2 Differential Equation PDF
2 Differential Equation PDF
2 Differential Equation PDF
Definition:
The differential equations of mass transfer are general equations describing mass transfer
in all directions and at all conditions.
The differential equation for mass transfer is obtained by applying the law of
conservation of mass (mass balance) to a differential control volume representing the
system.
The resulting equation is called the continuity equation and takes two forms:
(1) Total continuity equation [in – out = accumulation] (this equation is obtained if we
applied the law of conservation of mass on the total mass of the system)
(2) Component continuity equation[in – out + generation – consumption = accumulation]
(this equation is obtained if we applied the law of conservation of mass to an
individual component)
(1) Total continuity equation
Fig. 1
1
Apply the law of conservation of mass on this control volume [in – out = accumulation]
direction in out in - out
x
𝜌v𝑥 ∆𝑦∆𝑧⃒𝑥 𝜌v𝑥 ∆𝑦∆𝑧⃒𝑥+Δ𝑥 (𝜌v𝑥 ⃒𝑥 − 𝜌v𝑥 ⃒𝑥+Δ𝑥 ) ∆𝑦∆𝑧
y
𝜌v𝑦 ∆𝑥∆𝑧⃒𝑦 𝜌v𝑦 ∆𝑥∆𝑧⃒𝑦+Δ𝑦 (𝜌v𝑦 ⃒𝑦 − 𝜌v𝑦 ⃒𝑦+Δ𝑦 ) ∆𝑥∆𝑧
z
𝜌v𝑧 ∆𝑥∆𝑦⃒𝑧 𝜌v𝑧 ∆𝑥∆𝑦⃒𝑧+Δ𝑧 (𝜌v𝑧 ⃒𝑧 − 𝜌v𝑧 ⃒𝑧+Δ𝑧 ) ∆𝑥∆𝑦
𝜕𝑚 𝜕𝜌∆𝑥∆𝑦∆𝑧 𝜕𝝆
Accumulation = = = ∆𝑥∆𝑦∆𝑧 𝜕𝑡
𝜕𝑡 𝜕𝑡
Write the above terms in the overall equation [in – out = accumulation (rate of change)]
𝜕𝝆
(𝜌v𝑥 ⃒𝑥 − 𝜌v𝑥 ⃒𝑥+Δ𝑥 ) ∆𝑦∆𝑧 + (𝜌v𝑦 ⃒𝑦 − 𝜌v𝑦 ⃒𝑦+Δ𝑦 ) ∆𝑥∆𝑧 + (𝜌v𝑧 ⃒𝑧 − 𝜌v𝑧 ⃒𝑧+Δ𝑧 ) ∆𝑥∆𝑦 = ∆𝑥∆𝑦∆𝑧
𝜕𝑡
𝜕 𝜕 𝜕 𝜕𝜌
− 𝜕𝑥 𝜌v𝑥 - 𝜌v𝑦 - 𝜕𝑧 𝜌v𝑧 =
𝜕𝑦 𝜕𝑡
𝜕 𝜕 𝜕 𝜕𝜌
∴ 𝜕𝑥 𝜌v𝑥 + 𝜌v𝑦 + 𝜕𝑧 𝜌v𝑧 + =0
𝜕𝑦 𝜕𝑡
The above equation is the general total continuity equation (the velocity distribution can
be obtained from this equation)
It can be written in the following form (this form can be used in all coordination system):
𝜕𝜌
∇. 𝜌v
⃗⃗⃗⃗ + =0
𝜕𝑡
2
Special forms of the general continuity equation:
𝑑vx
=0
𝑑𝑥
The component continuity equation takes two forms depending on the units of
concentration; (i) mass continuity equation and (ii) molar continuity equation.
Component continuity
equation
It is used to get (describe) the concentration profiles, the flux or other parameters of
engineering interest within a diffusing system.
