ES 3002: Mass Transfer ASSIGNMENT 2 SOLUTIONS D Term, 2017

Assignment 2: Due Monday, March 27, 2017

Task 1: Read WRF 24 - 26

Problem 1: Rank the processes from fastest to slowest. Explain why each decision was made. Assume all
conditions are STP unless otherwise specified.

A. Diffusion of nitrogen in hydrogen

B. Diffusion of hydrogen in nitrogen
C. Diffusion of carbon in iron
D. Diffusion of 100 ppm nitrogen into hydrogen
E. Diffusion of hydrogen in iron
F. Diffusion of hydrogen in iron at T = 300 °C
G. Diffusion of nitrogen in hydrogen at P = 100 bar
H. Diffusion of hydrogen in water
I. Advection of hydrogen (100 m/s) in air

Problem 1 Solution: from fastest to slowest

I. Forced convective flow is much faster than diffusion. It will nearly always dominate if present.
D. Very dilute gas will diffuse similarly to pure gas, except fewer large molecules means fewer
molecular collisions which will allow a molecule to move greater distances faster, hence
making it faster.
B. The next fastest diffusion process is when a (pure) light gas diffuses into another (pure) gas
A. Arguably, binary diffusion coefficients of A into B and B into A are equal (i.e. 𝐷𝐴𝐵 = 𝐷𝐵𝐴 ) – so in
the equal molar counter diffusion case, F and E are tied. In the dillue case (i.e. A is dilute,
case H), it’s slightly different.
G. It’s difficult to quantify this numerically, but in general increasing pressure does increase the
diffusivity (particularly for gases).
H. Diffusion into liquids is slower (molecules are so closely packed that there are many collisions
restricting motion)
F. Diffusion increases with temperature (more molecular motion)
E. Diffusion into solids is even slower than liquids for the same reason as D.
C. Diffusion of larger molecules is generally slower than smaller molecules (confinement
effects/more collisions)
ES 3002: Mass Transfer ASSIGNMENT 2 SOLUTIONS D Term, 2017

Problem 2: Transient VLE Professor Teixeira decided to do some labwork despite the advice of his students.
Within the first five minutes, he dropped a 4 L bottle of methanol in an unventilated flammables cabinet, which
made a 100 cm2 puddle in his secondary containment. After evacuating the lab and sealing the cabinet (1 m3),
you are tasked with assessing the safety of the system. Vapor pressure of methanol at STP = 18 kPa.
a) Assume atmospheric air is 20.95% oxygen by volume. Within the cabinet, define the mole and mass
fractions of:
i. Methanol in the gas-phase.
Assume vapor pressure is approximately equal to STP vapor pressure

𝑝𝑀𝑒𝑂𝐻 = 18 𝑘𝑃𝑎

𝑝𝑀𝑒𝑂𝐻 𝑝𝑀𝑒𝑂𝐻 18
𝑦𝑀𝑒𝑂𝐻 = = = = 0.1508
𝑝 𝑝𝑀𝑒𝑂𝐻 + 𝑝0 18 + 101.325

ii. Methanol in the liquid puddle.

Assume solubility of gases in MeOH is very small

𝑥𝑀𝑒𝑂𝐻 ≅ 1

Alternative is to solve VLE directly (see iv), assuming other species in air are insoluble:

𝑥𝑂2 = 4.15 × 10−4 , 𝑥𝑀𝑒𝑂𝐻 = 1 − 𝑥𝑂2 = 0.9996 ≅ 1.0

iii. Oxygen in the gas-phase.

Assume partial pressure of O2 is same as initial state and total pressure is same as part i)

𝑝𝑂2 101.325 × 0.2095

𝑦𝑂2 = = = 0.178
𝑝 18 + 101.325

iv. Oxygen on the liquid puddle.

