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You are on page 1of 17

Lecture Notes

by

Yoram Cohen

Department of Chemical Engineering

University of California, Los Angeles

Published by

Multimedia Envirosoft Corporation

Los Angeles, California

http://www.mmenvirosoft.com

©1999

PREFACE

presented in the form of lecture notes. The chapters are grouped into a logical sequence and are

downloadable as separate files. A master file which allows the user to access the various chapters in

the various files is also available and serves as the Table of contents. Therefore, MTF is an electronic

book that can expand as new material is added or revised. The material is suitable for both graduate

and undergraduate students, although the level of development and detail is intended for advanced

mass transfer courses.

MTF begins with the development of the transport equations adopting an integral approach

which introduces the Reynolds’ transport theorem. After the introduction of the transport equations,

the emergence of the concept of a diffusion flux is introduced. Here diffusion is treated as a

phenomenon arising out of the difference in the capacity of different species in a mixture to transport

momentum. The concept of constitutive equations for the flux is introduced and the diffusion flux is

derived from both the mechanical theory of mixtures and from thermodynamic principles.

After the formulation of the mass transfer equations and the diffusion flux constitutive

equations, the concepts of diffusion and convection of mass are studied through a series of examples.

Detailed derivations are provided for the selected examples and analytical and numerical solution

procedures are introduced where appropriate. After the treatment of mass transfer in laminar flows,

turbulent mass transfer is introduced. The equations for turbulent mass transfer are introduced and

analogies for mass transfer coefficients are derived from first principles.

Throughout the MTF examples are drawn from industrial, biological and environmental

systems. Special topics include, membrane transport, multiphase transport in porous media, diffusion

in polymeric systems and dispersion in natural systems.

-ii-

Table of Contents for Chapters 1-3

1.11 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - 1 -

i. Molecular Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - 1 -

ii. Continuum Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - 1 -

1.12 Basic Conservation Laws . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -2 -

1.2 Eulerian and Lagrangian Coordinates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - 3 -

1.3 Material Derivative . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - 3 -

1.4 Control Volume . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - 4 -

1.5 Reynolds Transport Theorem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - 4 -

1.6 Conservation of Mass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - 6 -

1.7 Some Useful Relations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - 8 -

Partial Derivatives: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - 8 -

1.8 Multicomponent Mixture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - 9 -

Special cases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - 12 -

1.9 Kinematics and Continuity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - 14 -

1.10 Conservation of Linear Momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - 14 -

1.11 Macroscopic Balances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - 17 -

3.1 Mass Transfer Relations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - 22 -

3.2 Fluxes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - 22 -

3.3 Mass Transfer Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - 25 -

3.4 Derivation of A Molar form of the Mass Transfer Equation . . . . . . . . . . . . - 30 -

3.5 The Mechanical Theory of Diffusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - 33 -

3.6 The Diffusion Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - 34 -

- iii -

CHAPTER 1

CONSERVATION OF MASS AND MOMENTUM

Overview

In order to quantify the transport of mass, momentum and energy it necessary to first establish

the fundamentals laws (or conservation equations) that govern the transport of their transport through

and across the systems of interest. There are basically two approaches. The first relies on a

description of the movement of each molecule in the domain of interest. The second treats the domain

as a discrete set of infinitesimal volume element; the properties of each infinitesimal volume element

i. Molecular Approach

In this approach equations of motion and energy transport are developed for individual

molecules whereby the interaction among molecules are considered. The molecular approach provides

a detailed and fundamental description of the transport of matter. However, this approach requires

detailed theoretical treatment of the interactions among various species and tracking many molecules

in space and time. As a result, this approach is best suited for determining physicochemical and

transport properties of matter and predicting transport behavior over short spatial scales (e.g.,

In the continuum approach it is assumed that the domain consists of continuous matter. Each

point is identified by a unique values of field variables such as velocity, pressure, temperature and

mass density. The approach describes overall transport behavior of fluids to a reasonable degree of

-1-

accuracy; however, this approach is limited when the molecular dimensions approach the spatial

(1.1)

Equation 1.1 simply indicates that the continuum approach is valid when

1. Mass

2. Momentum

3. Energy

4. Thermodynamic Inequality

The conservation equations can then be used to describe the variation of different field

variables with space and time. In order to develop the conservation equations appropriate

derivatives that consider the evolution of material functions in time and space must be

defined. The appropriate derivatives and coordinate systems are discussed in the following

sections.

-2-

1.2 Eulerian and Lagrangian Coordinates

Eulerian coordinate - the independent variables are x, y, z and t or xi, t (i=1...3). This is a fixed

coordinate system. The basic conservation equations are in the Eulerian frame, R = R (xi,t). In the

Lagrangian frame attention is fixed on a particular mass of fluid as it flows, R = R (xoi,t), where the

(1.2)

then the total differential of " can be expressed as

(1.3)

(1.4)

After taking the limit *t 6 0 we obtain the following expression which defines the material derivative

in which vi is the fluid velocity in direction i. The material derivative (Lagrangian time derivative)

(1.5)

represents the total change in " as seen by an observer who is moving with a particular fluid element

In the Lagrangian frame we observe the particle for a time *t as it flows. The position of the particle

-3-

1.4 Control Volume

(1.6)

in which " is a fluid property, V is an arbitrary volume and L is a differential operator operating on

". The above integral equation can be satisfied for any arbitrary control volume only if L" = 0. Thus,

as we will see later, Eq. (1.6) can be used to convert an integro-differential equation to a differential

equation.

fluid domain. Fluid enters the volume element only through the open faces shown in the Figure 1.5.1.

