Mass Transfer

ChE 364

Chapter Three

Differential Equations of Mass Transfer

Dr. Mohammed H. Al-Saleh Department of Chemical Engineering

 Introduction
2

o In the previous chapter, we dealt with:

• Systems at steady-state (no change of concentration, pressure,
etc with time)
• Lumped-systems (change of amount, concentration, pressure,
etc. as function of time only)

o Typically, in all chemical processes a dynamic (unsteady-state)

period takes place before we reach the st.st conditions.

o In heat transfer course, an unsteady-state equation was

derived:
𝜕𝑇 𝜕2𝑇
=𝛼 2
𝜕𝑡 𝜕𝑥

o For mass transfer similar equation can be derived

 Equation of Continuity for a Binary Mixture
3

o In this section we will derive general equation for a binary

mixture of A and B for diffusion and convection including
unsteady state diffusion and chemical reaction nAzz+z
• Consider the element xyx fixed in space z
y
• Mass balance for component A: nAxx nAxx+x
y z
𝑨𝒊𝒏 − 𝑨𝒐𝒖𝒕 + 𝑨𝒈𝒆𝒏𝒆𝒓𝒂𝒕𝒆𝒅 = 𝑨𝒂𝒄𝒄𝒖𝒎𝒖𝒍𝒂𝒕𝒆𝒅
x
𝑛𝐴𝑥 Δ𝑦Δ𝑧 ቚ + 𝑛𝐴𝑦 𝛥𝑥𝛥𝑧 ቚ + 𝑛𝐴𝑧 𝛥𝑦𝛥𝑥 ቚ x
𝑥 𝑦 𝑧
nAzz
− 𝑛𝐴𝑥 𝛥𝑦𝛥𝑧 ቚ + 𝑛𝐴𝑦 𝛥𝑥𝛥𝑧 ቚ + 𝑛𝐴𝑧 𝛥𝑦𝛥𝑥 ቚ
𝑥+Δ𝑥 𝑦+𝛥𝑦 𝑧+𝛥𝑧
𝜕
+𝑟𝐴 Δ𝑥𝛥𝑦𝛥𝑧 = (𝜌𝐴 𝛥𝑥𝛥𝑦𝛥𝑧)
𝜕𝑡

• Divide by xyz and let x,y and z approach zero:

𝑛𝐴𝑥 ȁ𝑥 − 𝑛𝐴𝑥 ȁ𝑥+Δ𝑥 𝑛𝐴𝑦 ȁ𝑦 − 𝑛𝐴𝑦 ȁ𝑦+𝛥𝑦 𝑛𝐴𝑧 ȁ𝑧 − 𝑛𝐴𝑧 ȁ𝑧+𝛥𝑧 𝜕𝜌𝐴
+ + + 𝑟𝐴 =
Δ𝑥 Δ𝑦 Δ𝑧 𝜕𝑡
𝜕𝜌𝐴 𝜕𝑛𝐴𝑥 𝜕𝑛𝐴𝑦 𝜕𝑛𝐴𝑧
+( + + ) = 𝑟𝐴
𝜕𝑡 𝜕𝑥 𝜕𝑦 𝜕𝑧
• In vector notation:
𝜕𝜌𝐴 𝜕𝑛𝐴𝑥 𝜕𝑛𝐴𝑦 𝜕𝑛𝐴𝑧
+ 𝛻. 𝑛𝐴 = 𝑟𝐴 𝛻. 𝑛𝐴 = + +
𝜕𝑡 𝜕𝑥 𝜕𝑦 𝜕𝑧
• Dividing both sides by MA:
𝜕𝑐𝐴
+ 𝛻. 𝑁𝐴 = 𝑅𝐴 RA: kgmol A/s.m3
𝜕𝑡
𝜕𝑥𝐴
• Substituting NA and Fick’s law from: 𝑁𝐴𝑗 = −𝑐𝐷𝐴𝐵 + 𝑐𝐴 𝑣𝑚
𝜕𝑗
𝑗 = 𝑥, 𝑦 𝑜𝑟 𝑧
𝜕𝑐𝐴
+ 𝛻. 𝑐𝐴 𝑣𝑚 − 𝛻. 𝑐𝐷𝐴𝐵 𝛻𝑥𝐴 = 𝑅𝐴
𝜕𝑡
 If c and DAB are constants

𝜕𝑐𝐴 𝛻𝑐𝐴
+ 𝑐𝐴 𝛻. 𝑣𝑚 + (𝑣𝑚 𝛻𝑐𝐴 ) − 𝐷𝐴𝐵 𝛻 2 𝑐𝐴 = 𝑅𝐴 𝛻𝑥𝐴 =
𝑐
𝜕𝑡
𝜕 2𝑐 𝜕 2𝑐 𝜕 2𝑐
𝐴 𝐴 𝐴
o The Laplacian of the scalar cA is: 𝛻 2 𝑐𝐴 = + +
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2
𝜕𝑐𝐴 𝜕𝑐𝐴 𝜕𝑐𝐴
o The gradient of the scalar cA is: 𝛻𝑐𝐴 = 𝑖 +𝑗 +𝑘
𝜕𝑥 𝜕𝑦 𝜕𝑧
𝜕𝑣𝑚𝑥 𝜕𝑣𝑚𝑦 𝜕𝑣𝑚𝑧
o The divergence of the vector vm is: 𝛻. 𝑣𝑚 = + +
𝜕𝑥 𝜕𝑦 𝜕𝑧

