NATIONAL NUCLEAR ENERGY SERIES Manhattan Project Technical Section Division IIIVolume
1B
THE THEORY OF ISOTOPE SEPARATION AS APPLIED T O THE LARGESCALE PRODUCTION OF
u~~~
THE THEORY O F ISOTOPE SEPARATION AS A P P L I E D T O THE LARGESCALE PRODUCTION O F U235
KARL COHEN
Director, Atomic Energy Division, The H K. Ferguson Company; formerly Director, . Theoretical Division, S A M Laboratories
Edited by
GEORGE M. MURPHY
Washington Square College, New York University; formerly at SAM Laboratories, Columbia University
F i r s t Edition
New York
 Toronto . London
1951
McGRAWHILL BOOK COMPANY, INC.
FOREWORD
THE THEORY OF ISOTOPE SEPAMTION AS APPLIED TO THE LARGESCALE PRODUCTION OF
uZ3'
Copyright, 1951, by the McGrawHill Book Company, Inc.
P r i n t e d i n t h e United S t a t e s of A m e r i c a
Copyright assigned, 1951, to the General Manager of the United States Atomic Energy Commission. All rights reserved. This book, o r parts thereof, may not be reproduced in any form without p e r mission of the Atomic Energy Commission.
The wartime project f o r development of atomic energy was a r e markable feat of cooperation and accomplishment by government, science, industry, labor, and the military s e r v i c e s aimed exclusively at the military application of atomic energy. Our present national atomic energy program, expanding upon the previous developments, i s directed not only toward the assurance of national security but also toward the realization of the immense potential benefits atomic energy holds f o r our civilization. The record of progress and t h e r e sults of extensive scientific investigation~ and engineering development a r e contained in the National Nuclear Energy Series. This knowledge, which offers the basis of world wide benefits from nuclear science, i s being published in the established scientific tradition, not solely to meet the precise needs of science but a l s o in support of the high goals of the American people s e t forth in the Atomic Energy Act. The work reported in this s e r i e s is a tribute to all the scientists engaged in both the Manhattan Project and the postwar Atomic Energy Commission program. Gordon Dean, Chairman U. S. Atomic Energy Commission
Lithoprinted by Edwards Brothers, Incorporated Ann Arbor, Michigan
PREFACE This volume is one of a series which has been preparedas a record of the research work done under the Manhattan Project andthe Atomic Energy Commission. The name Manhattan Project was assigned by the Corps of Engineers, War Department, to the farflung scientific and engineering activities which had a s their objective the utilization of atomic energy for military purposes. In the attainment of this objective, there were many developments in scientific and technical fields which a r e of general interest. The National Nuclear Energy Series (Manhattan Project Technical Section) is a record of these scientific and technical contributions, a s well a s of the developments in these fields which a r e being sponsored by the Atomic Energy Commission. The declassified portion of the National Nuclear Energy Series, when completed, is expected to consist of some 60 volumes. These will be grouped into eight divisions, a s follows: Division I  Electromagnetic Separation Project Division I1  Gaseous Diffusion Project Division I11  Special Separations Project Division IV  Plutonium Project Division V  Los Alamos Project Division VI  University of Rochester Project Division VII  Materials Procurement Project Division VIII  Manhattan Project Soon after the close of the war the Manhattan Project was able to give its attention to the preparation of a complete record of the research work accomplished under Project contracts. Writing programs were authorized at all laboratories, with the object of obtaining complete coverage of Project results. Each major installation was requested to designate one o r more representatives to make up a committee, which was first called the Manhattan Project Editorial Advisory Board, and later, after the sponsorship of the Series was assumed by the Atomic Energy Commission, the Project Editorial Advisory Board. This group made plans to coordinate the writing programs at all the installations and acted a s an advisory group in all matters affecting the Projectwide writing program. Its last meeting was held on Feb. 9, 1948, when it recommended the publisher for the Series.
vii
ACKNOWLEDGMENT
The Manhattan Project Technical Section of the National Nuclear Energy Series embodies results of work done in the nation's wartime atomic energy program by numerous contractors, including Columbia University. The arrangements for publication of the s e r i e s volumes were effected by Columbia University, under a contract with the United States Atomic Energy Commission. The Commission, for itself and for the other contractors who contributed to this series, wishes to record here its appreciation of this service of Columbia University in support of the national nuclear energy program.
viii
PREFACE
PREFACE
ix
The names of the Board members and of the installations which they represented a r e a s follows:
Atomic Energy Commission Public and Technical Information Service Technical Information Division, Oak Ridge Extension Office of New York Operations Brookhaven National Laboratory Carbide & Carbon Chemicals Corporation (K25) Carbide & Carbon Chemicals Corporation (Y12) 'f Clinton Laboratories 1 General Electric Company, Hanford General Electric Company, Knolls Atomic Power Laboratory Kellex Corporation Los Alamos National Bureau of Standards Plutonium Project Argonne National Laboratory Iowa State College Medical Group SAM Laboratories
Â
Alberto F. Thompson Brewer F. Boardman Charles Slesser, J. H. Hayner,
W. M. Hearon
*
Richard W. Dodson R. B. Korsmeyer, W. L. Harwell, D. E. Hull, E z r a Staple Russell Baldock J. R. Coe
T. W. Hauff
John P. Howe John F. Hogerton, Jerome Simson, M. Benedict R. R. Davis, Ralph Carlisle Smith C. J. Rodden
R. S. Mulliken, H. D. Young
F. H. Spedding R. E. Zirkle
G. M. Murphy
Stone & Webster Engineering Corporation University of California University of Rochester
B. W. Whitehurst R. K. Wakerling, A. Guthrie D. R. Charles, M. J. Wantman
Many difficulties were encountered in preparing a unified account of Atomic Energy Project work. F o r example, the Project Editorial Advisory Board was the f i r s t committee ever organized with r e p r e sentatives from every major installation of the Atomic Energy Project. Compartmentation for security was s o rigorous during the war that it had been considered necessary to allow a certain amount of duplication of effort rather than to permit unrestricted circulation of r e s e a r c h information between certain installations. As a result, the writing programs of different installations inevitably overlap markedly in many scientific fields. The Editorial Advisory Board has exerted itself to reduce duplication in s o f a r a s possible and to eliminate discrepancies in factual data included in the volumes of the NNES. In particular, unified Projectwide volumes have been prepared on Uranium Chemistry and on the Analysis of Project Materials. Nevertheless, the reader will find many instances of differences in results o r conclusions on similar subject matter prepared by different authors. This has not seemed wholly undesirable for several reasons. F i r s t of all, such divergencies a r e not unnatural and stimulate investigation. Second, promptness of publication has seemed more important than the removal of all discrepancies. Finally, many Project scientists completed their contributions s o m e time ago and have become engrossed in other activities s o that their time has not been available for a detailed review of their work in relation to similar work done a t other installations. The completion of the various individual volumes of the Series has also been beset with difficulties. Many of the key authors and editors have had important responsibilities in planning the future of atomic energy research. Under these circumstances, the completion of this technical s e r i e s has been delayed longer than its editors wished. The volumes a r e being released in their present form in the interest of presenting the material a s promptly a s possible to those who can make use of it. The Editorial Advisory Board
*Represented Madison Square A r e a of the Manhattan District. The Y12 plant a t Oak Ridge w a s operated by Tennessee Eastman Corporation until May 4 , 1947, a t which time operations were taken over by Carbide & Carbon Chemicals Corporation. $Clinton Laboratories w a s the f o r m e r name of the Oak Ridge National Laboratory. Â§SA (Substitute Alloy Materials) was the code name for the laboratories operated by Columbia University in New York under the direction of D r . H. C. Urey, where much of the experimental work on isotope separation was done. On Feb. 1, 1945, the administration of these laboratories became the responsibility of Carbide & Carbon Chemicals Corporation. Research in progress t h e r e was t r a n s f e r r e d to the K25 plant a t Oak Ridge in June, 1946, and the New York laboratories were then closed.
COLUMBIA UNIVERSITY PROJECT FOREWORD Governmentsupported research on nuclear energy f i r s t occurred in early 1940 when certain funds made available by the Army, Navy, and National Bureau of Standards were used for experiments a t Columbia University. The subsequent history of this project a s it expanded in many other universities and industrial laboratories is told in detail in the Smyth Report. Two of the major programs began a t Columbia University: the uraniumgraphite pile reactor and the gaseous diffusion method of uranium 235 separation. Lack of sufficient laboratory space a t Columbia for the development of both programs led to the transfer in the spring of 1942 of the uraniumgraphite reactor program to the University of Chicago. The program of separation of uranium 235 by gaseous diffusion, and various ancillary projects, developed rapidly until not only all available space in the Columbia University buildings was occupied but, in addition, an even greater amount of rented space. The project for the separation of uranium isotopes by gaseous diffusion was first carried forward through various government cont r a c t s under the direction of Harold C. Urey, Professor of Chemistry, and John R. Dunning, Assistant Professor of Physics. In 1943 the work was unified under a single contract with the Manhattan Engineer District with Professor Urey as Director. An account of the research on the major assignment, the separation of the uranium isotopes, is to be found elsewhere in the National Nuclear Energy Series. The volumes that this preface introduces deal with the general mathematical theory of isotope separation, with some new experimental methods of separating isotopes, with spectroscopic properties of uranium compounds, and with the chemical and physical properties of heavy water and other deuterium compounds. Most of this work was done at Columbia, but parts of it were carried on a t the National Bureau of Standards and a t The Johns Hopkins University. George B. Pegram Chairman, Columbia University Division of War Research, 19411945
The Manhattan Project Technical Section of the National Nuclear Energy Series is intended to be a comprehensive account of the scientific and technical achievements of the United States program for the development of atomic energy. It is not intended to be a detailed documentary record of the making of any inventions that happen to be mentioned in it. Therefore, the dates used in the Series should be regarded a s a general temporal frame of reference, rather than a s establishing dates of conception of inventions, of their reduction to practice, o r of occasions of first use. While a reasonable effort has been made to assign credit fairly in the NNES volumes, this may, in many cases, be given to a group identified by the name of its leader rather than to an individual who was an actual inventor.
AUTHOR'S PREFACE
PUBLISHER'S NOTE
Although every effort has been made to ensure accuracy in references, at the time of publication of this book some of the other volumes of the Series had not been completed. It is therefore possible that some of the references to other volumes a r e in e r r o r . It is hoped that the extensive c r o s s checking which has been done in the preparation of this volume has resulted in keeping such e r r o r s to a minimum.
by the theoretical division of the SAM Laboratories and its antecedents, which the author was privileged to lead. The work was done over a period of years, from 1940 to 1945, under contract to various government agencies. However, we have in some instances drawn on outside sources for special topics, and some of the material in the volume is new. Since the reports have not been and probably will not be published, we have avoided distracting the reader with references in the body of the text which would be meaningless to him. At the end of each chapter a reference section of relevant reports is appended for purposes of record. Specific references to published articles a r e footnoted a s they occur in the text. Although the theory was developed piecemeal in response to various demands, it is exposed a s a logical whole according to our present understanding and experience. In Chaps. 1 to 5, on various aspects of cascade theory, certain generalities that a r e common to many different separation methods a r e collected. Chapter 6 treats the centrifugal method. Chapter 7 is composed of sections briefly outlining twophase separations (including chemical exchange and distillation) and the thermaldiffusion method, and a section presenting some remarks on the separation of deuterium. The studies given a r e a selection from a much larger volume of material. More emphasis is put on general principles and concepts than on an exhaustive collection of particular results, no matter how elegant. It is thought unlikely that any detailed problem will recur in exactly the same form and that a thorough grasp of the fundamentals will be more useful to the reader. In any event, the most important applications of the theory cannot yet be discussed. While the theory itself is intact, the reader may find that the motivations and explanations a r e occasionally somewhat sketchy. This is a result of security deletions. We did not feel that they were important enough to warrant extensive rewriting.
xiii
XIv
AUTHOR'S PREFACE
There is no reference to direct experimental proofs of the theory, although they a r e not lacking. This is only partly a question of space and security. In a large measure the theory is selfevident, in the fashion of demonstrations in thermodynamics. Karl Cohen
1
ACKNOWLEDGMENTS Development of the theory in this volume was influenced by many discussions with people whose names appear on no theoretical report. It is a pleasure to acknowledge indebtedness to Drs. J. R. Dunning, E. T. Booth, and H. A. Boorse, all of Columbia University, and Dr. F. G. Slack, of Vanderbilt University, for ideas and criticisms. A British team, composed of Drs. F. Simon, R. Peierls, K. Fuchs, and N. Kurti, worked out independently the theory of separation a s it applied to a particular separation. They obtained substantially the same results, in a different chronological order, corresponding to the different order in which the problems were attacked. Adequate liaison was accomplished in early 1942, at which time a very stimulating comparison of results and viewpoints was made. This and subsequent contacts contributed toward clarity of thought and expression. Much of the credit for the success of these investigations i s due to Dr. H. C. Urey: on an administrative plane, for his unwavering support of the theoretical group; and on a scientific plane, for imparting to us his fine intuitive grasp of the essentials of separation processes. The concept of separative work, which i s basic for the comparison of different methods, was first used by him in 1939. The author is personally indebted to E. V. Murphree, of the Standa r d Oil Development Company, for allowing him the time to write this volume. The role of our colleagues in the theoretical division does not really need to be mentioned here; their contributions will be amply demonstrated by the reference sections. Above all, Dr. I. Kaplan, H. Mayer, and Dr. R. D. Present have contributed substantially to the success of this work. The elegant derivation of the value functions and the separative power in Chap. 1, Sec. 3, is due to Prof. P. A. M. Dirac. The value function itself, Eq. 1.43, was first determined by Prof. R. Peierls. The relaxationtime phenomena for square cascades were worked out with the constant aid of Dr. I. Kaplan. The method of determining the fundamental constants in the steady state i s due to Dr. W. I. Thompson, of the Standard Oil Development Company. The mathematical method employed in Chap. 4 on losses was shown to the author by Dr. R. P. Feynman, then at Princeton University. The solution of the
August 1951
mi
ACKNOWLEDGMENTS
fluctuation problem, which avoids solving the differential equation f o r the second o r d e r , was devised by Dr. K. Fuchs. Without the aid of Mrs. L. W. Goodhart, of the Standard Oil Development Company, i n editing and in all phases of preparation of the manuscript, it could never have been finished; special thanks a r e due to h e r f o r this important s h a r e of the work.
1
CONTENTS Page Foreword Preface Columbia University Project Foreword Author's Preface Acknowledgments. Introduction
Karl Cohen
.................................... v . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii . . . . . . . . . . . . . . . . xi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiii . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xv .................................. 1
CHAPTER 1
Ideal Cascades.
................................
CHAPTER 2
5
Square Cascades
...............................
CHAPTER 3
30
Equilibrium Time of a Square Cascade
.................
39
CHAPTER 4 Determination of Cascade Constants
..................
62
CHAPTER 5 The Control Problem
............................
CHAPTER 6
79
Centrifuges
...................................
Ss
103
CHAPTER 7 Other Separation Methods
.........................
xvii
126
xviii
CONTENTS
Appendix ARoots
of a Transcendental Equation
.........
139
................................... Appendix C The Holdup Function . . . . . . . . . . . . . . . . . . . Appendix D Rayleigh Distillation . . . . . . . . . . . . . . . . . . . Appendix EProperties of Concurrent Twophase Elements. . Index.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
i
Appendix BEquilibrium for N 1

Time of Square Cascades
144 147 150 154 163 INTRODUCTION The separation of isotopes may be accomplished in many ways. In this volume consideration will be given, in more, or l e s s detail, to centrifuges, electromagnetic methods, electrolysis, chemical exchange, thermal diffusion, and distillation. Within each of these categories there is considerable variety. For example, chemical exchange may take place between a liquid phase, between a liquid phase and a vapor phase by countercurrent scrubbing, or between two liquid phases with concurrent contacting. All these methods, except the massspectrograph method in isolated instances, have the common feature that one elementary process does not produce the desired large change in isotopic abundance. The problem of efficiently multiplying elementary processes to reach large end results is thus of utmost practical importance, and indeed of greater importance the smaller the change produced by the elementary process. Fortunately, although the methods differ both physically and mathematically in fundamental ways, they a r e sufficiently alike so that their multiplication problems a r e very closely related. It will therefore be useful to examine thoroughly the multiplication problem per se before taking up any of the several separation schemes in detail. The purpose of the first five chapters is to develop the theory of cascades a s generally a s possible in order to permit the widest possible application to future separation problems. Existing applications of the theory will b e found in the subsequent chapters on particular separation methods. The point of view taken is that of a development engineer, and the main concern is the significance of the results in terms of cascade design. For example, the effect of losses is investigated in terms of the problem "How much larger do we have to build our stages to get the same quality and quantity of yield for a given loss?" rather than "In a given cascade how will the yield vary with loss?" Consideration is seldom given to problems of the second kindproblems that occur after the cascade is builtalthough naturally the same equations govern both questions.
2
THE THEORY OF ISOTOPE SEPARATION
INTRODUCTION
3
In Secs. 1 to 4 of Chap. 1 the concept of an ideal cascade is examined from three radically different points of view; Section 5 introduces the idea of equilibrium time. Section 6 gives the general par
tial differential equation showing the dependence of mole fraction in a cascade on time and stage number. The first portion of Chap. 2 is intended to show the steadystate behavior of single countercurrent columns, or square cascades. In Secs. 2 and 3 of the chapter, cascades of countercurrent columns a r e considered. Section 4 covers the squaring off of the top of a cascade. Timedependent phenomena in square cascades a r e dealt with in Chap. 3, along with the methods for experimental determination of the fundamental constants of a separating element. Chapter 4 considers the increase in size of a cascade with losses, the efficient combination of plants using different separation processes, and the prime operating problem of the control of a cascade. Chapter 5 deals with the mathematical theory of the effect of disturbances in operation on the production of the cascade. Chapter 6 describes the different types of centrifuges and gives the partial differential equation of the centrifuge. Other separation methods a r e presented in Chap. 7. Only for certain kinds of processes"infinitesimal" processes, countercurrent columns, and the mass spectrographis the theory developed explicitly, in such a way a s to permit immediate application. In the last chapter, which includes the deuterium problem, a r e introduced cascade problems that a r e not treated in Chaps. 1 to 5. But no one who has absorbed the first five chapters will be at a loss to solve the problems. Likewise, among the infinite variety of nonideal cascades, only square cascades have been selected a s being of universal interest. The reader will be able to work out for himself such variants a s cascades in the form of a lozenge (the "cascadeofcascades" in British terminology). The generality of the treatment still leaves something to be desired, since the entire treatment is restricted to binary isotope mixtures. This is a consequence of the practical origin of the theory. In a general way an attempt has been made to avoid lengthy mathematical demonstrations, except when they a r e indispensable to the argument. For this reason there is only a very general treatment of the control problem, which is beset with many purely mathematical difficulties. A detailed study of the equilibriumtime problem of an ideal cascade has also been omitted; here again the problem has more mathematical than physical interest. Some of the sections that a r e mostly mathematical might perhaps be omitted on a first reading.
They a r e Secs. 2 and 3 of Chap. 2; Secs. 1 and 2 of Chap. 3; Secs. 1,2, and 3 of Chap. 5; and Appendixes A and B. In the Appendixes a r e grouped a number of extensions and amplifications that have considerable practical interest. Appendixes D and E in particular contain special results upon which some work in the later chapters is based. The many graphs which a r e included were designed for use a s well a s illustration, and particular pains were taken to ensure their accuracy. The same applies to the tables, which were in some cases recalculated entirely for this book. Principles of Notation and Terminology. Because of the wide variety of topics that will be covered in this review, it will not be possible to set up a system of notation that will be general enough to cover every case and at the same time describe each special case naturally. However, certain principles of notation will be followed. A mole fraction of a particular isotope will always be denoted by the letter N. In our case of binary mixtures, the two mole fractions a r e of course N and (1N). In twophase systems, all lowercase letters will refer to one phase, uppercase letters to the other. Thus N and n will refer to mole fractions in different phases. With every binary mole fraction N we will associate the corresponding molecular abundance ratio R, where
Thus corresponding to n there will be r = n/(l n). AS material flows through a separating element, its mole fractions a r e changed. The mole fractions at the various orifices of a separating element will be distinguished by primes (for example, see Fig. 1.1). Quantities of materialgenerally expressed in moles per secondare designated by L's. The term "cascade') is used to mean any connected arrangement of elements. The "elementsv a r e the separative unitsindividual centrifuges o r fractionating columns. A "stagey7 of a cascade consists of all units operating in parallel on material of the same mole fraction. (In the special case of one element per stage, the terms "element" and "stage" will be used interchangeably.) The feed material of a cascade, generally of natural abundance ratio, is denoted by the subscript zero (No); the amount of feed is F moles/sec. The "stage number" (counting the bottom stage a s zero) is denoted by s. The mole fraction of material fed into the sth stage is Ng, and the amount is Lg.The subscript S indicates the top stage of a recti
4
THE THEORY O F ISOTOPE SEPARATION
fying cascade. The mole fraction a t the product end of a cascade is Np ;the amount of product is P. The mole fraction of the waste i s Nw; the amount of waste is W. Other general terminology and notation will be covered in the subsequent introductory discussion of cascades. Equations, figures, and tables a r e numbered decimally (viz., Eq. 6.4); the f i r s t digit indicates the chapter, the number after the decimal the order in the chapter. Chapter 1 IDEAL CASCADES
Consider a separating element that divides an entering stream of L moles/sec of a bicomponent mixture, with the mole fraction of one component designated a s N, into two s t r e a m s of 0L moles and mole fraction N', and (1  Q)L moles and mole fraction N", respectively (Fig. 1.1). Of course 0 < 0 < 1, where 0 is known as the "cut." Further suppose that the action of the unit is such that
The t e r m a is called the "simpleprocess factor" of the separation.' F r o m the conservation of matter
Now suppose that a cascade is built of such elements, the size of each stage being graduated s o that the flow entering the sth stage is L c . F o r purposes of this discussion it is irrelevant whether each stage is built of a single element, whose size differs from stage to stage, o r of identical small elements in parallel, whose number v a r ies. The elements a r e connected a s shown in Fig. 1.2, s o that the enriched fraction from each element is fed into the stage next above and the other fraction is fed into the stage immediately below it. At the top of the cascade, material is withdrawn continuously a t a rate P moles/sec. It should be observed that there is considerable latitude
This t e r m i s usually reserved f o r t r u e equilibrium ratios of abundance ratios (cf. Eq. 6.7 and Eq. 8 of Appendix D) which, however, have no universal relationship to the a of Eq. 1.1. If necessary to distinguish, a of Eq. 1.1 i s referred to a s the "effective"
6
THE THEORY OF ISOTOPE SEPARATION
IDEAL CASCADES
7
about the choice of the flows, Ls. For the instant they a r e completely arbitrary. The problem now at hand is one of choosing flows Ls and cuts 13~to get the most efficient cascade. Clearly, the remixing of materials of different mole fractions must be avoided. That is, i t is imperative that R&1= Rs = R;+l From Eqs. 1.1 and 1.3, Rs = RLI = a R s  i , whence (1.3)
Equation 1.11 gives the flow required in the sth stage of a cascade producing P moles/sec of material with mole fraction Np, and Eq. 1.6 gives the required cut to ensure that no mixing takes place in the
ENRICHED OUTPUT e L,N1
follows immediately by induction. Likewise R; From Eqs. 1.2 and 1.5,
=
1  Rs
a
STRIPPED OUTPUT (49)L.N''
Fig. 1.1A
simple
separating element.
Considering that section of the cascade above an imaginary line drawn between the 8th and (s + 1)th stages (see Fig. 1.2), we must have balance between the amount of materials entering and leaving this whole section, i.e.,
cascade. Such a cascade is called an "ideal" o r "nomixing" cascade. In exactly what sense this is the most efficient cascade will be made clear later. Equation 1. l l can be written a s
Substituting Eq. 1.7 in Eq. 1.8,
by replacing the N's by R's and remembering that Rs = asRo and that R Ro. In this form the Lie may be summed to get the total flow p in an ideal cascade. Noting that
Equation 1.9, which i s a consequence of the conservation of matter, holds generally for all cascades, even if mixing takes place. Introducing Eq. 1.3, the condition of no mixing, in Eq. 1.9,
it readily follows that
Using the properties of the separating element itself and eliminating N; by Eq. 1.1 and eS by Eq. 1.6,
THE THEORY OF ISOTOPE SEPARATION
IDEAL CASCADES
2
Since the size, o r number of elements, of a stage is proportional a the flow into the stage, the total flow measures the magnitude of the whole cascade.
1. THE INFINITESIMAL CASE
Because of the special importance of cascades when the simpleprocess factor is very nearly 1, the limiting f o r m s of the equations just found will be written for
a  1 = e
Ã
1
I
FROM s 2 STAGE
Equation 1.1 can be expressed a s NtN
=
+
R' 1 + R'
R R'  R = (a 1 + R  (1 + R') (1 + R)
s+4
which in the limit is the s a m e as
_
_
_ _ __I__


