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an Ix / E cI Chemical Engineering Fundamentals Review

Mathematics, Computers,
Operations Research, and Statistics
by Robert F. Sweeny , Applied Science Laboratories, Inc., State College, Pa.,
Robert S. Davis, Scientific Design Co., Inc., New York, N . Y.,
Leon Lapidus, Princeton University, Princeton, N . J., and
Sanford M. Roberts and
Edward Sax, Thompson-Ramo- Wooldridge Products Co., Beverly Hills,Calif.

b Process si mulation challenges mathematicians

b Statistics and computers combine for automatic process optimization

b Operations research emerges from “primitive” linear estimation with


nonlinear techniques

T,, W’ORD MOST FREQUENTLY en- interest to the chemical engineer con- tion of nonlinear optimization tech-
countered in the literature last year tinues at a fast and unabated pace. Of niques, such as steepest descent (ascent)
was “optimization,” the systematic treat- importance in the work published dur- and piecewise linear least-square fits.
ment of variables to find the combination ing the year is the fact that the level of In essence, these methods involve a type
which yields the most product, the best sophistication of the topics involved of search procedure which is ideally
product, or the most money. This seems to be rising. Chemical engineers suited for use with digital computers.
trend is especially interesting because are now using mathematical techniques Chanmugan and others ( 3 A ) have in-
all the sections of this review are in- which only a few years ago were the vestigated the possibility of using a
volved. T h e very reason for existence province of the applied mathematician. cosine-type input for determining the
of optimization is the best operation of Determining the optimum perform- process characteristics and following this
a plant; thus it might properly be called ance of chemical and petroleum units with an optimization procedure. The
operations research. Yet some of the has interested a number of authors. proceedings of the recent symposium on
mathematics used qualify the subject Berg ( I A ) , Johnson (4A), and Stout optimization (7A) also contain a num-
as a subdivision of applied mathematics. (70A) were concerned with the de- ber of extremely interesting reports.
One of the most important techniques velopment of process equations which Of interest is the extensive use of matrix
used for optimization is EVOP (evolu- could be used for optimization and/or terminology in most of these references.
tionary operation), which is admittedly control. Proceeding a step further, sev- T h e use of dynamic programming as
a statistical tool. Finally, computers eral authors ( 2 4 5 A , 71A) have in- an optimization technique has received
are used in solving the lengthy equations vestigated the optimization of various considerable attention during this past
formulated by the mathematicians and systems using linear programming tech- year. I n effect this method replaces
statisticians. When computers are used niques. a multidimensional or multistage opti-
for this purpose in “on-line” plant serv- However, it is well known that the mization with a series of single-stage
ice, process control takes over. concept of linearity for the process optimizations. T h e computational sim-
T h e review has been divided into the equations and the constraints may be plifications afforded by this procedure are
four title subjects. The mathematics too restrictive for practical use. Rosen quite significant. T h e application to
section covers Jan. 1 to Dec. 1, 1960. ( 8 A ) , in a monumental study, has ex- the static behavior of chemical engineer-
Computers and statistics covers Decem- tended the linear programming approach ing processes has been detailed by Aris
ber 1959 through November 1960. so that nonlinear process equations may and others (7B-5B)in a series of super-
Operations research reviews the same be used. This work as well as other non- lative reports and by Roberts (9B).
period. linear programming techniques has been In these, the optimum representation of
summarized most adequately by Wolfe various staged operations and of fixed
Mathematics (72A). bed reactors has been analyzed in de-
At the same time, Lapidus and others tail. Kalman and others (6A, 7B) and
T h e flow of publications whose con- ( 6 A ) and Rosenbrock (QA) have in- Merriam (8B) have also used this tech-
tent contains mathematics of direct vestigated the automatic implementa- nique for optimizing the behavior of

