Solved problems on Mass Transfer

1. With reaction
Consider the reaction 2A → A2 in a catalytic reactor. The reaction is not instantaneous but the rate
at which A disappears at the catalytic surface is proportional to the concentration of A at that
surface. Find the molar flux of A. NAZ = k1" cA = ck1" xA where k1" is a rate constant.

Solution:
It is clear from the figure that A has to diffuse through the gas film which surrounds each catalyst
particle

before it reaches the catalyst surface. For every two moles of A moving in the positive Z-direction,
there is one mole of A2 moving in the negative
Z-direction.
Therefore, at steady state
N(A)2Z = – (1 / 2) NAZ
For two component system, it is given that
NAZ = – cDAB {(∂XA) / ∂Z} + xA (NAZ + NBZ)
Substitute
NBZ = N(A)2Z = – (1 / 2) NAZ
Then,
NAZ = – cDA(A)2 {(dXA) / dZ} + xA(NAZ – (1 / 2) NAZ)
NAZ – (1 / 2)NAZxA = – cDA(A)2 {dXA / dZ}
 NAZ(1 – (1 / 2) xA) = – cDA(A)2 {dXA / dZ}
NAZ = [{– cDA(A)2} / {1 – (1 / 2)xA}]{dXA / dZ}
By performing a mass balance on species A over a thin slab of the
gas film of thickness ∆Z,
{(dNAZ) / dZ} = 0
But
NAZ = [{– cDA(A)2} / {1 – (1 / 2)xA}] {(dXA) / dZ}
Therefore
(d / dZ) [{(– cDA(A)2) / (1 – (1 / 2)xA)} {dXA / dZ}] = 0
(d / dZ) [{1 / (1 – (1 / 2)xA)} (dXA / dZ)] = 0
Integrating once
[1 / {1 – (1 / 2)xA}](dxA / dZ) = c1
Integrating again
– 2In(1– (1 / 2)xA) = c1z + c2
The integration constants are evaluated by using the boundary conditions.
B.C. (1) At Z = 0, xA = x(A)0
B.C (2) At Z = δ, xA = {(NAZ) / (cK1")}
Substituting the first boundary condition
– 2 In(1 – (1 / 2)x(A)0) = c2
Substituting the second boundary condition
– 2 In [1 – (1 / 2) {(NAZ) / (cK1")}] = c1δ + c2
But
c2 = – 2 In (1 – (1 / 2) x(A)0)
Hence
– 2 In[1 – (1 / 2) {(NAZ) / (cK1")}] = c1δ – 2 In(1 – (1 / 2)x(A)0)
c1δ = – 2 [In {1 –– (1 / 2) {(NAZ) / (cK1")}}] + 2 In (1 – (1 / 2)x(A)0)
c1 = (– 2 / δ)[In [(1 – (1 / 2) {(NAZ) / (cK1")}) / (1 – (1 / 2) x(A)0)]]
Substitute the values of c1 and c2 in
– 2ln (1 – (1 / 2) xA) = c1z + c2
– 2 In (1 – (1 / 2) xA) = (– 2 / δ) [In {(1 – (1 / 2){(NAZ) / (cK1")})
/ (1 – (1 / 2)x(A)0)}] Z – 2In(1 – (1 / 2)x(A)0)
In (1 – (1 / 2) xA) = In [{1 – (1 / 2){(NAZ) / (cK1")} / {1 – (1 / 2)x(A)0}]z/δ
+ In (1 – (1 / 2) x(A)0)
 In (1 – (1 / 2) xA) = In [{1 – (1 / 2){(NAZ) / (cK1")} / {1 – (1 / 2)x(A)0}] ∙
(1 – (1 / 2) x(A)0)
(1 – (1 / 2)xA) = [{1 – (1 / 2){(NAZ) / (cK1")} / {1 – (1 / 2)x(A)0)}] ∙
(1 – (1 / 2)x(A)0)
(1 – (1 / 2) xA) = [1 – (1 / 2){(NAZ) / (cK1")}]z/δ (1 – (1 / 2) x(A)0)1–z/δ
which is also equal to
In(1 – (1 / 2)xA) = (z / δ) In [1 – {(NAZ) / (cK1")}] + (1 – z/δ)
In (1 – (1 / 2) x(A)0)
Differentiating on both sides to find (dxA / dz)
[1 / {1 – (1 / 2) xA}] – (1 / 2) dxA
= [(1 / δ) In [1 – (1 / 2) {(N AZ) / (cK1")}] – (1 / δ) In (1 – (1 / 2) x(A)0)]dz
[1 / {1 – (1 / 2)xA}] – (δ / 2) {dxA / dz}
= In [{– (1 / 2) {(NAZ) / (cK1")}} / {1 – (1 / 2) xA0}]
(dx / dz)
= [{– 2(1 – (1 / 2) xA)} / δ] In [{1 – (1 / 2){(NAZ) / (cK1")}} / {1 – (1 / 2) x(A)0}]
But
NAZ = [{– c DA(A)2} / {1 – (1 / 2)xA}] {dxA / dz}
Substituting the value of (dxA / dz)
NAZ = [{– c DA(A)2} / {1 – (1 / 2) xA}] [{– 2 (1 – (1 / 2) xA)} / δ] In [{1 – (1 / 2){(NAZ) / (cK1")}} / {1 – (1 / 2)
x(A)0}]
NAZ = {(2c DA(A)2) / δ} In [{1 – (1 / 2){(NAZ) / (cK1")} / {1 – (1 / 2) x(A)0}]