(IMAGINARY DIVIDING LINE)

In the nomixing case Eq. 1.15 becomes Ns+l  Ns = eNs (1  Ns ) and Eqs. 1.4, 1.6, and 1.11 a r e replaced by the following:
Rs = e^R,
(1.17)
(1.18) (1.19)
   
ENRICHED FRACTION STRIPPED FRACTION FEED MIXTURE
1 6   + ^  ( 2 ~ ~ 1) 2 4
The total flow in the cascade may be determined from Eq. 1.20 a s follows:
I
i
I
I
Now Eq. 1.17 may be written
cascade of simple
Fig. 1.2A
elements.
10
THE THEORY OF ISOTOPE SEPARATION
ap
IDEAL CASCADES
11
Inserting in Eq. 1.21 and dropping the now superfluous subscript s,
very close to $$. Passing over to the limit, which i s clearly legitimate since Ns varies slowly,
which could have also been obtained directly from Eq. 1.13. Equation 1.19 shows that in the infinitesimal case Os varies very slightly with Ns Even if as they must be  e and 6 a r e related by the physical nature of the separating element, e will be constant throughout the cascade, to t e r m s of the o r d e r of e2, and the preceding analysis holds. But for the finite case, if an internal relation between a and 6 exists which differs from Eq. 1.6, a will vary from stage to stage, and the equations break down. Practically, this means that the cascade equations will not be universally applicable unless (a  1) is sma1l.l
Equation 1.27 gives the r a t e of increase of N per stage a s a function of the flow per stage, here considered a s an arbitrary function. Now consider a function such a s the total flow in the cascade Total flow = ds ds dN
.
L'L = l N p ~ ( ~ )
0
o r the total number of elements, each of which i s capable of processing G moles/sec, Number of elements =
1
N~
0
L(N)
ds
dN
2. RELATION BETWEEN IDEAL AND NONIDEAL CASCADES
Perhaps the best way of understanding the r e a l significance of ideal cascades is to consider their relation t o nonideal cascades. To do this the infinitesimal case must again be treated, this time allowing mixing. F r o m Eqs. 1.2 and 1.16,
o r more generally, the integral of any property proportional to the flow per stage
where Na and Nb a r e arbitrary; <A(N) does not change sign inthe range Na < N < Nb, and using N instead of Ns on the right to the same accuracy a s Eq. 1.16. ; From Eqs. 1.7 and 1.8, the ideal flow of Eq. 1.20. The asterisk (*) i s used in this volume to denote the Laplace transform of any function. The design problem f o r cascades may then be expressed a s follows: Of all possible cascades that produce P moles of product with a mole fraction Np, starting from raw material of mole fraction No, which cascade makes I a minimum? Or, since each function L(N) completely determines a cascade, what function L(N) makes I stationary? Clearly, I will be a minimum when
Combining Eqs. 1.24 and 1.25,
Now, from Eq. 1.7, if P is much smaller than Ls and if the values of Ls vary slightly from stage to stage, all the values of OS will be
' Cf. Appendix D:
Rayleigh Distillation.
12
THE THEORY OF ISOTOPE SEPARATION
IDEAL CASCADES
that is, when L =L* Therefore the ideal cascade minimizes the number of separating elements, and related quantities, in any section of a cascade. When L = L*, from Eq. 1.27,
3. VALUE FUNCTIONS AND SEPARATIVE POWER
Equation 1..23, for the total flow in an ideal cascade, is the ratio of a term
is half the maximum concentration gradient (which occurs when P/L = 0). Optimum rate of production of a stage i s that rate which reduces the concentration gradient to half its value at no production. It is well to bear in mind that the concept of an ideal cascade is a s sociated with the form of I. For example, to minimize expressions such a s
Total number of stages
= Js
ds =
LoNp
L 2L  L*
dN mFm
(1.34)
requires L = m and not L = L*. In practice it will be necessary to strike a balance between reducing the number of separating elements and reducing the number of stages. Furthermore an ideal cascade requires each stage to be of a different size. F o r these reasons actual cascades will deviate somewhat from ideal cascades. Nevertheless, the properties of ideal cascades a r e of great practical importance because of the proposition that follows. Developing I about L = L *,
which depends only on the amount and mole fraction of material produced, and a t e r m e2/2, which is characteristic of the separating element. This suggests that each t e r m separately has physical significance and also that Eq. 1.23 might be established in a more gene r a l way. An attempt should now be made to derive a function U that represents the value of a quantity of separated material, i.e., a function proportional to the number of separating elements required to produce it. Obviously U = P V(N), where P is the number of moles of material. Suppose G moles of material is passed through a separating element of the type shown in Fig. 1.1. There results a net change in value
Taking (a 1) = e s e r i e s about N,
K
1 and expanding V(N1) and V(Nt1) in Taylor's
(N" ~ [ ( N ~ '  Nd2v } + ~ [ ~ G ( ~ ' ~ ~ ) ' + (   ~ )+ G ) ](N) The first term on the right is called I*, the value of I for the ideal case. If IL  L* 1 =s y L * for y c 1, Eq. 1.35 gives, to higher powers of Y, (1.36) I  I* 5 y21* Expressed in words: If the flow in a cascade at no point differs from that in the corresponding ideal cascade by more than 20 per cent, integrals of the type in Eq. 1.30 will not differ from the ideal integrals by more than 4 per cent. It is this stationary property of integrals for the ideal cascade which makes them useful for all cascades.
I
...
(1.38)
The coefficients of V(N) and d v ( ~ ) / d N vanish by the conservation of matter. From Eq. 1.2, 6(Nr N) =  (1  6) (N" N) and from Eq. 1.16, N1  N = N(l  N). Thus Eq. 1.38 becomes (1.39)
14
THE THEORY O F ISOTOPE SEPARATION
IDEAL CASCADES
15
Now, specifying that this change in value be independent of N, the following equation must hold:
GUp Total flow =   2P V(Np) 1  6 6U c2 6 should be pointed out that, in o r d e r f o r Eq. 1.44 to hold, there t be no process taking place in the cascade which changes U exthe separation process; that i s , t h e r e must be no mixing.l Equa1.46 therefore gives the total flow in an ideal cascade, a s found viously f o r the special case2 6 = $$. A different choice of the integration constants is of course permisble. Taking V(0.50) = dv(0.50)/dN = 0, which means taking the equiolar mixture instead of the natural abundance a s the fiducial point, ves the simple formula
Then Eq. 1.40 becomes
The t e r m 6 U i s called the "separative power" of the element.' The differential expression of Eq. 1.41 defines V(N) except f o r two integration constants. Following Dirac, these may be chosen by r e quiring that V(No) = ~ v ( N ~ ) / = 0, where No i s the natural abundance. ~N The f i r s t condition is obvious; the second makes V(N) a minimum at N = No and s o e n s u r e s a positive value f o r V over the entire range of concentrations. Thus it is found that
the value, which has the obvious advantages of depending on only mole fraction and of being the same for all isotopes. However, equation like Eq. 1.46 takes the form Total flow =  (Up + U&  U;) 6U
G
V will be called the "value function." Obviously it i s the value p e r mole. Since one element produces a change in value 6U, r e g a r d l e s s of the mole fraction of the material on which it operates, the number of elements required to produce a change in value A is U
Total number of elements = A U / ~ U and Total flow = G
X
,
(1.44)
(number of units) = G
AU
=
2AU 1  0 77
(1.45)
F o r the cascade previously considered
and since U' i s always used in such differences, with two relations between the p a r a m e t e r s (Eqs. 1.61 and 1.62), i t s numerical value i s l e s s illuminating. F r o m the standpoint of calculations, if there is one particular isotopeseparation problem, with No known, values of V a s defined by Eq. 1.43 a r e most useful. These a r e found in Fig. 1.3 f o r the m a aium problem, No = 1/140. F o r a survey of many different separation problems, values of V a r e required. They a r e found in Table 1.1 and Fig. 1.4. V will be called the "elementary value function," to distinguish it from V, which is the value function relative to natural abundance. U' will be called the "elementary value, " and U will be defined a s the "value of a quantity of material." The value functions and the separative power have been derived f o r infinitesimal p r o c e s s e s . They may also be extended to cover the case of large values of a.
'Mixing reverses the process in Eq. 1.37 and hence decreases U. 'Since 8 has not been restricted, in general a more intricate cascade than the one shown in Fig. 1.2 will be required. F o r example, if 6 = '/5, the enriched fraction from stage s will have to be fed into stage s + 3, while the depleted fraction is fed into stage
s2.
where the subscripts r e f e r to the product, waste, and feed points. With the convention chosen, Uo = Uw = 0 and Eq. 1.45 is merely
'Note that e must be a function of 6. a s otherwise b U
  as 6
1.
16
THE THEORY O F ISOTOPE SEPARATION
46 0
IDEAL
CASCADES
I
I
I
I
I
I
I
I
Table 1.1The
Elementary Value Function
= V'(1
F o r N > 0.50 use V'(N) V = (2N

N 1) In 1 N
0
0.2
0.4 0.6 M O L E FRACTION
0.8
1. O
Fig. 1.3Functions
associated with infinitesimal cascade. No= 0007143.
Consider a symmetric process1 where (cf. Eqs. 1.5 and 1.6)
Then corresponding to Eq. 1.37
= constant
Now introduce s by the equation R = Roos and s e t (1 + R) V(R) = g(R) = g(RoCt3) = F(s)
'The problem i s also soluble for asymmetric processes, where quite complicated functions a r e found.
THE THEORY OF ISOTOPE SEPARATION
IDEAL CASCADES
a + 1 2N1 R V(R) = C  in+ a  1 lna Ro
[
a  N o ( a + l ) (NNo) a  1 No(l  NO)
]
(1.55)
Now take the constant C = 6u/G s o that
Thus R lna a(a+l)No (2N  1) In  + (NNo) a1 N ~ ( ~  N ~ ) RO
I
(1.57)
0
0.10
0.20
0.30
0.40
0.50
MOLE FRACTION
Fig. 1.4The elementary value function. For values of N > 0.50,use v'(N) = V f ( l N); for N > 0.46, V = 2(2N  I)'.
With these definitions Eq. 1.50 becomes
Equations 1.56 and 1.57 a r e closely analogous to Eqs. 1.42 and 1.43. The variation of U f fwith a exhibited in the second t e r m is caused by the varying concentration of byproduct waste material and has no theoretical significance. The elementary value for l a r g e a is of course still U ' . The separative power v a r i e s a s ( a  1)' f o r small (a  I ) , but f o r large a increases only a s In. Since the number of elements in a c a s cade varies inversely a s the separative power of an element, it i s important to design and operate the elements s o that their separative power (Eq. 1.42 o r Eq. 1.56) is a s l a r g e a s possible. This problem will be considered in detail in subsequent discussions on particular separation schemes. It i s also possible to calculate the separative power for some more general types of separating elements. If it i s assumed that instead of two s t r e a m s leaving the apparatus of Fig. 1 . I , t h e r e a r e many, each , of magnitude L ~ and furthermore
The general solution of Eq. 1.52 is
where A and B a r e constants, which gives a + 1 2N1 R AN V(R) = C In  + + a1 lna R O Ro B ( l N) (1.54)
Setting V(Ro) = 0, and establishing the convention that the waste m a t e r i a l from the feed stage, of abundance ratio Ro/a, has zero value also, the following relation holds:
20
THE THEORY O F ISOTOPE SEPARATION
IDEAL CASCADES
21
SO
The f i r s t two t e r m s onthe right vanish by the conservation of matter. Hence
ally both
Â
T
 NP
and N'  N a r e proportional to N(l  N); if
6u =
( T  NP)
(N'  N) ~ 2 (~ ) 2 1
(1.60)
of which Eq. 1.42 is a special case. For infinitesimal separating elements of the countercurrent type, 6U may be evaluated a s follows: Consider two large reservoirs (see Fig. 1.5) containing, respectively, M moles of material in which the
quantity T , i.e., the amount of desired isotope moved forward, is ed the "desired material transport." The factor T  NP is called "net transport." Equation 1.60 is an exceedingly important fora for the theory of countercurrent processes. he separative powers for two other important special types of ents a r e fully discussed in Appendix D (Rayleigh Distillation) and ndix E (Properties of Concurrent Twophase Elements).
4. CASCADES WITH STRIPPING SECTIONS
1
Fig. 1.5Separative
SEPARATING ELEMENT
1
In addition to a rectifying section, it will usually be desirable to e a stripping section in the cascade.l The function of the stripping tion is to economize raw material by recovering the desired isoe from the reject stream of the rectifier. Figure 1.6 shows the ions between rectifier and stripper. r any cascade, ideal o r otherwise, provided there is no loss of terial anywhere in the system, the following relations hold:
work of a countercurrent element.
mole fraction of desired material is N, and M' moles of slightly different mole fraction N' > N. The separating element puts P moles of mixed isotopes containing T moles of (pure) desired isotope into the upper reservoir, withdrawing the same amounts from the lower r e s ervoir. The upper reservoir increases in mole fraction by an amount
r e F, P , and W refer to the amount of feed, product, and waste, pectively, and No, Np, and Nw a r e the corresponding mole fracs. aking the mole fractions a s given and eliminating f i r s t F and then etween Eqs. 1.61 and 1.62, it is found that
W = P N~  N o
w No  N
(1.63)
and the lower decreases by the amount (T  PN)/(M  P). Then
he terms "rectifier" and "stripper" are taken from fractionatingtower usage. tower for producing alcohol from wine, for example, the section above the feed t rectifies the alcohol, i.e., concentrates it, while the lower section strips the aste water, i.e., recovers the last traces of alcohol from the reject.
THE THEORY OF ISOTOPE SEPARATION
IDEAL CASCADES
23
0
which relate the size of the waste stream and the feed stream to the rate of production.
resemble closely those for an ideal rectifier. A moment's conderation, referring again to Fig. 1.2, shows that Eqs. 1.4, 1.9, and .ll also hold for the stripping stages of a cascade, with W and Nw replacing P and Np, s running from 1 to B instead of from 0 to S, and Rw = ~ ~ / a ~ + l . Equation 1.11 f o r the flow in the sth stage of a rectifier becomes Ls =Equation 1.13 becomes Total flow (stripper)
=
s=1
a + 1 W(N, Nw) a  1 Ns(lNs)
(1.65)
a 1
1 (aB+s*l  1) + (aB+l  a"' ) Ro
I
a+1 =W[ 1 a
12Nw R In a In Rw
 a
1 =
WASTE W, N , .
N(,(a + 1) NoNw (a1) No(lNo)
I
a + 1 ( a1)lna
u '
(1.66)
FEED
where U$ is the value defined by Eq. 1.57. This expression vanishes a , for Rw = ~ ~ / in accordance with our convention of counting stage 0 a s part of the rectifier. The total flow in a cascade composed of both rectifier and stripper, combining Eqs. 1.13, 1.64, and 1.66, takes the simple forms
a+1 [P(2Np1)ln RP ( a  1) In a Ro
Total flow (rectifier and stripper)
=
+ W(2Nw  1) lnFig. 1.6Above, connections between rectifier and stripper. Below, detail
nections.
of con

a+1 ( a  1) In a (up + uw
a +1 (UP + U& Uo) (1.67) (a  1) In a
Since a stripping section is essentially no different from a rectifying section, except that i t produces material at a different rate and concentration, the equations for an ideal stripper should be expected

24
THE THEORY O F ISOTOPE SEPARATION
IDEAL CASCADES
The t e r m s Up + Uw and Up + U&  U a r e of course AU = AU" and g AU', respectively. Note that in Eq. 1.67 the distinction between U" and U has disappeared, since the t e r m s that differ because of different conventions have canceled out. F o r the infinitesimal case, in place of Eq. 1.65,
f r o m that of the product to that of the feed. Before the plant can oduce concentrated material a t the top i t must build up these inntories of partly enriched material. The time spent in this procis known as the "equilibrium time" o r "relaxation time" of the will be shown l a t e r the operation of a cascade f r o m startingup might be a s follows: At z e r o time the mole fraction a t the top the cascade i s No; hence operations begin with no withdrawal. The centrations increase gradually over the entire cascade, the top of cascade leading. The product end reaches design mole fraction st, while the r e s t of the cascade is still below design. Withdrawal a slow r a t e is then begun, maintaining the top mole fraction a t Np d gradually increasing to design production a s mole fractions in the t of the cascade build up to their steadystate values (Fig. 1.7). eneral definition of the equilibrium time that has meaning f o r this e of operation o r any other is the number of days production that lost between startingup time and steady state production. A useful approximate expression for the equilibrium time of a n eal rectifier by simple considerations will now be developed. The total amount of material in p r o c e s s in a section of a cascade called the "holdup" of the section.' In most cascades the amount holdup in a stage i s proportional to the flow in the stage. This i s rtainly t r u e if the cascade i s built up of identical small elements, that successive stages consist of different numbers of elements in rallel. It also holds when the stages a r e similar single units scaled size. The holdup p e r unit flow will be denoted by h, which i s a l s o e average p r o c e s s time p e r stage, expressed in seconds. The "net desired material holdup" (N.D.M.H.) is the amount of s i r e d isotope in a going plant over and above that which would be contained in a like quantity of material a t normal abundance. It is, the infinitesimal case,
In place of Eq. 1.66 Total flow (stripper) =
f.
Nw2
7
2 W(NNw) dN NO  N ) N(IN)=F~W
and in place of Eq. 1.67 Total flow (rectifier and s t r i p p e r ) =
2
â
(up+ Uw)
uy,  UO)
=  (up +
e2
2
F o r completeness the formulas f o r the number of stages may be added. Number of rectifying stages = S + 1 = In RP/RO In cr w Number of stripping stages = B = In ~ o h _ 1 In a Number of stages (rectifier and stripper) = lnRp/Rw  1 In a F o r the infinitesimal case, In a i s merely replaced by
e.
N.D.M.H. = y " " ' h ~ ,(N, No) d s (1.73)
 ( N P2NpNo+No)ln~2(~p [ No)]
R O
(1.74)
5. EQUILIBRIUM TIME
he equilibrium t i m e in any c a s e is equal to the N.D.M.H. divided by a suitable average transport of desired isotope over the initial period of operation. Without f o r the moment specifying too closely the operNomenclature again borrowed from fractionatingtower terminology.
Obviously some cascades f o r separating isotopes a r e very l a r g e and contain considerable material in p r o c e s s a t concentrations rang
THE THEORY O F ISOTOPE SEPARATION
IDEAL CASCADES
27
may be applied to other than ideal cascades. The usefulness of the expression will depend on the appropriateness of the choice of the average net transport, which will not in general be P(Np  No). The N.D.M.H. i s one of the functions that i s a minimum for ideal cascades, a s is the equilibrium time function E(Np) derived from it. E(Np) i s independent of P .
6. FUNDAMENTAL EQUATIONS O F ISOTOPE SEPARATION
TIME
The partial differential equations describing the timedependent ef fects in any infinitesimal cascade a r e easily derived by a slight extension of the previous analysis.' Ls and 6s a r e taken a s known functions that may vary with time. The mole fraction Ns i s also a function of time: No = Ns(t). Referring again to Fig. 1.2, Eq. 1.7 takes the more general form
where Ts(t) i s the amount of (mixed) material transported into the cascade above the sth stage. Explicitly, if t h e r e a r e no leaks o r losses,
Fig. 1.7Ã‘Productio a s a function of time.
ating schedule, this average transport may be taken a s the net t r a n s port of the rectifier in the steady state, that i s , P(Np  No). This gives
H i is the holdup in the jth stage and is a l s o a given function of time. Ts (t) i s defined in t e r m s of known functions (by Eq. 1.77 o r 1.78) and therefore is known. Likewise Eq. 1.8, the equation of conservation of desired material, holds in the form
Ã [(N,,
Equilibrium time =
2
 2NpN0 + No) In  2 ( ~ p No)] 
RP Ro
(Np  No)
where rS(t) is the amount of desired material transported into the section of the cascade above the sth stage. Unlike T, T is unknown. Explicitly
It should be remarked that the formula for the equilibrium time in the f o r m Equilibrium time = N.D.M.H. average net transport
' F o r finite a it i s difficult toformulate the problem without specifying the separation method.
28
THE THEORY O F ISOTOPE SEPARATION
IDEAL CASCADES
29
In using N,'(t) on the right the difference between the mean concentration of the stage and Ni has been tacitly neglected. Combining Eqs. 1.77 and 1.79
Because special cases of Eqs. 1.81 and 1.82 describe the properties of apparatus in widely differing separation methods and because all the theory s o f a r developed for infinitesimal cascades can be deduced from them by purely formal operations, Eqs. 1.81 and 1.82 a r e called the "fundamental equations of isotope separation. " If L is not a function of t , and H = hL, then T = P, and Eqs. 1.81 and 1.82 combine to give
Assuming Eq. 1.24 t o hold unchanged (what is involved is neglecting the holdup of one stage compared to in the last equation, Equation 1.83, with the initial condition N(s,O) = No, describes the approach to equilibrium of a cascade. F o r an ideal cascade, L is the extremely complicated function defined by Eqs. 1.18 and 1.20. Equation 1.83 will not be solved f o r this case, since the utility of the solution i s slight. In Chap. 3 it will be solved for the practical (and considerably easier) case of a square cascade, taking L a s a constant. Should L (and also H and e ) be a functionof t, fluctuating about some mean value, then Eqs. 1.81 and 1.82 describe the effect of fluctuations on separation, which is covered in Chap. 5, on the control problem.
2
s
Hj) and introducing Eq. 1.24
On passing over t o the limit of continuous functions, OsLs K ( t ) N(s,t), etc., this becomes