Assume either:
1. Pure O2 over MeOH, so concentration = solubility
Literature: 𝑥𝑂2 = 4.15 × 10−4
T. Sato et al.,“Solubility of Oxygen in Organic Solvents and Calculation of the Hansen
Solubility Parameters of Oxygen,” Ind. Eng. Chem. Res. 2014, 53, 19331−19337

2. Dilute O2 in MeOH, related by Henry’s law

Textbook: Oxygen in water (table 25.1) at STP, H = 2550 kPa
𝑝𝐴 = 𝐻 ∙ 𝑥𝐴

𝑝𝐴 101.325 × 0.2095
𝑥𝐴 = = = 0.00832 = 8.32 × 10−3
𝐻 2550
ES 3002: Mass Transfer ASSIGNMENT 2 SOLUTIONS D Term, 2017

b) From a safety perspective, this air/methanol mixture is most dangerous between the lower explosive
limit (LEL = 6.7 mol%) and upper explosive limit (UEL = 36.0 mol%). In this range, the vapor makes
an explosive mixture with air. Is Professor Teixeira’s lab an explosion risk?

Yes, it is an explosion risk! (𝑦𝑀𝑒𝑂𝐻 = 15.1%)

c) If the 10 cm2 ventilation port was left open at the top, what equations would we use to determine the
flux of methanol out of the cabinet? Qualitatively draw a partial pressure vs. time profile describing the
methanol vapor within the flammables cabinet. Label key regions (e.g., LEL, UEL, vapor pressure).

At the outlet:
𝑝 𝜕𝑦𝐴
𝑁𝐴 = −𝑐𝐷𝐴𝐵 ∇𝑦𝐴 + 𝑦𝐴 (𝑁𝐴 + 𝑁𝐵 ) = − 𝐷𝐴𝐵 + 𝑦𝐴 (𝑁𝐴 + 𝑁𝐵 )
𝑅𝑇 𝜕𝑧

𝑝 𝜕𝑦𝐴
𝑊𝐴 = 𝐴𝑣𝑒𝑛𝑡 𝑁𝐴 = (10 𝑐𝑚2 ) (− 𝐷𝐴𝐵 + 𝑦𝐴 (𝑁𝐴 + 𝑁𝐵 ))
𝑅𝑇 𝜕𝑧

(101.325 𝑘𝑃𝑎) 𝜕𝑦𝐴

𝑊𝐴 = (10 𝑐𝑚2 ) (− 𝐷𝐴𝐵 + 𝑦𝐴 (𝑁𝐴 + 𝑁𝐵 ))
(8.314 × 103 𝑐𝑚3 𝑘𝑃𝑎 𝐾 −1 𝑚𝑜𝑙 −1 )(298 𝐾) 𝜕𝑧

Evaporation Vapor being depleted

(vapor is saturated) (counter diffusion only)
NMeOH (yA = yAsat))

NMeOH

0
0 time
ES 3002: Mass Transfer ASSIGNMENT 2 SOLUTIONS D Term, 2017

Problem 3: Steady Counter Diffusion with Reaction A marathon runner is continuously consuming O2 (species
A) and producing CO2 (species B) through a uniform biological reaction within her muscles. Each species must
diffuse from/to the neighboring blood capillaries, respectively. One hour into the race, at distances of 100 μm
from the capillaries, the oxygen is completely depleted and the CO2 levels are constant (high). The capillary walls
are at a constant oxygen concentration (𝐶𝐴0 ) and buffered CO2 concentration (𝐶𝐵𝑒𝑞 ). Analyze this system:
a) Draw a schematic of the system and define all apparent modes of mass transfer and reaction. List at least
five assumptions.

R1=100 μm CA1 = 0
CB1

r Muscle NO2 Rrxn

NCO2

R0 CA0
Blood CB0 = CBeq
r=0
External convection (Diffusion + advection)

Assumptions:
- Steady state
- Radial diffusion only through muscle
- Fast convective mass transfer at boundary (in blood), (i.e. constant C at this boundary)
- Constant concentrations at R1 = 100 um
- Homogeneous reaction A --> B
- No advection in muscle (v = 0)
- Blood/muscle barrier is equilibrated in B

b) Define and simplify Fick’s law (molar) for the two species (A = CO2, B = O2).