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direction in out in - out
x
𝑛𝐴,𝑥 ∆𝑦∆𝑧⃒𝑥 𝑛𝐴,𝑥 ∆𝑦∆𝑧⃒𝑥+Δ𝑥 (𝑛𝐴,𝑥 ⃒𝑥 − 𝑛𝐴,𝑥 ⃒𝑥+Δ𝑥 ) ∆𝑦∆𝑧
y
𝑛𝐴,𝑦 ∆𝑥∆𝑧⃒𝑦 𝑛𝐴,𝑦 ∆𝑥∆𝑧⃒𝑦+Δ𝑦 (𝑛𝐴,𝑦 ⃒𝑦 − 𝑛𝐴,𝑦 ⃒𝑦+Δ𝑦 ) ∆𝑥∆𝑧
z
𝑛𝐴,𝑧 ∆𝑥∆𝑦⃒𝑧 𝑛𝐴,𝑧 ∆𝑥∆𝑦⃒𝑧+Δ𝑧 (𝑛𝐴,𝑧 ⃒𝑧 − 𝑛𝐴,𝑧 ⃒𝑧+Δ𝑧 ) ∆𝑥∆𝑦
𝜕𝜌𝐴
(𝑛𝐴,𝑥 ⃒𝑥 − 𝑛𝐴,𝑥 ⃒𝑥+Δ𝑥 ) ∆𝑦∆𝑧 + (𝑛𝐴,𝑦 ⃒𝑦 − 𝑛𝐴,𝑦 ⃒𝑦+Δ𝑦 ) ∆𝑥∆𝑧 + (𝑛𝐴,𝑧 ⃒𝑧 − 𝑛𝐴,𝑧 ⃒𝑧+Δ𝑧 ) ∆𝑥∆𝑦 + 𝑟𝐴 ∆𝑥∆𝑦∆𝑧 = ∆𝑥∆𝑦∆𝑧
𝜕𝑡
(𝑛𝐴,𝑥 ⃒𝑥 − 𝑛𝐴,𝑥 ⃒𝑥+Δ𝑥 ) (𝑛𝐴,𝑦 ⃒𝑦 − 𝑛𝐴,𝑦 ⃒𝑦+Δ𝑦 ) (𝑛𝐴,𝑧 ⃒𝑧 − 𝑛𝐴,𝑧 ⃒𝑧+Δ𝑧 ) 𝜕𝜌𝐴
+ + + 𝑟𝐴 =
∆𝑥 ∆𝑦 ∆𝑧 𝜕𝑡
𝜕 𝜕 𝜕 𝜕𝜌𝐴
− 𝜕𝑥 𝑛𝐴,𝑥 - 𝑛𝐴,𝑦 - 𝜕𝑧 𝑛𝐴,𝑧 + 𝑟𝐴 =
𝜕𝑦 𝜕𝑡
𝜕 𝜕 𝜕 𝜕𝜌𝐴
𝑛𝐴,𝑥 + 𝑛𝐴,𝑦 + 𝑛𝐴,𝑧 + − 𝑟𝐴 = 0 (1)
𝜕𝑥 𝜕𝑦 𝜕𝑧 𝜕𝑡
Equation 1 is the component mass continuity equation and it can be written in the form:
𝜕𝜌𝐴
∇. 𝑛⃗𝐴 + − 𝑟𝐴 = 0 (2)
𝜕𝑡
(The above equation can be written in different coordinate systems since it is written in a
vector form)
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But from Fick’s law
𝑛𝐴 = −𝜌𝐷𝐴𝐵 ∇𝜔𝐴 + 𝜌𝐴 v
𝜕𝜌𝐴
−∇. 𝜌𝐷𝐴𝐵 ∇𝜔𝐴 + ∇. 𝜌𝐴 v + − 𝑟𝐴 = 0 (3)
𝜕𝑡
Equation 3 is a general equation used to describe concentration profiles (in mass basis)
within a diffusing system.
