Conservation of species

Prof (Dr) Ujjaini Sarkar

Department of Chemical Engineering
JADAVPUR UNIVERSITY,
Calcutta- 700032
Conservation of Species

• In a binary mixture which consists of species concentration gradient, a

relative transport of the species is observed and the conservation of
species is fulfilled at every point in the fluid.
• The appropriate form of the species conservation equation is obtained
by selecting the process that affects
• the transport and
• generation of species A in differential control volume of the fluid.
• Consider the control volume shown in Fig. 1.
• Species A may be transported either by advection (with the mean
velocity of the fluid) and by diffusion (relative to the mean flow) in each
of the coordinate directions shown.
• The concentration in the control volume varies due to the chemical
reactions, and the rate of generation of species A because of such
reaction is referred by the term 𝑛𝐴 .
Conservation of species: Basics and
derivation

• The mass balance equation, considering species A

enters the control volume by advection in the x
direction is given by the following equation:
• 𝑀𝐴,𝑎𝑑𝑣,𝑥 − 𝑀𝐴,𝑎𝑑𝑣,𝑥+𝑑𝑥 =
𝜕 𝜌𝐴 𝑢 𝜕 𝜌𝐴 𝑢
𝜌𝐴 𝑢 𝑑𝑦 − 𝜌𝐴 𝑢 + 𝑑𝑥 𝑑𝑦 = − 𝑑𝑥 𝑑𝑦
𝜕𝑥 𝜕𝑥
(1)
• Correspondingly, the mass balance equation of species
A enters the control volume by diffusion in the x
direction, assuming an incompressible fluid (constant ρ)
and using Fick’s law to assess the diffusion flux, is given
by
Conservation of species: Basics and derivation

Fig.1 Differential control volume (dx.dy.l) for species conservation in

two-dimensional flow of a viscous fluid with mass transfer.
Conservation of species: Basics and derivation
𝑀𝐴,𝑑𝑖𝑓,𝑥 − 𝑀𝐴,𝑑𝑖𝑓,𝑥+𝑑𝑥 =
𝜕𝜌𝐴 𝜕𝜌𝐴 𝜕 𝜕𝜌𝐴
−𝐷𝐴𝐵 𝑑𝑦 − −𝐷𝐴𝐵 + −𝐷𝐴𝐵 𝑑𝑥 𝑑𝑦 =
𝜕𝑥 𝜕𝑥 𝜕𝑥 𝜕𝑥
𝜕 𝜕𝜌𝐴
𝐷𝐴𝐵 𝑑𝑥 𝑑𝑦 (2)
𝜕𝑥 𝜕𝑥

Similarly for y direction, the mass balance equation can be written as

𝑀𝐴,𝑎𝑑𝑣,𝑥 − 𝑀𝐴,𝑎𝑑𝑣,𝑥+𝑑𝑥 + 𝑀𝐴,𝑎𝑑𝑣,𝑦 − 𝑀𝐴,𝑎𝑑𝑣,𝑦+𝑑𝑦 + 𝑀𝐴,𝑑𝑖𝑓,𝑥 −
𝑀𝐴,𝑑𝑖𝑓,𝑥+𝑑𝑥 + 𝑀𝐴,𝑑𝑖𝑓,𝑦 − 𝑀𝐴,𝑑𝑖𝑓,𝑦+𝑑𝑦 + 𝑀𝐴,𝑔 = 0
(3)
Substituting from equation (1) and (2), and from similar forms for the y
direction, it can be given by
𝜕(𝜌𝐴 𝑢) 𝜕(𝜌𝐴 𝑣) 𝜕 𝜕𝜌𝐴 𝜕 𝜕𝜌𝐴
+ = 𝐷𝐴𝐵 + 𝐷𝐴𝐵 + 𝑛𝐴 (4)
𝜕𝑥 𝜕𝑦 𝜕𝑥 𝜕𝑥 𝜕𝑦 𝜕𝑦
Conservation of species: Basics and derivation