%L(s,t),
REFERENCES
which is the required generalization of Eq. 1.27. F r o m Eqs. 1.78 and 1.80 i t is found1 that
Cohen, K., Report A60, October 1941;Report A96, Jan. 5, 1942. Cohen, K.,Columbia Ser. No. 4LX28, Dec. 22, 1942 (letter to J. 8.Dunning). Cohen, K., and I. Kaplan, Report A98, Jan. 14, 1942. Dirac, P. A. M., British MS, 1941. Fuchs, K., British MS 29, Dec. 18, 1941. Fuchs, K., and R. Peierls, British MS 12A, February 1942; British MS 47, June 26, 1942. Kurti, N., and F. Simon, British MS, 1940. Peierls, R., British MS 12, summer 1940; British MS 13, September 1940.
Differentiating Eq. 1.81 with respect t o s and using Eq. 1.82, 9 ~ / 9 s may be eliminated and a secondorder partial differential equation f o r N will result. Thus Eqs. 1.81 and 1.82, with appropriate boundary conditions, completely determine N.
' T h e integral form of Eq. 1.78, for example, i s ~ ( s , t= P )
+f
a
H(j,t) dj
and differentiating with respect t o s gives Eq. 1.82.
SQUARE CASCADES
31
lies to both square cascades and countercurrent units. Indeed, it o preserve this generality that the notation of Eq. 2.1 has been
1. STEADY STATE OF A SQUARE CASCADE (OR COUNTERCURRENT
COLUMN)
Chapter 2 SQUARE CASCADES
In the steady s t a t e t h e f i r s t integral of Eq. 2.1 i s
PNp
=
dN PN + c1N(l  N)  c ds
Ideal cascades a r e characterized by a smoothly varying flow function which i s next to impossible to realize in practice. Fortunately, a s the discussion in Chap. 1 of the relation between ideal and nonideal cascades has shown,it is by no means necessary to adhere strictly to the shape of the ideal cascade. The outlines of this cascade roughly follow those of an ideal cascade, and the properties of the blockedoff cascade closely resemble those of the ideal cascade. A cascade thus obtained from an ideal cas cade is called a "squaredoff cascade." Each section of a squaredoff cascade i s itself a square cascade. F o r a square cascade Eq. 1.83 takes the form
'
ch separates to give a second integral,
ls iNs +
ds = c1N2
S =
c, dN (c1 + P)N  PNp
1 tanhI
6
A($)
(Ng  No) A(+) [(Ns + No) (1 + $)  2NsNo  2Np+
]
(2.5)
a~ a2N c 6 Ã ‘tÃ ‘ = c 5 Ã ‘ a
as2
a
^=
[PN + c ~ N  N)] ( ~ (2.1)
A($)
6
5
P/C,
as
where cl, P, c5, and c6 a r e constants. Specifically c, = hL = holdup p e r stage c5 = L/2 c1 = e L Proof will be given later that precisely the same equation governs the behavior of a countercurrent centrifuge, a fractionating column, a thermaldiffusion column, and most other countercurrent devices. In each of these cases c, and c5 have different but analogous meanings, and s is replaced by z , the coordinate along the length of the column. A countercurrent unit i s therefore equivalent to a square cascade of simple elements of the type of Fig. 1.1, and a cascade of countercurrent units i s like .a squaredoff cascade. The ensuing discussion
[I + 2$(1  2 = c1/2c5
~+ ~
)
(2.6)
The use of <= in Eq. 2.5 agrees with Eq. 2.2; f o r countercurrent colmnns in which the constants c, and c5 a r e fundamental, l i s understood to be defined by 6 = c1/2c5. The dimensionless quantity is thought of as a normalized rate of production. Equation 2.5 gives the distribution in the cascade, for given Np and P,a s a function of s. At the top of the cascade, Ns = No and s = S = number of stages (or length of column, depending on the definition nd units of f ). Equation 2.5 becomes
+
THE THEORY OF ISOTOPE SEPARATION
SQUARE CASCADES
33
g=
1
e A(@)tanhl
f
(NP  No) A(@) (Np  2NpNo  No)  (Np  No)@
  (1 + @)e2*^^ N~
N~
1 + i/fe2N1++)
(2.14)
If values a r e assigned to Np and @, Eq. 2.7 i s an explicit equatio which determines the necessary number of stages (or length of countercurrent column). I S is given, Eq. 2.7 i s an implicit relatio f between Np and @. When P = 0, then 0 = 0, A ( @ ) 1, and Eq. 2.5 becomes =

s
or
=  tanhW1
1 e
N N S O 1 =In RsFt,, Ns 2NsNo + No 2e
ezfS =FRACTIONATION
AT NO PRODUCTION

Rs = ~~e~~~ Equation 2.9 is in no way peculiar to square cascades, since at P = 0 a l l cascades, regardless of their shape, have the s a m e distribution of concentrations, because Eq. 1.27 with P = 0 i s dN ds
$ = YC,= NORMALIZED


=
2eN(l  N)

  26R dR
ds
2
4 6 10'
2
4
6
1" 0
2
4 6
1
2
4 6
1 0
N O R M A L I Z E D PRODUCTION
whence Eq. 2.9 follows. However, although the distribution in an ideal cascade with production a t the designed rate i s again exponential (with half the slope of Eq. 2.9), Rs = RoeEs square cascades have the much more complicated distribution of Eq. 2.5. In the special c a s e when both No<l and Np< 1 , . Eq. 2.7 takes the simpler f o r m s
Fig. 2.1The
effect of production on fractionation.
Referring to Eq. 2.3, since the t e r m s PN + c,N(l  N) increase with s o also must dN/ds. The smallest value of dN/ds is therefore a t foot of the cascade where N i s smallest, N = No. The maximum
@
=
No(l  No)
o NP  N F o r this value of @ Eq. 2.7 becomes
g=6
s = 2c(l 1 @ ) +
No l n N 0 @(Np  No)
A(@)
tanh'll=
34
THE THEORY O F ISOTOPE SEPARATION
SQUARE CASCADES
35
Equation 2.7, for a given value of Np , may be satisfied by an infinite range of pairs of values of S and ip, ranging from S = m, ip = N ( 1  No)/ (Np  No), to S = 1/26 In R ~ / % , $!J = 0. The optimum length of cascade and rate of production a r e that pair of values (S,$!J) which makes the average transport per stage P/S a maximum o r , what is the same thing, makes s/c1ip a minimum. From Eq. 2.7
whose integral is (cf. Eq. 2.5)
where
4s =
A(&)
pAsc1
(2.20)
= [l +
Us (1  2Np) + @
The righthand side i s now a function of ip alone. Since differentiating Eq. 2.17 gives a transcendental equation, the minimum i s best found by direct computation.
The length of columns in the entire sth stage which changes mater i a l of mole fraction Ns to material of mole fraction Ns+l, while the cascade a s a whole produces material of mole fraction Np a t the r a t e P, is
2. SQUAREDOFF CASCADES (CASCADES OF COUNTERCURRENT ELEMENTS)
In the problem of squaringoff an ideal cascade which was previously considered, i t was possible to use square sections of any des i r e d length1 and breadth, i.e., Z and c5 arbitrary. The usual cascade problem is to make a cascade from elements that a r e identical countercurrent columns o r smallcapacity square cascades. Each element has the same constants, cl and c5, and the same length, Z ? Subsequent examples will show that cascades that a r e very close to ideal may be expected, provided the square elements a r e sufficiently small2 Instead of solving the problem just s e t up, i.e., the best Ns with Zs given, i t is much more convenient to proceed indirectly. Suppose that the steps of the cascade, i.e., the Ns, a r e given, and solve for the best lengths Zs to fit this cascade. Then it will be seen how the solution of the second problem solves the desired one. The number of columns in parallel in the sth stage is denoted by vs. The mole fraction fed into the sth stage is Ns , as before. In place of Eq. 2.3, for each of v columns,
vs Zs is a function of <*sand its minimum (e.g., at A, = &) gives the minimum length of column for stage s. From <As i t is possible to obtain the corresponding optimum value of us,
the number of columns in parallel, and also of each individual column,
Es, the appropriate
length
3. RAPID APPROXIMATE SOLUTION FOR SQUAREDOFF CASCADES
'Use is made of Z instead of S for the length of the square subcascades, retaining s a s the stage number of the grand cas.cade. "'Sufficiently small" is here used to mean the transport per element a cascade net transport, and length of stage a ideal cascade length [qNo(l No)Ã P(N  No) and z a 1/e ~n RJRJ.
The solution, Eqs. 2.21 to 2.23, takes a simple form for moderate values of Rs+i/Rs. It may be presumed, subject to later check, that the argument of the arctanh is small. Since tanhI x = x + Ysx3 + , neglecting t e r m s of third and higher order,
...
36
THE THEORY OF ISOTOPE SEPARATION
SQUARE CASCADES
37
which i s a minimum for
With this value of As the argument of the arctanh becomes
A column of length ZS operating with no production will, according to Eq. 2.11, produce an enrichment of e2&. Consequently the theor e m has been proved that a column o r square cascade in the body of a cascade should be operated a t the square rootof i t s maximum f r a c tionation. The foregoing result is really another manifestation of the s i m i l a r relation found for ideal cascades (Chap. 1, Sec. 2). Although the approximate expressions (Eqs. 2.25 and 2.26) a r e fairly inaccurate unless (Rs+l  Rs ) / R ~ is small, experience has shown that the final relation
F o r any stage of a cascade except the top, a s Rs+l Rs, As Ns (1  Ns ) / 2 ( ~ p Ns ) = finite, and the argument 0. But f o r the topmost stage the argument is not s m a l l even for Rp very nearly equal t o Re . F o r , when NS+, = Np,


and the squareroot theorem, which follows f r o m it, both hold for
~ s + l / ~ s 2.
and, a s Rp R e , A (&.) &., and the argument 1. Thus, except for the last stage of a cascade, the approximations in Eqs. 2.24 and 2.25 will be valid f o r sufficiently s m a l l values of R ~ + ~ / R ~ . Using the value Eq. 2.25 for As, from Eq. 2.24 i s obtained



F r o m Eqs. 2.22 and 2.25,
The recommended rapid procedure f o r finding optimum lengths and numbers of columns when the Ns a r e given i s therefore a s follows: The value of Zs is found from Eq. 2.30. Using this value in Eq. 2.23, (ps i s found. (This gives a better value than Eq. 2.25.) Then Vs may be found from Eq. 2.22. It should be remarked that even though Zs from Eq. 2.30 will be slightly i n e r r o r , and likewise V g , vsZs will be indistinguishable from the t r u e minimum because of the stationary properties of a minimum. The solution to the original problem of finding optimum Ns and us when the Z a r e given follows immediately. The Ns a r e found from Eq. 2.30, and the r e s t of the procedure i s the same a s in the preceding paragraph. The final proof that the procedure outlined gives a satisfactory answer is the comparison of the resulting cascade with an ideal (infinitesimalstep) cascade. As NS+l Ns, from Eq. 2.26,


and from Eqs. 2.26 and 2.27,
and Solving Eq. 2.28 f o r R ~ + ~ /leads to R~
where V i s the value function of Eq. 1.43. Equation 2.32 shows that, for a square cascade o r column defined by Eq. 2.31, the separative power p e r unit length o r per stage i s
THE THEORY OF ISOTOPE SEPARATION
In the case of the square cascade whose elements a r e of the type shown in Fig. 1.1, where c, = L/2 and c, = EL,Eq. 2.33 reduces to
Chapter 3 which coincides withthe previous expressionfor the separative power of such elements, Eq. 1.42.
4. SQUARINGOFF THE TOP O F A CASCADE
EQUILIBRIUM TIME OF A SQUARE CASCADE
In the problem and example of squaringoff treated in the last two sections, a scheme was adopted which would make the squaringoff uniform over the entire cascade. If the cascade is built up of small standard elements, this represents no difficulty. F o r example, i f the whole cascade is assumed to consist of 10,000 centrifuges, then the top stage i s made of 9 centrifuges, the twelfth of 28, etc. Consider a cascade that is ideal up to a mole fraction NA and then square up to the top. The square section is taken to have the same flow a s the ideal section a t the point of intersection. It is necessary to compare the properties of an ideal cascadefrom NA to Np with that of a square cascade from NA to Np in which the flow is
The equilibriumtime phenomenon s e e m s a t f i r s t glance to be merely an obstacle to be overcome in successful cascade operation. Indeed, it causes serious production losses in large plants by causing delays when operation i s changed, a s well a s in the initial incubation period. Even for small experimental cascades, it prevents rapid attainment of steadystate conditions and thus slows up the accumulation of data and necessitates long continuous operation for each experiment. However, it is possible to use the r a t e of approach to equilibrium a s a powerful tool f o r determining the constants c, and c5 of the fundamental equation (Eq. 2.1), and consequently to turn the disadvantage into an asset. The theory will be expounded below primarily with this end in view. Solutions will be found for those c a s e s which occur experimentally, and the results will be developed with the aid of tables and graphs for immediate application. The fundamental partial differential equation (Eq. 2.1)
The equilibrium time increases about twentyfive times a s rapidly a s the total flow and is usually the factor that decides the number of stages that can be squaredoff. The squaredoff cascade is shorter than the part of the ideal cascade which it replaces.
is quasilinear and parabolic and can be solved by an iteration method. When N <s: 1, Eq. 2.1 becomes linear, reducing to
REFERENCES
Cohen, K., Report A530, Feb. 4, 1943. Cohen, K , Packed Fractionating Columns and the Concentration of Isotopes, J. Chem. . Phys., 8: 588 (1940). Cohen, K., Columbia Ser. No. 4LX28, Dec. 22, 1942 (letter to J. R. Dunning). Cohen, K., and I. Kaplan, Report A101, Jan. 28, 1942.
Equation 2.1 also becomes linear even for large mole fractions provided the change in mole fractions is small. The substitution N = No + x gives the linear equation
THE THEORY O F ISOTOPE SEPARATION
EQUILIBRIUM TIME O F A SQUARE CASCADE
41
whose solution closely resembles that of Eq. 3.1.
PRODUCTION
RESERVOIR
4
t
HOLDUP
1 1
HOLDUP
p
RESERVOIR TOP
column (by convention the "top"). The other end i s maintained a t a constant composition by supplying fresh feed continuously, which is equivalent to connecting the bottom of the columns to an infinite r e s ervoir. There i s usually a certain amount of external holdup a t the product end in connecting piping, surge tanks, etc. The holdup in this top reservoir i s denoted H. In Type I1 operation (Fig. 3.1) no material i s withdrawn. Both ends feed into and out of finite reservoirs. The holdup of the bottom r e s ervoir (at s = 0) i s called H'. Type I operation with P = 0 coincides with Type I1 operation with H' = w . A still more general type of operation (H and H ' finite; P # O), of which both Types I and I1 a r e special cases, is of no physical significance, since the system is gradually emptied of material and there i s no steady state. Before solving Eq. 3.1 it is convenient to divide through by c5, giving
where
CONSTANTCOMPOSITION FEED
WASTE TYPE
+
I
I
HOLDUP
H '
TYPE
BOTTOM RESERVOIR
The definitions of 0 and c. a r e repeated f o r convenience. F o r square cascades of elements of the type illustrated in Fig. 1.1, A. = 2h by Eq. 2.2. If s i s dimensionless, A. i s expressed in units of time. In Type I1 operation, = 0 in Eq. 3.2. The boundary conditions for Type I operation are1
J! , I
I
I t
Fig. 3.1Diagrammatic columns.
representation of the two main types of experiment on
Consider f i r s t the solution of Eq. 3.1, with N Ã§ (For N 1, s e e 1. Appendix B.) There a r e two main types of experiments: In Type I operation (Fig. 3.1) material i s withdrawn continuously from one end of the

'The difference in concentration between the reservoirs and the ends of the column < may be neglected if K/X? < 1, which i s almost always the case.
THE THEORY OF ISOTOPE SEPARATION
EQUILIBRIUM TIME O F A SQUARE CASCADE
The boundary conditions under Type I1 operation a r e Ats=O,
Â
aN 2eN=K
as

aN at
Ats=S, At t = 0,
aN a N 2.5N =  K  a t as
N = No
F o r , integrating by parts,
In Eqs. 3.4 and 3.5 the factors introduced were
K =H c5
K ' =
The remaining boundary conditions likewise transform. F o r Type I operation Eq. 3.4 becomes
H' c5 F o r Type I1 operation Eq. 3.5 becomes
By f a r the most expeditious method of solving Eq. 3.2 under these boundary conditions i s the use of the Laplace transform. Briefly stated, the method i s a s follows: By the transformation
the partial differential equation (Eq. 3.2) i s transformed into an ordinary differential equation for G with p a s a parameter. The solution of the ordinary differential equation gives G(s,p) explicitly. The inv e r s e operation to Eq. 3.7,
The general solution of Eq. 3.9 is
where Ci and C2 a r e constants and ml and m2 a r e the solutions of then gives the required solution. In Eq. 3.8, B r , i s the f i r s t Bromwich contour in the complex p plane, a line from im to +i, deformed if necessary to pass to the right of the poles of G(s,p). Equation 3.2 will now be solved according to the above outline. Multiplying Eq. 3.2 by ePt dt and integrating from 0 to m gives the equation
The constants Cland C2a r e determined by substituting in Eq. 3.10 f o r Type I operation o r Eq. 3.11 for Type I1 operation. Omitting these details, the results a r e a s follows. Type I Operation:
with
, r Here again b = 0 in Type I1 operation. In establishing Eq. 3.9 the boundary condition a t t = 0 has been used to evaluate
44
THE THEORY OF ISOTOPE SEPARATION
EQUILIBRIUM TIME OF A SQUARE CASCADE
Type I1 Operation: No 2eN0ecs sin y s  f(S,p) g(s,p) G(s,p) =  + PD(S,P) P PY where the functions f , g, and D a r e defined by
1
( e  pK) sin yS  cos yS
where the p j a r e the roots of (3.16) Type I1 Operation: tan yS
=
r
~ (  A )  KP 1
P g(s,p) = ecs (cos y s D(S,P) s
(K'  K) 6
+
pK1 + e
Y
I
(3.17) where the p j a r e the roots of D(S,p) = 0, o r tan yS and
=
sin y s)
' sin y~  (K + K') cos yS
p
~A ~
Y
(K + K' ) Y
E ( K '  K)  ~ K K A
and y is the same a s in Eq. 3.15, but with $ = 0,
The inversion of either expression for G(s,p) can be carried out in two ways, giving two different infinite s e r i e s for the same function N(s,t). The difference between the two methods is that one s e r i e s converges rapidly for small values of t, the other for large values. Although either expansion can be used over the entire range of t by carrying enough t e r m s , it i s more convenient to use both expressions, each in i t s appropriate range. It i s possible in this way to find N(s,t) with considerable accuracy for all values of t, using only the first two t e r m s of the series.

A cos y j s S
7
[(K'  K)E  P ~ K K ' A ]
1, ~ ( s , t )FOR VALUES O F t > h s 2 / l 0
The inverse of G(s,p) suitable for calculations for large t i s the usual Heaviside expansion. It i s obtained by evaluating Eq. 3.8 A s the sum of the residues a t the poles of G. Carrying out the indicated operations, the following i s obtained. Type I Operation:
Equations 3.19 and 3.21 describe N a s a function of stage number and time for square cascades (N Ã‡1). A discussion of the roots of Eqs. 3.20 and 3.22 i s given in Appendix A. It i s shown there that all the roots pj (there a r e an infinite number of them) a r e negative. Thus the t e r m s in the sums a r e transient, and the constant t e r m s represent N(s,m). The second root is shown to be approximately
+s
i
2e sin yjs ec(lirttS~) p, sin y, S
Since the coefficient of epzt i s much smaller than that of eW, the second transient t e r m i s negligible when o,t < 2; that is, when
epjt
AS A K ++[Kpj~e(l$)~ 2 2y7
+ 1] [Kpe(1I))]
(3.19)
46
THE THEORY O F ISOTOPE SEPARATION
EQUILIBRIUM TIME O F A SQUARE CASCADE
47
Consequently, f o r most purposes only the leading transient t e r m need be considered after t = ASVlO. Equations 3.19 and 3.21 a r e valid both for strippers and rectifiers. When the cascade o r column i s acting a s a stripper, c5, P, and S remain positive, but cl is negative. Consequently e and >/Ã a r e also negative. The same formal solutions hold. It i s quite incorrect to analyze a stripper a s if it were a rectifier of the s a m e length, since the equations a r e not symmetrical about eS = 0. Particular examples of the solutions given by Eqs. 3.19 and 3.21 may be found in the reports listed in the references for this chapter. The most important special case of the two types of experiment, namely K ' = , P = 0, has been considered in detail. This is the case of a column operated under total reflux (no production), with the concentration at the bottom maintained a t No. The concentration a t the top of the column, o r in the reservoir a t the top, varies with time according to the relation
Accordingly Eq. 3.24 takes the form
Tables of the functions A and B for K/AS between 0.0 and 0.5 and for 0<2cS<1.20 a r e given in Table 3.1 and a r e plotted in Figs. 3.2 and 3.3. A wider range of these functions for the special case K = 0 is given in Table 3.2, where values of 2eS ranging from 5.0 to +4.0 a r e covered.
2 ~ ( s , t ) VALUES O F t < X . FOR
S ~
Of interest here a r e the inverses of Eqs. 3.14 and 3.16 in the s,t plane near t = 0, that is, the expressions for G(s,p) in the s,p plane f o r p near + W. Dropping t e r m s of the order e2@small compared to unity, Eqs. 3.14 and 3.16 may be written a s follows. Type I Operation:
neglecting the higher transients. Now Type 1 Operation: 1
and yl S is the smallest root of
Therefore ylS is a function of the form
6s and K/\S,
and pl may be exhibited in
The t e r m 6 is defined by Eqs. 3.15 and 3.18. This f o r m is obtained by writing
Likewise
2< = A(2eS, K/kS)(ezes  1)
and s o on. Equations 3.29 and 3.30 hold to within a few per cent provided 0S = 6 s > fi; that is, replacing p by 1/t,
A
AS
(Kp,S  6 S + 1) (Kp,  e )
1
(3.27)
48
THE THEORY O F ISOTOPE SEPARATION
EQUILIBRIUM TIME O F A SQUARE CASCADE
49
Thus they hold in precisely the range of t where the Heaviside expansion begins to become inconvenient. The inversion of Eqs. 3.29 and 3.30 a s they stand, in all their generality, is difficult and not illuminating. Instead, consideration will
0.98
Table 3.1 Functions for the Time Equation
N(S,t) = e 2 t s  ~ ( ~ 2 6 s ¥ i ) e  ~ t / ~ s Â
NO
2eS = In of steady state enrichment
0.96
K  holdup in reservoir
A S holdup in column
0.94
If)
'0.92
. 4 \
x
K/XS
=
HOLDUP IN RESERVOIR HOLDUP IN COLUMN
Fig. 3.2A
function for the time equation A(ZeS,K/XS).
be given various special cases one by one, thereby reducing the complexity of the equations before inversion. For the moment attention should be confined to the mole fractions at the endsof the column (s = 0 and s = S). These a r e usually the only measurable mole fractions anyway, and the restriction greatly simplifies the inversi0ns.l
'The rest of the column will be considered in Sec. 3.
F i r s t consider special cases of Type I1 operation. Type 1 , Case I: K = K' = 0 (no reservoirs at either end) 1
THE THEORY O F ISOTOPE SEPARATION
EQUILIBRIUM TIME OF A SQUARE CASCADE
Table 3.2Functions
51
f o r Approach to Equilibrium of a Square Cascade with No External Holdup
74
..,
,. =
HOLDUP IN RESERVOIR HOLDUP IN COLUMN
3
M(s^
NO Rectifier
= e 2 ~ S Ate%s  l l e  ~ t / ~ ~ '
Stripper
= LN OF STEADYSTATE ENRICHMENT FACTOR
2eS
with M (V2, %;  e2t/X) a confluent hypergeometric function. Values of the function a r e listed in Table 3.3.
Fig. 3.3A
function for the time equation B(2cS,K/AS).
whence
whence
tables of inverses, see G. A. Campbell and R. M. Foster, Fourier Integrals f o r Practical Application, Bell Telephone System Monograph B584 (1931).
or
Equations 3.32 and 3.33 a r e the desired expressions. Type 11, Case 11: K ' = , K = 0 (infinite reservoir a t bottom, no reservoir on top)
52
THE THEORY OF ISOTOPE SEPARATION
Table 3.3The Confluent Hypergeometric Function
M(Y2,%;
EQUILIBRIUM TIME OF A SQUARE CASCADE
x)
53
The condition in Eq. 3.36 is more stringent than in Eq. 3.31 if 2eS > 1; but if 2eS 5 1 it i s automatically satisfied when Eq. 3.31 holds. Type 11, Case 111: K ' = W, K = finite; 2e S < 1 (infinite reservoir at bottom, finite reservoir on top; short column)
whence
1 Type 1 , Case IV: K , K ' both finite; 2eS < 1 (finite r e s e r v o i r s a t both ends; short column)
whence whence
whence
whence Simple expressions f o r more complicated c a s e s can only be found by further specialization. Appreciable simplification of a l l formulas would be obtained if e 2 with respect to Ap could be neglected. The condition for validity of this procedure to a t least 2.5 per cent i s
54
THE THEORY OF ISOTOPE SEPARATION
EQUILIBRIUM TIME O F A SQUARE CASCADE
Some c a s e s of Type I operation will now be considered. In the most general case,
whence
I 2.5(1+ i^) S < l , s o that e 2 ( l + iA)' with respect to X may be neglected, f p the r e s u l t is precisely the s a m e expressions f o r G a s in Type 1 , 1 Case 111. To show the essential difference between operation with production and operation without, the following case is given: Type I, Case 1: k = 0 (no holdup in the column itself)
whence
N(0,t) is given by Eq. 3.42.
3 . DESCRIPTIVE MATERIAL ON RELAXATION PHENOMENA FOR COLUMNS
If the results of the preceding two sections a r e combined, the approach to equilibrium of square cascades over the entire period of operation may be followed. Figures 3.4 and 3.5 illustrate Type 11, Case 11, which i s a cascade of a r b i t r a r y length, with no r e s e r v o i r a t the top and an infinite r e s e r v o i r a t the bottom, operating under total Vi reflux. Plotted in these graphs i s N(s7t) against for N o N(S 4 various values of 2eS = In 2 The initial p a r t s of the curves (for . N O t/hs2 < 0.1) a r e plotted from Eq. 3.34, and the subsequent sections
(&)
THE THEORY OF ISOTOPE SEPARATION
EQUILIBRIUM TIME OF A SQUARE CASCADE
58
THE THEORY OF ISOTOPE SEPARATION
EQUILIBRIUM TIME OF A SQUARE CASCADE
come from the twoterm Heaviside expansion (Eq. 3.28). The two different p a r t s of the curve coalesce quite satisfactorily. The curves a r e straight lines n e a r the origin, the deviation appearing sooner on this s c d e for long columns (large 2eS) than for short columns. Another way of presenting the same r e s u l t s may be obtained by noting'that Eq. 3.34 gives N(S,t)/No a s a function of e2t/A. The expression breaks down a t ~ / A s ^ o . ~ , o r e2t/A= (2&)'/40. Figure 3.6,