Equations 1, 2 and 3 can be written in the form of molar units to get the component
continuity equation in molar basis by replacing:
𝑛𝐴 𝑏𝑦 𝑁𝐴; 𝜌 𝑏𝑦 𝑐; 𝜔𝐴 𝑏𝑦 𝑦𝐴 ; 𝜌𝐴 𝑏𝑦 𝑐𝐴 𝑎𝑛𝑑 𝑟𝐴 𝑏𝑦 𝑅𝐴
𝜕 𝜕 𝜕 𝜕𝑐𝐴
𝑁𝐴,𝑥 + 𝑁𝐴,𝑦 + 𝑁𝐴,𝑧 + − 𝑅𝐴 = 0 (4)
𝜕𝑥 𝜕𝑦 𝜕𝑧 𝜕𝑡
Equation 4 is the component molar continuity equation and it can be written in the form:
𝜕𝑐𝐴
⃗𝐴 +
∇. 𝑁 − 𝑅𝐴 = 0 (5)
𝜕𝑡
But from Fick’s law
𝑁𝐴 = −𝑐𝐷𝐴𝐵 ∇𝑦𝐴 + 𝑐𝐴 V
𝜕𝑐𝐴
−∇. 𝑐𝐷𝐴𝐵 ∇𝑦𝐴 + ∇. 𝑐𝐴 V + − 𝑅𝐴 = 0 (6)
𝜕𝑡
Equation 6 is a general equation used to describe concentration profiles (in molar basis)
within a diffusing system.
Note: you may be given the general form and asked to apply specific conditions to get a
special form of the differential equation.
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Special forms of the component continuity equation
1. If the density and diffusion coefficient are constant (assumed to be constant)
𝜕𝜌𝐴
−𝐷𝐴𝐵 ∇2 𝜌𝐴 + 𝜌𝐴 ∇. v + v ∇. 𝜌𝐴 + − 𝑟𝐴 = 0
𝜕𝑡
For constant density ∇. v = 0 [from the total continuity equation] (page 3 no. b)
𝜕𝜌𝐴
∴ −𝐷𝐴𝐵 ∇2 𝜌𝐴 + v ∇. 𝜌𝐴 + − 𝑟𝐴 = 0
𝜕𝑡
𝜕𝑐𝐴
∴ −𝐷𝐴𝐵 ∇2 𝑐𝐴 + V ∇. 𝑐𝐴 + − 𝑅𝐴 = 0
𝜕𝑡
𝜕𝜌𝐴
∴ −𝐷𝐴𝐵 ∇2 𝜌𝐴 + v ∇. 𝜌𝐴 + =0
𝜕𝑡
𝜕𝑐𝐴
−𝐷𝐴𝐵 ∇2 𝑐𝐴 + V ∇. 𝑐𝐴 + =0
𝜕𝑡
𝜕𝜌𝐴
∴ = 𝐷𝐴𝐵 ∇2 𝜌𝐴
𝜕𝑡
6
For molar concentration:
𝜕𝑐𝐴
= 𝐷𝐴𝐵 ∇2 𝑐𝐴 (7)
𝜕𝑡
Note: what are the conditions at which there is no fluid motion? (bulk motion = 0.0)
The assumption of no fluid motion (bulk motion) restricts its applicability to:
a) Diffusion in solid
b) Stationary (stagnant) liquid
c) Equimolar counterdiffusion (for binary system of gases or liquids where 𝑁𝐴 is equal
in magnitude but acting in the opposite direction to 𝑁𝐵
𝑑𝑦𝐴
𝑁𝐴 = −𝑐𝐷𝐴𝐵 + 𝑦𝐴 (𝑁𝐴 + 𝑁𝐵 )
𝑑𝑧
If 𝑁𝐴 = −𝑁𝐵 the bulk motion term will be cancelled from the above equation
∇2 𝜌𝐴 = 0
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For mass concentration:
∇2 𝑐𝐴 = 0
Note: see page 438 in the reference book for the differential equation of mass transfer in
different coordinate systems.
The general differential equation for mass transfer of component A, or the equation of
continuity of A, written in rectangular coordinates is
To describe a mass transfer process by the differential equations of mass transfer the
initial and boundary conditions must be specified.
Initial and boundary conditions are used to determine integration constants associated
with the mathematical solution of the differential equations for mass transfer
1. Initial conditions:
It means the concentration of the diffusing species at the start (t = 0) expressed in mass or
molar units.
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Note: Initial conditions are associated only with unsteady-state or pseudo-steady-state
processes.
2. Boundary conditions:
Examples:
I. For a liquid mixture in contact with a pure solid A, (liquid-solid interface) the
concentration of species A in the liquid at the surface is the solubility limit of A in
the liquid, 𝑐𝐴𝑠
II. For a contacting gas and liquid, (gas-liquid) where transferring species A is
present in both phases, there are two ways to specify the concentration at the gas–
liquid interface.