𝜕𝐶𝐴
𝑁𝐴,𝑟 = −𝐷𝐴 ∇𝐶𝐴 = −𝐷𝐴
𝜕𝑟
𝜕𝐶𝐵
𝑁𝐵,𝑟 = −𝐷𝐵 ∇𝐶𝐵 = −𝐷𝐵
𝜕𝑟
ES 3002: Mass Transfer ASSIGNMENT 2 SOLUTIONS D Term, 2017

c) For species A, mathematically describe the simplified form of the general differential equation for mass
transfer in terms of flux of species A. Which term(s) is/are ‘constant’ over the diffusion path?

𝐷𝐶𝐴
= 𝐷𝐴 ∇2 𝐶𝐴 + 𝑅𝐴
𝐷𝑡
𝑑𝐶𝐴
+ 𝑉 ∙ ∇𝐶𝐴 = 𝐷𝐴 ∇2 𝐶𝐴 + 𝑅𝐴
𝑑𝑡
𝑑𝐶
Steady state: 𝑑𝑡𝐴 = 0
No bulk flow: 𝑉 = 0
1 𝜕 𝜕
Radial gradients only: ∇2 = ∇2𝑟 = 𝑟 𝜕𝑟 (𝑟 𝜕𝑟)

1𝜕 𝜕𝐶𝐴
0 = 𝐷𝐴 (𝑟 ) + 𝑅𝐴
𝑟 𝜕𝑟 𝜕𝑟

d) Propose two boundary conditions for species A. Is an initial condition required?

At 𝑟 = 𝑅0 𝐶𝐴 (𝑟 = 𝑅0 ) = 𝐶𝐴0
𝑑𝐶𝐴
At 𝑟 = 𝑅1 | =0 (i.e. completely consumed instantly)
𝑑𝑟 𝑟=𝑅1

Note: if blood convective flow rate is slow, convective-conductive B.C. can be used.
𝑑𝐶𝐴 𝑘
At 𝑟 = 𝑟1 | = 𝐷 𝑚 (𝐶𝐴,𝑅1 − 𝐶𝐴∞ ) (though we assume fast external convection)
𝑑𝑟 𝑟=𝑅1 𝐴𝐵

Note: we would not typically assume a reaction rate unless otherwise specified.

𝑑𝐶𝐴
No initial condition because at steady state ( = 0)
𝑑𝑡

e) Repeat parts c) and d) for species B.

1𝜕 𝜕𝐶𝐵
0 = 𝐷𝐵 (𝑟 ) + 𝑅𝐵 , 𝑅𝐵 = −𝑅𝐴
𝑟 𝜕𝑟 𝜕𝑟
At 𝑟 = 𝑟0 𝐶𝐵 (𝑟 = 𝑅0 ) = 𝐶𝐵0

𝑑𝐶𝐵
At 𝑟 = 𝑅 | =0
𝑑𝑟 𝑟=𝑅1
ES 3002: Mass Transfer ASSIGNMENT 2 SOLUTIONS D Term, 2017

Problem 4: Equilibrium and Membrane Diffusion Hydrogenations comprise a major fraction of industrially
relevant reactions; however, the atomistically efficient reductions with H2 gas are typically avoided due to the
inherent safety risks associated with a highly pressurized explosive gas. To mitigate this risk, a tube-in-tube design
(length, L = 1 m) is proposed whereby the outer tube is impermeable to gases, and the inner tube (inner radius, 𝑟0
= 1 mm; outer radius 𝑟1=2 mm) is composed of Teflon-AF, a gas-permeable polymer. Assume pure hydrogen
flows into the outer tube, and slowly flowing liquid solvent (no gas bubbles) passes through the inner tube.
a) Draw the tube-in-tube geometry. Label all given dimensions and the fluxes of species A and B. Also
define the domain for the Teflon-AF tube wall.

Domain: 𝑟0 ≤ 𝑟 ≤ 𝑟1

b) What is the interfacial area for solvation of H2 into the solvent (at 𝑟0 )? At a certain liquid flowrate, the gas
flow rate was measured as 𝐹𝐺 =0.25 sccm. Calculate the flux of hydrogen into the control volume
(𝑁𝐴 [=] 𝑚𝑜𝑙 𝑚𝑖𝑛−1 𝑚−3). Also symbolically define Fick’s law for hydrogen transporting through the
inner tube.