2. With reaction
Carbon dioxide undergoes the following irreversible reaction with sodium carbonate
CO2 + Na2CO3 + H2O →(k)1 2NaHCO3
As shown in the figure, CO2 dissolves in a solution of sodium carbonate in water and diffuses into
the bulk phase. As it diffuses, it undergoes the above irreversible reaction. Develop an expression
for the concentration profile of CO2 in the liquid phase and its average concentration.
Solution: The material balance over an infinitesimal cross-section of
thickness Δz, gives
N(CO)2|z s – N(CO)2|z+Δz s – k1c(CO)2sΔz = 0
Dividing throughout by sΔz, we get
{(N(CO)2|z – N(CO)2|z+Δz) / Δz} – k1c(CO)2 = 0
Taking the limit as Δz → 0 yields,
{(dN(CO)2) / dz} + k1c(CO)2 = 0
Assuming CO2 and NaHCO3 concentrations are small,
N(CO)2 = – D {(dc(CO)2) / dz}
– D {(d2c(CO)2) / (dz2)} + k1c(CO)2 = 0
Solving this differential equation with the boundary conditions
at z = 0 c(CO)2 = c(CO)2*
at z = L N(CO)2 = 0
where c(CO)2* is the solubility of CO2 in water, we get
{(c(CO)2) / (c(CO)2*)} = [{cosh[√(k1L2/D){1 – (z/L)}]} / {cosh √(k1L2/D}]
The average concentration of CO2 = c(CO)2aV
= [{L∫0 (c(CO)2 / c(CO)2*)dz} / {L∫0 dz}]
= [{L∫0 (cosh [√(k1L2/D) (1 – z/L)] / cosh √(k1L2/D))dz} / {L∫0 dz}]
= [1 / {√(k1L2/D)}] tanh √(k1L2/D)

3. With reaction
Gas A diffuses into a catalyst pellet through its pores and is converted to B through chemical
reaction on the catalyst surface. Develop an expression for the concentration profile for species A
within the catalyst pellet.

Solution: Let cAs be the concentration of A at the catalyst surface.

Making a mass balance on a spherical shell of thickness Δr, gives:

(d / dr) (r2NAr) = r2RA
where RA is the rate of reaction in lb moles/ft3. But NAr = – DA {(dcA) / (dr)}
where DA is the effective diffusivity of A in the porous catalyst medium.
therefore – DA (d / dr) [r2 {(dcA) / (dr)}] = r2RA
But RA = – k1'acA where k1' is the reaction rate constant and a is surface
area per unit pellet volume.
therefore {(– DA) / (r2)} [r2 {(d2cA) / (dr2)} + 2r {(dcA) / (dr)} = – k1'acA
or
{(d2cA) / (dr2)} + (2/r) {(dcA) / (dr)} = {(+k1'acA) / DA}
The general solution for the above equation is
{(cA) / (cAs)} = (c1 / r) cosh [√{(k1'a) / DA}]r + (c2 / r) sinh [√{(k1'a) / DA}]r
The boundary conditions are
at r = 0, {(dcA) / (dr)} = 0
r = R, cA = cAs
Using the above boundary conditions yields the concentration profile as
{cA / (cAs)} = (R/r) [{sinh(r√{k1'a/DA})} / {sinh(R√{k1'a/DA})}]
PROBLEM 16 – 0358: What are the compositions of the gas and liquid phases
existing under equilibrium? Assume ideality in both phases,
i.e., Raoult's law and Dalton's law are valid.

Solution: Let gas be denoted by A and liquid by B.