If 𝒗𝒎 =0 & No Chemical Reaction

𝜕𝑐𝐴 𝑣𝑚 = 0 for:
= 𝐷𝐴𝐵 𝛻 2 𝑐𝐴 • Equimolar counter diffusion
𝜕𝑡 • Mass transfer in solids
• Dilute system
 Boundary Conditions
o When a fluid is outside the solid, convective mass transfer is
occurring at the surface.

o Convective mass-transfer coefficient (kc) is similar to convective

heat transfer (h), and is defined as follows:

𝑁𝐴 = 𝑘𝑐 (𝑐𝐿1 − 𝑐𝐿𝑖 )

▪ kc = mass transfer coefficient, in m/s Solid

▪ cL1= bulk fluid concentration, in kg
mol A/m3
▪ cLi= fluid concentration just adjacent
to the surface, in kg mol A/m3

o The conc. of the solute in the fluid adjacent to the surface(cLi)is

related to its concentration in the solid(ci) by the following
equilibrium equation:
𝑐𝐿𝑖
o K is called the distribution coefficient 𝐾=
6 𝑐𝑖
7
 Case Study: Unsteady diffusion in a solid
o Develop a model for the diffusion of component A in an infinite
flat plate under the following conditions:
• The initial concentration in the solid is co
• The concentration at the interfaces is always c1
• Negligible surface resistance
c0 @ t =0
• Constant diffusion coefficient c at t > 0
(t = t)
• Constant overall concentration
c1 c1
• No chemical reaction in the solid
• Consider a plate of thickness 2x1
𝜕𝑐𝐴
+ 𝛻. 𝑐𝐴 𝑣𝑚 − 𝛻. 𝑐𝐷𝐴𝐵 𝛻𝑥𝐴 = 𝑅𝐴
𝜕𝑡
𝜕𝑐𝐴
− 𝛻 2 𝑐𝐴 = 0
𝜕𝑡 x
0 x1 2x1
𝜕𝑐𝐴 𝜕 2 𝑐𝐴 𝜕 2 𝑐𝐴 𝜕 2 𝑐𝐴 The thickness of the slab
= 𝐷𝐴𝐵 2
+ 2
+
10 𝜕𝑡 𝜕𝑥 𝜕𝑦 𝜕𝑧 2 is very small compared
to its length and width
 𝜕𝑐𝐴 𝜕 2 𝑐𝐴 To solve the equation we need:
= 𝐷𝐴𝐵 • 2 boundary conditions
𝜕𝑡 𝜕𝑥 2 • One Initial condition
𝑐1 − 𝑐𝑜
t=0 & x=x c = c0 𝑌= =1
Define 𝑐1 − 𝑐𝑜
𝑐1 − 𝑐 𝑐1 − 𝑐1
t=t & x=0 c = c1 𝑌= 𝑌= =0
𝑐1 − 𝑐𝑜 𝑐1 − 𝑐𝑜
𝑐1 − 𝑐1
t = t & x = 2x1 c = c1 𝑌= =0
𝑐1 − 𝑐𝑜
𝜕𝑌 𝜕2𝑌
= 𝐷𝐴𝐵 2
𝜕𝑡 𝜕𝑥
𝑛 = 1,3,5 …
∞
4 1 𝑛𝜋𝑥 − 𝑛𝜋 2
𝑌 = ෍ sin 𝑒 2 𝑋 𝐷𝑡
𝜋 𝑛 2𝑥1 𝑋= 2
𝑛=1 𝑥1

4 1 𝜋𝑥 𝜋2 1 3𝜋𝑥 − 32 𝜋 2
− 4 𝑋 4 𝑋
𝑌= sin 𝑒 + sin 𝑒 +⋯
𝜋 1 2𝑥1 3 2𝑥1
11
 Diffusion and Homogeneous Reaction in a Phase
o Consider component A undergoes an irreversible chemical
reaction in the homogeneous phase B while diffusing, as
follows: A → C.
o Assuming A is very dilute in phase
B, which can be a gas or a liquid,
thus at steady state the bulk term
is dropped (no movement):