K
\S
holdup in top r e s e r v o i r holdup in column
At high ratios this gives practically a straightline graph. (But compare with Figs. 3.4 and 3.5, where the abscissa i s the square root of t/\S2, and a straight line i s found when there i s no holdup on top.) Obviously N increases l e s s and l e s s rapidly a s K increases.
Fig. 3.8Variation Fig. 3.7Graph of a short column o r cascade (finite reservoir at top; infinite r e s e r voir at bottom).
of enrichment with production. Constants: 2eS = 0.8, S = 100 cm,
A = 2 sec/sq cm, K = 0.
which gives
, shows how columns with differing N O 2eS follow the s a m e curve until they break away to approach their equilibrium values. Figure 3.7 gives a graph of Eq. 3.37 (infinite r e s e r v o i r a t the bottom, finite r e s e r v o i r a t the top) for short columns. This i s Type 11, Case 111, o r Type I for 2eS(l + V / ) < 1. Here N(S,t)  No has been (2eS)No plotted against t/AS2 for differing values of the ratio
N(S,t)  No
In Fig. 3.8 the effect of changing r a t e of production on equilibrium time i s shown. Here 2eS = 0.8, \ = 2 sec/sq cm, S = 100 cm, and K = 0. F o r this graph the solution of Eq. 3.19 was used, keeping two transient t e r m s . Increasing the production r a t e d e c r e a s e s both the eventual enrichment and the relaxation time of the column. A cascade operating a t a lower production r a t e will reach any particular value of the enrichment sooner than one operating a t a higher production rate, except in the very earliest stages of the operation, in which the concentration increase i s independent of 1/1. It is of interest to follow theoretically the development of the concentrations along the entire column, especially since it i s very diffi
THE THEORY OF ISOTOPE SEPARATION
EQUILIBRIUM TIME OF A SQUARE CASCADE
61
I
I
I
I
I
cult to do s o experimentally. Referring, therefore, to the master equations (Eqs. 3.29 and 3.30), an infinite r e s e r v o i r i s taken a t the bottom, no r e s e r v o i r on top, and 2.5s < 1 (Type 11, Case I1 f o r short columns), and it i s found that
The inverse of Eq. 3.44 i s
erfc
2eS(l  s/S) 4 lGq%
d$
exp  [ 2 e ~ ( + s/s)12 l 16e2t/A erfc 2eS(l  s/S)
+ 2eS(l + s/S)
4Ve^tA
1
(3.45)
which holds a s long a s &/A < (2e~)'/40. F o r large values of e2t/A Eq. 3.28 may be used with K = 0. Figure 3.9 shows the behavior of such a column whose equilibrium fraction is twofold. Thus 2eS = In 2 = 0.693, and the critical value of e 2 t A i s 0.0125. Here N(s't) is plotted a s a function of s / S for No various values of 4e2t/A. The upper curves (e2t/A 5: 0.0125) were plotted from Eq. 3.28, the lower (e2t/A =s 0.0125) from Eq. 3.45. The two s e t s of curves fit admirably. It should be added that, during the early stages of the experiment, enriched material accumulates only a t the top of the column; when this enriched slug has extended itself down to the foot of the column, the nature of the p r o c e s s changes, and there is a change from one form of asymptotic equation to the other.
REFERENCES
Cohen, K., Report A530, Feb. 4, 1943. Cohen, K., and I. Kaplan, Report A195, June 17, 1942; Report A395, Nov. 19, 1942; Report A1276, May 1, 1944; Report A1292, May 29, 1944. Kaplan, I., Columbia Ser. No. 4LX136, Oct. 12, 1942 (letter t o C. A. Hutchison).
FRACTIONAL LENGTH OF COLUMN
Fig. 3.9Cascade of fixed length (2eS = In 2) (infinite reservoir at the bottom, no reservoir at the top).
DETERMINATION O F CASCADE CONSTANTS
63
An experiment should be considered in which the withdrawal of product at the top i s balanced by the introduction of an equal amount of feed at the same place (Fig. 4.1). In this way the flows up and down a r e equa1,so that the operation of the unit resembles that of a column in the base stages of a cascade; and the equations a r e appreciably simp1ified.l
Chapter 4 DETERMINATION OF CASCADE CONSTANTS
PFg;CT
FEED
A complete analysis of certain transient phenomena of square cascades was given in the last chapter. This amount of material would not be justified were its purpose purely descriptive. The r e a l need for the detailed results just obtained i s given in this chapter, in which it i s shown how to turn the equilibrium effects into a tool for deter mining the cascade constants. It i s always desirable todetermine the fundamental constants of the steady state, cl and c5, by direct experiment. In some cases, such a s in thermal diffusion, the constants cannot be predicted because of ignorance of the theory. In other cases, such a s centrifuges, in which the constants a r e known functions, subsidiary parameters (viscosity, diffusion coefficients, etc.) a r e not known to sufficient accuracy. In all cases it i s useful to have experimental confirmation that cascade operation follows calculation. This restriction i s mainly responsible for the elegance of the r e sultsthe generalization to N 1 will be much more cumbersome. Take the holdup per stage o r per unit length, c , the production, P , and the number of stages, S, a s known; c and c a r e to be determined. Consider f i r s t the evaluation of the constants along conventional lines, i.e., by experiments on the steady state. Equation 2.13, which may be written

Fig. 4.1 An
experiment for the determination of column constants.
Following out the same kind of analysis a s in Chap. 1, Sees. 2 and 6, this case gives, analogous to Eq. 2.3, contains the two parameters e and c , which ostensibly may be determined by any two observations of P and Np. Such a naive procedure i s subject t o considerable experimental e r r o r , and another method, allowing the use of many data, will be presented.
his device furnished
by W. I. Thompson.
64
THE THEORY OF ISOTOPE SEPARATION
DETERMINATION O F CASCADE CONSTANTS
65
The solution of Eq. 4.1 i s
(compare with Eq. 2.14). Now, s e t up f o r this system the function
which gives directly the separative work. At the same time there i s experimental determination of the optimum production r a t e and fractionation. Next, consideration should be given to the methods based on the equilibrium phenomenon. These a r e chiefly useful in c a s e s where the time to reach complete equilibrium i s of the order of days o r weeks, so that a s e r i e s of steadystate experiments would be excessively time consuming. T o illustrate the use of relaxation phenomena for determining cl and c5, consider an experiment of Type I1,Case 111 (K' = m, K = finite, 2eS < I).' The pertinent equation for short t i m e s i s (Eq. 3.37) N(S t) 1 +
NO
which i s a generalization of the work function of Eq. 1.60, defined for infinitesimal concentration changes. The function i s plotted against P, from the experimental values of N p / ~ o and P. The maximum value of W i s a t
4
2cK e " (exp
( )
$ erfc ^y  1)
X S
= l + % ( ~ Y + 2 e s 
6
xs2
[ (yy AS^
exp   e r f c  ^ _ AS t \ K AS
(
and the maximum is
H, the holdup in the top r e s e r v o i r , i s known, a s well a s c6. Thus XS/K = c6S/H i s known, but e, \, and K individually a r e unknown. Equation 3.37 holds until t/& = 0.1. Unless XS/K Ã 1 (holdup in column much greater than holdup in r e s e r v o i r ) , the argument of the e r r o r function
It is worth noting that at P =
3 ( ?h L )
K AS2 will be small a s long as the equation is valid. Expanding the e r r o r function in ascending powers of the argument, Eq. 3.37 behaveslike
The values of
and
W
a r e chosen f r o m the curve. Then c1 = 2 V P W
(4.7)
0. The deviation from this formula becomes l e s s and l e s s a s t On the other hand, should the holdup in the r e s e r v o i r be negligible (e.g., XS/K > l o ) , then unless t/AS2 i s very small the argument of the e r f c will be large,
and

= F o r small enrichments, eZEs 1 + 2 4 and the maximum of W is
\ S l t \ " K ( W  / i S f t erfc    exp   A S rt K xS2 AS2
he sample size i s supposed to be negligibly small.
p ~ : isr_*
%,
9
%
66
THE THEORY OF ISOTOPE SEPARATION
DETERMINATION OF CASCADE CONSTANTS
67
and Eq. 3.37 behaves like
As an example of how simple the whole procedure can be made, take the special case K = 0. From a graph of N(S,t)/No against t , the equilibrium fractionation may be found, along with tv,, the time when
over a considerable region. Depending: on which i s the appropriate case, N's9t'  1 i s plotted N o against t or t%. The slope of the straightline portion of the curve is found, which i s either 2e/K = ci/H, o r 4e/* = 2 c 1 / i G . In either case a relation for the desired constants is obtained. The data for long times, which a r e more abundant, a r e worked up in quite a different manner. The pertinent equation i s (Eq. 3.28) The nomograph (Fig. 4.2) then gives c,.c5/c2 on the righthand line when a straightedge i s laid against N(S,)/Noon the lefthand line and ti/, on the center.
1. IDEAL CASCADE WITH LOSSES
Here the procedure i s to find e2" by extrapolation and then to plot 1 [ e 2 â‚
No]against t. N o
If the initial choice of e2" is good,this
graph will be a straight line1 whose intercept i s In [ ~ ( e  I)].~ (A is ~ ' found from Fig. 3.2.) If this i s not the case, a slightly different choice of ezCs must be made. From the straight line finally obtained, pl i s found a s the slope. A consistent set of values of 2eS and p, i s thus found. From the former, c1/c5 = 2e. From pi and the relation
So f a r , cascades, both ideal and otherwise, in which no losses of material occur have been considered. In actual cascades, sources of loss a r e always present. In most chemical processes the effect of small losses i s not serious. It is obvious that, in a given cascade, a s the losses increase the production diminishes, so that a cascade which has losses will have to be bigger to produce the same quantity and quality of material. Consider the problem of constructing a nomixing cascade that will accommodate losses. To solve it a different procedure1 from that of Chap. 1 should be employed. It i s necessary to introduce the following notation (see Fig. 4.3):
Ls = esLsN; = flow of desired isotope i n enriched fraction Me = (1  es)LsN? = flow of desired isotope in stripped fraction
(4.12)
ZS = Os L s ( l  NL) = flow of other isotope in enriched fraction
ms where B is found from Fig. 3.3, cs is determined. The weak point of this procedure is the choice of e2cs,the equilibrium fractionation, which i s not always unambiguous. However, the value of the separative power of the cascade per stage, which i s the really important property of the cascade for design purposes,
= (1  & ) L s ( l
 N' = flow of other isotope in stripped fraction i)
From the conservation of matter, Ls + Me
=
LsNs = flow of desired isotope into the separator (4.13)
ls + me = Ls(l  Ns) = flow of other isotope into the separator
i s unaffected by considerable e r r o r s in 26s when determined in this manner.
'Except, of course, for small values of t.
THE THEORY OF ISOTOPE SEPARATION
DETERMINATION OF CASCADE CONSTANTS
ENRICHED FRACTION
t
FEED
LsMOLES I s MOLES
OF DESIRED ISOTOPE OF OTHER ISOTOPE
STRIPPED FRACTION
Me MOLES ms
OF DESIRED ISOTOPE MOLES OF OTHER ISOTOPE MOLES OF DESIRED ISOTOPE
<(L~+ ~ ) M ( l s tmsl
MOLES OF DESIRED ISOTOPE MOLES OF OTHER ISOTOPE
Fig. 4.3Diagramof a cascade with losses. Only the desired isotope flows areshown. Flows of the other isotope are obtained by using lowercase rather than capital italic letters.
The nomixing condition leads to the analogues of Eqs. 1.3 to 1.5, the most convenient of which i s
From Eqs. 4.14 and 4.15, eliminating rns/L, Ls = a M s Now the cascade i s connected in such a way (Fig. 4.3) that Ls + Ms
Fig. 4.2 Nomograph for determining column constants.
=
Ls.l + M g + 1  losses of desired isotope
(4.17)
The losses per stage a r e often proportional to the flow in the stage. Thus the losses from the sth stage of a cascade a r e set a s yLs,where y i s a constant and Ls i s a s usual the flow entering the stage. Equation 4.17 becomes
THE THEORY O F ISOTOPE SEPARATION
DETERMINATION O F CASCADE CONSTANTS
71
o r , introducing Eq. 4.16,
&+I
 (a + 1) (1
+ y) Ls + G  1 = 0
(4.19)
Equation 4.19 i s a secondorder difference equation for Lg.The general solution i s
That <t;,(l/a) = ( l / a ) u l ( a ) and u 2 ( l / a ) = ( l / a ) a i 2 ( a )i s shown b y Eq. 4.21. Also since ul(a)u,(a) a , the following schedule may be = written:
where u1 and u2 a r e the roots of the characteristic equation
^  ( a + 1) ( 1 + y ) u + a = o
and can be expressed a s with A defined a s
The boundary conditions a r e
Using the form of Eq. 4.27 to simplify Ls and Is,
Solving for A and B,
 2 P N p ( f f + 1 ) (1 + A)a(ss1)/2 sinh ( S [ a ( l + A)'  l ] N s
+ 1  s) In
(1 + A)
/a (4.28)
Now from Eqs. 4.14 and 4.15,
This i s the required flow per stage with a fractional loss per stage y. The total flow in a cascade i s obtained by summing the Ls with r e spect to s from 0 to S. This gives
while Eq. 4.18 holds with Z and m substituted for L and M. Therefore Z S i s the same function of l / a that L s i s of a , and in place of Eq. 4.23 the result i s
72
THE THEORY O F ISOTOPE SEPARATION
DETERMINATION O F CASCADE CONSTANTS
73
As before, Rs = o^Ro and R p = crS+lRo. When A 0, Eqs. 4.28 and 4.29 reduce to the familiar expressions of Eqs. 1.11 and 1.13. Equations 4.28 and 4.29 take more easily understandable forms if a = 1 + e. For then

The above results a r e quite sensitive to the mole fraction produced by the cascade. Figure 4.5 shows that value of y/e2 which demands a compensatory increase of 20 per cent in the total flow of the cascade a s a function of Np. A cascade producing a concentration of 10 per cent can afford more than five times the losses of one producing 90
It is found convenient to define an auxiliary symbol 6 by
From Eqs. 4.30 and 4.31, place of Eq. 4.28,
6 = A/â‚
Using these relations gives, in
4PNp Ls = Ns e ( l + 26) exp [$(ss)] and for Eq. 4.29,
sinh
[i( S
 s) (1
+ 2611
(4.32)
The relative increase in size of a stage caused by the loss of material i s given by the ratio
Fig. 4.4Curve showing the effect of losses on total flow (the loss per stage i s proportional to the flow per stage). N p = 0.90, y = fraction of flow lost per stage, e = enrichment per stage.
which i s a function of 6. Since 6 i s in turn a function of y/e2 = yL/Le2, it i s seen that the increase in size of a stage i s a function of the ratio of l o s s to separative work. The bottom stages a r e enlarged propor tionally more than the upper stages. The increase in total flow for a (rectifying) cascade i s found by comparing Eq. 4.33 with Eq. 1.23, which i s its limit for y = 0. Figure 4.4 shows the percentage increase in total flow a s a function of y/e2 for the standard case. It will be seen that a 20 per cent increase in size of the cascade i s required when y = 0.025 e 2 .
per cent. Intuitively it should be understood that this effect is due to the increasing penalty for losing highconcentration material on which much work has been done. Obviously it i s worth while to take considerable pains to avoid losses in the small upper stages of the cascade. It may well turn out to be economical to use expensive methods and materials in the upper stages if by so doing losses can be cut and thus the amount of overbuilding required in the bulk of the cascade can be diminished.
74
THE THEORY O F ISOTOPE SEPARATION
DETERMINATION OF CASCADE CONSTANTS
75
The effect of losses on a stripping section i s somewhat different. The usual objective i s not that of producing a given quantity of waste, but rather that of economizing feed. A loss in stage s of the stripper means that a small amount of material i s stripped down to Ns and not
The amount of material transferred between two cascades depends on the mole fraction of the return stream from the upper cascade a s follows: Let PC and Nc be the rate of production and mole fraction of the product from the upper cascade, respectively. Let PB and NB be
MIXI N G
F I N A L M O L E FRACTION FOR WHICH P L A N T WAS DESIGNED
Fig. 4.5Loss of process material resulting in 20 per cent increase in total flow (the loss per stage i s proportional to the flow per stage). The symbol e denotes the enrichment per stage, and y represents the fraction of flow lost per stage.
N w . The result i s to decrease the size of the stripper and increase the required feed. This problem will not be pursued any further here. The problem solved above (loss proportional to flow) is about the only one that admits a closed analytical solution. But, since in practice the only cases of interest a r e those in which the effect of losses is small, iteration methods a r e reasonably successful in dealing with more complicated conditions (see References).
Y
LOWER CASCADE
Fig. 4.6Diagram
showing the combination of cascades.
2. COMBINATION O F PLANTS USING DIFFERENT SEPARATION PROCESSES
In this section consideration will be given the connections between two plants with different separation processes, giving expressions with whose aid the factors of plant size and amount of material transferred between the plants may be balanced.
the corresponding quantities for the lower cascade. Pn i s at the same time the feed to the upper cascade. Pp and NÃ a r e the waste stream and its concentration from the upper cascade; Pp i s the return stream to the lower cascade (refer to Fig. 4.6).
76
THE THEORY OF ISOTOPE SEPARATION
DETERMINATION O F CASCADE CONSTANTS
77
The conservation of matter gives the relations
Furthermore the return stream to cascade A i s made up of two parts so that
Substituting f o r lA lBfrom Eq. 4.41, From Eqs. 4.35 and 4.36, and rearranging, LANA lAnA= LBNA lBnB PN In these two expressions, P C and Nc a r e given (they a r e the specifications on the final product), and No i s the mole fraction at which the change from the lower to the upper cascade is made. NA, the mole fraction of the return stream, i s the only variable. If the upper cascade is an ideal rectifier, Eq. 1.5 gives
C A
= P NB  P N B C
A
Equations 4.42 and 4.43 show that cascade A is just the part up to NA of a cascade that produces material (Pc,Nc). Expressions for the flows and holdups in these sections may easily be found on the assumption that they a r e ideal cascades. The total flow in cascade section A is
For (a  1) small, (Nn  NA) is very small, and PB and Pc a r e very large. Thus in general it will be advisable to add a stripper to the upper cascade, a s indicated in Fig. 4.6. The connections of the return stream, between p a r t s A and B of the lower cascade, a r e also shown. The upper cascade consists of an ordinary rectifier stripper combination. Cascade B i s clearly a rectifier, receiving a feed of mater i a l at mole fraction NA and producing material of mole fraction NB. From the conservation of matter
i f 1 + â ‚ is the simpleprocess factor in the lower cascade. The total flow in cascade section B is
The total flow in cascade section C is
The conservation of matter in the reservoir (actually i t s size i s immaterial) requires that
where 1 + ec is the simpleprocess factor in the upper cascade. The total flow in the stripper section A is
78
THE THEORY OF ISOTOPE SEPARATION
and in the stripper section C is
Analogous expressions hold for the finite case. Expressions for the desired material holdup and the contribution to the equilibrium time of the various sections above the feed point can also be obtained without any trouble (see Appendix C). Cascades A, A, and C a r e the same a s the corresponding sections of a single ideal cascade producing (Pc,Nc). But it will b e observed that cascade B is not the same as the section between NA and NB of a single cascade. B and C together a r e equivalent to (and slightly larger than) this section. An inefficiency in the combined cascades caused by the mixing of the constituents of the return stream to cascade A causes a l o s s in value of
Chapter 5 THE CONTROL PROBLEM
which is made up for by the increased size of B and It will be remarked that a combined cascade, for maximum efficiency, i s considerably different from two cascades designed for other duties and connected together. There is a considerable premium on foresight in this problem. The separation into two cascades which i s illustrated here can clearly be carried on further, giving any number of subcascades. The chief feature which makes continued subdivision attractive, even when the subcascades use identical equipment, i s that the flow between cascades (each of which i s a rectifierstripper) i s much l e s s than the flow between stages of a single cascade (cf. Eqs. 4.37 and 4.38). This is an advantage in removing accumulated impurities (caused by inleaks, decomposition, etc.) o r in control.
e.
REFERENCES
Cohen, K., Report A60, October 1941; Report A530, Feb. 4, 1943; Report A781, Aug. 13, 1943. Cohen, K., Columbia Ser. No. 4RX143, May 13, 1942. Cohen, K., and W. I. Thompson, Columbia Ser. No. 4R104, Sept. 4, 1943. Kaplan, I., Columbia Ser. No. 4M133, Jan. 18, 1944 (memorandum to K. Cohen); Columbia Ser. No. 4M160, Apr. 17, 1944 (memorandum to M. Kilpatrick). Lefkowitz, H., and B. Schwartz, Columbia Ser. No. 4R18, Feb. 4, 1943. Lefkowitz, H . , B. Schwartz, and H. Mayer, Columbia Ser. No. 4R42, Apr. 12, 1943. Mayer, H., I. Kaplan, and K. Cohen, Report A396, Dec. 2, 1942. Thompson, W. I., Experimental Operation of a Single Centrifuge, S.O.D. Report, June 14, 1943.
The problem of maintaining certain specified variables a t preassigned values is common to any planned operation. In a chemical reaction, for example, these quantities a r e usually the temperature, the pressure, and the amount of material in process. The control problem for isotopeseparation plants differs f r o m that of other manufacturing operations in the degree of complexity. The cascades considered in this volume contain thousands of different interdependent stages or elements. Methods of analysis which a r e successful with systems containing, for example, a dozen related units will fail here. F o r this reason the control problem for isotopeseparation cascades must be treated a s a distinct subject. Furthermore it is often possible to break up a cascade into smaller units. For example, a cascade of 10,000 centrifuges with nine centrifuges in the top stage (Chap. 2, Sec. 4) might be broken up into nine completely independent cascades in parallel, o r a cascade might be broken down into subcascades along the lines discussed in Chap. 4, Sec. 2. The desirability of such expedients will not be clear until the difficulties of controlling a single large cascade a r e known. In the discussion that follows, therefore, consideration will be given to a single large rectifier stripper. It was shown in Chap. 1, Sec. 2, that for an ideal plant deviations up to 20 per cent from the calculated flows a r e without appreciable effect on the separation. This also holds true to a considerable extent for nonideal plants of intelligent design. Thus to have a cascade operate according to plan, it is only necessary to s e e that the flows throughout the plant a r e approximately correct. This question, of maintaining the temperatures, pressures, flows, etc., near their design values, of seeing that material does not accumulate in o r drain out of any part of the plant, and of seeing that small distrubances do not build up to large ones, is one part the hydrodynamic partof the control problem.
80
THE THEORY OF ISOTOPE SEPARATION
THE CONTROL PROBLEM
81
There is in addition a second part which deals not with the average conditions but with the effects of fluctuations from the average. A slight change in the operating conditions may produce a variety of effects: a change in the transport of material from stage to stage, a mixing of material of different concentrations from different stages, o r a change in the separating power of the element. In general, a fluctuation causes mixing, and mixing means a lowering of the concentration of the product. Both parts of the control problem a r e essential. Without the hydrodynamic part, the types, magnitudes, and frequencies of variations that a r e to be expected a r e unknown. Without a knowledge of the effects of fluctuations on concentration an evaluation cannot be made of the effectiveness of the hydrodynamic control measures s o far a s plant productivity is concerned. By i t s nature, the hydrodynamic problem is intimately associated with the particular separation method, equipment, and control instruments used. Since this problem cannot be generalized without destroying its illustrative value, an explanatory example will be presented. The problem of the effect of fluctuations on separation is more susceptible of general treatment. Even s o there a r e aspects which differ from one case to another. A cascade of centrifuges, for instance, has certain problems in common with all squaredoff cascades; i t also has effects due to variations in the behavior of parallel units which a diffusion cascade lacks. But the theory developed in the succeeding sections is basic to all the problems. In Sec. 1 consideration is given to equations governing the change of mole fraction with fluctuations in the operating constants. Their solution in the general case is developed in such a way that the results of the hydrodynamic problem may be used in their most compact form (in the s,p plane of the Laplace transform). In Sec. 2 the average change in transport for periodic fluctuations is derived. Section 3 treats a particular example: the effect of variations in the rate of withdrawal of product on a square cascade. Sinusoidal variations a r e considered, and the effect of batch (instead of continuous) withdrawal of product is treated.
1. E F F E C T O F FLUCTUATIONS ON CONCENTRATION
The effect of perturbations in the fundamental quantities cl, c5, c6, and P on the separation performed by the cascade is found by solving Eqs. 5.1 and 5.2 with these four quantities preassigned functions of time. Of primary interest a r e the small fluctuations, which if imposed on a system already in the steady state will give small changes in concentration. Gross upsets and phenomena associated with the approach to equilibrium a r e excluded from consideration. The desired solution may thus be obtained by ordinary perturbation theory, with the steady state a s the unperturbed system. The quantities c,, c5, and c6 a r e given a s functions of stage number. In cascades with more than one element per stage, they a r e to be understood a s averages over the elements. The mixing losses caused by deviations of parallel elements from their average a r e not included here. Suppose that there is a primary disturbance of some nature from an outside source. It will be written a s
The parameter u is not necessarily smallits function is to distinguish between the various o r d e r s of t e r m s resulting from the primary disturbance. As a consequence of of there will be induced disturbances in cl, c5, c6, and P. Thus c,, which before the disturbance is a function of s only, becomes a function of s , t, and u. Expanding in powers of a,
The fundamental equations of isotope separation a s developed in Chap. 1, Sec. 6, using the generalized notations of Chap. 2, are1
The terms c,, cc, and c. were introduced in Chap. 2, Square Cascades, by the schedule in Eq. 2.2,but there i s no reason why they cannot be employed a s functions of s and t, a s indicated.
where cm(s) is the undisturbed value of c,. Generally the symbol c1(s,t;u) will be shortened to cl(s,t). Likewise
82
THE THEORY O F ISOTOPE SEPARATION
THE CONTROLPROBLEM
The notation is selfexplanatory and defines the coefficients c5,, cS2, etc. As a result of Eq. 5.5 and the f i r s t line of Eq. 5.2,
The functions c,(s,t) . . T(s,t) a r e considered known, a s well a s the coefficients of their expansions. They a r e in fact the solutions of the hydrodynamic part of the control problem. Now, inserting Eqs. 5.4, 5.5, and 5.6 in Eqs. 5.1 and 5.2, it is desirable to find N(s,t) and r(s,t). These will also be functions of a, which will be written asi N(s ,t)
=
.
No(s) + aNl (S ,t) + a2N2(s ,t) + . . .
To
= T(s,~)
+ C T T ~ ( S o~T ~ ( s , ~ )+ . . +, ' )
(5.7)
Of course
and s o on for higher orders. The boundary conditions for each order equation can likewise be found by expansion. This will be done later in the section (Eqs. 5.23 e t seq.). When the boundary conditions a r e known the equations may be solved successively. In the paragraphs immediately following an investigation will be made of the properties of the differential equations, and method of solving them will be considered. Equation 5.9 gives the steady state of the unperturbed system. The expression for T , has the form
where N p is the undisturbed mole fraction of the product. The convergence of Eq. 5.7 is now of concern. The natural period of a cascade with respect to concentration disturbances is the equilibrium time, which we have seen in Chap. 3, Sec. 1, is of the order Physically this means that Eq. 5.7 will converge c.n~50/cfo. \/e2 provided the average values of the disturbances on most of the stages, over periods of time smaller than \/e2, a r e small compared to the undisturbed quantities. Introducing the expansions of Eqs. 5.4 to 5.7 into Eqs. 5.1 and 5.2, , the following sysand separating the coefficients of uO, ul, 02, tems of equations a r e obtained:
where D is the linear operator, independent of t,