The Raoult's law states that the partial pressure p of a solute gas A equals
the product of its vapor pressure p at the same temperature and its mole
fraction in the solution x.
Therefore
pA = xApA
pB = xBpB
According to Dalton's law, the sum of partial pressures is equal to the total
pressure.
Then, p = pA + pB
= xApA + xBpB
= (1 – xB)pA + xBpB
Solving for xB, gives
xB = [(p – pA) / (pB – pA)]
This implies that the liquid composition is a linear function of only total
pressure, because for a constant temperature the vapor pressures
pA and pB are fixed. The total pressure varies from p = pA at xB = 0 to
p = pB at xB = 1.
The vapor composition is given by
pB = yBp = xBpB
Then,
yB = xBpB / p
Substituting for xB gives
yB = (pB / p) [(p – pA) / (pB – pA)]
The composition of gas is given as
 4. To find out the mass transfer coefficient and rate.
Consider an air stream flowing over a solid naphthalene plate with a velocity of 16 ft/sec at points
far away from the surface of the plate. The air stream pressure is 1 atm and the temperature of the
system is 115°F. Determine:
(a) the average coefficient of mass transfer over first 1.5 ft from leading edge.
(b) the average mass transfer rate per unit width over first 1.5 ft from leading edge of the plate.
(c) the local coefficient of mass transfer at 1.5 ft from leading edge of the plate.
(d) the local concentration gradient of naphthalene at the surface at 1.5 ft from the leading edge.
(e) the local thicknesses of the momentum and concentration boundary layers at 1.5 ft from the
leading edge of the plate.

Solution: The vapor pressure of naphthalene as a function of temperature

are given by
log PA = 12.198 – (6881 / T) (1)
where PA in lbf/ft2 and T in °R
and log PA+ = 11.84528 – (3857 / T) (2)
where PA+ in mm Hg and T in °K.
For the vapor pressure of naphthalene the approximate temperature taken
is 115°F.
(a) From air tables, for air at 115°F and 1 atm.
ρ = [{14.7 (144) 29} / {1545 (575)}]
= 0.0691 lbm/ft3
μ = 0.0194 cp
= 0.0469 lb/ft–hr
DAB = 0.2727 ft2/hr
The Reynolds number is given by
Re = [(ρVL) / μ]
at L = 1.5 ft
Re = [{(0.0691) (16) (3600) (1.5)} / (0.0469)]
= 127297.22
This implies the flow in the boundary layer is laminar. The Schmidt
number is given by
Sc = [μ / (ρDAB)]
 = [(0.0469) / {(0.0691) (0.2727)}]
= 2.489
The average mass transfer coefficient is given by
kρm = 0.646 [(DAB) / L] (Re)(1/2) (Sc)(1/3) (3)
Substituting the known quantities gives
kρm = 0.646 [(0.2727) / (1.5)] (127297.22)(1/2) (2.489)(1/3)
= 56.8 ft/hr
Therefore the average coefficient of mass transfer over first 1.5 ft from
leading edge is 56.8 ft/hr.
(b) ρA∞ = 0, since the gas stream is of pure air. Then ρA0 is calculated from
the ideal gas law using the saturation vapor pressure of naphthalene
at 115°F.
From eq. (1)
log PA = 12.198 – [(6881) / (575)]
= 0.2310
PA = 1.702 lbf/ft2
ρA0 = [(PAM) / RT]
= [{1.702 (128.16)} / {1545 (575)}]
= 0.000246 lbm/ft3
The mass transfer rate is given by
qAW = kρm (1.5 × 1) (ρA0 – ρA∞) (4)
qAW = 56.8 (1.5 × 1) (0.000246 – 0)
= 0.0210 lbm/hr
(c) For local mass transfer coefficient
(Sh)x = [(kρx) / (DAB)] = 0.323 Re(1/2) Sc(1/3) (5)
and for a mean mass transfer coefficient
(Sh)m = [(kρmL) / (DAB)] = 0.646 Re(1/2) Sc(1/3) (6)
For a given x, dividing eq. (6) by eq. (5) gives
[(kρm) / kρ] = 2
Therefore
kρ = [(kρm) / 2]
= [(56.8) / 2]
= 28.4 ft/hr
 Hence the local coefficient of mass transfer at 1.5 ft from leading edge of
the plate is 28.4 ft/hr.
(d) The local concentration gradient of naphthalene at the surface is given
by
[(∂ρA) / ∂y]y=0 = [{kρ (ρA0 – ρA∞)} / (DAB)] (7)
Substituting the known quantities in eq. (7) gives
[(∂ρA) / ∂y]y=0 = [{28.4 (0 – 0.000246)} / (0.2727)]
= – 0.02562 lb/ft4
(e) the local thicknesses of the momentum and concentration boundary
layer at 1.5 ft are
δ = [(4.64 L) / {Re(1/2)}]
= [{4.64 (1.5)} / {(127297.22)(1/2)}]
= 0.01951 ft
δc = 0.0162 [μ / (ρDAB)]–(1/3)
= 0.0162 [(0.0469) / {(0.0691) (0.2727)}]–(1/3)
= 0.01195 ft.

