Fundamental Definitions

• Chemical Kinetics – the rate at which a given

Reaction Kinetics reaction proceeds from products to reactants
• Homogeneous Reactions – reactions that take
place in a single phase
• Heterogeneous Reactions – reactions that occur at
surfaces

What are some examples of homogeneous and

heterogeneous reactions?

Rate of Reaction Factors Influencing Reaction Rates

Rate of reaction equals the rate either the reactant(s)
disappears or a product(s) is formed.
aA + bB cC + dD
r = -k [A]α [B] β
r = overall rate of reaction
k = reaction rate constant
[ ] = reactant concentration (Moles/Liter)
α, β = empirical constants
• Concentration
• Physical Conditions – such as temperature
and pressure
• Intensity of Adsorbed Radiation – sunlight
or room light may alter the rate of reaction
• Properties of the Solvent – salt water vs.
fresh water

1
 Zero Order Reactions
Order of Reaction
• Order of reaction – the sum of the • Zero Order Reactions – reactions that occur
exponents in the reaction rate equation at a constant rate, independent of the
concentration of the material involved in the
Overall order of the reaction = α + β reaction
dC
Order with respect to A = α r =
dt
Order with respect to B = β r = - k [C]0 = - k
dC
Note : α and β values are usually between 0 r = = -k
and 2, decimal values are possible.
dt

Zero Order Reactions (cont.) Zero Order Reactions (cont.)

Rearrange the equation:
C = Co - k t
dC = -kdt Co
Integrate between time t = 0 and time t, where A
changes from Ao to A.
C t C -k
∫ dC = −k ∫ dt
Co 0

C – Co = -k t
C = Co - k t
t

2
 First Order Reactions First Order Reactions (cont.)
• First Order Reaction – reaction rate increases 10
with the concentration present
Co ln C = ln Co - k t
dC
r= =-kC
dt
C -k
C t
dC
∫Co C = −k ∫0 dt
ln C = - k t 1
Co 0 2 4 6 8

ln C = ln Co - k t time

Second Order Reactions

• Second Order Reaction – reaction rate increases Second Order Reactions (cont.)
by the second power of the concentration present
dC
r= = - k C2
dt
C t
dC
∫Co C 2 = −k ∫0 dt 1
k
C
1 1 1
= +kt
C Co Co

3
 Chlorine Decay in the Drinking
Water Distribution System Fe+2 Fe+3/Fe+2
Intermediate (aq)
Cl2 Decay Cl2
(b) (c)
• It is typically assumed that Chlorine in the
(e) (d) Intermediate (surface) + Cl2
distribution system follows first order kinetics

C t = Co e − kt
NOM + Cl2 Intermediate (aq) + Cl2 TTHM and HAA

(f)
(a) Non-DBP
• The complexity comes from how we break-up Intermediate (surface) + Cl2
(b) (c)
the reaction rate constant (k) Cl2
NOM (surface) HAA (surface)

kwk f Fe+3/Fe+2 Fe+2

k = kb +
RH (k w + k f )

Chlorine Decay in the Drinking Chlorine Decay in the Drinking

Water Distribution System Water Distribution System
kwk f • EPAnet will help us determine the overall
k = kb + chlorine decay coefficient
RH (k w + k f )
Where:
k = Overall reaction rate constant
RH = Hydraulic radius of pipe
kw = Wall reaction coefficient
kf = Mass transfer coefficient