ea / kJ mol-1 1.ubc.40 mass ratio 0.00 .

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 ( ‡ ) .

Reaction coordinate = path of minimum energy leading from reactants to products. 180o D + H2  DH + H Most favorable at: Calculate energy of interaction at different r1. . r2 and θ .Potential Energy Surfaces Potential Energy Surfaces Consider: D r1 HA r2 θ r1= dH-D r2 = dH-H HB θ = 0o . Get 3D Energy Map.

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

η = viscosity k diff 8 ⋅ R ⋅T = 3 ⋅η .Diffusion Controlled Solutions Diffusion Controlled Solutions Smoluchowski (1917): D = diffusion coefficient k diff = 4 ⋅ π ⋅ d AB ⋅ L ⋅ ( D A + DB ) k ⋅T D= 6 ⋅ π ⋅η ⋅ a a = radius.

8904⋅ 10 8R⋅ T 3⋅ η ⋅s η 95C := 0.3145⋅ J⋅ mol −1 ⋅K −1 T1 := ( 25 + 273.15) ⋅ K T2 := ( 95 + 273.74 × 10 − Ea 10 k25C = 7.15) ⋅ K k25C := 8⋅ R⋅ T1 3⋅ η 25C 9 −1 −1 k95C := 8⋅ R⋅ T2 3⋅ η 95C k95C = 2. .Diffusion Controlled (Aqueous) Reactions viscosity η −3 Diff-paper kg⋅ m −1 −1 η 25C := 0.7 × 10 J⋅ mol 4 −1 Ea = 17kJ⋅ mol −1 Therefore all aqueous solutions whose rate is determined by the diffusion of species should have an Activation Energy of about 17kJ/mol.2975⋅ 10 −3 kg⋅ m −1 −1 ⋅s k R := 8.42 × 10 L⋅ mol ⋅s L⋅ mol −1 −1 ⋅s Arrhenius Equation: k A⋅e R⋅ T kJ := 10 ⋅ J 3 Ea := −R⋅ T1⋅ T2 T2 − T1 ⋅ ln  k25C    k95C  Ea = 1.

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 .

B o l t z m a n n D i V e l o c i t iD e e s r i v a t i Eo n se r g i e s C o 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 s 4  dN / N  3/ 2 2 − a⋅u 2 ⋅a ⋅u ⋅e   = π  du  3D ( x ) average  dN  = x ⋅   N x ∫ n .Boltzmann’s Concepts of Reaction Rates Boltzmann’s Concepts of Reaction Rates B o l t z m a n n D i s t r i b u t i o B a r o m e t r i c F o r m u l a t i M a x w e l l .

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 P o t e n 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 f T S P a r t i t i o n F u n c t i o n s U n i m o 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 d M Q I s u M o o n T t o p i u u e n m n E e K i n l l i n e g t i c s f f e c k diff t s 8 ⋅ R ⋅T = 3 ⋅η k 2 ( AB ) =1 3 ⋅ L ⋅π⋅d AB 0 2 8 ⋅k ⋅T ⋅ π⋅ µ A B      1/ 2 ⋅e E a − R⋅ T .