As the volume element moves, volume-specific properties (e.g., density, enthalpy/volume) can change

spatially and temporally. In order to describe the change of any specific volume-specific property, we

can express the total time derivative of the selected property (integrated over the volume element)

using a finite difference approximation over an infinitesimal time interval, *t. Accordingly, the change

-4-

of a volume specific property, ", with time can be expressed as

(1.7)

(1.8)

The volume can change as the control volume moves in space during a specified time period. Thus,

the differential control volume is determined by the fluid inflow into the element (i.e., the velocity

perpendicular to the face of the element) velocity perpendicular to the area of the element

(1.9)

where ds is the surface area, v is the velocity and n is the unit normal. Using Eq. 1.9, the balance

(1.10a)

(1.10b)

In order to reduce the above equation to a more convenient form we make use of the "divergence

(1.11)

in which a is any vector and n is the unit normal. Therefore, the first integral term on the R.H.S of

-5-

Eq. 1.10b can be written as

(1.12)

(1.13)

(1.14)

Equations 1.13 and 1.14 are two alternative forms of the Reynolds’Transport Theorem. In Eqs. 1.13

and 1.14 the LHS represents the Lagrangian Derivative and the RHS represents the Eulerian

Derivatives.

The equation for conservation of mass can be derive by considering the density of the medium

as the property of interest. The density is substituted for " in the Reynolds transport equation ( eq.

(1.15)

Conservation of mass requires (excluding nuclear reactions) that the mass of the system

remains unchanged, assuming that there are no nuclear reactions in the domain of interest.

-6-

Therefore, the total derivative of the system’s mass is zero

(1.16)

Another way of stating eq. 1.16 is to set the right-hand-side of equation 1.15 to zero

(1.17)

where mass = . Since we are dealing with an arbitrary volume, the integrand on the R.H.S of

(1.18)

We now apply the argument presented in section 1.4 (eq. 1.6) and thus eq. 1.19a can be converted

(1.19)

For an incompressible fluid the density is invariant with respect to position and time, i.e.,

(1.20)

which leads to the alternative form of the continuity equation for an incompressible fluid

(1.21)

-7-

1.7 Some Useful Relations

Partial Derivatives:

(1.22)

(1.23)

where Vi is the mass average velocity of the mixture, and vi" is the velocity of component ". From

(1.24)

also if we define

(1.25)

(1.26)

(1.27)

or

(1.28)

-8-

1.8 Multicomponent Mixture

The continuity equation for a mixture of soluble components can be derived using the

Reynolds’ Transport Theorem. We consider a mixture in which each component " (in a mixture of

N components) is present in the mixture at partial density1 D" (e.g., units of g/cm3). From the

Reynolds' Transport Theorem we have

(1.29)

(1.30)

In which R" is the reaction rate for component " on a mass basis. For an arbitrary control volume

(1.31)

(1.32)

Equation 1.32 can be presented in a different form by defining a velocity difference or “diffusion

velocity”, ui"

(1.33)

where Vi is the average velocity of the mixture along axis i. The diffusion velocity of component "

The partial density of component " is the contribution of component " (while in a

1

-9-

Using eq. 1.33, eq. 1.32 can be written in the following form

(1.34)

(1.35)

or if we define a diffusion flux, J" = D"u", for component " then we can rewrite eq. 1.35 as

(1.36a)

Equation 1.36a is the continuity equation for component " in the mixture. The continuity equation

for the mixture (neglecting nuclear reactions) can be obtained by summing Eq. 1.36a over all

components (note that = 0), resulting in the continuity equation which we derived earlier

(1.36b)

We often deal with incompressible mixtures and it is therefore convenient to expand eq. 1.36b

as given below

(1.37)

we note that for an incompressible fluid DD/Dt=0 and thus . Therefore, the continuity

(1.38)

The diffusion equation for component " can be written in terms of the mass flux by introducing the

- 10 -

total flux variable,

(1.39)

"

We then introduce a component flux due to the component convective velocity (N ) and a component

(1.40)

The mass average velocity of the mixture is defined based on a mass fraction average

(1.41)

in which T" is the mass fraction of component ". Given eq. 1.41 we arrive at a diffusion flux given

by

(1.42)

(1.43)

therefore, the continuity equation for " can also be written as

(1.44)

Equation 1.44 is a general form of the mass transfer equation for a given component in a mixture. The

problem that we face, however, is that we cannot achieve closure until a proper equation is specified

Without proof let’s accept that the diffusion flux for component " can be represented by the

following equation:

(1.45)

- 11 -

where D"m is the diffusion coefficient for component " is a mixture defined as

(1.46a)

(1.46b)

(1.47)

(1.48)

Special cases

(1.49)

(1.50)

- 12 -

Solids2:

(1.51a)

If the diffusion coefficient is constant then eq. 1.51 can be simplified to yield

(1.51b)

The above diffusion equations can be solved once the velocity field is known and appropriate

boundary and initial conditions are specified. The information required includes:

Initial conditions:

Boundary Conditions

It should be noted that in principle, the diffusion of components in a mixture can affect the

diffusion coefficients and other physicochemical properties of the mixture such as viscosity and

thermal conductivity. Therefore, the mass transfer equation and the equations of motion are

intrinsically coupled. However, for dilute solutions it is generally accepted that concentration changes,

throughout the flow field, do not appreciably change the transport properties of the mixture; thus,

the equations of motion can in most instances be decoupled from the mass transfer equation.

2

Is the omission of Vi in Eq. (1.51) justified for diffusion in solids?

- 13 -

1.9 Kinematics and Continuity

(1.52)

in which D" is the density of component ". The mass average velocity of the mixtures, v, is defined

by

(1.53)

(1.54)

let u" = v"-V; J" = D"u", then we can show that in a mixture the following restriction must hold

(1.55)

- 14 -

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