𝐴𝑟0 = 2𝜋𝑟0 𝐿 = 2𝜋(1.0 × 10−3 𝑚)(1 𝑚) = 6.28 × 10−3 𝑚2

̇
𝑃𝑆𝑇𝑃 𝑉𝑆𝑇𝑃 1 (1.01 𝑏𝑎𝑟)(0.25 × 10−6 𝑚3 𝑚𝑖𝑛−1 ) 1 𝑚𝑜𝑙
𝑁𝐴 = = −6 3 −1 −1 −3 2
= 0.00177
𝑅 𝑇𝑆𝑇𝑃 𝐴 (83.14 × 10 𝑏𝑎𝑟 𝑚 𝑚𝑜𝑙 𝐾 )(273 𝐾) (6.28 × 10 𝑚 ) 𝑚𝑖𝑛 𝑚2

∂𝐶𝐴
𝑁𝐴 = 𝑁𝐴,𝑟 = −𝐷𝐴
𝜕𝑟

c) Given the following data, plot the flow rate of gas versus flow rate of liquid and identify regions of: gas-
liquid equilibrium and diffusion-limited transport. Using the asymptotic value, estimate the diffusivity of
hydrogen through Teflon-AF. Assume at high flow rates the hydrogen concentration at the inner-most
wall is effectively zero.

FG [sccm] 0.25 0.55 0.68 0.88 1.11 1.3 1.51 1.59 1.63 1.65
FL [ml/min] 2.5 5 7.5 10 12.5 15 20 30 50 100
ES 3002: Mass Transfer ASSIGNMENT 2 SOLUTIONS D Term, 2017

1.8
Equilibrium
1.6
(FG/FL = const,
1.4
FL exits saturated)
1.2

FG, [sccm]
1
Non-equilibrium
0.8
(FL exits unsaturated)
0.6
0.4
0.2
0
0 20 40 60 80 100
FL, [ml/min]

̇
𝑃𝑆𝑇𝑃 𝑉𝑆𝑇𝑃 1 (1.01 𝑏𝑎𝑟)(1.7 × 10−6 𝑚3 𝑚𝑖𝑛−1 ) 1
𝑁𝐴 = =
𝑅 𝑇𝑆𝑇𝑃 2𝜋𝑅𝐿 (83.14 × 10 𝑏𝑎𝑟 𝑚 𝑚𝑜𝑙 𝐾 )(273 𝐾) 2𝜋(1.0 × 10−3 𝑚)(1 𝑚)
−6 3 −1 −1
𝑚𝑜𝑙
= 0.01204
𝑚𝑖𝑛 𝑚2

∂𝐶𝐴 𝑚𝑜𝑙
(−𝐷𝐴 ) = 0.01204
𝜕𝑟 𝑚𝑖𝑛 𝑚2
∂𝐶𝐴
𝑁𝐴 = −𝐷𝐴
𝜕𝑟
∂𝐶𝐴 𝑁𝐴
=
𝜕𝑟 −𝐷𝐴
Integrate ODE, where B.C.
𝑚𝑜𝑙
𝐶𝐴 (𝑟0 ) ≅ 0
𝑚3

𝑃 (1.01 𝑏𝑎𝑟) 𝑚𝑜𝑙

𝐶𝐴 (𝑟1 ) = 𝐶𝐴,𝑔𝑎𝑠 = = = 40.4
𝑅𝑇 (83.14 × 10−6 𝑏𝑎𝑟 𝑚3 𝑚𝑜𝑙 −1 𝐾 −1 )(298 𝐾) 𝑚3
CA,1 𝑟1
𝑁𝐴
∫ ∂𝐶𝐴 = ∫ 𝜕𝑟
CA,0 −𝐷𝐴 𝑟0
𝑁𝐴
(𝐶𝐴,1 − 𝐶𝐴 ) = (𝑟 − 𝑟0 )
−𝐷𝐴 1
(𝑟0 − 𝑟1 )
𝐷𝐴 = 𝑁𝐴
(𝐶𝐴,1 − 𝐶𝐴,2 )

