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Chemical Engineering. Solutions to the Problems in Chemical Engineering

Richardson J.F., Backhurst J.R., Harker J.H.

Chapter 10

Mass Transfer - all with Video Answers

Educators


Chapter Questions

01:03

Problem 1

Ammonia gas is diffusing at a constant rate through a layer of stagnant air 1 mm thick. Conditions are fixed so that the gas contains $50 \%$ by volume of ammonia at one boundary of the stagnant layer. The ammonia diffusing to the other boundary is quickly absorbed and the concentration is negligible at that plane. The temperature is 295 K and the pressure atmospheric, and under these conditions the diffusivity of ammonia in air is $0.18 \mathrm{~cm}^2 / \mathrm{s}$. Calculate the rate of diffusion of ammonia through the layer.

Narayan Hari
Narayan Hari
Numerade Educator
10:21

Problem 2

A simple rectifying column consists of a tube arranged vertically and supplied at the bottom with a mixture of benzene and toluene as vapour. At the top, a condenser returns some of the product as a reflux which flows in a thin film down the inner wall of the tube. The tube is insulated and heat losses can be neglected. At one point in the column, the vapour contains $70 \mathrm{~mol} \%$ benzene and the adjacent liquid reflux contains $59 \mathrm{~mol} \%$ benzene. The temperature at this point is 365 K . Assuming the diffusional resistance to vapour transfer to be equivalent to the diffusional resistance of a stagnant vapour layer 0.2 mm thick, calculate the rate of interchange of benzene and toluene between vapour and liquid. The molar latent heats of the two materials can be taken as equal. The vapour pressure of toluene at 365 K is $54.0 \mathrm{kN} / \mathrm{m}^2$ and the diffusivity of the vapours is $0.051 \mathrm{~cm}^2 / \mathrm{s}$

Chareen Guzman
Chareen Guzman
Numerade Educator

Problem 3

By what percentage would the rate of absorption be increased or decreased by increasing the total pressure from 100 to $200 \mathrm{kN} / \mathrm{m}^2$ in the following cases?
(a) The absorption of ammonia from a mixture of ammonia and air containing $10 \%$ of ammonia by volume, using pure water as solvent. Assume that all the resistance to mass transfer lies within the gas phase.
(b) The same conditions as (a) but the absorbing solution exerts a partial vapour pressure of ammonia of $5 \mathrm{kN} / \mathrm{m}^2$.

The diffusivity can be assumed to be inversely proportional to the absolute pressure.

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Problem 4

In the Danckwerts' model of mass transfer it is assumed that the fractional rate of surface renewal $s$ is constant and independent of surface age. Under such conditions the expression for the surface age distribution function is $s \mathrm{e}^{-s t}$.

If the fractional rate of surface renewal were proportional to surface age (say $s=b t$, where $b$ is a constant), show that the surface age distribution function would then assume the form:

$$
(2 b / \pi)^{1 / 2} \mathrm{e}^{-b t^2 / 2}
$$

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Problem 5

By consideration of the appropriate element of a sphere show that the general equation for molecular diffusion in a stationary medium and in the absence of a chemical reaction is:

$$
\frac{\partial C_A}{\partial t}=D\left(\frac{\partial^2 C_A}{\partial r^2}+\frac{1}{r^2} \frac{\partial^2 C_A}{\partial \beta^2}+\frac{1}{r^2 \sin ^2 \beta} \frac{\partial^2 C_A}{\partial \phi^2}+\frac{2}{r} \frac{\partial C_A}{\partial r}+\frac{\cot \beta}{r^2} \frac{\partial C_A}{\partial \beta}\right)
$$

where $C_A$ is the concentration of the diffusing substance, $D$ the molecular diffusivity, $t$ the time, and $r, \beta, \phi$ are spherical polar coordinates, $\beta$ being the latitude angle.

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Problem 6

Prove that for equimolecular counter diffusion from a sphere to a surrounding stationary, infinite medium, the Sherwood number based on the diameter of the sphere is equal to 2.

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Problem 7

Show that the concentration profile for unsteady-state diffusion into a bounded medium of thickness $L$, when the concentration at the interface is suddenly raised to a constant value $C_{A i}$ and kept constant at the initial value of $C_{A o}$ at the other boundary is:

$$
\frac{C_A-C_{A o}}{C_{A i}-C_{A o}}=1-\frac{z}{L}-\frac{2}{\pi}\left[\sum_{n=1}^{n=\infty} \frac{1}{n} \exp \left(-n^2 \pi^2 D t / L^2\right) \sin (n z \pi / L)\right]
$$

Assume the solution to be the sum of the solution for infinite time (steady-state part) and the solution of a second unsteady-state part, which simplifies the boundary conditions for the second part.

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Problem 8

Show that under the conditions specified in Problem 10.7 and assuming the Higbie model of surface renewal, the average mass flux at the interface is given by:

$$
\left(N_A\right)_t=\left(C_{A i}-C_{A o}\right) D / L\left\{1+\left(2 L^2 / \pi^2 D t\right) \sum_{n=1}^{n=\infty}\left[\frac{\pi^2}{6}-\frac{1}{n^2} \exp \left(-n^2 \pi^2 D t / L^2\right)\right]\right\}
$$

Use the relation $\sum_{n=1}^{\infty} \frac{1}{n^2}=\pi^2 / 6$

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10:13

Problem 9

According to the simple penetration theory the instantaneous mass flux:

$$
\left(N_A\right)_t=\left(C_{A i}-C_{A o}\right)\left(\frac{D}{\pi t}\right)^{0.5}
$$

What is the equivalent expression for the instantaneous heat flux under analogous conditions?