and
...
PoNpo = PoNo(s) Cgo aNo
s
, cioNo(l No) +
+
(5.9)
i s , after substituting No(s), which is a solution to Eq. 5.9, an explicit function of s and t. Combining Eq. 5.12 with the second equation of Eq. 5.10 gives
TPo
'51
'60
atl + a D N l =  + N a s aN s
a
aQ
o
"s a1
(5.15)

9No
+
cllNo(l

No) (5.10)
The lefthand side of Eq. 5.15 is a linear homogeneous expression in N17with coefficients independent of t; the righthand side is an explicit function of s and t. It is therefore easily solvable by standard methods. In particular the Laplace transform of Eq. 5.15,
'The symbols N,,(s), N,(s,t) . introduced in Eq. 5.7 a r e not in contradiction with the previously used symbols of Nc, which have been supplanted by N(s,t) and have no
..
84
THE THEORY O F ISOTOPE SEPARATION
THE CONTROL PROBLEM
85
is an ordinary linear secondorder differential equation in s. It be remembered that the asterisk (*) was introduced to denote Laplace transform of any function. Thus if x(s,t) is a function and t,
where D i s the linear operator of Eq. 5.13 and
The chief advantage1 of using the Laplace transform of Eq. 5.15besides the fact that i t solves the equation without trouble in spite complicated boundary conditions is that the transforms TT , cz , a c * a r e used on the righthand side. Since the hydrodynamic par the control problem will also be solved by using the Laplace t r a form, these quantities a r e immediately available. In fact, s i the inversion of T* to TI, etc., i s the last and hardest step of hydrodynamic solution, very considerable difficulties a r e avoi by using Eq. 5.16. The solution of Eq. 5.15 or 5.16 may be facilitated by transforming the dependent and independent variable^.^ The expression DNl becomes, using the integrating factor, J ( s ) = exp 
Combining Eq. 5.19 with the second part of Eq. 5.11,
The Laplace transform of Eq. 5.21 is1
[ Ls
'lo('
'50
+0 '
ds]
The process can, a t least in principle, be continued indefinitely f o r NS, N4 . . . . The boundary conditions for the differential equations will now be obtained. First of all the initial condition N(s,O) = No(s) leads to
The dependent variable is then chosen a s JN,. In many cascades the quantities clo, cco, etc., a r e most conveniently expressed in terms of the No. For example, an ideal cascade is defined in terms of the No so that
i^ =
'50
c
26 = constant
This suggests changing the independent variable from s to No, which can be done with the aid of Eq. 5.9. The expression for T, has the form
Assume that there a r e reservoirs a t each end of the plant, of holdup H (product end) and H' (waste end). The product and waste a r e withdrawn from the reservoirs. The mole fractions in the reservoirs a r e therefore called Np(t) and Nw(t), respectively. i t is not legitimate to neglect the difference between Np and N(S,t) . A rapid fluctuation in N(S,t), for example, leaves Np relatively unchanged because of the buffer effect of the holdup.] The waste stream is called W(t). The flow from the cascade into the top reservoir i s called c5(P,t);the flow from the cascade into the bottom reservoir is c5(W,t). These quantities also have expansions a s powers of o.
e ere
'The formula for the transform of the product of two functions i s 1 [x1(t)x;(t)]* = %/ x (P  q)x;* (q) dq : 'This feature was pointed out by H. Mayer. 2Following the practice of K. Fuchs.
Br,
The contour i s to the right of the poles of x;*(q) and to the left of the poles of x* (p  q).
THE THEORY O F ISOTOPE SEPARATION
THE CONTROL PROBLEM
87
W(t) = Wo H = Ho H1=H; Np(t) = Npo
+ a w l (t)
+uH'(t)
+ 0 (1) % + u ~ , ( t ) + u2H2(t)
+u2Hn(t)
+
.. . + . ..
(5.24)
The boundary conditions a t the top of the rectifier a r e obtained from the relations
+ uNpl (t) + o w 2(t)
+... + ...
a
Nw(t) = Nwo + uNwl(t)
+ cr2Nw2(t) + . . .
On expanding in powers of o and collecting, it i s found that
. c5(W,t) = cso(W)+ ucgl(W,t) + U ~ C ~ ~ + W. ,. ~ ) ( .
The mole fractions, N(s,t), and the transports, T(s,t) and ~ ( s , t ) , will r e f e r to the stripper if s has negative values. Equations 5.9 to 5.22 hold for the stripper if Po and N p a r e replaced throughout by Wo and N W . The stage number of the lowest stage of the stripper will be called "B" (a negative number). The discontinuity in T and T a t s = 0 implied in the change in the equations is accounted for by the introduction of feed (F,Np).
c5(P,t) = c ~ ~ ( + uc5,(P,t) + u ~ c , ~ ( P +~.) P) ,
These obvious relations have already been incorporated in the preceding equations (cf. Eqs. 5.6 and 5.8). Likewise, combining the f i r s t two equations of Eq. 5.29,
Note, however, that Np does not have to be the same a s N(O,t), o r even N F the s a m e a s No(0). F and Np may both vary with time (the cascade under consideration might be theupper cascade of a combination of plants). Expanding Eq. 5.25 in powers of u,
The boundary conditions a t the bottom of the stripper a r e very similar. Corresponding to Eq. 5.29,
88
THE THEORY OF ISOTOPE SEPARATION
THE CONTROL PROBLEM
In z e r o order
F r o m Eq. 5.31, The firstorder t e r m s a r e
and the secondorder t e r m s a r e
and from Eq. 5.35,
This elaborate s e t of conditions is very expeditiously condensed by using the Laplace transform. With the aid of Eq. 5.23, Substituting for 7, from Eq. 5.12 in the boundary conditions (Eqs. 5.27, 5.31, and 5.35), a complete s e t of boundary conditions may be found for the firstorder differential equation (Eq. 5.25). F i r s t a n expression for
and therefore N: and N: may be eliminated altogether by the second p a r t s of Eqs. 5.39 and 5.40, which give
is needed. This can be obtained from Eq. 5.26 by substituting Eq. 5.9 and its analogue with Wo for Po and N W for N p . It is found that1
with the definitions Then from Eq. 5.27, for the boundary condition at s = 0,
I N p  No(0) i s found by substituting the solution of Eq. 5.9, giving N p in terms of
N,(O), and N,,, in terms of No(0), into Eq. 5.26
a s in Chap. 3. With Eq. 5.41, the transforms of Eqs. 5.39 and 5.40 a r e
90
THE THEORY O F ISOTOPE SEPARATION
THE CONTROL PROBLEM
91
The transform of Eq. 5.38 i s
answer. Usually1 the leading t e r m in the answer is the average secondorder change in concentration o r in transport. Of course the average secondorder quantities can be found by solving straightforwardly for N,(s,t), a s indicated in Sec. 1, and then averaging. But this procedure requires considerable work to get superfluous detail; it is possible to obtain2 T Z and Nz(s) directly without solving the secondorder differential equation. The method for doing this, which was devised by K. Fuchs, follows. Suppose that the solution N,(s,t) o r N*(s,p) of the equation of the f i r s t order in u has been determined. Taking the average of Eq. 5.19 and using the relation Eq. 5.18 for D,
Similar expressions can be found for the boundary conditions of the higherorder differential equations. It must seem to the reader that the work required has been increased by carrying the intermediate quantity r all through the expansions and then eliminating it at the last step, instead of eliminating i t at once from Eqs. 5.1, 5.25, 5.29, and 5.33. The procedure was adopted to prepare for the work of the next section, where i t s usefulness will become apparent. With this cataloguing of the boundary conditions all the development that can be made without special assumptions has been completed. The treatment has been more detailed than the novelty of the content strictly merits; i t i s hoped that i t s reference value will make up for the difference.
F r o m Eq. 5.2, a ~ / &=  a(c,.~)/at.The righthand side must be zero; otherwise there i s no steady state. Therefore T i s constant, except for a discontinuity a t s = 0, and s o a r e all o r d e r s of i t s expansion, including G. The solution of the problem r e s t s on this property of Z , which permits i t s evaluation f r o m the boundary condi4' r .ions. Equation 5.46 integrates out to give, for the rectifier,
and, for the stripper (negative values of s ) ~
2. AVERAGE TRANSPORT LOSS FOR PERIODIC FLUCTUATIONS
There a r e two aspects of the effect of perturbations which a r e i m portant. The f i r s t is to predict the concentration changes in detail, s o that the success of corrective m e a s u r e s can be verified. The second i s to find the l o s s of production over long periods of time. If the primary disturbance uf(s,t) is nonperiodic, like a simple pulse o r a damped oscillation, both aspects a r e of interest. The leading t e r m in the answer is N,(s,t), but often N2(s,t) is also required to give a correct evaluation of the production loss. If the primary disturbance i s periodic, a new average steady state, with concentrations lower than before, will result. In this c a s e we a r e more interested in the new steady statethe l o s s of production and average change in concentrationsthan in the full detail of the
'It may be supposed without loss of generality that af(s,t) has a vanishing time a v e r age. It will then usually be t r u e that the firstorder t e r m s in the fundamental quantities c,, cs, co, P . have vanishing time averages:
..
Should this b e the case, then N,(s,t) = T , = 0, for, on averaging Eq. 5.10 and the bounda r y conditions (Eqs. 5.27, 5.31, and 5.35), i t will be found that % satisfies a n equation almost exactly like Eq. 5.9, but with the feed concentration z e r o instead of NF Note, o however, that in the solution to b e given for N3 and T we shall not assume that c,,(s,t), 2 etc., and hence q , equals zero. 2 T h e time average of x(s,t) will be written a s X(s) instead of the cumbersome x(s,t). The average of the product xl(s,t)x,(s,t) will, however, be written a s x,(s,t)x,(s,t).

92
THE THEORY O F ISOTOPE SEPARATION
THE CONTROLPROBLEM
93
It will be recalled that (Eq. 5.17)
 These linear relations will be shown, but the process of eliminating
N2(S) and N,(B) and solving for the % will not be undertaken here.
In the second equation of Eq. 5.32,
for the rectifier. J' has been used to denote the corresponding function for the stripper.
J' (s) = exp 
2) 1 [ lS
~ l O (l
 Wo dS
o r else N p (t) increases o r decreases indefinitely. Thus on averaging i t is found that
It now remains only to evaluate the a s yet unknown constants T2(S) and T(B) from the boundary conditions, and the problem is solved. From the boundary conditions of Eq. 5.28, at s = 0, on averaging,
The f i r s t equation of Eq. 5.32 gives
where A i s a known constant. Also

Eliminating Np2 between Eqs. 5.53 and 5.54 gives N2(S) in t e r m s of
= N2(0)
N2(0+)
T , (S), a s required. Similarly, from the boundary condition (Eq. 5.36)
at s
=
B,
Now J(0)
=
Jr(0) = 1. Thus with the aid of Eq. 5.51, (JN2Io = (J'N,).
Setting s
=
S in Eq. 5.47 and s
=
B in Eq. 5.48 and subtracting,
It should be understood that J in the last integral is given by Eq. 5.49 from B to 0 and by Eq. 5.17 from 0 to S. Now the boundary conditions (Eq. 5.32) a t the top of the rectifier give a linear relation between N2(S) and T2(S); those a t the bottom of the stripper (Eq. 5.36) give another between N,(B) and T,(B). Using ) these to eliminate &(s) and N 2 ( ~from Eq. 5.52, a linear relation between ~ ~ ( and T ~ ( Bis obtained, which, together with Eq. 5.52, 8 ) ) allows the determination of both quantities.
For many purposes Tz(S), which is the average (secondorder) change in production of desired material, is a sufficient answer, and it is unnecessary to return to Eqs. 5.47 and 5.48 to find N2(s). The solution just given requires the averaging of some secondorder quantities, and of products of firstorder quantities. If these functions a r e known explicitly in t e r m s of t, the averaging is done by elementary integration. However, they will usually be given a s Laplace transforms. To perform the averaging without taking the inverse the following theorem: which holds if a steady state exists, can be used: If lim px* = C(s) as p 0 by positive r e a l values, then X(s) = C(s); otherwise ~ ( s =) 0.
>
G. Doetsch, "Theorie und Anwendung der Laplace Transformation," p. 193, Dover Publications, New York, 1943.
'
THE THEORY O F ISOTOPE SEPARATION
THE CONTROL PROBLEM
95
3 . VARIATIONS IN PRODUCTION RATE FOR A SQUARE CASCADE
In this section the theory of the preceding sections will be illustrated and clarified by applying it to a special case. The abstractness of the demonstrations just given will be relieved by discussing further properties of the solutions with a particular example. The example chosen i s that of a square cascadepractical comparison may be made with a fractionating columnon which a r e imposed a r bitrary variations in P , the rate of production. Suppose that the hydrodynamics of the cascade a r e such that a t the same time everything else is invariant: the holdups, the flows and separation factors, and the feed rate and composition. To simplify the arithmetic a rectifier alone will be considered, with the feed concentration held fixed. It is further supposed that N i s always small. A reservoir i s included at the top. The t e r m s cm, ego, and ego do not vary with stage number. Let cc0(P) = cHO (flow into reservoir = flow between stages). Introducing the s a m e notation a s in Chap. 3,
The boundary conditional the top is still Eq. 5.29 and i t s descendants, notably Eq. 5.43. The solution of the zeroorder differential equation (Eq. 5.9) contains nothing new. As in Chap. 2, Sec. 1, it is found that
The firstorder differential equation (Eq. 5.16) requires the evaluation of QQ:/QS. From Eq. 5.14, in the present c a s e
and Eq. 5.16 becomes
where
The general solution of Eq. 5.62 i s
N :
=
eCts(Acosh B s
CP* + B sinh /3s)  Ã‘Ã‘ P
e2~Is
(5.64)
The new constant e' is used to condense the notation. The expansions of the coefficients reduce to
As in Chap. 3,
Everything else (except of course N and r ) has only zeroorder terms. In place of the boundary conditions a t s = 0 and s = B previously used, there is the simple expression N(0,t) = Np
an.d hence
=
The constants A and B a r e evaluated from the boundary conditions (Eqs. 5.43 and 5.59). The latter in the present example reduces to
constant where
Performing the indicated operations and collecting,
96
THE THEORY O F ISOTOPE SEPARATION
THE CONTROL PROBLEM
97
N,'(S,~) =
"*
P
[
ec,S I M  c t ) sinh ;3(S s) + 13 cosh ^(S
(M
el)
sinh 8s + 8 cosh
(3s
 s)
a 2 c ~
+ eels
~ e sinh 0s " ~ (M  ct) sinh (3s + 13 cosh
(3s
1
(This is a particular example of the general result proved in Sec. 2.) To get the average loss of production, the secondorder t e r m s a r e thus necessary. Equation 5.52 of Sec. 2 reduces now t o
and the boundary condition which determines Tn i s , from Eqs. 5.53 and 5.54, If the disturbance is taken to be sinusoidal, i.e., P, = cos u t and
Now from Eq. 5.17,
J
=
and then Eq. 5.68 is inverted, contributions a r e obtained from the poles a t 2 iw, also from the roots of (M  e ' ) sinh )3S + )3 cosh BS = 0, which lie on the negative r e a l axis. There is no pole at p = 0. Thus
exp
( f ' 2 ~ cis) = exp (2ets)
(5.75)
Combining Eqs. 5.73, 5.74, and 5.75 and simplifying the result with the aid of Eq. 5.60, then
i.e., t e r m s of the same period a s the disturbance, plus transients. This is a general result. Note also that the form of Eq. 5.68, which is linear in P r , allows superposition of solutions, i.e., a Fourier analysis of the variations in P , c , c , etc., is permissible. In what follows a type disturbance more complicated than the sinusoidal will be discussed. Suppose that the product is withdrawn in batches a t regular intervals a , instead of continuously. Then the disturbance function is P I (t) =  Po + pulses including a quantity aPo a t t The transform of Pl i s easier to write
=
Accordingly it i s necessary to evaluate the expressions on the righthand side of Eq. 5.76. From Eq. 5.20, Q2 = NIPl,
0, a, 2a.
..
(5 .TI) This integral i s equal1 to the sum of the residues a t the poles of P^(q). These a r e a t q = 2k3ri/a (k = 51, Â± .). Each residue has the value
..
PF(p) has no pole a t p 5.68 and 5.72:
=
0. The average of N,(s,t) i s found from Eqs.
'Strictly speaking