(i) if both of the species in the liquid phase are volatile, then the boundary condition
at the gas–liquid surface is defined for an ideal liquid mixture by Raoult’s law
𝑝𝐴𝑠 = 𝑥𝐴 𝑝𝐴
𝑝𝐴𝑠
𝑐𝐴𝑠 =
𝑅𝑇
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(ii) for solutions where species A is only weakly soluble in the liquid, Henry’s law
may be used to relate the mole fraction of A in the liquid to the partial pressure of
A in the gas
𝑝𝐴 = 𝐻 ∙ 𝑥𝐴
H: Henry’s constant
(iii) at gas solid interface
𝑐𝐴𝑠𝑜𝑙𝑖𝑑 = 𝑆 ∙ 𝑝𝐴
𝑐𝐴𝑠𝑜𝑙𝑖𝑑 : is the molar concentration of A within the solid at the interface in units
of kg mol/m3 and 𝑝𝐴 is the partial pressure of gas phase species A over the
solid in units of Pa.
𝑆: solubility constant (partition coefficient)
(2) A reacting surface boundary is specified
𝑁𝐴 ⃒𝑧=0 = 𝑘𝑐 𝑐𝐴𝑛𝑠
where 𝑘𝑐 is a surface reaction rate constant with units of m/s. n is the reaction order
Note: the reaction may be so rapid that 𝑐𝐴𝑠 = 0 if species A is the limiting reagent in the
chemical reaction.
𝜕𝑐𝐴
𝑁𝐴 ⃒𝑧=0 = −𝐷𝐴𝐵 ⃒ =0
𝜕𝑧 𝑧=0
𝜕𝑐𝐴
𝑜𝑟 ⃒ =0
𝜕𝑧 𝑧=0
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Solved problems:
Problem 1:
The following sketch illustrates the gas diffusion in the neighborhood of a catalytic
surface. Hot gases of heavy hydrocarbons diffuse to the catalytic surface where they are
cracked into lighter compounds by the reaction: H → 2L, the light products diffuse back
into the gas stream.
a. Reduce the general differential equation for mass transfer to write the specific
differential equation that will describe this steady-state transfer process if the catalyst
is considered a flat surface. List all of the assumptions you have made in simplifying
the general differential equation.
b. Determine the Fick’s law relationship in terms of only compound H and insert it into
the differential equation you obtained in part (a).
c. Repeat the solution for spherical catalyst surface.
Solution
𝜕 𝜕 𝜕 𝜕𝑐𝐴
𝑁𝐴,𝑥 + 𝑁𝐴,𝑦 + 𝑁𝐴,𝑧 + − 𝑅𝐴 = 0
𝜕𝑥 𝜕𝑦 𝜕𝑧 𝜕𝑡
Apply these assumptions on the general equation we get the specific differential equation:
𝜕
𝑁𝐻,𝑧 + 𝑅𝐻 = 0
𝜕𝑧
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but 𝑁𝐿 = −2𝑁𝐻
𝑐𝐷𝐻𝐿 𝑑𝑦𝐻
𝑁𝐻 = −
(1 + 𝑦𝐻 ) 𝑑𝑧
Problem 2:
a. After drawing a picture of the physical process, select a coordinate system that
will best describe this diffusion process, list at least five reasonable assumptions
for the mass-transfer aspects of the water-evaporation process and simplify the
general differential equation for mass transfer in terms of the flux 𝑁𝐴 .
b. What is the simplified differential form of Fick’s equation for water vapor
(species A)?
Solution:
Basic assumptions:
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Apply these assumptions on the general differential equation:
𝜕𝑐𝐴
⃗𝐴 +
∇. 𝑁 − 𝑅𝐴 = 0
𝜕𝑡
⃗𝐴 = 0
∴ ∇. 𝑁
1 𝑑 2
𝑟 𝑁𝐴 = 0
𝑟 2 𝑑𝑟
b. The simplified differential form of Fick’s equation for water vapor (species A)?
𝑑𝑦𝐴
𝑁𝐴 = −𝑐𝐷𝐴𝐵 + 𝑦𝐴 (𝑁𝐴 + 𝑁𝐵 )
𝑑𝑟
𝑁𝐵 = 0
𝑐𝐷𝐴𝐵 𝑑𝑦𝐴
𝑁𝐴 = −
(1 − 𝑦𝐴 ) 𝑑𝑟
Problem 3:
A large deep lake, which initially had a uniform oxygen concentration of 1kg/m3, has its
surface concentration suddenly raised and maintained at 9 kg/m3 concentration level.