Pure sulphur dioxide is absorbed at 295 K and atmospheric pressure into a laminar water jet. The solubility of $\mathrm{SO}_2$, assumed constant over a small temperature range, is $1.54 \mathrm{kmol} / \mathrm{m}^3$ under these conditions and the heat of solution is $28 \mathrm{~kJ} / \mathrm{kmol}$.

Calculate the resulting jet surface temperature if the Lewis number is 90 . Neglect heat transfer between the water and the gas.

Chareen Guzman
Chareen Guzman
Numerade Educator
12:16

Problem 10

In a packed column, operating at approximately atmospheric pressure and 295 K , a $10 \%$ ammonia-air mixture is scrubbed with water and the concentration is reduced to $0.1 \%$. If the whole of the resistance to mass transfer may be regarded as lying within a thin laminar film on the gas side of the gas-liquid interface, derive from first principles an expression for the rate of absorption at any position in the column. At some intermediate point where the ammonia concentration in the gas phase has been reduced to $5 \%$, the partial pressure of ammonia in equilibrium with the aqueous solution is $660 \mathrm{~N} / \mathrm{m}^2$ and the transfer rate is $10^{-3} \mathrm{kmol} / \mathrm{m}^2 \mathrm{~s}$. What is the thickness of the hypothetical gas film if the diffusivity of ammonia in air is $0.24 \mathrm{~cm}^2 / \mathrm{s}$ ?

Chareen Guzman
Chareen Guzman
Numerade Educator

Problem 11

An open bowl, 0.3 m in diameter, contains water at 350 K evaporating into the atmosphere. If the air currents are sufficiently strong to remove the water vapour as it is formed and if the resistance to its mass transfer in air is equivalent to that of a 1 mm layer for conditions of molecular diffusion, what will be the rate of cooling due to evaporation? The water can be considered as well mixed and the water equivalent of the system is equal to 10 kg . The diffusivity of water vapour in air may be taken as $0.20 \mathrm{~cm}^2 / \mathrm{s}$ and the kilogram molecular volume at NTP as $22.4 \mathrm{~m}^3$.

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Problem 12

Show by substitution that when a gas of solubility $\mathrm{C}^{+}$is absorbed into a stagnant liquid of infinite depth, the concentration at time $t$ and depth $y$ is:

$$
C^{+} \operatorname{erfc} \frac{y}{2 \sqrt{D t}}
$$

Hence, on the basis of the simple penetration theory, show that the rate of absorption in a packed column will be proportional to the square root of the diffusivity.

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Problem 13

Show that in steady-state diffusion through a film of liquid, accompanied by a firstorder irreversible reaction, the concentration of solute in the film at depth $y$ below the interface is:

$$
\frac{C_A}{C_{A i}}=\sinh \frac{\sqrt{\frac{k}{D}}(L-y)}{\sinh \sqrt{\frac{k}{D}} L} C_i
$$

if $C_A=0$ at $y=L$ and $C_A=C_{A i}$ at $y=0$, corresponding to the interface.
Hence show that according to the "film theory" of gas-absorption, the rate of absorption per unit area of interface, $N_A$ is given by:

$$
N_A=k_L C_{A i} \frac{\beta}{\tanh \beta}
$$

where $\beta=\sqrt{D k / k_L}, D$ is the diffusivity of the solute, $\boldsymbol{k}$ the rate constant of the reaction, $K_L$ the liquid film mass transfer coefficient for physical absorption, $C_{A i}$ the concentration of solute at the interface, $y$ the distance normal to the interface and $y_L$ the liquid film thickness.

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23:16

Problem 14

The diffusivity of the vapour of a volatile liquid in air can be conveniently determined by Winkelmann’s method, in which liquid is contained in a narrow diameter vertical tube maintained at a constant temperature, and an air stream is passed over the top of the tube sufficiently rapidly to ensure the partial pressure of the vapour there remains approximately zero. On the assumption that the vapour is transferred from the surface of the liquid to the air stream by molecular diffusion, calculate the diffusivity of carbon tetrachloride vapour in air at 321 K and atmospheric pressure from the following experimentally obtained data:
$$
\begin{array}{cc}
\hline \begin{array}{c}
\text { Time from commencement } \\
\text { of experiment }(\mathrm{ks})
\end{array} & \begin{array}{c}
\text { Liquid level } \\
(\mathrm{cm})
\end{array} \\
\hline 0 & 0.00 \\
1.6 & 0.25 \\
11.1 & 1.29 \\
27.4 & 2.32 \\
80.2 & 4.39 \\
117.5 & 5.47 \\
168.6 & 6.70 \\
199.7 & 7.38 \\
289.3 & 9.03 \\
383.1 & 10.48 \\
\hline
\end{array}
$$
The vapour pressure of carbon tetrachloride at 321 K is $37.6 \mathrm{kN} / \mathrm{m}^2$, and the density of the liquid is $1540 \mathrm{~kg} / \mathrm{m}^3$. The kilogram molecular volume is $22.4 \mathrm{~m}^3$.