5. With reaction

Gas A diffuses through a stagnant film of gas surrounding a catalyst particle. A undergoes the
following reaction 3A → B at the particle surface, instantaneously, B diffuses back through the
stagnant film into the bulk. Assuming isothermal conditions, obtain an expression for the local
reaction rate in terms of the effective gas-film thickness and the bulk gas stream compositions,
xAO and xBO.
Solution:
It can be seen from the following reaction that for every 1 mole of B diffusing back, there are 3
moles of A diffusing into the film towards the catalytic surface.
NB = – (NA /3)
Since NA = – cDAB [(∂xA) / ∂r] + xA (NA + NB)
NA = – cDAB [(∂xA) / ∂r] + (2/ 3) xA NA
or NA = – [(cDAB) / {1 – (2/3) xA}] [(∂xA) / ∂r]
A shell balance yields (d / dr) (r2NA) = 0
or r2 N A = C 1
or [(cDAB) / {1 – (2/3) xA}] r2 [(∂xA) / ∂r] = C1
or [(dxA) / {1 – (2/3) xA}] = [C 1 / (cDAB)] (dr / r2)
Integrating – (3/2) [ln (1 – (2/3) xA)] = – [C1 / (cDAB)] (1/r) + C2
Boundary conditions:
at r = R 1, xA = 0
r = R2 = R1 + δ, xA = xAO where δ → thickness of gas film
∴ – (3/2) (ln (1)) = – [C1 / (cDAB)] (1 / R2) + C2
– (3/2) [ln (1 – (2/3) xAO] = – [C1 / (cDAB)] (1 / R2) + C2
∴ [C1 / (cDAB)] [(1 / R2) – (1 / R1)] = (3 / 2) [ln [{1 – (2 / 3) xAO} / 1]]
where by C1 can be evaluated.
The local reaction rate = the rate of diffusion at the catalyst surface
 = – cDAB [(∂xA) / ∂r] |r=(R)1
= – cDAB [C1 / (cDAB)] [{1 – (2/3) xA} / r2] |r=(R)1
= – cDAB [C1 / (cDAB)] [1 / (R12)]
= – cDAB (3/2) [{ln (1 – (2/3) xAO)} / (R12)] [(R2R1) / (R1 – R2)]
= + cDAB (3/2) [{ln (1 – (2/3) xAO) R2} / {R1 (R1 – R2)}]
= (3/2) cD AB (R2 / R1) [{ln (1 – (2/3) xAO)} / (R1 – R2)]

6. With evaporation
A cylindrical vessel of diameter 7.0 ft is filled to 2.5 ft below the open top with pure n-butanol.
Inside the tank, the air is stationary, but currents above it maintain a small enough concentration of
n-butanol there to allow it to be neglected. The system is at 77.0°C and 1 atm. The diffusivity of n-
butanol in air at these conditions is 0.438 ft2 / hr. Determine the rate of evaporization of n-
butanol from the vessel at steady state conditions.

Solution:
Equation (1) describes this situation, where the subscript A refers to the n-butanol and subscript b
will refer to the air. Integration of equation (1) provides equation (2), which can be solved for the
evaporation rate,
NA. Equation (1) states:
(NA / A) = – [Dp / (RTpbz)] [(dpA) / dx] (1)
where A = [(πD2) / 4] = [{π (7)2} / 4] = 38.5 ft2
and p b = P – pA
Therefore, equation (1) can be rewritten as:
[NA / (38.5)] = – [DP / (RTz)] (p)A2∫(p)A1 [(dpA) / (P – pA)]
Integration yields:
[NA / (38.5)] = [DP / (RTz)] ln [(P – pA2) / (P – pA1)] (2)
where:
pA1 = vapor Pressure of n-butanol at 77.0°C
= 144 mm Hg
pA2 = 0.0 atm
R = 0.7302 ft3–atm / lb mole–R
z = 2.5 ft
T = 630 R
Substituting in equation (2):
NA = [{(38.5) (0.438) (1)} / {(0.7302) (630) (2.5)}]
ln [(760 – 0) / (760 – 144)]
= 3.08 × 10–3 lb moles/hr