Nl (s) = lim pN;(s,p)
P 0
=
0
Q = :
lirn
vm
+
9
k=v
(residues)
98
THE THEORY O F ISOTOPE SEPARATION
THE CONTROL PROBLEM
99
Then
In the same way the effect of disturbances of the same frequency which a r e out of phase by an angle a can be realized. Corresponding to Eq. 5.70, Nl is
and likewise, using the relation (Eq. 5.41) for NG,, and on calculating NIPl (or similar t e r m s ) there will result the contributions of the separate disturbances plus a crossproduct t e r m with cos a a s a factor. Now if the two disturbances a r e unrelated cos a i s , on the average, zero, and the resultant is purely additive. Note, however, that fluctuations in P and, for example, c5 caused by a common primary disturbance a r e correlated through the hydrodynamic response of the plant and cannot be treated separately. The r e m a r k s of the preceding two paragraphs contain the results necessary f o r the composition of disturbances of different sources and types. Returning t o the derivation of iaccording to Eq. 5.76 and picking up the thread of the argument a t the expressions Eqs. 5.78 and 5.80, consider ( l / i u ) \ ~ ( s , i u )  F(s, iu)] a s a function of u. T e r m F(s,p) is defined by Eq. 5.68. The t e r m e 2 " ~ does not depend on u and hence gives nothing. Then F = (M e') sinh (3(S  s) + (3 cosh (3(S  s) + (M  e') sinh /3S + (3 cosh (3s where sinh (3s (5.81)

The meaning of Eq. 5.78 will be clear by returning to the disturbance Pl = cos u t and following through the s a m e procedure. From Eq. 5.70 and .On = NIP,, this time averaging by direct integration with respect t o t, F(s,iu)eiwt  F(s, iu)eiwt] cos u t dt 2iu
c
Equation 5.80 is the contribution to D2(s) of a sinusoidal variation of frequency w/27r. Now, if the (improper) disturbance function (Eq. 5.71) is analyzed, representing batch withdrawal a s
M
and if contributions of the individual frequencies given by Eq. 5.80 a r e summed, the result is precisely Eq. 5.78. This is a general result, which can be understood a s follows: In a disturbance, two different frequencies (in Ply for example) contribute independently to N , each giving a t e r m of its own frequency. In taking time averages, t e r m s like e^itlu:'t always vanish. The result is a sum of contributions from each frequency acting as if it were alone. This whole process i s taken c a r e of automatically by the use of the averaging theorems1
'In comparing the solution of thedifferential equation by the functionally closely r e lated methods of the Laplace transform o r the Fourier expansion, i t should be r e marked that the former method gives a t the same time the solution for the transients.
=
2 e @ 5 iuky
lÂ iuky
F o r C.A Ã e2(l + i/Ãˆ)2 a condition fulfilled by all but the lowest f r e quencies because of the smallness of e ,
(3
Vd>x(iÂ±i
(ss)(W
sinh (3(S s )
 cosh'(3(~ s)  %e^
.
F(s, 5 iu) Then
esV^(l?i)
1 2 [F(s,iu)F(~,iu)]=e~^
lu
Ill
sinsYt^X"
(5.82)
100
THE THEORY O F ISOTOPE SEPARATION
THE CONTROLPROBLEM
101
The contribution to T J ' P ~ N ~from the disturbance Pi = cos u t is, by Eq. 5.76,
In case B, T2 is already quite large; in fact it may be suspected that higherorder t e r m s a r e needed. In case A, Tn becomes large if a i s taken much larger, even though ae2/^ is still small. Thus in both cases T becomes appreciable a t a = I/&, although pi does not appear in the formula (Eq. 5.85). This can be understood after an examination of the transient t e r m s in N, (s,t). The f i r s t transient has the factor
(5.84) The integral was evaluated by Eqs. 5.80 and 5.83 and by the definitiorof C , Eq. 5.63. The contribution from the term Pl (t)Np/Pg vanishes in the same manner a s e  s G / u and can b e neglected. The disturbance in Eq. 5.71 caused by batch withdrawal gives likewise, comparing Eq. 5.78 with Eq. 5.80, This factor increases rapidly for fixed pl a s apl becomes large. For example, taking pl = 1: for a = 0, f = 0; for a = 0.1, f = 0.048; for a = 1, f = 0.42; for a = 10, f = 100. Thus the transients get large a s a l/pl, implying that the new steady state differs significantly from the initial state. Holdup a t the top increases l/pl and must therefore permit larger values of a , even though this is not exhibited by the rough formula, Eq. 5.85.

Table 5.1 Production
Loss Due to Batch Withdrawal Case A Case B 30fold 3.40 1 day
provided a <s: 2rA/e2(l + fl. The holdup in the reservoir has no influence to this degree of approximation. For larger values of a, numerical summations a r e needed. The factors in the solution (Eq. 5.85) a r e a t e r m in the ratio of a to the natural period, X/e2; a factor <//' that i s related to the s i z e of the disturbance; and a factor NpO/Np that shows that the sensitivity is proportional to the enrichment factor of the column. It is interesting to note that the period X/e2 and not 1/p,, the relaxation time, enters in; also that the magnitude of disturbance Po enters in a s I+!J = Po/% and not P / C ~ ~ . idea of the o r d e r s of magnitude involved is given An in Table 5.1, which compares two cases. In both cases a is about equal to the time f o r the column to reach ~ . the enrichment N ~ ~ / NHowever, in case A, ae2/A = 1/40, whereas in case B ae2/X = 1, s o that the loss in case B is much more serious. The second most important factor is the severity of the disturbance: I+!J = 2 in case A and t+b = 0.2 in case B. The weight of this factor i s irthe other direction. By comparison the differences in the factor N ~ / N r ~ slight. a e
Equilibrium enrichment (no production) 2tS
k/e2
2fold 0.693 40 days
First transient period:'
1 day 3.5 %
1 day 29 %
'Taking the holdup in the top reservoir a s zero.
The evaluation of the loss in production by the single term T2 will b e correct only if the higherorder t e r m s a r e negligible, i.e., only if T i s quite small. This slightly discouraging conclusion does not deprive the calculation of i t s usefulness, which is mainly to assign permissible upper limits t o the disturbances. It i s difficult to generalize from the problems just solved to other problems. Even the most interesting result, that the effect of highfrequency disturbances vanishes a s w%, is only true for a disturb
102
THE THEORY OF ISOTOPE SEPARATION
ance in P alone. It does not subsist when fluctuations in the coefficients c6, c5, and c, a r e taken into consideration. The correlations to be expected between disturbances of the various coefficients a r e different from one separating apparatus to another. Hence this is about a s far a s the investigation can proceed without specifying the type of equipment in question. The reader may have noted that, leaving out the explanations and digressions, the solution to the problem of this section was obtained fairly easily. This is not generally true; problems on more intricate cascade shapes and for intermediate frequencies run into heavy computation. However, it should be remembered, in spite of the space required to expose the theory, that small correction terms a r e involved. It is therefore quite proper to reduce the numerical work by rather drastic approximations.
Chapter 6 CENTRIFUGES
1. HISTORICAL INTRODUCTION
REFERENCES
Fuchs, K., British MS 71, January November, 1943. Fuchs, K., British Supply Council reports: MSN 4, Feb. 11, 1944; MSN 5, Mar. 4,1944; MSN 8, Mar. 7 and Mar. 17, 1944; MSN 10, Apr. 6, 1944; MSN 12, June 6, 1944; MSN 14, June 28, 1944; MSN 15, July 11, 1944; MSN 17, July 20, 1944.
The effect of the earth's gravitational field on the composition of the gases in the atmosphere at various heights has long been recognized. For, if pi is the partial pressure of a gas of molecular weight Mi, according to the Boltzmann distribution law pi(h) = pi(0) exp where h is the height; g is the gravitational constant; R is the gas constant, 8.314 X lo7 ergs/OK/mole; and T is the absolute temperature. Then for two gases of different molecular weights M, and M,
The suggestion that gravitational o r centrifugal fields a r e suitable for isotope separation was made by Lindemann and Astonl in 1919. In fact, they proposed that samples of neon taken at ground level and at 100,000 ft would show a sensible shift in the isotopic abundance ratio. In a centrifuge, vastly more powerful fields a r e available. The energy per mole at radius r in a centrifuge rotating with angular velocity u is% Mi(ur),. This expression for the energy replaces Migh in Eq. 6.1, giving pi(r) = pi@) exp Mi (u r)2 2RT
104
THE THEORY O F ISOTOPE SEPARATION
CENTRIFUGES
105
Between the periphery r = r, and axis r = 0, for two different gas from Eq. 6.3, Pl(r2) _ PI(O) exp (M,  M2) ( u r 2 ) 2 ~ ~ ( 0 ) 2RT
~2b2)
where w r , i s the velocity of the inside wall of the rotor, the peripheral velocity. In a binary system, if N is the mole fraction of the isotope ha m a s s Mi, Pi
+
P =P 2
N
1 N
= Pl/P
=
ing the spinning of the rotor, vapor is removed slowly through a shaft along the axis. In this way a Rayleigh distillation (Appendix D) of the liquid i s accomplished, with simpleprocess factor given by Eq. 6.31. An increased concentration change in the residual liquid i s thus obtained. The development by Beams1 of vacuumchamber centrifuges, which were f r e e from vibration and thermally isolated to eliminate convection currents, finally permitted successful centrifugal isotope s e p a r a tion to be obtained in 1939. Beams and Skarstrom2 a t the University of Virginia, using the evaporative centrifuge method on CC14,reported a 13 p e r cent change in the C135/C137ratio. Shortly thereafter Hump h r e y ~ ; using the s a m e technique on ethyl bromide, altered the ~ r ~ ' / ~ r " abundance ratio by 11 p e r cent. The simpleprocess factor of centrifugal separation depends only on the m a s s difference. Unlike other methods (e.g., diffusion through b a r r i e r s , where a v a r i e s a s AM/M) it i s no more difficult for heavy elements than for light. In addition, it is possible to calculate a p r i o r i the separation to be expected from centrifugal apparatus without any undetermined constants o r theoretical uncertainties. The simpleprocess "flowthrough centrifuge," a s the concurrent flow type was called, i s a n application to gaseous flow of the continuous c r e a m separator. As originally conceived, a single s t r e a m of g a s e n t e r s one end of a rotor through a hollow shaft, and two s t r e a m s a r e taken off the other end, one from the periphery and the other near the axis. This method produces a s m a l l change in concentration per machine. The countercurrent flow type was designed to attain considerable separation in a single centrifuge, thus reducing the number of stages required and the amount of material circulated between stages. As originally proposed by u r e y , circulation was to be established by continuous distillation of UFs from the bottom cap of the rotor. The vapor was to be condensed on the top cap. The heavy liquid would then be forced out to the periphery and would flow down the walls to the bottom cap, countercurrent to the vapor flow, and complete the cycle. Bramley and Brewer5 and Martin and Kuhn6 in Germany proposed to establish countercurrent flow by thermal convection.
' ~ e v s .Modern Phys., 10: 245 (1938); Rev. Sci. Instruments, 9: 413 (1938). 'Phys. Rev., 56: 266 (1939). 3 ~ h y s Rev., 56: 684 (1939). . Reports on P r o g r e s s in Physics, VI: 72 (1939). 'Science, 92: 427 (1940). '2. physik. Chem., A189: 219 (1940).
p2/p
and p  p(r) i s the total pressure. Then Eq. 6.4 becomes (Ml  1%) (urn)' 2RT
= () &o
exp
It is usual to take M, > Ml, and accordingly
a n = exp
so that Eq. 6.6 takes the form
(Ma  MI) ( u r J 2 2RT
R(0) = a o R ( r 2 ) where a ni s the (equilibrium) simpleprocess factor of the separat The value of the simpleprocess factor for a peripheral velocity 300 meters/sec, T = 300Â°K and a m a s s difference of one unit i s , Eq. 6.6, a. = 1.0183. Shortly after the suggestion of Lindemann and Aston was made, tempts were made, in rather crude apparatus, by Joly and Poole1 by Mulliken2 to realize this separation factor, but these were uns cessful. The idea of the evaporative centrifuge was introduced at same time by Mulliken. In this method a small amount of liquid introduced into the centrifuge, forming a layer a t the periphery. DuPhil. Mag., 39:,, 372 (1920). 'J. Am. Chem. Soc., 44: 1033 (1922).
106
THE THEORY OF ISOTOPE SEPARATION
CENTRIFUGES
107
The aim of this chapter is to expose the theory of centrifugal separation for various types of centrifuges. The important question of mechanical design will be dealt with only in so far a s it is essential to the understanding of the process design. The partial differential equation of centrifugal separation is derived in Sec. 2. In Sec. 3 the theoretical maximum separative power of a centrifuge is found. The solution for the evaporative centrifuge i s given in Sec. 4, that for the concurrent centrifuge in Sec. 5, and that for the countercurrent centrifuge in Sec. 6. Section 6 investigates at length the properties of the countercurrent centrifuge. The writer was introduced to the a r t of centrifugation by C. Skarstrom, formerly of the University of Virginia and later with the Standa r d Oil Development Company. Harold C. Urey participated actively in the early work, until his other responsibilities became too heavy, contributing ideas and physical interpretations of mathematical results. Irving Kaplan shared in all the developments subsequent to December 1941, notably the work on cascades of centrifuges (incorporated largely in Chaps. 1 to 5) and the design problem.
2. PARTIAL DIFFERENTIAL EQUATION OF CENTRIFUGE
The density distribution (Eq. 6.10), considered from a molecular point of view, is a dynamic equilibrium between the effect of random motion of the molecules (diffusion), which tends to erase density gradients, and the effect of the centrifugal field, which tries to pile all the molecules at the periphery. The diffusion counter to the density gradient gives a current density (in grams per second per square centimeter)
Here D is the coefficient of selfdiffusion. The outward current per square centimeter caused by the centrifugal force, which balances this inward current, must therefore be
In mixtures, Eq. 6.11 holds for each component separately
As a preliminary to the derivation of the differential equation, consider for a moment a centrifuge containing a single pure gas. The gas is supposed to rotate uniformly at the same speed a s the rotor, i.e., w radians/sec; to have no other motions; and to be isothermal. Choose a cylindrical coordinate system, rotating with the gas, with the origin at the axes of rotation. The effect of the rotation is to set up a centrifugal force w 2 r per unit mass. Under the influence of this force, a pressure gradient is established according to the hydrodynamic equation
Di i s the diffusion coefficient for molecules of type i through the whole mixture. For isotopic mixtures the exact meaning of the diffusion coefficient is of no significance, and henceforth the subscript will be dropped. Equation6.12 i s the desired expression for the flux of molecules caused by a centrifugal field, and it i s now possible to derive the differential equation. Consider then a centrifuge containing a perfect binary gas mixture, isothermal and rotating uniformly. In order to accomplish separation, the gas i s made to flow radially and axially. In t e r m s of the cylindrical coordinate system chosen a s before, the motion of the gas a s a whole (drift velocity) is given by the components
Here p i s the density of the gas mixture in grams per cubic centimeter. The quantities p and p a r e related by the gas law
(Radial) (Azimuthal) (Axial)
u = u(r,z) v =0 w = w(r,z)
Combining Eqs. 6.8 and 6.9 gives Eq. 6.3 of its equivalent ~ ( r = ~ ( 0exp ) ) Mw2r2 (6.10)
Because of this motion of the gas, the equilibrium distribution (Eq. 6.3 o r 6.10) i s continually upset. The system moves material in an effort to reestablish equilibrium; in this way a transport of the desired material i s set up.
CENTRIFUGES
Imagine a small annular region in the rotor, bounded by the cylind e r s r = roand r = r o+ 6r and by the planes z = z0 and z = z0 + 6z. In a short time interval 6t t h e r e flows a c r o s s the cylindrical face r = rn an amount of desired isotope (denoted by the subscript 1). which i s the desired partial differential equation of centrifugal separation. The three kinds of centrifuge described in Sec. 1 a r e governed by special c a s e s of Eq. 6.19. In the evaporative centrifuge w = 0 and r u = constant; in the concurrent and countercurrent centrifuges u = 0, and w describes the respective types of flow. The solution of Eq. 6.19 for these c a s e s i s the subject of the subsequent sections devoted to the particular centrifuge types.
3 . MAXIMUM SEPARATIVE POWER OF A CENTRIFUGE
In this equation p,u is the flow caused by the drift velocity, p$cl i s the flow impressed by the centrifugal field, D ap1/ar i s the contribution f r o m diffusion against the density gradient, and 2 r r O6z i s the a r e a of the cylindrical face. Likewise the flow a c r o s s the plane face z = z0 i s
The change in content of desired material in the volume element i s therefore
In this section the maximum separative work that can be performed by a centrifuge1 will be determined. It will be used a s a standard to evaluate the efficiency of the various centrifuge designs. Using the result of Sec. 6 (Eq. 1.60),
Introducing Eqs. 6.13 and 6.14 into 6.15 and making use of the relation of Eq. 6.12 for u C (dropping the subscript O),
The net transport of desired material (in moles per second) a c r o s s a surface element do is, according to the analysis given in a preceding section,
Now
and
where To i s a unit vector along a radius through do, TIcl i s the vector velocity created by the centrifugal field directed along F0 and with magnitude given by Eq. 6.12, and the symbol v is the vector gradient operator. Thus the separative power for a s m a l l slab of thickness ds, with f a c e s do normal to VN and sides parallel to VN, i s
=
Substituting Eq. 6.17 in Eq. 6.16, using Eq. 6.18 and noticing that Dp constant, it i s found that
Following Dirac.
110
THE THEORY O F ISOTOPE SEPARATION
CENTRIFUGES
Ill
The symbol indicates the scalar product. Taking VN a s a variable and do d s and everything else constant. Eq. 6.21 i s a maximum when
dependent of the radius. The radius affects the holdup, and in counter current centrifuges the flow into the rotors, but is otherwise irrelevant. It is usually chosen by mechanical considerations.
that is, along the direction of the centrifugal field, and onehalf the equilibrium value. Then
SURFACE do
\
\
\
\I
Integrating over the whole centrifuge, of length Z and radius r2,
/ ,
A
Note that the expression in brackets is the exponent of an (Eq. 6.7). The minimum number of centrifuges of length Z and peripheral velocity w r 2 required to perform a given separation is, by Eqs. 1.44 and 6.23, AU/(6U)rnax. The value of (i5U)max depends on the peripheral velocity of the fourth power, which puts a premium on high periphe r a l velocities. The separative power is also proportional to the length. But for constant peripheral velocity1 the separation is in'The peripheral velocitynot the angular velocityis determined by the tensile strength of the rotor wall, s o that it i s the fundamental characteristic of the machine. The demonstration follows: Consider the equilibrium of forces acting on a sector of the rotor wall, subtending a small angle 4. Then the triangle of f o r c e s gives (Fig. 6.1; r + d u u 2 r = 2 T d u s i n  = T dff 4 2 *
<t>
Fig. 6.1Stresses diagram.
in a thin rotating cylinder. (a) S t r e s s e s in a wall sector. (b)Vector
4. THE EVAPORATIVE CENTRIFUGE
In the evaporative centrifuge N is independent of z, and w = 0. Considering the steady state, a ~ at/ = 0 and Eq. 6.19 reduces to
where
where T is the s t r e s s in the wall and p i s its density. The rotor will break when T = p d r 2 i s greater than the tensile strength of a metal.
112
THE THEORY O F ISOTOPE SEPARATION
CENTRIFUGES
113
Suppose vapor i s removed from the axis a t a r a t e L moles/sec. Then
 J 2mzu = L L
RT
(6.26j
ducti0n.l If it i s assumed that the production i s only a small fraction of the charge, o r that successive batches of product a r e kept separate, the separative power of the centrifuge i s (cf. Appendix D)
Multiplying Eq. 6.24 by the constant 2 i i Z / R ~ and integrating, 3N
y r
5U = 2L
( ($1
5
(6.32) a n y+L  1 ) 2 = ~ L 2 ~ ) + ( l n a o ) 2 ( ~ L2
+ 2flAr2 N ( l  N)
I
= L M(0)  L N(r)
(6.27~
The value of 6U is a maximum when L = 2 ~ : ( ~ = (ln ~ a0)2 =~Dp (ln ) ~ 4 RT
Y
where
y = 27rZ  (moles/sec)
u 2
z
(6.33)
DP RT
(6.28)
The integration constant was evaluated by noting that the left side of Eq. 6.27 vanishes a t r = 0. Replacing N by R a s dependent variable,
+ 2AAr2 R
Now
) [
= L R(0)  R(r)
] [ + K%]
1
Ãˆ6s29
 R(0) s  AAr2 N(O), which can be neglected with respect to 1 + R(0) unity. After thus simplifying Eq. 6.29, the solution is readily found to be
R = R(0) exp  A A r 2
which i s the same a s the theoretical maximum separative power of a centrifuge (Eq. 6.23). In the development just given the gas was assumed to be isothermal. This picture i s f a r too simple. When vapor i s withdrawn a t the axis, the gas cools by expansion and a temperature gradient i s induced. The gradient i s determined by the balance between the r a t e of cooling of the g a s and thermal conductivity. As L increases, the gradient increases until the gas reaches the dew point o r the adiabatic g r a dient. The mean effective temperature Teff i s therefore reduced a s a function of L. An attempt may be made to account f o r this effect by writing in place of Eq. 6.31
I)&(
R(0) = R ( r 2 ) a o
fc^)
T
2
(6.34)
and on introducing Eq. 6.7, which in t e r m s of AA i s
a = exp [ + A A ~ ; ] .
(6.30)
this expression may be written R(0) = R(r2)ffo
(&)
(6.31)
Since T / T ~increases with L, the separation will not fall off quite so ~ ~ fast with L in practice a s Eq. 6.31 would indicate. A unit weight of gas rotating near the periphery with angular velocity w has the angular momentum r & ; at the axis it has none. When g a s i s moved from t h e periphery toward the axis, means must be provided to absorb this excess angular momentum, which otherwise tends to increase the angular velocity of the gas a t smaller radii. This i s accomplished by radial baffles2 (looking down along the axis, a s t a r ) which prevent the g a s from rotating a t angular velocities dif ferent from that of the rotor. 'This result was found by Humphreys, Phys. Rev., 56: Yearns and Skarstrom, Phys. Rev., 56: 266 (1939).
Equation 6.31 gives the relation for mole fraction of product N(0) in t e r m s of the composition of the charge N(r2) and the r a t e of pro
684 (1939).
114
THE THEORY O F ISOTOPE SEPARATION
CENTRIFUGES
Although the evaporative centrifuge, with L = 2y, delivers 100 per cent of the theoretical separative power, it is not easily adapted to continuous operation.
5. THE CONCURRENT CENTRIFUGE
Like the evaporative centrifuge, the concurrent centrifuge is a simpleprocess machine since the enrichment factor per machine is limited to a , ,. In this device axial flow i s used to obtain an axial a s well a s a r a dial concentration gradient. The gas enters (Fig. 6.2) in two streams a t one end of the rotor and flows axially to the other end, where the s t r e a m s a r e removed separately. During the passage through the centrifuge the s t r e a m s tend to assume the (radial) equilibrium distribution (Eq. 6.6). The flow pattern adopted for the concurrent centrifuge consists of two thin cylindrical s t r e a m s located a t radii r, and r (periphery) and flowing parallel to the z axis. (The optimum position for the inner stream i s not a t the axis, a s will be seen subsequently.) There i s no radial m a s s flow. A rotor with a double entrance (so that entering streams of two different concentrations can be used) will be considered; previously the literature has covered only singleentrance machines. The doubleentrance centrifuge i s more flexible than the latter. Cascades of these elements, which a r e more general than the element .of Chaps. 1 to 5, a r e studied in detail in Appendix E. Among the more interesting features of this study i s the result that the nomixing case (both entering s t r e a m s of the same composition) i s not an optimum. The solution given here follows roughly the demonstration by Murphree, which for the case considered i s superior to the more general method that was originally used. The value of u i s zero, and the flows a r e generally so large that backdiffusion is negligible. Then Eq. 6.19 reduces for the steady state to
WALL
In the region between r grates to
=
rl and r
=
r2,w = 0, s o that Eq. 6.35 inte
Fig. 6.2Simple
model of a gaseous concurrent centrifuge.
116
THE THEORY OF ISOTOPE SEPARATION
CENTRIFUGES
117
where f (z) is the transport of desired isotope a c r o s s a cylindrical element of unit length between the two streams. But also, if L(rJ i s the flow in the stream at r = r2,
The separative power when N(r2,0) and N(rl,O) a r e most favorably related1 is, according to Eq. 11 of Appendix E,
and L(r2) N(r2,z) + L(rl) N(rl,z) = L(r2) N(r2,0) + L(rl) N(rl,O)
=
and the separative power per unit length is
B
(a constant)
(6.38)
Integrating Eq. 6.36 between rl and r2, considering AA N(l  N) constant to t e r m s of the order of (AA)',
which i s a maximum with respect to rl/r2 for any value of bz when rl/r2 = 0.534,
and substituting for f (2) from Eq. 6.37 and for N(r2,z) from Eq. 6.38,
and a relative maximum with respect to bz when bz = 0, namely,
(F)
Integrating this ordinary differential equation for N(rl,z) and r e arranging the result,
DP =0.~07247r(~nit~)~
max
RT
If this result is compared with Eq. 6.23, it is seen that this i s 81.45 per cent of the theoretical efficiency. For a single entrance centrifuge, it is necessary to take N(r2,0) = N(rl,O). The separative power is then, according to Eq. 8 of Appendix E,
and per unit length where
118
THE THEORY OF ISOTOPE SEPARATION
CENTRIFUGES
The maximum with respect to rl/r2 is the same a s before. The expressionl (1  e^)'/bz has a true maximum a t bz = 1.25643 and thus
6. THE COUNTERCURRENT CENTRIFUGE
(y)
=
max
27rDp (In (0.40724)'  aJ2 KT
which has an efficiency of 66.34 per cent. The condition bz = 1.25643 gives a definite relation between the length of the rotor and the flow, namely,
I it i s remembered that the separative power i s the product of the f concentration difference and the transport, the maximum of 5U with respect to rl/r2 is easily understandable. The concentration difference is the maximum when r,/r2 = 0, but the transport (through the cylinder of radius zero) is zero. The transport i s a maximum when r1/r = 1, but the concentration difference is zero. The maximum of the product thus lies somewhere in between.
A fuller discussion of the significance of the dependence of the r e sults on 1  e^, the degree of equilibrium attained, is given in Appendix E. The phenomenon i s a quite general one. Notice that b contains the factor 0(1  0) (L, + LJ. Decreasing 0(1  0) and increasing L, + Ln leaves this factor unchanged, but small total flows a r e desirable and 0(1  0) should obviously be made a s large a s possible, which requires 0 = % (cf. Eq. 6.44).
Countercurrent separating devices in general have the property of multiplying the equilibrium simpleprocess factor many times in one unit. Because of the nature of the flow, a concentration gradient whose size i s limited only by backdiffusion i s established in the direction of the flow. Since a large separation i s obtained in one unit, much of the recycling between units which is otherwise necessary to multiply the simpleprocess factor i s avoided. Furthermore, the problem of cascade operation i s very considerably simplified since the number of units in s e r i e s required to effectuate a given fractionation decreases enormously. The cascade becomes broad instead of long and i s easily broken down into independent parallel sections. Countercurrent flow i s also efficient from a process standpoint because it i s possible to maintain maximum separative power through the entire unit.' F o r all these reasons, which have long been appreciated by chemical engineers, countercurrent processes a r e preferred if at all possible. The differential expression of Eq. 6.19 becomes for the countercurrent centrifuge
Further properties2 of the concurrent centrifuges may be obtained from the equations given.
'Note that the correspondence eb2
 </I$ makes this take the form
The solution of Eq. 6.45 may be found by following the standard methods for solution of partial differential equations. This method was utilized in June and July of 1940. However, Eq. 6.45 i s particularly simple since the gradients of the concentration in all directions a r e small. Thus the equation for a countercurrent centrifugal column can also be solved by the method used by Furry, Jones, and Onsager2 for the thermaldiffusion column. This possibility was first pointed out, and partially worked out, by B r a m l e ~ .A similar procedure was ~ employed by Martin and ~ u h n . ~ The results of the two methods a r e of course identical. The second method will be demonstrated here because it i s easier and because it
'1n contrast to concurrent devices, in which aN/ar changes with z, s o that if the separative power i s an optimum in one place it is necessarily l e s s in every other place. v h y s . Rev., 55: 1083 (1939). 'Science, 92: 427 (1940). Z . physik. Chem., A189: 219 (1940).
'For example, for any r l / r 2 the dependence on z/(L1 + L2) i s the same, and the maximum for the single entrance centrifuge is at t h e s a m e place, bz = 1.256 [with the appropriate value of In (r2/rl) in b]. But for z/(Ll + LJ preassigned (and not bz) the maximum with respect to r 1 / r varies.
120
THE THEORY OF ISOTOPE SEPARATION
CENTRIFUGES
121
permits the c a s e in which the mole fraction of the product i s large to be included without added complications. The method depends essentially on the fact that aN/ar i s of the o r d e r of N(l  N)2AAr, which i s a s m a l l quantity. Thus the variation of N with respect t o r, a s compared to the variation of r, p, o r pw, may be neglected. F o r example
pw r d r , which i s just a s useful for present purposes. Substiar o tuting Eq. 6.46 in Eq. 6.49, it i s found that
rr
CJ^L
pw r d r
 ?z ! a
r
pw r d r + t e r m s of the o r d e r of A A ~
where
Consequently Eq. 6.45 may be integrated with respect to r. The f i r s t integration gives directly, dropping a2N/az2 and aN/at,which a r e of second o r d e r ,
The integration constant ( a function of z and t) w a s evaluated by r e membering that r ( a N / a r ) 0 a s r 0. The second integration with respect to r r e q u i r e s a little more artifice in o r d e r to get a form in which the integration constant can be evaluated. The boundary conditions a r e