Chareen Guzman
Chareen Guzman
Numerade Educator
20:05

Problem 15

Ammonia is absorbed in water from a mixture with air using a column operating at atmospheric pressure and 295 K . The resistance to transfer can be regarded as lying entirely within the gas phase. At a point in the column the partial pressure of the ammonia is $6.6 \mathrm{kN} / \mathrm{m}^2$. The back pressure at the water interface is negligible and the resistance to transfer can be regarded as lying in a stationary gas film 1 mm thick. If the diffusivity of ammonia in air is $0.236 \mathrm{~cm}^2 / \mathrm{s}$, what is the transfer rate per unit area at that point in the column? If the gas were compressed to $200 \mathrm{kN} / \mathrm{m}^2$ pressure, how would the transfer rate be altered?

Chareen Guzman
Chareen Guzman
Numerade Educator

Problem 16

What are the general principles underlying the two-film penetration and film-penetration theories for mass transfer across a phase boundary? Give the basic differential equations which have to be solved for these theories with the appropriate boundary conditions.

According to the penetration theory, the instantaneous rate of mass transfer per unit area $\left(N_A\right)_t$ at some time $t$ after the commencement of transfer is given by:

$$
\left(N_A\right)_t=\Delta C_A \sqrt{\frac{D}{\pi t}}
$$

where $\Delta C_A$ is the concentration driving force and $D$ is the diffusivity.
Obtain expressions for the average rates of transfer on the basis of the Higbie and Danckwerts assumptions.

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Problem 17

A solute diffuses from a liquid surface at which its molar concentration is $C_{A i}$ into a liquid with which it reacts. The mass transfer rate is given by Fick's law and the reaction is first order with respect to the solute. In a steady-state process, the diffusion rate falls at a depth $L$ to one half the value at the interface. Obtain an expression for the concentration $C_A$ of solute at a depth $y$ from the surface in terms of the molecular diffusivity $D$ and the reaction rate constant $\boldsymbol{k}$. What is the molar flux at the surface?

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19:02

Problem 18

$4 \mathrm{~cm}^3$ of mixture formed by adding $2 \mathrm{~cm}^3$ of acetone to $2 \mathrm{~cm}^3$ of dibutyl phthalate is contained in a 6 mm diameter vertical glass tube immersed in a thermostat maintained at 315 K . A stream of air at 315 K and atmospheric pressure is passed over the open top of the tube to maintain a zero partial pressure of acetone vapour at that point. The liquid level is initially 11.5 mm below the top of the tube and the acetone vapour is transferred to the air stream by molecular diffusion alone. The dibutyl phthalate can be regarded as completely non-volatile and the partial pressure of acetone vapour may be calculated from Raoult's law on the assumption that the density of dibutyl phthalate is sufficiently greater than that of acetone for the liquid to be completely mixed.
Calculate the time taken for the liquid level to fall to 5 cm below the top of the tube, neglecting the effects of bulk flow in the vapour. 1 kmol occupies $22.4 \mathrm{~m}^3$. Molecular weights of acetone, dibutyl phthalate $=58$ and $279 \mathrm{~kg} / \mathrm{kmol}$ respectively. Liquid densities of acetone, dibutyl phthalate $=764$ and $1048 \mathrm{~kg} / \mathrm{m}^3$ respectively. Vapour pressure of acetone at $315 \mathrm{~K}=60.5 \mathrm{kN} / \mathrm{m}^2$. Diffusivity of acetone vapour in air at $315 \mathrm{~K}=$ $0.123 \mathrm{~cm}^2 / \mathrm{s}$.

Chareen Guzman
Chareen Guzman
Numerade Educator
25:11

Problem 19

A crystal is suspended in fresh solvent and $5 \%$ of the crystal dissolves in 300 s. How long will it take before $10 \%$ of the crystal has dissolved? Assume that the solvent can be regarded as infinite in extent, that the mass transfer in the solvent is governed by Fick's second law of diffusion and may be represented as a unidirectional process, and that changes in the surface area of the crystal may be neglected. Start your derivations using Fick's second law.

Chareen Guzman
Chareen Guzman
Numerade Educator

Problem 20

In a continuous steady state reactor, a slightly soluble gas is absorbed into a liquid in which it dissolves and reacts, the reaction being second-order with respect to the dissolved gas. Calculate the reaction rate constant on the assumption that the liquid is semi-infinite in extent and that mass transfer resistance in the gas phase is negligible. The diffusivity of the gas in the liquid is $10^{-8} \mathrm{~m}^2 / \mathrm{s}$, the gas concentration in the liquid falls to one half of its value in the liquid over a distance of 1 mm , and the rate of absorption at the interface is $4 \times 10^{-6} \mathrm{kmol} / \mathrm{m}^2 \mathrm{~s}$.

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Problem 21

Experiments have been carried out on the mass transfer of acetone between air and a laminar water jet. Assuming that desorption produces random surface renewal with a constant fractional rate of surface renewal, $s$, but an upper limit on surface age equal to the life of the jet, $\tau$, show that the surface age frequency distribution function, $\phi(t)$, for this case is given by:

$$
\begin{array}{lll}
\phi(t)=s \exp (-s t /[1-\exp (-s t)]) & \text { for } & 0<t<\tau \\
\phi(t)=0 & \text { for } & t>\tau
\end{array}
$$

Hence, show that the enhancement, $E$, for the increase in value of the liquid-phase mass transfer coefficient is:

$$
E=\left[(\pi s \tau)^{1 / 2} \operatorname{erf}(s \tau)^{1 / 2}\right] /\{2[1-\exp (-s \tau)]\}
$$

where $E$ is defined as the ratio of the mass transfer coefficient predicted by conditions described above to the mass transfer coefficient obtained from the penetration theory for a jet with an undisturbed surface. Assume that the interfacial concentration of acetone is practically constant.

