10.

37 Chemical and Biological Reaction Engineering, Spring 2007

Prof. William H. Green
Lecture 2: The Reaction Rate & Reaction Mechanisms

The lecture covers: Definitions in terms of reacting compounds and reaction extent,
rate laws, Arrhenius equation, elementary, reversible, non-elementary, catalytic
reactions.

From previous lecture:

dN A
= FAo − FA + GA , GA = ∫ rA dV
dt

Example:
A + B → 2C
*Reactions are reversible (often will neglect reverse)
N Ao − N A FAo − FA FC
XA = XA = XC =
N Ao FAo 2 FAo

A,B C,A,B

FAo
FBo

Figure 1. A reactor with reactants A and B constantly flowing in and product C and
unused reactants A and B flowing out.
moles A flowing in
FAo = = [ A]input vin = [ A]o vo
sec liters
sec

moles A flowing out

FA = = [ A]output vout
sec
[ A]output vout
X = 1−
[ A]in vin
Closed reactor, const. V

Detailed balance- all steps in equilibrium, total system

d [ A]
= rA = − k [ A][ B ]
dt
[C ]
2

K eq =
[ A][ B ]
[C ]
2

when [ A][ B ] = the rxn. stops -> rA=0

K eq
Cite as: William Green, Jr., course materials for 10.37 Chemical and Biological Reaction Engineering,
Spring 2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology.
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 ⎛ [ C] ⎞
2
k
rA = − k [ A][ B ] −
⎜ ⎟ , krev = for , forward-reverse in one expression
⎜ K eq ⎟ K eq
⎝ ⎠
same!

Catalysis

rA, forward = kcat [ catalyst ][ A] f ( [ B ])

may be included
i.e. when B is
very small

Rate limiting step determines the kinetics (slow step). The kinetics are insensitive to
[B] because B is not part of this slow step.

[C ]
2

rA,reverse = rA, forward

K eq [ A][ B ]
⎛ [ C] ⎞
2

rA,net = − kcat [ catalyst ] ⎜ [ A] − ⎟

⎜ K eq [ A][ B ] ⎟
⎝ ⎠
Standard state
K eq = e − ΔG RT ΔG = ΔG of , products − ΔG of ,reactants

A→ B+C
[ B ][C ] = moles
K eq = [ ]
[ A] liter
KC
Partial Pressures

pB pC
= K eq =
[ B ][C ]
pA Po Po
[ A] RT
n P
Ideal Gas: pV = nRT ⇒ =
V RT
Po is the standard state pressure (1 atm), this makes the units cancel. Using partial
pressures is accurate within 10%, more error with liquids.

Stoichiometric coefficient
N A = N A,initial + ∑ν A,iξi
Extent of rxn.

N rxn
N C = N C ,initial + ∑ν C ,iξi
i =1

10.37 Chemical and Biological Reaction Engineering, Spring 2007 Lecture 2

Prof. William H. Green Page 2 of 3

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column column
vector vector matrix vector

N = No + ν i ξ

Do columns span space? Often no, limits on what is achievable.

NC Reaction trajectory-
Plot state of system
ξ=ΝΑο
t=10

ξ
d
t=0.01 (N ) = F (N)
dt
NB

ξ1=0

NA

Figure 2. A plot of the reaction trajectory. ξ is the extent of reaction.

Conservation Laws

Conserve atoms
2CH 4 + O 2 → C2 H 4 + 2H 2 O
C A N A + CB N B + CC N C = const.
constant moles

C :1× NCH 4 + 2 × NC2 H 4 = N C ,initial

H : 4 × NCH 4 + 4 × NC2 H 4 + 2 N H 2O = N H ,initial

10.37 Chemical and Biological Reaction Engineering, Spring 2007 Lecture 2

Prof. William H. Green Page 3 of 3

Cite as: William Green, Jr., course materials for 10.37 Chemical and Biological Reaction Engineering,
Spring 2007. MIT OpenCourseWare (http://ocw.mit.edu), Massachusetts Institute of Technology.
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