c6 =
27 7
/
'Â¥
p r d r = holdup p e r unit length (moles/cm)
Equation 6.48 may be transformed by integrating by p a r t s the f i r s t t e r m on the lefthand side,
Equation 6.50 h a s the f o r m of Eq. 2.1, the typical equation f o r isotope separation in a square cascade o r column. The properties of such columns, individually and in cascades, f o r fixed values of c,, c , and c6 were studied in Chaps. 2, 3, and 4. The following discussion covers the investigation of how these coefficients vary a s a result of changes in operating conditions. The material in the e a r l i e r chapters will be r e f e r r e d to constantly. In order to examine properties of the countercurrent centrifuge, attention will be confined for the moment to a single centrifuge. F o r convenience it will a l s o be assumed that N<1, although t h i s i s by no means essential to the argument. Then the steadystate solution of Eq. 6.50 i s (Eq. 2.14)
Equation 6.49, although it does not give the integration constant that would permit the integration of a ~ / a ritself, tells how to integrate
122
THE THEORY O F ISOTOPE SEPARATION
CENTRIFUGES
123
where
and the maximum possible value of N(Z)/N(O) for a given length of centrifuge and for a given type of countercurrent flow i s
N(z)
NO)
 exp 2cOz
where 2e0 is the maximum of c2 + a3L2 with respect to L and i s
The quantities cl and c5 depend on the function pw, which measures the upanddown flow, in two ways: They depend on the flow pattern, o r the locations and relative size of the s t r e a m s , and on the absolute magnitude of the flow. The pattern i s built into the rotor by the position of orifices in the end caps and position (or absence) of baffles. But the magnitude of the flow i s an operating variable and can be adjusted f r o m outside. This independence of flow rate and internal construction in a properly conceived centrifuge gives it more flexibility than the otherwise analogous thermaldiffusion column. Therefore a new quantity L is introduced.
The corresponding value of L i s
which is the flow up the column plus the flow down the column. Then
does not depend on L, and Eq. 6.52 becomes
The existence of a maximum in e i s physically due to the phenomenon of backdiffusion. The concentration gradient is proportional to e . When L, the total flow in the centrifuge, is large and the concentration gradient i s small, backdiffusion i s negligible (c, < a,L2) and e v a r i e s inversely a s L. But a s soon a s L is small and e and the concentration gradient a r e large, backdiffusion plays an important role, finally limiting the attainable fractionation. It will be found convenient to measure all flows in t e r m s of Lo. Therefore s e t
Substituting in e,
where a, = c,/L and a 3 = C J L ~ do not vary with L. N(z)/N(o) i s now a function of L and ip. F o r any value of L, N(z)/N(o) is greatest when the rate of, production i s zero. Then N(Z)  exp (c2 ' t L 2 NO) In t e r m s of the dimensionless parameters m and
ib.
P is given a s (6.61)
z,
P = m^P0
*
124
THE THEORY O F ISOTOPE SEPARATION
CENTRIFUGES
o h K., memorandum to H. C. Urey, May 14, 1940. Cohen, K., and I. Kaplan, Report A101, Jan. 28, 1942. Cohen, K., and C. Skarstrom, Columbia S e r . No. 4RX138, Feb. 6, 1941. Dirac, P. A. M., British MS, 194'1. Kaplan, I., and K. Cohen, Report A195, J u n e 17, 1942. Murphree, E. V., Separation of G a s e s by Diffusional Methods, February 1942.
where
Equations 6.57 to 6.62 constitute a complete description of the behavior of the countercurrent centrifuge. When the type of flow pw i s specified, co, Lo, and Po a r e determined. L and P a r e the conditions imposed and a r e measured on flowmeters by the experimenter. By Eqs. 6.59 and 6.61, m and $ a r e therefore known. And finally, substituting co, m, and ~,LJ in Eq. 6.60, the fractionation of the column i s predictable. The maximum separationfactor occurs a t L = Lo, but this i s clearly not the most efficient circulation rate f r o m the standpoint of separative power, since the parasitic phenomenon of backdiffusion is very important at this flow. The relative weight of backdiffusion i s reduced by increasing L (thus decreasing the concentration gradient). These qualitative considerations a r e confirmed by examining SU. From Eq. 2.33,l
whose largest value i s reached asymptotically a s m m. It should be noticed that the limiting value of 6U i s approached very rapidly: When m = 3 the separative power i s 90 per cent, and when m = 5 it i s 96per cent of c;Z/4c3. At these valuesof m the concentration gradient i s 60 and 38 p e r cent, respectively, of the r n a x i m ~ m . ~ Thus it i s not necessary to discard the advantages of large separation in one unit, o r to increase the flows inordinately, to get adequate separation efficiency.

REFERENCES
Bramley, A., The Centrifugal Separator, Oct. 7, 1940. Cohen, K., Report A54, October 1940; Report A52, Jan. 21, 1941; Report A50, Jaz. 30, 1941.
C o n s i s t e n t with the e a r l i e r sectionsof t h i s chapter, the symbol 6U is being used k? the total separative power, and not the separative power p e r unit length a s in Chap. Z Sec. 3. 'The f a c t o r is 2m/(l + m2).
OTHER SEPARATION METHODS
127
isotopic solutions a r e perfect solutions and because the simpleprocess factor is nearly one; and (2) the inclusion of the equilibriumtime phenomenon, which is generally omitted although it is more often significant than is commonly susnpfted It i s clear that the two phases need  not be liquid and gas; two liquids, o r a liquid and a solid, would be equally suitable. The phase Chapter 7 OTHER SEPARATION METHODS
1, TWOPHASE SEPARATIONS
The classic case of a twophase separation is fractional distillation, one of the most widely used unit operations of chemical industry. The earliest use of this process in isotope separation was the fractionation of Ne20 from liquid neon by Keesom. The method was later used to r a t e deuterium from liquid hydrogen andin the fractionation of H,0 to give 0 8(Urey e t al.). 1 The scope of this process was much enlarged by Urey's invention of the chemicalexchange method. Here the driving force of the separation is the chemical equilibrium constant of a reaction such a s
Such a reaction can be carried out entirely analogously to ordinary fractional distillation (refer t o Fig. 7.1). In the example shown, HCN gas is scrubbed countercurrently with a water solution of NaCN in a packed tower, just a s vapor and liquid a r e contacted in fractional dis tillation. The condenser of the fractionating tower is replaced by NaOH, which converts the gas phase to the liquid phase. Although the theory of such processes was fairly well understood before the war, an account of it is included here by reason of its probable great future importance. Also, the generality of development of cascade theory now allows the theory to be given in a clearer and m e concise form. The theory has some points of resemblance with the ordinary theory of fractional distillation. The two chief differences a r e (1)the closed form of the results, which is possiblebecause
126
Fig. 7.1 A
chemicalexchange tower.
in which enrichment of desired isotope takes place will be denoted by small letters and the other phase by capitals. Thus n, 1 , h, and d a r e , respectively, the mole fraction,flow in moles per second, holdup in moles per centimeter, and diffusion coefficient in one phase; and N, L, H, and D a r e the corresponding quantities for the other phaseAt equilibrium1
'A complete discussion of the theory of the equilibrium constant may be found in 3. Bigeleisen and M. G . Mayer, J. Chem. Phys., 15: 261 (1947).
THE THEORY O F ISOTOPE SEPARATION
OTHER SEPARATION METHODS
Eliminating ni and N, between Eqs. 7.5 and 7.6,
Countercurrent contacting (Fig. 7.1) will be considered first. The direction of flow of the enriched phase will be taken a s positive, and length along the column will be measured in this direction. Then if T is the rate of transfer of desired isotope to the enriched phase across the interface per unit length of column,
=+
1 k
B DCu
b dcu
The rate of transfer T depends on two processes : the rate of at tainment of the chemical equilibrium and the rate of diffusion through fluid boundary layers. If the equilibrium process is rate determining, then T has the form of the rate constant for a bimolecular reversible reaction
where c and C a r e the concentrations in moles per liter of the proce s s material in two phases. Usually the slow process is the diffusion through the boundary layers. Referring to Fig. 7.2 and denoting the mole fractions a t the interface by ni and Ni, and the a r e a of the interface per unit length of column by a , then
Fig. 7.2Relations at a gasliquid interface. a relation that is quite familiar to chemical engineers. Equation 7.7 can be simplified by the assumption that the interfacial concentrations do not differ appreciably f r o m the concentrations in the body of the fluid, giving T =  k [(n  N)  (a 1)N(1  n)]
=  k [n(l  N)  aN(1  n)]
The differential coefficients may be replaced k y (Ni  N)/B and (n  ni)/b, respectively, when B and b a r e the film thicknesses. Thus
(7.9)
At the same time ni and N, a r e related by Eq. 7.1, s o that
which is the s a m e a s Eq. 7.3 but with a different meaning for k. It should be noted that in deriving Eq. 7.9 it has not been assumed that, '.a  1) i s small. Inserting Eq. 7.9 in Eq. 7.2,
THE THEORY OF ISOTOPE SEPARATION
OTHER SEPARATION METHODS
13 1
h
an an + 1 =  k az at
[(n  N)  (a  1)N(1  n)] (7.10)
The solutionof these equations i n t h e steady state (aN/at = &/at = 0) f o r ( a  1) small has been treated at length in Appendix E, a s well a s the associated cascading problem.
2. THERMAL DIFFUSION
These two equations may now be combined, using the assumption that ( a  1) i s very s m a l l (for the c a s e of large values of a , s e e Sec. 3). Noting that the operator a/at i s proportional t o (a  1)' and that 9/9z i s of the o r d e r (a 1).
The history and theory of the thermaldiffusion process has been the subject of a number of recent papers which have been widely read.' The treatment here, therefore, will be confined to a rapid review of the theory to show how i t fits in with other separation methods in the general scheme. The equation f o r thermal diffusion corresponding to Eq. 6.45 that was derived f o r a centrifuge is easily a r r i v e d a t by replacing
which is the form of the fundamental equation of isotope separation (Eq. 2.1) with the correspondences by the corresponding expression for thermal diffusion2
The theory of square cascades developed in Chap. 2 can thus be applied directly. The exact solution of Eq. 7.10 in the steady state for values of ( a  1) that a r e not small i s also of some interest. Eliminating N by the relation In  LN = Pnp, defining $J = P / ( a  111, (. = k(o1  1 ) / 2 ~ , the following is obtained:
where a is known a s the thermaldiffusion coefficient. Then, i n place of Eq. 6.45,
where A($) = {[I + $ + ( a  l)$np)2  4a$Jnp}% and no, nz, and n~ are the mole fractions a t the bottom of the column, the top of the column, and the top of the cascade, respectively. Equation 7.13 is directly analogous to Eq. 2.5, to which it reduces f o r small values of ( a  1). The equations for concurrent contacting a r e easily obtained f r o m Eq. 7.10 by changing L to L. This gives 3N 3N H + L  = k [ ( n  N )  ( a  l ) N ( l  n ) I az at
h a n + at
where x is the distance from one wall in a thin annular space between two concentric cylinders. It must be remembered that because of the severe temperature drop a c r o s s the annulus pD varies with x. Proceeding now precisely a s i n Sec. 6 of Chap. 6, it is found that Eq. 7.15 resolves to
(7 .14)
an 1  =  k [(n  N )  ( a  1)N(1  n ) l az
*L. Waldmann, 2. Physik, 114: 53 (1939); H. Furry, R . C. Jones, and L. Onsager, Phys. Rev., 55: 1083 (1939); P . Debye, Ann. Physik, 36: 284 (1939); K. Wirtz, Ann. Physik, 36: 295 (1939); A Bramley, Science, 92: 477 (1940); J. Bardeen, Phys. Rev., 57: 35 (1940), 58: 94 (1940). 'see S. Chapman and T. G.Cowling, "Mathematical Theory of NonUniform Gases," p. 244, Cambridge University Press, London, 1939.
132
THE THEORY O F ISOTOPE SEPARATION
OTHER SEPARATION METHODS
133
where now
which requires a catalyst. It was f i r s t proposed by Urey in late 1940 to use this p r o c e s s by countercurrent washing of water and hydrogen in a tower packed with catalyst. At the time of writing, water must be converted into hydrogen a t the product end of a cascade using the process of Eq. 7.17. The steadystate equations corresponding to Eq. 1 of Appendix E a r e , from Eq. 6.14,l
I  =  k [(n  N)  (a  1)N(1  n) ] az
Appreciable simplification occurs when N s: 1; since this i s the major part of the Dn problem (initial concentration = 1/7,000) this case will be considered. Then
an
In Eq. 7.17, p is the density, r i s the radius of the annulus, and a is the spacing a c r o s s the annular gap. The relations of Eqs. 7,16 and 7.17 hold f o r any fluid, liquid a s well a s gas. Values of cl and c,; depend on the spacing, the temperature drop a c r o s s the gap, and the intrinsic properties of the fluid. The further theory of the thermaldiffusion column closely r e s e m bles that of the centrifuge, except that in the present instance the m a s s flow is caused by convection and i s dependent on the temperat u r e drop and the spacing. Corresponding to ^>O, the flow that gives the maximum fractionating factor in a centrifuge, there i s a charact e r i s t i c width an for which the fractionation in a thermaldiffusion column i s a maximum. However the maximum efficiency from the standpoint of separative work per unit of heat loss i s at a spacing other than a. which corresponds to the maximum separative effi, . ciency in a centrifuge f o r flows l a r g e r than & F r o m the standpoint of flow geometry, it i s easy to show, by the method of Chap. 6, Sec. 6, that the model described has an absolute efficiency of about 71 per cent and that the most efficient flow pattern corresponds to flow immediately adjacent to the walls of the annulus, but with no flow in the middle.
The solutions of Eq. 7.20 a r e
The cascade is shown in Fig. 7.3. Then f o r the (s + 1)th stage, the following identifications can be made:
Equation 7.2 1 becomes
3 , CONCENTRATION OF DEUTERIUM
A possible basis f o r the production of deuterium i s the exchange reaction
HD + HgO=
+ HDO
(7.18)
'Since (a 1 ) i s large, we may no longer s e t N(l