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Problem 22

Solute gas is diffusing into a stationary liquid, virtually free of solvent, and of sufficient depth for it to be regarded as semi-infinite in extent. In what depth of fluid below the surface will $90 \%$ of the material which has been transferred across the interface have accumulated in the first minute? Diffusivity of gas in liquid $=10^{-9} \mathrm{~m}^2 / \mathrm{s}$.

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13:24

Problem 23

A chamber, of volume $1 \mathrm{~m}^3$, contains air at a temperature of 293 K and a pressure of $101.3 \mathrm{kN} / \mathrm{m}^2$, with a partial pressure of water vapour of $0.8 \mathrm{kN} / \mathrm{m}^2$. A bowl of liquid with a free surface of $0.01 \mathrm{~m}^2$ and maintained at a temperature of 303 K is introduced into the chamber. How long will it take for the air to become $90 \%$ saturated at 293 K and how much water must be evaporated?

The diffusivity of water vapour in air is $2.4 \times 10^{-5} \mathrm{~m}^2 / \mathrm{s}$ and the mass transfer resistance is equivalent to that of a stagnant gas film of thickness 0.25 mm . Neglect the effects of bulk flow. Saturation vapour pressure of water $=4.3 \mathrm{kN} / \mathrm{m}^2$ at 303 K and $2.3 \mathrm{kN} / \mathrm{m}^2$ at 293 K .

Eduard Sanchez
Eduard Sanchez
Numerade Educator
01:38

Problem 24

A large deep bath contains molten steel, the surface of which is in contact with air. The oxygen concentration in the bulk of the molten steel is $0.03 \%$ by mass and the rate of transfer of oxygen from the air is sufficiently high to maintain the surface layers saturated at a concentration of $0.16 \%$ by weight. The surface of the liquid is disrupted by gas bubbles rising to the surface at a frequency of 120 bubbles per $\mathrm{m}^2$ of surface per second, each bubble disrupts and mixes about $15 \mathrm{~cm}^2$ of the surface layer into the bulk.

On the assumption that the oxygen transfer can be represented by a surface renewal model, obtain the appropriate equation for mass transfer by starting with Fick's second law of diffusion and calculate:
(a) The mass transfer coefficient
(b) The mean mass flux of oxygen at the surface
(c) The corresponding film thickness for a film model, giving the same mass transfer rate.

Diffusivity of oxygen in steel $=1.2 \times 10^{-8} \mathrm{~m}^2 / \mathrm{s}$. Density of molten steel $=7100 \mathrm{~kg} / \mathrm{m}^3$.

Narayan Hari
Narayan Hari
Numerade Educator
18:14

Problem 25

Two large reservoirs of gas are connected by a pipe of length $2 L$ with a full-bore valve at its mid-point. Initially a gas A fills one reservoir and the pipe up to the valve and gas B fills the other reservoir and the remainder of the pipe. The valve is opened rapidly and the gases in the pipe mix by molecular diffusion.

Obtain an expression for the concentration of gas $\mathbf{A}$ in that half of the pipe in which it is increasing, as a function of distance $y$ from the valve and time $t$ after opening. The whole system is at a constant pressure and the ideal gas law is applicable to both gases. It may be assumed that the rate of mixing in the vessels is high so that the gas concentration at the two ends of the pipe do not change.

Luis Amaro
Luis Amaro
Numerade Educator

Problem 26

A pure gas is absorbed into a liquid with which it reacts. The concentration in the liquid is sufficiently low for the mass transfer to be governed by Fick's law and the reaction is first order with respect to the solute gas. It may be assumed that the film theory may be applied to the liquid and that the concentration of solute gas falls from the saturation value to zero across the film. Obtain an expression for the mass transfer rate across the gas-liquid interface in terms of the molecular diffusivity, $D$, the first-order reaction rate constant $\boldsymbol{k}$, the film thickness $L$ and the concentration $C_{A S}$ of solute in a saturated solution. The reaction is initially carried out at 293 K . By what factor will the mass transfer rate across the interface change, if the temperature is raised to 313 K ? Reaction rate constant at $293 \mathrm{~K}=2.5 \times 10^{-6} \mathrm{~s}^{-1}$. Energy of activation for reaction (in Arrhenius equation) $=$ $26430 \mathrm{~kJ} / \mathrm{kmol}$. Universal gas constant $\mathbf{R}=8.314 \mathrm{~kJ} / \mathrm{kmol} \mathrm{K}$. Molecular diffusivity $D=$ $10^{-9} \mathrm{~m}^2 / \mathrm{s}$. Film thickness, $L=10 \mathrm{~mm}$. Solubility of gas at 313 K is $80 \%$ of solubility at 293 K .

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Problem 27

Using Maxwell's law of diffusion obtain an expression for the effective diffusivity for a gas $\mathbf{A}$ in a binary mixture of $\mathbf{B}$ and $\mathbf{C}$, in terms of the diffusivities of $\mathbf{A}$ in the two pure components and the molar concentrations of $\mathbf{A}, \mathbf{B}$ and $\mathbf{C}$.