Reduce the general differential equation for mass transfer to write the specific differential
equation for
a. the transfer of oxygen into the lake without the presence of a chemical reaction;
b. the transfer of oxygen into the lake that occurs with the simultaneous
disappearance of oxygen by a first-order biological reaction.
Solution:
a. the transfer of oxygen into the lake without the presence of a chemical reaction
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𝜕𝑐𝐴
⃗𝐴 +
∇. 𝑁 − 𝑅𝐴 = 0
𝜕𝑡
Basic assumptions:
But
𝑑𝑦𝐴
𝑁𝐴 = −𝑐𝐷𝐴𝐵 + 𝑐𝐴 𝑉
𝑑𝑧
𝑑𝑦𝐴
∴ 𝑁𝐴 = −𝑐𝐷𝐴𝐵
𝑑𝑧
𝑑𝑁𝐴 𝑑 2 𝑐𝐴
= −𝐷𝐴𝐵
𝑑𝑧 𝑑𝑧 2
𝜕𝑐𝐴 𝑑 2 𝑐𝐴
= 𝐷𝐴𝐵
𝜕𝑡 𝑑𝑧 2
b. The transfer of oxygen into the lake that occurs with the simultaneous disappearance
of oxygen by a first-order biological reaction.
Basic assumptions:
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Problem 4:
A liquid flows over a thin, flat sheet of a slightly soluble solid. Over the region in which
diffusion is occurring, the liquid velocity may be assumed to be parallel to the plate and
to be given by 𝑉𝑥 = 𝑎𝑦, where y is the vertical distance from the plate and a is a constant.
Show that the equation governing the mass transfer, with certain simplifying
assumptions, is
Solution:
Basic assumptions:
𝜕 𝜕 𝜕 𝜕𝑐𝐴
𝑁𝐴,𝑥 + 𝑁𝐴,𝑦 + 𝜕𝑧 𝑁𝐴,𝑧 + + 𝑅𝐴 = 0
𝜕𝑥 𝜕𝑦 𝜕𝑡
𝜕𝑁𝐴,𝑥 𝜕𝑁𝐴,𝑦
∴ + =0 (i)
𝜕𝑥 𝜕𝑦
𝑑𝑦𝐴
𝑁𝐴,𝑥 = −𝑐𝐷𝐴𝐵 + 𝑐𝐴 𝑉𝑥
𝑑𝑥
𝑑𝑐𝐴
∴ 𝑁𝐴,𝑥 = −𝐷𝐴𝐵 + 𝑎𝑦𝑐𝐴
𝑑𝑥
𝑑𝑐𝐴
𝑁𝐴,𝑦 = −𝐷𝐴𝐵 + 𝑐𝐴 𝑉𝑦
𝑑𝑦
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But 𝑉𝑦 = 0 (based on the assumptions)
𝑑𝑐𝐴
∴ 𝑁𝐴,𝑦 = −𝐷𝐴𝐵
𝑑𝑦
𝜕 2 𝑐𝐴 𝜕𝑐𝐴 𝜕 2 𝑐𝐴
−𝐷𝐴𝐵 + ay − 𝐷𝐴𝐵 =0
𝜕𝑥 2 𝜕𝑥 𝜕𝑦 2
𝜕 2 𝑐𝐴 𝜕 2 𝑐𝐴 𝜕𝑐𝐴
∴ 𝐷𝐴𝐵 [ 2 + ] = ay
𝜕𝑥 𝜕𝑦 2 𝜕𝑥
Boundary conditions:
1. 𝑐𝐴 = 𝑐𝐴𝑠 at y = 0
2. 𝑐𝐴 = 0 at y = ∞
3. 𝑐𝐴 = 0 at x = 0
Note:
The specific differential equation of mass transfer for a given system can be obtained by
two methods:
1. Select the general equation according to the system coordinates and omit the
unnecessary terms
2. Make a mass balance over a control volume, divide by the volume and take limits
as values of length approaches zero
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Supplementary data:
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