Another form of the above equation can be acquired by expanding the

terms on the left-hand side of equation (4) and then substituting from
the overall continuity equation for an incompressible fluid, equation (4)
can be given as
𝜕𝜌𝐴 𝜕𝜌𝐴 𝜕 𝜕𝜌𝐴 𝜕 𝜕𝜌𝐴
𝑢 + 𝑣 = 𝐷𝐴𝐵 + 𝐷𝐴𝐵 + 𝑛𝐴 (5)
𝜕𝑥 𝜕𝑦 𝜕𝑥 𝜕𝑥 𝜕𝑦 𝜕𝑦
Also in molar form as given below
𝜕𝑐𝐴 𝜕𝑐𝐴 𝜕 𝜕𝑐𝐴 𝜕 𝜕𝑐𝐴
𝑢 +𝑣 = 𝐷𝐴𝐵 + 𝐷𝐴𝐵 + 𝑁𝐴 (6)
𝜕𝑥 𝜕𝑦 𝜕𝑥 𝜕𝑥 𝜕𝑦 𝜕𝑦
Conservation of species: Basics and derivation
Mass Diffusion Equation
Cylindrocal Coordinates
1 𝜕 𝜕𝐶𝐴 1 𝜕 𝜕𝐶𝐴 𝜕 𝜕𝐶𝐴
𝐷𝐴𝐵 𝑟 + 2 𝐷𝐴𝐵 + 𝐷𝐴𝐵
𝑟 𝜕𝑟 𝜕𝑟 𝑟 𝜕∅ 𝜕∅ 𝜕𝑧 𝜕𝑧
𝜕𝐶𝐴
+ 𝑁𝐴 =
𝜕𝑡
Spherical Coordinates
1 𝜕 2
𝜕𝐶𝐴 1 𝜕 𝜕𝐶𝐴
2
𝐷𝐴𝐵 𝑟 + 2 2 𝐷𝐴𝐵
𝑟 𝜕𝑟 𝜕𝑟 𝑟 𝑠𝑖𝑛 𝜃 𝜕∅ 𝜕∅
1 𝜕 𝜕𝐶𝐴 𝜕𝐶𝐴
+ 2 𝐷𝐴𝐵 𝑠𝑖𝑛𝜃 + 𝑁𝐴 =
𝑟 𝑠𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃 𝜕𝑡
Conservation of species: Problems
Problem #1
Consider a spherical aggregate of bacterial cells (assumed homogeneous) of radius R.
Under certain circumstances, the oxygen metabolism rate of the bacterial cells is almost
zero order with respect to oxygen concentration and may be approximated by an effective
volumetric reaction rate rO2 = -k0'''. The diffusion may be described by Fick's law with an
effective pseudobinary diffusivity for oxygen in the bacterial medium DO2-M. Neglect
transient and convection effects because the oxygen solubility is very low in the system. Let
r0 be the oxygen mass concentration at the aggregate surface. It is then convenient to
define the following dimensionless quantities:

If N is large enough, then an oxygen - free core may exist in the aggregate such that c = 0
for x < x0. This requires that cand dc/dx both be zero at x = x0.
a) Establish the pseudo-steady-state oxygen concentration distribution c(x).
b) Derive an expression from which the dimensionless oxygen - free core radius x0 may be
determined as a function of N.
c) For what values of N does an oxygen - free core exist?
d) Sketch the oxygen concentration profile c for different values of N.
Conservation of species: Problems
Problem #2
A diffusion problem that occurs in the field of microelectronics is the oxidation of silicon
according to the reaction Si + O2 SiO2. Consider the the oxidation of a material M given by the
general reaction M + (1/2)x O2 MOx (with x = 2 for silicon oxidation). When a slab of the
material is exposed to gaseous oxygen (species A), the oxygen undergoes a first-order reaction
with rate constant k1" to produce a layer of the oxide (species B). The task is to predict the
thickness δ of the very slowly-growing oxide layer as a function of time t using a quasi-steady-
state approach (which suggests that the rate of change of the dissolved oxygen content in the
layer is small compared to the rate of reaction). Let the oxygen, whose dissolved concentration
is cA0 at the free surface of the oxide layer at z = 0, diffuse through the layer as per Fick's law to
reach the reaction surface at z = d as in the figure below.

Diffusion of oxygen through an oxide layer formed by oxidation of silicond

Conservation of species: Problems
a) Write unsteady-state molar balances on the oxide and oxygen over the thickness of
the layer.
b) Find the concentration profile of oxygen in the layer at steady-state.
c) Using quasi-steady-state arguments, show that the oxygen concentration at the
reaction plane (z = d) is given by

where DAB is the oxygen diffusivity through the oxide film and cB is the molar
density of the oxide layer.
d) Derive an expression for the thickness of the very slowly-growing oxide layer
when the quadratic term on the right-hand side of the above equation is
negligible.
e) Reduce the above results for the limiting case of diffusion - controlled oxidation
where the reaction rate constant k1"tends to infinity.
Conservation of species: Problems
Problem #3
A solid sphere (of radius R and density r) made of substance A (of molecular weight M)
is suspended in a liquid B. Solid A undergoes a first-order homogeneous chemical
reaction with rate constant k1''' being slightly soluble in liquid B. Let cA0 be the molar
solubility of A in B, and DAB be the diffusivity of A in B.

Diffusion with Chemical Reaction of sphere in liquid

a) Establish the concentration profile for A at steady state (i.e., when the mass
diffusion is in exact balance with the chemical reaction).
b) Using a quasi-steady-state approach, derive an expression for the time t required
for the sphere radius to decrease from an initial radius R0 to R.