𝑚𝑜𝑙 (2 × 10−3 𝑚) − (1 × 10−3 𝑚)

𝐷𝐴 = (0.01204 )
𝑚𝑖𝑛 𝑚3 (40.4 𝑚𝑜𝑙 𝑚−3 ) − (0 𝑚𝑜𝑙 𝑚−3 )

𝑚2
𝐷𝐴 = 2.98 × 7 = 4.87 × 10−5 𝑐𝑚2 /𝑠
𝑚𝑖𝑛
ES 3002: Mass Transfer ASSIGNMENT 2 SOLUTIONS D Term, 2017

d) At low liquid flow rates (2.5 ml/min), a gas flow rate of 0.25 sccm was measured at 298 K. What are the
species molar fluxes into the control volume for of hydrogen (𝑁𝐴 [=] 𝑚𝑜𝑙 𝑚𝑖𝑛−1 𝑚−3) and solvent
(𝑁𝐵 [=]𝑚𝑜𝑙 𝑚𝑖𝑛−1 𝑚−3) (hint: consider multiple directions)? If the liquid exits the system fully saturated,
𝑚𝑜𝑙 𝐴
calculate the solubility of hydrogen in the solvent (𝑆[=] 𝑚𝑜𝑙 𝐵). Assume: 𝜌𝐵 = 0.792 𝑔/𝑚𝑙, 𝑀𝑊𝐵 =
32.04 𝑔/𝑚𝑜𝑙.

From part a)
𝑚𝑜𝑙 𝑚𝑜𝑙
𝑁𝐴 𝐴𝑟0 = (0.00177 2
) (6.28 × 10−3 𝑚2 ) = 1.11 × 10−5
𝑚𝑖𝑛 𝑚 𝑚𝑖𝑛

(𝑉̇ ∙ 𝐶𝐵0 )
𝑁𝐵 = 𝑁𝐵,𝑧 =
(𝜋𝑟12 )

𝑚𝐿 𝑔 𝑚𝑜𝑙
(2.5 min) (0.792 × ) 𝑚𝑜𝑙
𝑚𝑙 32.04 𝑔
𝑁𝐵 = −3 2
= 1.97 × 104
𝜋 (1.0 × 10 𝑚) 𝑚𝑖𝑛 𝑚2

𝑚𝑜𝑙 𝑚𝑜𝑙
𝑁𝐵 𝐴𝑧 = (1.97 × 104 2
) (𝜋 (1.0 × 10−3 𝑚)2 ) = 0.0618
𝑚𝑖𝑛 𝑚 𝑚𝑖𝑛

−5 𝑚𝑜𝑙
𝑁𝐴 𝐴𝑟 1.11 × 10 𝑚𝑖𝑛 𝑚𝑜𝑙 𝐴
𝑆= = = 1.80 × 10−4
𝑁𝐵 𝐴𝑧 𝑚𝑜𝑙 𝑚𝑜𝑙 𝐵
0.0618 𝑚𝑖𝑛

e) Obtain a more accurate solubility measurement by using all the data in the equilibrium regime.

1E+2
Method 1: Average of 6 solubility measurements
y = 146.69x + 3.6489 6
1E+2
1 𝑁𝐴 (𝑖)
𝑆𝑎𝑣𝑔 = ∑
6 𝑁𝐵 (𝑖)
𝑖=1
8E+1 1
FG, [umol/min]

= (1.80 + 1.98 + 1.63 + 1.58 + 1.60

6
6E+1 𝑚𝑜𝑙 𝐴
+ 1.56) × 10−4 = 1.69 × 10−4
𝑚𝑜𝑙 𝐵
4E+1
Method 2: Slope of FG vs FL
𝜇𝑚𝑜𝑙 𝐴 𝑚𝑜𝑙 𝐴
2E+1 𝑆𝑠𝑙𝑜𝑝𝑒 = 146.7 = 1.47 × 10−4
𝑚𝑜𝑙 𝐵 𝑚𝑜𝑙 𝐵
0E+0
0 1 FL, [mol/min] 2 3