VOL. 53 NO. 4 APRIL 1961 329


4-1
an Chemical Engineering Fundamentals Review

dynamic processes. The book of HoTvard illustrated the use of the transfer
(6B)considers the application to Mar- function concept for analyzing the re- Table 1. Mathematical Studies of
kov-type processes. sponse of large complex systems. General Interest
The past year has seen the develop- Many of the ideas embodied in the
ment in this country of the use of Lya- analysis of linear systems have been Subject
punov's second method for analyzing summarized by Williams (120) in a Momentum Transport
the stability of nonlinear dynamic sys- recent series of articles, and Gibson (30)
Flow of non-Newtonian fluids
tems. This method involves an ex- has discussed in detail the implications past surface
tensive use of matrix notation, the and mathematics of adaptive (learning) Study of climbing 6lm evaporator
properties of ordinary differential equa- type systems. Motion of sphere in infinite cylin-
tions, and attempts to find a scalar Previous work involved with character- der
Dispersion in flow through capil-
function which can be used to define izing axial dispersion caused by im- laries
stability limits. The classic study in the perfect mixing or radial gradients by Boundary layer theory to power-
field is that of Kalman and others (7C). an axial diffusivity has been extended law fluids
Levin and others tZC) have applied the during this year. As a general rule, the Dynamics of a Newtonian fluid
interface
Lyapunov method to chemical reactor mathematics involve the solution of Interfacial turbulence
stability. The tremendous interest in linear parabolic partial differential equa-
this subject was exhibited by a full-day tions; the specific equations depend on H e a t Transport
series of papers a t the September the particular process under study. H e a t transport i n gases with
Joint Automatic Control Conference at The method of solution is usually by chemical reaction
Massachusetts Institute of Technology. Laplace transform, but other methods, Radiative and conductive transfer
As further evidence of the importance such as separation of variables, are also i n packed bed
Analysis of rectangular fixed bed
and interest for chemical engineers as- used. In some cases the residence time reactor
sociated with the above mentioned curves (the commonly used name for the Transient heat transfer i n sta-
mathematic techniques is the fact that experimental technique) are analyzed tionary packed beds
the special lecture series for the Decem- by the moments of the residence time dis- Transport i n presence of phase
conversion
ber American Institute of Chemical tribution (7E). One-dimensional heat equation
Engineers meeting was devoted to Diffusion type models for the axial with variable parameters
fundamental ideas and applications for dispersion in homogeneous flow reactors Thermal radiation between par-
optimization techniques in design and or pipes with imperfect mixing havc bccn allel plates
control. Such topics as the optimization analyzed (2Ej 8E, I I E ) , and Hawthorn M a s s Transport
of nonlinear static and linear dynamic (IOE) considered the effect of a radial
processes using steepest ascent, linear Laminar boundary layer flows
temperature gradient. Axial dispersion with finite velocities
programming, and dynamic program- i n fixed and fluidized bed operation with Variable diffusivity in solids
ming were detailed, as well as the stability no reaction (3E-725 9 E ) , in chromato- Multicomponent diffusion
of nonlinear systems using Lyapunov's graphic beds ( I E ) ,and in slurried chem- Transfer from sphere to laminar
method. An extensive set of notes was fluid
ical reactors with heat sources (7223) have Diffusion within developing
prepared for this presentation. A re- been analyzed. boundary layer
cent issue of the Chemical Engineering Consideration of Sturm-Liouville type Vaporization of superheated drops
ProgTess Symfiosium Series (No. 31) con- systems continued during the past year. in liquids
tains a number of reports from meetings Simultaneous transport and
In general, the problem is one of solving chemical reaction
on optimization held a t n'ew York a linear boundary-value partial dif- Extractive reaction in CSTR
University and in Mexico City (4H). ferential equation, with the solution in- Vaporization in t h e hypersonic
A number of authors have concerned volving an infinite set of eigenvalues. laminar boundary layer
Entrainment a n d efficiency of
themselves with the mathematical analy- The solution is explicitly obtained by mixer-settlers
sis of linear dynamic systems. In par- Laplace transform or another standard Spherical diffusion with nonlinear
ticular, a few have considered the re- procedure. Among the specific systems isotherm
sponse of such systems to random fluctua- of interest were the transfer of heat, Ion exchange system
tions on the process inputs ( I D ) and to mass, or momentum from a fluid flowing
Miscellaneous
the determination of the process dynamics between a fixed coordinate system
of continu.ous stirred tank reactors ( I F , 4F, 6F, 7 F ) , chernical reaction in Implicit algebraic functions for
rate constants
(CSTR) by correlation techniques (50). tubular flow reactors (ZF, 5 F ) >and fixed Analysis of fixed bed reaction
Another author (GD) has presented a bed operation ( 3 F ) . system
highly detailed analysis of the linear In addition to the mathematical refer- Generalized CSTR systems
prediction problem. In all cases, m a - ences already discussed, there also have Calculation procedure for batch
rectification
trix algebra and the concepts of random been a large number of reports covering
Gaussian concentration or temperature a wide variety of diflerent topics (Table Miscellaneous
distributions are employed. The recent I). Of particular interest is the book of Activity levels i n reactor-regen-
translation of the book by Solodovnikov Ralston and others (Z4G) which, while erator system
(IOD) is another example of this type digital computer oriented, presents a Matrix algebra, ordinary and
of analysis. mathematical analysis of certain topics partial differential equations,
The concept of a transleer function and/ regression, and nonlinear
\vhich are both informative and im- functions
or frequency response has also been portant. This book is recommended Mechanics of particle bounce
used by many authors to develop suit- highly to all readers of this revieiv.. Catalyst utilization with continu-
able models for linear dynamic chemical ous replacement
Moving boundary problem
engineering proccsses. This implies Numerical differentiation using
the use of the Laplace transform. The Computers least-square fit
CSTR has been considered ( 2 0 ; 4D, Transient response of distillation
9 D ) in this light and also the heat ex- Delivery of the large solid-state digital column
changer (70, I I D ) . Mesarovic ( 8 0 ) computers was started during the past