Carbon dioxide is absorbed in water from a 25 per cent mixture in nitrogen. How will its absorption rate compare with that from a mixture containing 35 per cent carbon dioxide, 40 per cent hydrogen and 25 per cent nitrogen? It may be assumed that the gas-film resistance is controlling, that the partial pressure of carbon dioxide at the gas-liquid interface is negligible and that the two-film theory is applicable, with the gas film thickness the same in the two cases. Diffusivity of $\mathrm{CO}_2$ in hydrogen $=3.5 \times 10^{-5} \mathrm{~m}^2 / \mathrm{s}$; in nitrogen $=$ $1.6 \times 10^{-5} \mathrm{~m}^2 / \mathrm{s}$.

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Problem 28

Given that from the penetration theory for mass transfer across an interface, the instantaneous rate of mass transfer is inversely proportional to the square root of the time of exposure, obtain a relationship between exposure time in the Higbie model and surface renewal rate in the Danckwerts model which will give the same average mass transfer rate. The age distribution function and average mass transfer rate from the Danckwerts theory must be derived from first principles.

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12:16

Problem 29

Ammonia is absorbed in a falling film of water in an absorption apparatus and the film is disrupted and mixed at regular intervals as it flows down the column. The mass transfer rate is calculated from the penetration theory on the assumption that all the relevant conditions apply. It is found from measurements that the mass transfer rate immediately before mixing is only 16 per cent of that calculated from the theory and the difference has been attributed to the existence of a surface film which remains intact and unaffected by the mixing process. If the liquid mixing process takes place every second, what thickness of surface film would account for the discrepancy? Diffusivity of ammonia in water $=$ $1.76 \times 10^{-9} \mathrm{~m}^2 / \mathrm{s}$.

Chareen Guzman
Chareen Guzman
Numerade Educator
12:16

Problem 30

A deep pool of ethanol is suddenly exposed to an atmosphere consisting of pure carbon dioxide and unsteady state mass transfer, governed by Fick's Law, takes place for 100 s. What proportion of the absorbed carbon dioxide will have accumulated in the 1 mm thick layer of ethanol closest to the surface? Diffusivity of carbon dioxide in ethanol $=$ $4 \times 10^{-9} \mathrm{~m}^2 / \mathrm{s}$.

Chareen Guzman
Chareen Guzman
Numerade Educator

Problem 31

A soluble gas is absorbed into a liquid with which it undergoes a second-order irreversible reaction. The process reaches a steady-state with the surface concentration of reacting material remaining constant at $C_{A s}$ and the depth of penetration of the reactant being small compared with the depth of liquid which can be regarded as infinite in extent. Derive the basic differential equation for the process and from this derive an expression for the concentration and mass transfer rate (moles per unit area and unit time) as a function of depth below the surface. Assume that mass transfer is by molecular diffusion.

If the surface concentration is maintained at $0.04 \mathrm{kmol} / \mathrm{m}^3$, the second-order rate constant $\boldsymbol{k}_2$ is $9.5 \times 10^3 \mathrm{~m}^3 / \mathrm{kmol} \mathrm{s}$ and the liquid phase diffusivity $D$ is $1.8 \times 10^{-9} \mathrm{~m}^2 / \mathrm{s}$, calculate:
(a) The concentration at a depth of 0.1 mm .
(b) The molar rate of transfer at the surface $\left(\mathrm{kmol} / \mathrm{m}^2 \mathrm{~s}\right)$.
(c) The molar rate of transfer at a depth of 0.1 mm .

It may be noted that if:

$$
\frac{\mathrm{d} C_A}{\mathrm{~d} y}=q \text {, then: } \frac{\mathrm{d}^2 C_A}{\mathrm{~d} y^2}=q \frac{\mathrm{~d} q}{\mathrm{~d} C_A}
$$

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Problem 32

In calculating the mass transfer rate from the penetration theory, two models for the age distribution of the surface elements are commonly used - those due to Higbie and to Danckwerts. Explain the difference between the two models and give examples of situations in which each of them would be appropriate.
(a) In the Danckwerts model, it is assumed that elements of the surface have an age distribution ranging from zero to infinity. Obtain the age distribution function for this model and apply it to obtain the average mass transfer coefficient at the surface, given that from the penetration theory the mass transfer coefficient for surface of age $t$ is $\sqrt{ }[D /(\pi t)]$, where $D$ is the diffusivity.
(b) If for unit area of surface the surface renewal rate is $s$, by how much will the mass transfer coefficient be changed if no surface has an age exceeding $2 / s$ ?
(c) If the probability of surface renewal is linearly related to age, as opposed to being constant, obtain the corresponding form of the age distribution function.
It may be noted that:

$$
\int_0^{\infty} \mathrm{e}^{-x^2} \mathrm{~d} x=\frac{\sqrt{\pi}}{2}
$$

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Problem 33

Explain the basis of the penetration theory for mass transfer across a phase boundary. What are the assumptions in the theory which lead to the result that the mass transfer rate is inversely proportional to the square root of the time for which a surface element has been expressed? (Do not present a solution of the differential equation.) Obtain the age distribution function for the surface:
(a) On the basis of the Danckwerts' assumption that the probability of surface renewal is independent of its age.
(b) On the assumption that the probability of surface renewal increases linearly with the age of the surface.
Using the Danckwerts surface renewal model, estimate:
(c) At what age of a surface element is the mass transfer rate equal to the mean value for the whole surface for a surface renewal rate ( $s$ ) of $0.01 \mathrm{~m}^2 / \mathrm{m}^2 \mathrm{~s}$ ?
(d) For what proportion of the total mass transfer is surface of an age exceeding 10 seconds responsible?