THE THEORY O F ISOTOPE SEPARATION
OTHER SEPARATION METHODS
135
where
ft = 1  e x p
[
k(L ~
~
1 fraction of equilibrium attained = ) 2
(7.23)
Now Eq. 7.22 can be combined with the conservation equation
to give three equations in the four quantities Ns+l, Ns, ns, and ns.i which can be solved in t e r m s of any one of them. For example
The difference equation (Eq. 7.25) is easily solved to give
where
and No is the concentration of HDO in the feed. The number of sections in the cascade, a s a function of the initial and final concentration, is accordingly
m
KEY
(GAS) LIQUID
Since L  1 = P, A and B (and hence S) a r e functions of P/L, the percentage withdrawal1 The volume of catalyst required can be obtained by writing
The
reciprocal, L/P, is known as the
"reflux ratio."
136
THE THEORY O F ISOTOPE SEPARATION
where V i s the volume of catalyst p e r stage and k' i s the transfer coefficient per unit of catalyst. Then Crom Eq. 7.23,
and the total volume i s VS, a function of (3 and P . The total volume of catalyst has i t s smallest value when 0,the fractional attainment of equilibrium, i s zero. Without proof, this limiting volume i s taken to be the same a s that f o r the operation of a countercurrent column and corresponds to an infinite number of stages. The minimum number of stages o c c u r s for (3 = 1 and of course requires an infinite amount of catalyst. It can also be shown that t h e r e i s a maximum in the function
P 
APPENDIXES Appendix A Roots of a Transcendental Equation Time of Square Cascades for N
Appendix BEquilibrium Appendix C The
1
VS
production volume of catalyst
Holdup Function Distillation of Concurrent Twophase Elements
Appendix DRayleigh Appendix E Properties
which gives the economic operating conditions when the catalyst volume i s limiting. However, it is usual.1~expedient to run a t higher values of P and get more complete recovery of heavy water from feed.
REFERENCES
Cohen, K., Report A118, May 1941; R e p o r t A530, Feb. 4, 1943; Report A531, Feb. 5, 1943. Cohen, K., Columbia S e r . No. 4MX148, June 25, 1941; Columbia S e r . No. 4RX133, August 1941. Cohen, K., Columbia S e r . No. 4L35, M a r . 17, 1943 (letter t o P. C . Keith). Cohen, K., Packed Fractionating Columns, J. Chem. Phys., 8: 588 (1940). Cohen, K., and I. Kaplan, Columbia S e r . No. 4R6, Nov. 5, 1942. Hutchison, C. A,, J r . , "Chemical Separation of the Uranium Isotopes," Division 111, Volume 3, National Nuclear Energy S e r i e s . Kaplan, I., and K. Cohen, Report A335, Oct. 19, 1942; Report A1276, May 1 , 1944. Thompson, W. I., and K. Cohen, S e r . No. 4R104, Sept. 3, 1943.
Appendix A ROOTS OF A TRANSCENDENTAL EQUATION
The features of the solution of the characteristic relations of Eq. 3.20 o r Eq. 3.22 for the roots pi, will be made clear by completely discussing the simplest special case, namely K' = , K = 0, and P = 0. In this case it is necessary to solve for all the roots pi, of the equation YS tan Y S = â
s
where
If both s i d e s of Eq. 1 a r e plotted a s functions of yS (Fig. I), the solutions of the equation a r e the intersections of the curves y = tan yS If and y = y ~ / c ~ . cS is positive and l e s s than 1, there i s a root yS = (yS), in the f i r s t branch of the tangent function, a s well a s other roots " which approximate to
in all succeeding branches. Since p depends on (yS)', the symmetrical negative roots may be neglected. The smallest root is i n the f i r s t
140
THE THEORY O F ISOTOPE SEPARATION
APPENDIX A
141
branch and gives pi; the other roots in the l a t e r branches give pa,
Plotting both sides of Eq. 4 a s functions of flS (Fig. 2) a root of (fiS), i s observed. Since tanh (fiS), i s always l e s s than 1, s o also i s (fi~},/es, and consequently p, i s negative. F o r negative eS, there i s no root of Eq. 4. All the roots yS a r e r e a l and satisfy Eq. 1. Referring to Fig. 1, there i s a root tyS), between TS/Z and n in the f i r s t branch of the tangent, and t h e r e a r e l a t e r roots which approximate to (2K  l)n/2 (K = 2.3.4.. ) i n all succeeding branches. Again, p i s negative.
h
.
Q3
Fig. 2Graph of both sides of the equation tanh BS = SS/CS a s functions of BS.
Approximate expressions may be obtained f o r the roots (yS), when eS (of either sign) i s small o r large, o r when S i s positive and nearly 1. eS Large and Positive. The value of tanh (PS), is very nearly 1. Equation 4 i s expressed a s tanh pS = 1  2e2'3s + 2e4'3s +
Fig. 1 :Graph of both sides of the equation tan yS = @ / C S a s functions of y S .
 13S . ..  eS
(6)
Solving by successive approximations, If eS is positive and g r e a t e r than 1, the root in the f i r s t branch disappears (dashdotted line, Fig. 1). In this c a s e t h e r e is a pure imaginary root, y , = ip,. Substituting /3 in Eq. 1, tanh PS = cs and
PS
Equation 7 to the number of t e r m s given i s good to 0.002 f o r eS > 2. eS Large and Negative. The value of (yS), i s nearly TS. We set (YS), = TS + x. Then Eq. 1 becomes
142
THE THEORY O F ISOTOPE SEPARATION
Table 1 Roots
APPENDIX A
of the Equation yS =
(6s) tan y~
143
and solving by successive approximations,
Equation 9 also gives ( Y S )for eS very l a r g e and positive, and to the ~ number of t e r m s given i t i s good to 0.06 for  eS > 2. eS Small, Positive o r Negative. The value of tan (yS), is nearly infinite, and ( Y S ) ~s nearly 7r/2. Set (yS), = (7r/2)  x. Then Eq. 1 i becomes
IT
expanding the cotangent. The s i z e of x i s very small and the root is accordingly
S Equation 11 to the number of t e r m s given is good to 0.001 for l e ~ l 0.20. The expression also gives the succeeding roots ($Ik by substituting (2K  l)7r/2 for 7r/2. Explicitly,
eS Nearly 1. Since (YS), is s m a l l , Eq. 1 may be written as
Equation 14, derived h e r e f o r eS < 1, can be shown to hold for ES > 1, giving the expected imaginary values f o r It holds to 0.001 for I s  1 =Â 0.1. Roots of Eq. 1 for eS = [2.0(0.1)  1.0; 1.0(0.5) + 1.0; 1.0(0.1)2.0; 5D] a r e listed in Table 1.
(a.
whose solution is
REFERENCES
Cohen, K., Packed Fractionating Columns and the Concentration of Isotopes, J.Chem. Phys., 8: 588 (1940). Cohen, K., Report A530, Feb. 4, 1943.
APPENDIX B
145
Now it is known f r o m the theory of partial differential equations1 that equations of the form
Appendix B EQUILIBRIUM TIME OF SQUARE CASCADES FOR N
1
with boundary conditions of the type in Eq. 3 a r e solvable by iteration. It remains t o choose the most efficient procedure. The expression in parentheses on the righthand side of Eq. 4 i s , in t e r m s of N, aR 2eR   =
2 (  NT) ~
This section outlines the procedure that will solve Eq. 2.1 in the general case when N is not small. The differential equation i s , when P = 0,
according to Eq. 1.77, where T  NT is the net transport of desired material. Since a ~ / a sis always positive and since the transport f o r the initial conditions chosen is also positive, the entire expression Consider the simple case (K'= 0 0 , K = 0, P = 0) a cascade operated under total reflux, with no reservoir on top, and the concentration a t the bottom maintained constant. The boundary conditions a r e
is essentially positive. Thus an iteration process in which we begin by overestimating this t e r m will converge to the solution from low estimates of the equilibrium time; whereas if we begin by underestimating the t e r m we will overestimate the equilibrium time. 2 aR The expression  is the difficult term; the most efficient l+Rds iteration would seem to be performed onthis expression alone, getting successive equations of the form
The substitution of R instead of N as dependent variable makes the boundary conditions linear.
to solve, where Rk is the kth approximation to R and
At the same time, Eq. 1 takes the form
^Maurice Gevrey, "Sur l e s equations aux deriv6es partielles du type parabolique," GauthierVillars. Paris. 1913.
146
THE THEORY O F ISOTOPE SEPARATION
We might take f o r fo either zero o r 4e%e2's/(l+ b e 2 " ) corresponding to the initial and final values of R and aR/as (underestimates and overestimates of f ) . However, unless fir is particularly simple, Eq. 5 also has to be solved by iteration. Thus practically the solution by way of Eq. 5 +l stoo fails after RO. Even the choice f,, = 4 e ~ o e ~ ' ~ / ( ~ ~ e ~ ' ~ ) i cumbersome; f i r s t  o r seconddegree rational algebraic functions of s which lead to special c a s e s of the confluent hypergeometric equation a r e more convenient. An iteration method that can be continued indefinitely is obtained by solving equations of the f o r m
Appendix C THE HOLDUP FUNCTION
The flow in any section of an ideal cascade i s equal to ~AU/E'. Over a s m a l l section AU d ' v / d ~ ~ .Consider, instead of U = PV, the expression H = PhK, where h i s the holdup p e r unit flow and

where
Here the homogeneous p a r t of the equation has constant coefficients, which permits the particular solutions to be obtained operationally.
i t is clear that (2/e2) AH for the small section will be equal to the holdup of desired isotope. Now a large cascade section may be considered a s composed of small sections, the product of one section being the feed of the next. Likewise AH f o r the l a r g e section i s the sum of the AH'S of the s m a l l sections. Hence (~/E')AHover any s e c tion of an ideal cascade, l a r g e o r small, represents the desired mater i a l holdup in that section. The integral of Eq. 1 with the constants chosen s o that K(0.50) = d ~ ( 0 . 5 0 ) / d= 0 i s ~
This is called the "elementary holdup function." It i s the analogue of V (not V). To illustrate the use of H, consider the net desired material holdup i n the cascade section B of Fig. 4.6. Evaluating AU' around this section,
148
THE THEORY O F ISOTOPE SEPARATION
APPENDIX C
149
If we define a general function
F2(N1,N2,N3,N4) = N1 ln
gives the expression
"2 + (N1  1) (R2  R3)  N. Ra
Fl(Nl,N2,N3)
(5)
where the function Fl i s
i u l = pBV ! ( N ~ )+ ( I B 
L ~ v'(NA) + Z B ~ B  NA) )
VN A ) (
R Fl(Nl,N2,Ns) = (2N1  1 ) In Ã ‘ R3
+ (N1  1) (R2  R3) +
Nl (R,  Rd RyRa
F r o m Eqs. 4.39 and 4.40, this reduces to
Then in a s i m i l a r fashion it i s found that
2h PC (N.D.M.H.)~ = 7 F2(Nc,N~,No,No)
â‚
i U f = PBVfINB)  PB V f ( N ~ PB (NB  NA) dN V' (NA) )
In exactly the s a m e manner,
(N.D.M.HJB
d
= 7 F2(NB9NB,NA,No) PB
â‚
2h
AH
hPB K(NB)  hPB K(N,i)  hpefNa  NA)
K(NA)
(N.D.M.H.)~ =
2h pCF2(Nc,Nc,NB,No) ec 2h
â‚
Substituting for V = (2N  1 ) In R , K from Eq. 2, and
(N.D.M.H.)~ =
PA F~(N~,N*,N,,,N~)
(N.D.M.H.)?
= 7 F2(NA9NA9NB,~J Pp
2h cc
gives
REFERENCES
Lefkowitz, H., B. Schwartz, and H. Mayer, Columbia Ser. No. 4R42, Apr. 12, 1943. Mayer, H.,I. Kaplan, and K. Cohen, Report A396, Dec. 2, 1942.
and
Then the equation for the net desired material holdup i s
2 2 N.D.M.H. = 2 AH  2 (hNo) AUf
APPENDIX D
151
which integrates to give Q" Q ( a o  l ) lp= R" ln+ R 1N ( a o  1 ) in 1  N"
Appendix D RAYLEIGH DISTILLATION
Here Q i s the initial quantity of the charge in the distilling flask, and N i s i t s mole fraction. Introducing the cut 6 = Q'/Q = (Q  Q")/Q, where Q' i s the volume of the distillate,
cascades which was presented in Chaps. 1 to 5 was The theory built upon elements that separate according to the law R' = QR R~~ =
The mole fraction of the destillate, N', i s given by
a = constant)
( ft = constant)
$R
Another common type of element which does not obey this simple law will now be considered. An example of such an element was f i r s t encountered by Lord Rayleigh while he was investigating batch distillation. Consider the course of a distillation. At any instant the vapor (mole fraction n) i s in equilibrium withthe composition of the liquid remaining in the flask (mole fraction N") according to the relation
It is evident that Eq. 5 is fundamentally different from Eq. 1 and represents a new kind of separating element. However if a.  1 i s small, then
 = 1 + (ao  1 ) In (1 6) R
R"
+ order
16
of (ao 
R' 16 R I + ( %  1 )  i n = 9
1
(7)
+ o r d e r of ( a o 
Since the composition of the vapor leaving the liquid is different from that of the liquid, the composition of the residue changes a s the distillation proceeds. This is expressed by the conservation relation ~ ( N " Q) = n d ~ ~ ' "
Provided 6 i s constant o r nearly so,' Eq. 7 is approximately of the form of Eq. 1. Thus the infinitesimal c a s e of Rayleigh distillation can be treated according to the theory of Chaps. 1 to 5, with effective simpleprocess factor a = 1 + e given by
(3)
where Q" i s the quantity (in moles) of the liquid residue a t any instant. Combining Eqs. 2 and 3,
The change in concentration of the residue (N") and distillate (N') relative to the initial concentration has characteristic peculiarities. F r o m Eq. 7,
'1t was seen in Eq. 1.19 that it is so in an ideal infinitesimal cascade.
THE THEORY OF ISOTOPE SEPARATION
APPENDIX D
153
from which Table 1 is constructed.
Table 1 Separation and Separative Power in Rayleigh Distillation
 I)'] for 0 = 0, decreasing steadily because of mixing of the successive distillate fractions (which a r e of changing mole fraction). The value of 6V itself (column 4) increases initially a s 6 increases, in spite of the mixing effect, just because more is distilled: a s 0 approaches 1 the mixing is so serious that it causes a decrease in 6U in spite of the increase in amount distilled. (If everything is distilled, evidently no separation is accomplished.) The maximum separative power per unit distillate may be obtained for the entire charge by dividing the distillate into many small portions, instead of collecting it all together. Then the separative power developed reaches G ( f f o 1)'/2. It is perfectly plain that any separation process that obeys Eqs. 2 and 3 is formally equivalent to Rayleigh distillation. Of interest is the evaporative centrifuge (Chap. 6, Sec. 4), where the process is indeed a distillation, but the concentration change (Eq. 2) is caused by the centrifugal field instead of by a difference in vapor pressures.
is a maximum [=
REFERENCES
Cohen, K., Report A50, Jan. 30, 1941; Report A60, October 1941. Cohen, K., and I. Kaplan, Report A163, Apr. 25, 1942. Rayleigh, J. W. S., Phil. Mag., 42: 493 (1896).
6 = cut; fraction of charge in distillate N = mole fraction of charge N1=mole fraction of distillate N" = mole fraction of residue a,,= equilibrium simpleprocess factor SU = separative power G = rate of feed to unit
By taking larger cuts it is possible to increase indefinitely the changein concentrationof the residue (column 3 of Table 1). However, the separativepower remains finite. If it is supposed that the element continually separates G moles/sec of charge into 0G moles/sec of distillate and (1  6)G moles/sec of residue, then by Eq. 1.42,
The value of 6U is found in column 4. More fundamental than 6V is 6 V / 6 ~ which gives the separative , power per unit amount distilled (column 5). It is seen that this term
APPENDIX E
155
provided
Appendix E PROPERTIES OF CONCURRENT TWOPHASE ELEMENTS
A type of element which occurs inthe case of concurrent contacting of two separate phases, and in many other instances, e.g., the concurrent centrifuge, is illustrated in Fig. 1. Figure 2 shows a simple cascade of such units. The element has entrances for two separate
in the equilibrium state. Here k > 0 is a transfer coefficient and z is a parameter expressing the size of the unit. F o r example, in a catalyticexchange process, z would be the volume of catalyst and k would be proportional to the surface a r e a per unit volume of catalyst. These equations a r e consistent with the equations of conservation
L N(z) + 1 n(z) = constant = L N(0)
+ 1 n(0)
(2)
and solving Eqs. 1 and 2 together it is found that, after some r e arranging, ) N(Z) N(0) = (1  9) [n(0)  ~ ( 0 + ( f f  1)N(1  N)] (1  ebz) n(z)  n(0) where
=9
[n(O)  N(0) + (a  1)N(1  N)] (1 e^)
(3)
Fig. 1 A
concurrent twophase element.
When z streams, and unlike the element of Fig. 1.1 (Chap. I ) , there is no particular necessity for the s t r e a m s to be of the same composition. This extra degree of freedom gives considerable flexibility and r e sults in more efficient cascades. There will be exhibited phenomena associated with the degree of equilibrium attained in each unit, and the dependence on cut characteristic of Rayleigh distillation elements (Appendix D) is absent. The equations governing the transfer of material from one phase to another a r e dN L = k [(N  n)  ( a  1 ) ~ (  N)] 1 dz

W,
the last t e r m in Eq. 3 approaches 1, s o that
is the percentage of equilibrium attained in the unit. The separative power of the element is
Expanding the value functions about V [ N ( ~ )and collecting, ]
+
1 y
[ d o )  n(z)]
and substituting from Eq. 3,
1
156
THE THEORY OF ISOTOPE SEPARATION
APPENDIX E
STH OR TOP STAGE
It is seen that fU is a function of (3 and N(0)  n(0). Taking N(0) = n(O), i which corresponds to the nomixing case for singleentrance elements, the following is obtained:
and from Eq. 4, the separative power per unit length is
(s
+ 11TH STAGE
5U  
z
k(ff  l y , p 2  ln(1  6 )
(nomixing case)
which has a maximum at (3 = 0.715.
=
5U
z
0.40724
2
(nomixing case)
sTH STAGE
*
However, this choice of N(0)  n(0) is not the most efficient. Differentiating 6V from Eq. 7 with respect to N(0)  n(0), it is found to be a maximum when
" ( a N(O) n(0) = 26
 DNO
 N)
(s  W
H STAGE
which is
and a relative maximum with respect to 6 when 6 = 0, namely,
f ST STAGE
6U z

k(aIf 4
(optimum concentration relation)
By comparing Eq. 12 with Eq. 9 it i s seen that the optimum concentration relation permits an increase in separative power of 19.6 per cent over the nomixing case.
Fig. 2A
cascade of concurrent doubleentrant units (rectifying section).
158
THE THEORY OF ISOTOPE SEPARATION
APPENDIX E
159
It i s further evident from Eqs. 4, 8, and 11 that 0 = % i s the most efficient cut, because this value r e s u l t s in a minimum value of ( L + Z) for a given 6. It is instructive to compare these two c a s e s (nomixing and optimumconcentration relation) by considering the net transport for the cascade of Fig. 2 with 9 = ?h. This is
Total volume =  (2 13) In (1  6 ) dl  q ) 6 Total pumping =
1
2/3
(3
 q)
Number of stages = 2  5 (1  q)(3 On the other hand, f o r a given flow Ls the maximum possible t r a n s port through the sth stage is Ls (  1)Ns+l(l  Ns+l)
ff
which occurs when
 vs 
1
Ns+1
1vs
a lNs+l
The percentage transport ( r e f e r r e d t o the maximum) is therefore
When N(0)  n(0) a r e related by Eq. 10 and 9 = ?h,q turns out to be %; when they a r e equal, q = (3/2. Thus in the nomixing c a s e the net transport is related to the degree of equilibrium. The r e s u l t s just obtained may be generalized by introducing the parameter q directly into the formula (Eq. 7) for <5U.It i s then found that (for 0 = lh)
Fig. 3Factors for total pumping,volume, and number of stages; a comparison of nomixing cascade and "constant per cent transport" cascade (q = 0.5).
F r o m Eqs. 14 and 15 expressions a r e obtained for the total volume of a cascade, the total pumping, and the total number of stages. These a r e , for the constanttransport case,
The volume and pumping a r e both minimum with respect to q for q = ?h. Figure 3 gives the three factors a s a function of fi for the two choices q = 0.5 (minimum volume) and q = (3/2 (no mixing). The minimum volume for q = 0.5 i s a t 6 = 0 and i s 19 p e r cent l e s s than the
160
THE THEORY OF ISOTOPE SEPARATION
APPENDIX E
161
minimum volume for the nomixing case which occurs at 0 = 0.715. Unfortunately both the pumping and the number of stages a r e infinite
It is obvious that the more general "constant per cent transport" cascade offers greater opportunities than does the nomixing case which might a priori be considered the most efficient. A few interesting possibilities a r e noted which illustrate the flexibility of the constanttransport cascades. The factor for minimum volume in the nomixing case is 9.82 and corresponds to a 71.5 per cent approach to equilibrium. In the constanttransport case this volume factor corresponds to many choices among others, to q = 0.5 and?! , = 0.82. In this case, howof q and 0; ever, the total pumping is 24 per cent l e s s than in the nomixing case, whereas the number of stages is only 3 per cent higher. It is thus possible to save a considerable amount of pumping while losing only slightly on the number of stages. Another constanttransport possibility with the volume 9.82 is the choice q = 0.4 and ft = 0.77. The pumping is 15 per cent l e s s and the number of stages 4 per cent l e s s than the nomixing values for ft = 0.715. The nomixing case thus represents no extremal. A good balance between volume, pumping, and stages will be struck by the choice q = 0.40 and = 0.80. But if one of these three factors overweighs in importance the others, different values should be chosen. Thus if it is especially desirable to reduce the volume to a minimum, the choice might be q = 0.5 and (3 = 0.5. If it is desirable to reduce to the limit both the pumping and the number of stages, the choice should be q = 0.4 and 0 = 0.90, o r even 0 = 0.95. If the number of stages is not important, then q = 0.5 would be chosen.
REFERENCES
I

NO MIXING
Cohen, K., and I. Kaplan, Report A302, Sept. 19, 1942. Kaplan, I., and K. Cohen, Report A301, Oct. 29, 1942.
Fig. 4Factors and fi.
for total pumping, volume, and number of stages as functions of q
at 0 = 0. It is seen, therefore, that the significant region will lie between ft = 0.95 and ft = 0.50. Figure 4 gives the factors for volume, pumping, and number of stages for q = 0.3, 0.4, 0.5, and 0/2 within this range of 0.
INDEX
Cascade, square, Type I1 operation of, 41 44, 4753 squaredoff, of countercurrent elements, 3435 rapid approximate solution for, 3538 scheme for, 38 stages of, 35 number of, 3, 12 size of, 9 stripping sections of, 2124, 7778 Centrifuge, concurrent flow, 105, 114 countercurrent flow, 105, 119, 121122 evaporative, 104105, 111114 separative power of, 1091 11 Centrihge separation, design of, 105106 differential equation of, 106, 109 history of, 103106 maximum separative power of, 109111 theory of, 105 Chapman, S., 131 Cohen, K., 29, 38, 61, 78, 124125, 136, 143, 149, 153, 161 Column, countercurrent, 31 number of stages, 31 32 fractionating, 30 relaxation phenomena for, 5461 thermal diffusion, 30 Combination of separation plants, 7478 Concurrent contacting, 131 Concurrent twophase elements, 154161 Control, hydrodynamic, 72102 Control problem, 79102 Countercurrent centrifuge, 30 Countercurrent column, 31 number of stages, 31 32 Countercurrent contacting, 129 Countercurrent devices, 303 1 Cowling, T. G., 131 Cut in cascade, 5
Aston, F. W . , 103
Bardeen, J., 131 Beams, J. W., 105, 113 Boundary conditions, rectifier, 87 stripper, 8788 Bramley, A., 105, 119, 124, 131 . Brewer, A. K , 105
Campbell, G. A., 50 Cascade, 3, 5 combined, 78 cut in, 5 design of, 11 efficiency of, 6 equilibrium time of, 2427, 38, 82 flow in, 1315 total, 9, 7778 ideal, 510 stages of, 5 ideal and nonideal, 1012 losses in, 6774 per stage, 69 production rate of, 12, 94102 rectifier of, 21 relaxation time of, 25 square, 3044 equilibrium time of, 39, 144146 production loss of, 101 production rate of, 94, 96 disturbance function of, 96 steady state of, 31, 62, 65 transient phenomena of, 62 64 Type Ioperation of, 4043, 47, 54
THE T m O R Y O F ISOTOPE SEPARATION
INDEX Transport, loss of, 9091 maximum, 33
Debye, P., 131 Deuterium, separation of, 126, 132 Deuterium separation, catalytic exchange method, 132136 Diffusion, thermal, 131132 Dirac, P, A. M., 29, 109, 125 Distillation, Rayleigh, 1501 53 separation in, 152 separative power in, 152 Doetsch, G., 94 Dunning, J. R., 29, 38
Joly, J., 104 Jones, R. C., 119, 131
Kaplan, I., 29, 38, 61, 78, 106, 125, 136, 143, 149, 161 Keith, P. C., 136 Kuhn, W., 105, 119 Kurti, N., 29
Schwartz, B., 78, 149 Separation, isotope (see Isotope separation) twophase, 126131 Separation plants, combination of, 74 78 Separative power, 1315, 1921, 3738 (See also Centrifuge; Distillation) Separative work, 72 . Simon, F , 29 Skarstrom, C., 105106, 113 Square cascade (see Cascade, square) Stages of cascade (see Cascade)
Urey, H. C., 105106, 125, 133
Value function, 1314 elementary, 15, 17
Elements, number of, 14, 19 Equilibrium fractionation, 67 Equilibrium time, 2427, 38, 82 of square cascades, 39, 144146
Laplace transform, 84, 89, 93 Lefkowitz, H., 78, 149 Lindemann, F. A., 103
Thermal diffusion, 131132 Thompson, W. I., 62, 78, 136 Transcendental equation, roots of, 139 143
Waldman, L., 131 Waste material, 18 Wirtz, K., 131 Work function, 64
Feynman, R. P., 67 Flow, total, 9, 15, 23 Fluctuations, 80 90 nonperiodic, 90 periodic, 90 Foster, R. M., 50 Fuchs, K., 29, 84, 91, 102 Furry, H,, 119, 131
Martin, H., 105, 119 Mayer, H., 78, 84, 149, 161 Mixing, 6, 1 5 Mole fraction, 5 Mulliken, R. S., 104 Murphree, E. V., 125
,
Net transport, 21, 26
Gevrey, M., 145
Onsager, L., 119, 131
Holdup function, 25, 7778, 147149 in column, 59 net desired material (N.D.M,H.), 2527 in top reservoir, 59 Humphreys, R. F., 105, 113 Hutchison, C. A., 61, 136
Peierls, R., 29 Plants, separation, combination of, 7478 Poole, J. H. J., 104 Process factor, centrifuge, 105 infinitesimal, 9 large, 1 5 simple, 5 Production rate, variations in, 94102
Isotope separation, 2729 by chemical exchange, 126127 by thermal diffusion, 131 uranium, 15
Rayleigh, J. W. S., 150, 153 Relaxation phenomena, 5461