Mass Transport with Reaction

1. Mass Conservation Statement

– Mass conservation statement incorporates porous medium serving as source/sink terms

– Mass inflow rate ! Mass outflow rate ± Mass production rate = Change in mass storage with
time, [MT !1] (1)

2. Reaction Classification

Homogeneous—operating within a single phase

Heterogeneous—operating between two phases

Equilibrium vs kinetic—depending on reaction rate relative to mass transport rate

3. Rate Law and Reaction Order

Rate law—an equation that relates the rate of a reaction to the Cs of reactants (and catalyst) or
products raised to various powers
Consider the reaction
C = catalyst
The rate law for reactants is

Rate
, ,
– often, but not always, integers
– must be determined experimentally
– have no relationship to the coefficients in the balanced equation

Reaction order—equals the exponent of the concentration of that species in the rate law

4. General Form of 1-d Equation with

(2)

r, mass produced or consumed per unit volume per unit time, moles/L3/T

5. Equation for First-order Kinetic Reactions

For first-order decay

(3)
, decay constant, [T!1]

1
 Substituting (3) into (2) gives

(4)

6. Equation for Sorption Reactions

For sorption of mass from solution

(5)

, C of species on the solid phase, or mass sorbed per unit medium volume, [M L!3]

Substituting (5) into (2) yields

For kinetic non-equilibrium sorption reactions

– a function of both C of mass in solution and mass sorbed on the solid.

For equilibrium sorption reactions

– a function of only C of mass in solution

Given a linear equilibrium sorption

(6)
, bulk density or total mass of solids per unit volume of porous medium, [M L!3]
S, amount of mass sorbed on the solid per unit mass of solid, [moles M!1]

(7)
, is mineral particle density

The linear Freundlich isotherm is

(8)
3 !1
, distribution coefficient, [L M ]

2
Differentiating (8) with time gives

(9)

Combining Eq 6, 7 and 9 leads to

(10)

Substituting (10) into (2) gives

(11)

Rearranging (11) gives

(12)

The bracketed quantity is a constant termed retardation factor, Rf

Eq 12 is thus rewritten as

(13)

The retardation factor serves to decrease the values of the transport parameters of D and v