330 INDUSTRIAL AND ENGINEERING CHEMISTRY


an r dChemiical Engineering Fundamentals Review
year. I t is surprising how many com- Wolfe (77K), and large step gradient
Table II. Computer Reports panies have made the change. Some procedures using the simplical method
are even making the big j u m p from were described ( 7 7 K ) . Quadratic pro-
Subject Ref.
medium to very large (IBM 650 to 7090). graming or fixed-tableau simplical
Heat, Mass Transfer, and Fluid Flow A list of analog equipment available procedures were also covered ( 7 K , 6 K ,
was given ( 6 H ) , along with a list of ref- 76K).
Graetz equation (IBM 650) for (IF) Three excellent reports on chemical
heat and mass transfer in laminar erences on analog simulation.
flow I n the midst of the activity concerning engineering applications of optimiza-
Sample program, block diagram for (8J) larger computers, a description was tion techniques appeared (4B,9B, 4 K ) in
hear exchanger selection published (2”) showing how a small one volume. Cochran ( 4 K )discussed the
Computation of natural convection (2 SJ) computer can be programed to solve general optimization problem and con-
behavior in a horizontal cylinder large problems (a complicated flash trasted linear programing or matrix
Equations predicting temperature (14J) vaporization problem was used as an problem types with nonlinear or response
profiles on plate heat exchangers
(IBM 704) example). I n more general matters surface types. This article gives a good
Equations for solving multicompo- (1SG) of programing much discussion was example of an approach to chemical
nent diffusion problems (IBM heard concerning Algorithmic language plant design optimization.
650) (ALGOL) and other similar or related T h e application of dynamic program-
Mathematical model for pipeline (IOJ) methods. The subject of universal pro- ing to three representative chemical
operation with surge graming is attracting very high interest. engineering problems included ( 4 B ):
During the year, the American In- optional multistage compression of a
Distillation and Extraction stitute of Chemical Engineers has made gas, optional multistage cross-current
Multicomponent flash vaporization (1J) available three complete program man- extraction, and optimal temperature
curves by integration of differen- uals ( 7 H ) . They have continued the sequences in reactors. Roberts (9B)
tial equations
monthly publication of abstracts in presented the application of dynamic
Binary batch rectification with hold- (14G) Chemical Engineering Pr2gress. Other programing to the formulation of the
up (IBM 650)
New coverage method for multi- (15J) literature available is a description of catalyst replacement problem. Four dif-
component distillation catcula- how to solve multicomponent distilla- ferent models of the catalyst replacement
tions tion problems on the analog Dystac problem were given, the solutions of
Pulse extractor simulated on IBM (4J) ( 5 H ) ; a collection of reports (47); which yield the maximum profit, the
650 and computer abstracts on cards, an maximum profit-time relationship, and
Miner-settler extractor simulated (S2C) abstracting service ( 3 H ) . Table I1 lists the operating policy of when to shut
on digital computer
other reports of interest. down and replace or regenerate the cat-
alyst.
Kinetics and Reactiors Some interesting new applications of
Operations Research
Iterative process of estimating rate (SG) linear programming techniques also
constant ratios from nonlinear Operations research (OR) has been appeared. O n e method (77A) makes
differential equations
defined as “a scientific method of pro- optimum use of available storage tanks
Frost-Schwemer kinetics equations ( 8 J )
for competing reactions (IBM viding executive departments with a in spite of random fluctuations in supply
650) quantitative basis for decisions regard- and demand. Another study ( Q K )
Computer solution of catalyst supply ( S J ) ing the operations under their control.” shows the use of linear programing for
problem in gas shift converters This is perhaps a little too broad, but scheduling and planning large scale
Reaction coefficients from experi- f7J) it does delineate the area of interest. engineering projects.
mental rate data using trial and This past year might be referred to as The so-called “critical path” method
error (IBM 650)
the one in which the literature started can be used in scheduling engineering
EqIJations for solving backmixing in (11J)
design of chemical reactors (IBM to indicate that the world is round rather work and research and development
650) than flat, as shown by the emphasis on projects, as well as annual plant mainte-
the use of dynamic or nonlinear pro- nance turn-arounds. With this technique
Thermodynamics graming techniques as contrasted with one can evaluate the cost of various al-
Calculating detonation and impact (6J) the now classical linear programing ternates, including crash programs, and
characteristics for hydrogen- approach. arrive at the optimum solution. T h e
oxygen mixtures (IBM 650) An extremely interesting report by method is available as a computer pro-
Multicomponent eutectic systems (1OJ) Singer (75K) deals with simulation and gram from Remington Rand, in con-
calculated for binary data (IBM optimization of oil refinery design. junction with D u Pont.
650)
The report treats the simulation and An application of linear programing
Extension to azeotropes (QJ )
optimization of the design of a 10-vari- to the problem of assembly line balanc-
able oil refinery with the objective of ing was given (ZK),and the use of
Optimization and Planning by Simulation maximizing net profit after amortiza- a modification of linear programing to
Planning and scheduling oil refinery (SJI tion costs. T h e example illustrates the solve certain types of nonlinear problems
operations using computer application of several new nonlinear in tetraethyllead blending was discussed
methods optimization techniques. Three new ( 5 A ) . Another application to produc-
Optimization of distillation opera- (Ian techniques for handling nonlinear op- tion scheduling ( 5 K ) uses random sam-
tion using calculation method timization problems were presented : pling techniques for picking the optimum
Reaction kinetics optimization using (16J) the gradient projection method ( 8 A ) ,
nonlinear estimation schedule from a large number of pos-
Dynamic programing formulation (17J)
the leap and creep method, and the tech- sibilities. T h e use of operations research
of catalyst replacement problem nique of deflected ascent. T h e ap- techniques in planning production was
Simulating refinery to plan opera- (18J) proaches outlined should find wide ap- discussed ( S K ) , and an interesting ap-
tions, optimize plication in the chemical and petroleum plication of operations research to opti-
Optimization methods in process (19.1) industries. mization of a kraft pulping process ap-
equipment design An excellent bibliography on non- peared ( 3 K ) .
linear programing was presented by A symposium on case histories in op‘