𝜕𝑐𝐴 𝜕𝑁𝐴𝑥 𝜕𝑁𝐴𝑦 𝜕𝑁𝐴𝑧

+( + + ) = 𝑅𝐴
𝜕𝑡 𝜕𝑥 𝜕𝑦 𝜕𝑧

𝜕𝑐𝐴 𝑑 𝑑𝑐𝐴
𝑁𝐴𝑧 = −𝐷𝐴𝐵 + 𝑐𝐴 𝑣𝑚 −𝐷𝐴𝐵 = 𝑅𝐴
𝜕𝑧 𝑑𝑧 𝑑𝑧
o For first order reaction (𝑹𝑨 = −𝒌′𝒄𝑨) and constant DAB:
𝑑 2 𝑐𝐴 𝑘′ The boundary cA = cAo @ z = 0
2
− 𝑐𝐴 = 0
𝑑𝑧 𝐷𝐴𝐵 conditions: cA = 0.0 @ z = 𝜹:
 𝑘′ 𝑘′
𝑐𝐴 = 𝐴𝑐𝑜𝑠ℎ 𝑧 + 𝐵𝑠𝑖𝑛ℎ 𝑧
𝐷𝐴𝐵 𝐷𝐴𝐵

o Apply the boundary conditions to find

𝑧 = 0 → 𝑐𝐴 = 𝑐𝐴𝑜 ∴ 𝑐𝐴𝑜 = 𝐴𝑐𝑜𝑠ℎ 0 + 𝐵𝑠𝑖𝑛ℎ 0
→ 𝐴 = 𝑐𝐴𝑜

𝑧 = 𝛿 → 𝑐𝐴 = 0 ∴ 0 = 𝑐𝐴𝑜 𝑐𝑜𝑠ℎ 𝑘 ′ /𝐷𝐴𝐵 𝛿 + 𝐵𝑠𝑖𝑛ℎ 𝑘 ′ /𝐷𝐴𝐵 𝛿

→ B = −cAo /tanh 𝑘 ′ /𝐷𝐴𝐵 𝛿

𝑘′ 𝑘′
𝑐𝐴 = 𝑐𝐴𝑜 𝑐𝑜𝑠ℎ 𝑧 − cAo 𝑠𝑖𝑛ℎ 𝑧 /tanh 𝑘 ′ /𝐷𝐴𝐵 𝛿
𝐷𝐴𝐵 𝐷𝐴𝐵
• Diffusion Flux
𝑑𝑐𝐴 𝐷𝐴𝐵 𝑐𝐴𝑜 𝑘 ′ /𝐷𝐴𝐵 𝛿
𝑁𝐴 ቚ = −𝐷𝐴𝐵 ቚ =
𝑧=0 𝑑𝑧 𝑧=0 𝛿 tanh 𝑘 ′ /𝐷𝐴𝐵 𝛿

• If there is no chemical reaction, the flux equation would be:

𝑑𝑐𝐴 𝑐𝐴𝑜
𝑁𝐴 ቚ = −𝐷𝐴𝐵 ቚ = 𝐷𝐴𝐵
𝑧=0 𝑑𝑧 𝑧=0 𝛿

• Hatta Number
Shows the effect
𝑘 ′ /𝐷𝐴𝐵 𝛿 of reaction on
𝐻𝑎 = absorption
tanh 𝑘 ′ /𝐷𝐴𝐵 𝛿

• As the 𝒌′ increases 𝐭𝐚𝐧𝐡 𝒌′ /𝑫𝑨𝑩 𝜹 → 𝟏. 𝟎

𝐷𝐴𝐵 𝑐𝐴𝑜 𝑘 ′ /𝐷𝐴𝐵 𝛿

𝑁𝐴 ቚ = = 𝐷𝐴𝐵 𝑘 ′ 𝑐𝐴𝑜
𝑧=0 𝛿 1.0
 2.5

𝑐𝐴𝑜 = 2 𝑚𝑜𝑙/𝑚3

𝑘′ = 0
1.5
𝑘′ ↑
𝑚𝑜𝑙
𝑚3

1
𝑐𝐴

0.5

0
0 0.2 0.4 0.6 0.8 1
15 𝑧 (𝑐𝑚)
 Unsteady Diffusion for Various Geometries
16

o In Geankoplis, charts for unsteady

HT can be used to find
concentrations in unsteady MT
after relating the HT parameters to
those for MT [Table 7.1-1 shows the
relations]
 Semi infinite solid (Fig 5.3-3)
 Flat plate (Fig 5.3-5/6)
 Long cylinder (Fig 5.3-7/8)
 Sphere (Fig 5.3-9/10)

o In Welty, use Appendix F.

 Example
A solid slab of 5.0 wt% agar gel at 278 K is 20 mm thick and contains
a uniform concentration of urea of 0.1 mol/m3. Diffusion is only in
the x-direction through two parallel flat surfaces 20 mm apart. The
slab is suddenly immersed in pure turbulent water, so the surface
resistance can be assumed to be negligible; that is, the convective
coefficient kc is very large. The diffusivity of urea in the agar is 4.72
× 10-10 m2/s. The distribution coefficient for this system is 1.0 (K=1.0)
1) Calculate the concentration at the midpoint of the slab
and 2.0 mm from the surface after 30 h.
2) If the thickness of the slab is halved, what would be the
midpoint concentration in 30 h?

17
 0.12

0.1
t= 0

0.08 t=1 hr

t=3 hr
c (mol/m3)

0.06 t=7 hr

t=10 hr
0.04
t= 30 hr

t=50 hr
0.02
t=100 hr

0
0 2 4 6 8 10 12 14 16 18 20
18
x