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10:21

Problem 34

At a particular location in a distillation column, where the temperature is 350 K and the pressure 500 m Hg , the mol fraction of the more volatile component in the vapour is 0.7 at the interface with the liquid and 0.5 in the bulk of the vapour. The molar latent heat of the more volatile component is 1.5 times that of the less volatile. Calculate the mass transfer rates ( $\mathrm{kmol} \mathrm{m}^{-2} \mathrm{~s}^{-1}$ ) of the two components. The resistance to mass transfer in the vapour may be considered to lie in a stagnant film of thickness 0.5 mm at the interface. The diffusivity in the vapour mixture is $2 \times 10^{-5} \mathrm{~m}^2 \mathrm{~s}^{-1}$.

Calculate the mol fractions and concentration gradients of the two components at the mid-point of the film. Assume that the ideal gas law is applicable and that the Universal Gas Constant $\mathbf{R}=8314 \mathrm{~J} / \mathrm{kmol} \mathrm{K}$.

Chareen Guzman
Chareen Guzman
Numerade Educator
08:54

Problem 35

For the diffusion of carbon dioxide at atmospheric pressure and a temperature of 293 K , at what time will the concentration of solute 1 mm below the surface reach 1 per cent of the value at the surface? At that time, what will the mass transfer rate $\left(\mathrm{kmol} \mathrm{m}^{-2} \mathrm{~s}^{-1}\right)$ be:
(a) At the free surface?
(b) At the depth of 1 mm ?

The diffusivity of carbon dioxide in water may be taken as $1.5 \times 10^{-9} \mathrm{~m}^2 \mathrm{~s}^{-1}$. In the literature, Henry's law constant $\boldsymbol{K}$ for carbon dioxide at 293 K is given as $1.08 \times 10^6$ where $K=P / X, P$ being the partial pressure of carbon dioxide $(\mathrm{mm} \mathrm{Hg})$ and $X$ the corresponding mol fraction in the water.

Chareen Guzman
Chareen Guzman
Numerade Educator
12:00

Problem 36

Experiments are carried out at atmospheric pressure on the absorption into water of ammonia from a mixture of hydrogen and nitrogen, both of which may be taken as insoluble in the water. For a constant mole fraction of 0.05 of ammonia, it is found that the absorption rate is 25 per cent higher when the molar ratio of hydrogen to nitrogen is changed from $1: 1$ to $4: 1$. Is this result consistent with the assumption of a steady-state gas-film controlled process and, if not, what suggestions have you to make to account for the discrepancy?

Neglect the partial pressure attributable to ammonia in the bulk solution.
Diffusivity of ammonia in hydrogen $=52 \times 10^{-6} \mathrm{~m}^2 / \mathrm{s}$
Diffusivity of ammonia in nitrogen $=23 \times 10^{-6} \mathrm{~m}^2 / \mathrm{s}$

Chareen Guzman
Chareen Guzman
Numerade Educator
10:21

Problem 37

Using a steady-state film model, obtain an expression for the mass transfer rate across a laminar film of thickness $L$ in the vapour phase for the more volatile component in a binary distillation process:
(a) where the molar latent heats of two components are equal.
(b) where the molar latent heat of the less volatile component (LVC) is $f$ times that of the more volatile component (MVC).

For the case where the ratio of the molar latent heats $f$ is 1.5 . what is the ratio of the mass transfer rate in case (b) to that in case (a) when the mole fraction of the MVC falls from 0.75 to 0.65 across the laminar film?

Chareen Guzman
Chareen Guzman
Numerade Educator

Problem 38

Based on the assumptions involved in the penetration theory of mass transfer across a phase boundary, the concentration $C_A$ of a solute $A$ at a depth $y$ below the interface at a time $t$ after the formation of the interface is given by:

$$
\frac{C_A}{C_{A i}}=\operatorname{erfc}\left[\frac{y}{2 \sqrt{(D t)}}\right]
$$

where $C_{A i}$ is the interface concentration, assumed constant and $D$ is the molecular diffusivity of the solute in the solvent. The solvent initially contains no dissolved solute. Obtain an expression for the molar rate of transfer of $A$ per unit area at time $t$ and depth $y$, and at the free surface $(y=0)$.

In a liquid-liquid extraction unit, spherical drops of solvent of uniform size are continuously fed to a continuous phase of lower density which is flowing vertically upwards, and hence countercurrently with respect to the droplets. The resistance to mass transfer may be regarded as lying wholly within the drops and the penetration theory may be applied. The upward velocity of the liquid, which may be taken as uniform over the cross-section of the vessel, is one-half of the terminal falling velocity of the droplets in the still liquid.

Occasionally, two droplets coalesce forming a single drop of twice the volume. What is the ratio of the mass transfer rate $(\mathrm{kmol} / \mathrm{s})$ at a coalesced drop to that at a single droplet when each has fallen the same distance, that is to the bottom of the column?

The fluid resistance force acting on the droplet should be taken as that given by Stokes' law, that is $3 \pi \mu d u$ where $\mu$ is the viscosity of the continuous phase, $d$ the drop diameter and $u$ its velocity relative to the continuous phase.

It may be noted that:

$$
\operatorname{erfc}(x)=\frac{2}{\sqrt{\pi}} \int_x^{\infty} \mathrm{e}^{x^2} \mathrm{~d} x
$$

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Problem 39

In a drop extractor, a dense organic solvent is introduced in the form of spherical droplets of diameter d and extracts a solute from an aqueous stream which flows upwards at a velocity equal to half the terminal falling velocity $u_0$ of the droplets. On increasing the flowrate of the aqueous stream by 50 per cent, whilst maintaining the solvent rate constant, it is found that the average concentration of solute in the outlet stream of organic phase is decreased by 10 per cent. By how much would the effective droplet size have had to change to account for this reduction in concentration? Assume that the penetration theory is applicable with the mass transfer coefficient inversely proportional to the square root of the contact time between the phases and that the continuous phase resistance is small compared with that within the droplets. The drag force $F$ acting on the falling droplets may be calculated from Stokes' Law, $F=3 \pi \mu d u_o$, where $\mu$ is the viscosity of the aqueous phase. Clearly state any assumptions made in your calculation.

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Problem 40

According to the penetration theory for mass transfer across an interface, the ratio of the concentration $C_A$ at a depth $y$ and time $t$ to the surface concentration $C_{A s}$ at the liquid is initially free of solute, is given by

$$
\frac{C_A}{C_{A s}}=\operatorname{erfc} \frac{y}{2 \sqrt{D t}}
$$

where $D$ is the diffusivity. Obtain a relation for the instantaneous rate of mass transfer at time $t$ both at the surface $(y=0)$ and at a depth $y$.

What proportion of the total solute transferred into the liquid in the first 90 s of exposure will be retained in a 1 mm layer of liquid at the surface, and what proportion will be retained in the next 0.5 mm ? The diffusivity is $2 \times 10^{-9} \mathrm{~m}^2 / \mathrm{s}$.

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Problem 41

Obtain an expression for the effective diffusivity of component $\mathbf{A}$ in a gaseous mixture of A, B and $\mathbf{C}$ in terms of the binary diffusion coefficients $D_{A B}$ for $\mathbf{A}$ in B, and $D_{A C}$ for A in $\mathbf{C}$.

The gas-phase mass transfer coefficient for the absorption of ammonia into water from a mixture of composition $\mathrm{NH}_3 20 \%, \mathrm{~N}_2 73 \%, \mathrm{H}_2 7 \%$ is found experimentally to be $0.030 \mathrm{~m} / \mathrm{s}$. What would you expect the transfer coefficient to be for a mixture of composition $\mathrm{NH}_3 5 \%, \mathrm{~N}_2 60 \%, \mathrm{H}_2 35 \%$ ? All compositions are given on a molar basis. The total pressure and temperature are the same in both cases. The transfer coefficients are based on a steady-state film model and the effective film thickness may be assumed constant. Neglect the solubility of $\mathrm{N}_2$ and $\mathrm{H}_2$ in water.

Diffusivity of $\mathrm{NH}_3$ in $\mathrm{N}_2=23 \times 10^{-6} \mathrm{~m}^2 / \mathrm{s}$.
Diffusivity of $\mathrm{NH}_3$ in $\mathrm{H}_2=52 \times 10^{-6} \mathrm{~m}^2 / \mathrm{s}$.

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03:23

Problem 42

State the assumptions made in the penetration theory for the absorption of a pure gas into a liquid. The surface of an initially solute-free liquid is suddenly exposed to a soluble gas and the liquid is sufficiently deep for no solute to have time to reach the far boundary of the liquid. Starting with Fick's second law of diffusion, obtain an expression for (i) the concentration, and (ii) the mass transfer rate at a time $t$ and a depth $y$ below the surface.

After 50 s , at what depth $y$ will the concentration have reached one tenth the value at the surface? What is the mass transfer rate (i) at the surface, and (ii) at the depth $y$, if the surface concentration has a constant value of $0.1 \mathrm{kmol} / \mathrm{m}^3$ ?

Lottie Adams
Lottie Adams
Numerade Educator

Problem 43

In a drop extractor, liquid droplets of approximately uniform size and spherical shape are formed at a series of nozzles and rise countercurrently through the continuous phase which is flowing downwards at a velocity equal to one half of the terminal rising velocity of the droplets. The flowrates of both phases are then increased by 25 per cent. Because of the greater shear rate at the nozzles, the mean diameter of the droplets is, however, only 90 per cent of the original value. By what factor will the overall mass transfer rate change?

It may be assumed that the penetration model may be used to represent the mass transfer process. The depth of penetration is small compared with the radius of the droplets and the effects of surface curvature may be neglected. From the penetration theory, the concentration $C_A$ at a depth $y$ below the surface at time $t$ is given by:

$$
\frac{C_A}{C_{A S}}=\operatorname{erfc}\left[\frac{y}{2 \sqrt{(D t)}}\right] \text { where } \operatorname{erfc} X=\frac{2}{\sqrt{\pi}} \int_X^{\infty} \mathrm{e}^{-x^2} \mathrm{~d} x
$$

where $C_{A S}$ is the surface concentration for the drops (assumed constant) and $D$ is the diffusivity in the dispersed (droplet) phase. The droplets may be assumed to rise at their terminal velocities and the drag force $F$ on the droplet may be calculated from Stokes' Law, $F=3 \pi \mu d u$.

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03:23

Problem 44

According to Maxwell's law, the partial pressure gradient in a gas which is diffusing in a two-component mixture is proportional to the product of the molar concentrations of the two components multiplied by its mass transfer velocity relative to that of the second component. Show how this relationship can be adapted to apply to the absorption of a soluble gas from a multicomponent mixture in which the other gases are insoluble, and obtain an effective diffusivity for the multicomponent system in terms of the binary diffusion coefficients.

Carbon dioxide is absorbed in alkaline water from a mixture consisting of $30 \% \mathrm{CO}_2$ and $70 \% \mathrm{~N}_2$, and the mass transfer rate is $0.1 \mathrm{kmol} / \mathrm{s}$. The concentration of $\mathrm{CO}_2$ in the gas in contact with the water is effectively zero. The gas is then mixed with an equal molar quantity of a second gas stream of molar composition $20 \% \mathrm{CO}_2, 50 \%, \mathrm{~N}_2$ and $30 \%$ $\mathrm{H}_2$. What will be the new mass transfer rate, if the surface area, temperature and pressure remain unchanged? It may be assumed that a steady-state film model is applicable and that the film thickness is unchanged.

Diffusivity of $\mathrm{CO}_2$ in $\mathrm{N}_2=16 \times 10^{-6} \mathrm{~m}^2 / \mathrm{s}$.
Diffusivity of $\mathrm{CO}_2$ in $\mathrm{H}_2=35 \times 10^{-6} \mathrm{~m}^2 / \mathrm{s}$.

Lottie Adams
Lottie Adams
Numerade Educator

Problem 45

What is the penetration theory for mass transfer across a phase boundary? Give details of the underlying assumptions.

From the penetration theory, the mass transfer rate per unit area $N_A$ is given in terms of the concentration difference $\Delta C_A$ between the interface and the bulk fluid, the molecular diffusivity $D$ and the age $t$ of the surface element by:

$$
N_A=\sqrt{\frac{D}{\pi t}} \Delta C_A \quad \mathrm{kmol} / \mathrm{m}^2 \mathrm{~s} \text { (in SI units) }
$$

What is the mean rate of transfer if all elements of the surface are exposed for the same time $t_e$ before being remixed with the bulk?

Danckwerts assumed a random surface renewal process in which the probability of surface renewal is independent of its age. If $s$ is the fraction of the total surface renewed per unit time, obtain the age distribution function for the surface and show that the mean mass transfer rate $N_A$ over the whole surface is:

$$
N_A=\sqrt{D s} \Delta C_A \quad\left(\mathrm{kmol} / \mathrm{m}^2 \mathrm{~s}, \text { in SI units }\right)
$$

In a particular application, it is found that the older surface is renewed more rapidly than the recently formed surface, and that after a time $s^{-1}$, the surface renewal rate doubles, that is it increases from $s$ to $2 s$. Obtain the new age distribution function.

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Problem 46

Derive the partial differential equation for unsteady-state unidirectional diffusion accompanied by an $n$ th-order chemical reaction (rate constant $k$ ):

$$
\frac{\partial C_A}{\partial t}=D \frac{\partial^2 C_A}{\partial y^2}-k C_A^n
$$

where $C_A$ is the molar concentration of reactant at position $y$ at time $t$.
Explain why, when applying the equation to reaction in a porous catalyst particle, it is necessary to replace the molecular diffusivity $D$ by an effective diffusivity $D_e$.

Solve the above equation for a first-order reaction under steady-state conditions, and obtain an expression for the mass transfer rate per unit area at the surface of a catalyst particle which is in the form of a thin platelet of thickness $2 L$.

Explain what is meant by the effectiveness factor $\eta$ for a catalyst particle and show that it is equal to $(1 / \phi) \tanh \phi$ for the platelet referred to previously where $\phi$ is the Thiele modulus $L \sqrt{\left(k / D_e\right)}$.

For the case where there is a mass transfer resistance in the fluid external to the particle (mass transfer coefficient $h_D$ ), express the mass transfer rate in terms of the bulk concentration $C_{A o}$ rather than the concentration $C_{A S}$ at the surface of the particle.

For a bed of catalyst particles in the form of flat platelets it is found that the mass transfer rate is increased by a factor of 1.2 if the velocity of the external fluid is doubled.
The mass transfer coefficient $h_D$ is proportional to the velocity raised to the power of 0.6 . What is the value of $h_D$ at the original velocity?

$$
k=1.6 \times 10^{-3} \mathrm{~s}^{-1}, \quad D_e=10^{-8} \mathrm{~m}^2 / \mathrm{s}
$$

catalyst pellet thickness $(2 L)=10 \mathrm{~mm}$.

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Problem 47

Explain the basic concepts underlying the two-film theory for mass transfer across a phase boundary and obtain an expression for film thickness.

Water evaporates from an open bowl at 349 K at the rate of $4.11 \times 10^3 \mathrm{~kg} / \mathrm{m}^2 \mathrm{~s}$. What is the effective gas-film thickness?

The water is replaced by ethanol at 343 K . What will be its rate of evaporation in $\mathrm{kg} / \mathrm{m}^2 \mathrm{~s}$ if the film thickness is unchanged?

At the surface of the ethanol, what proportion of the total mass transfer will then be attributable to bulk flow?

Data.
Vapour pressure of water at $349 \mathrm{~K}=34 \mathrm{~mm} \mathrm{Hg}$
Vapour pressure of ethanol at $343 \mathrm{~K}=544 \mathrm{~mm} \mathrm{Hg}$
Neglect the partial pressure of vapour in the surrounding atmosphere
Diffusivity of water vapour in air $=26 \times 10^{-6} \mathrm{~m}^2 / \mathrm{s}$
Diffusivity of ethanol in air $=12 \times 10^{-6} \mathrm{~m}^2 / \mathrm{s}$
Density of mercury $=13,600 \mathrm{~kg} / \mathrm{m}^3$
Universal gas constant $\mathbf{R}=8314 \mathrm{~J} / \mathrm{kmol} \mathrm{K}$

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