VOL. 53,‘NO. 4 0 APRIL 1961 331


an Chemical Engineering Fundamentals Review

erations research five years after the and then used least square curve fitting on a Poisson process, the expression Ivas
programs were instituted was published techniques to evaluate the coefficients developed for mean polymerization
(12K), and a survey of OR techniques and exponents of the functional groups. rate.
in British industry appeared ( 7 3 K ) . This represents a great improvement Design of Experiments. A number
T h e long-range future of OR was dis- over the conventional method of “eye- of studies related to the design of experi-
cussed (7K, IOK)? and the problem oi balling” in a curve and coming u p with ments were concerned with evaluating
finding the optimum solution in OR a “law.” pilot plant processes efficiently or running
\vas considered (14K). A discussion of Kron’s animated poly- tests on commercial plants. As in the
I n contrast with 1959, fewer new books hedral model for multidimensional iiiodel past, G.E.P. Box and his associates have
apppared last year. .4n interesting col- making was given (,5iM). A clever tech- set the pace which others follow. I n
lection of lectures on operations research nique (7E)of developing the transient addition, they have developed the
and systems engineering appeared (3L). response of gas flow through a packed bed theoretical background. A review of
It is a good introductory Tvork and de- was discussed. By introducing a step Box’s contributions appeared (41V).
scribes such techniques as linear pro- function of helium concentration into One of the most interesting statistical
graming, systems engjneering, simu- the system, the investigators were able reports of the year, by Chanmugan and
lation techniques, theory of games, and to evaluate from the first and second Box ( 3 A ) , described a procedure for
information theory. No previous back- moments of the time distribution the bed automatic optimization of continuous
ground by the reader is assumed in the porosity and axial dispersion of the gas. processes by statistical techniques. For a
areas covered. The activity level of a catalyst in a response of the form:
An excellent discussion of large-stcp reactor-regenerator system was studied
gradient procedures in nonlinear pro- ( 8 M ) using theoretical residence time- ’M = Bo + 01 (x - xo! + 1/2P11 (x - .Y0)2
graming was published (5L), and a distribution functions: activation, and
monumental bibliography (TL), con- deactivation distribution functions. The and an imposed forcing function:
taining 41 95 references on operations
research u p to 1957, is an outstanding
approach is novel for chemical engineers
and deserves attention.
x = xo + 6 x cos wt

piece of work. Maximum stable droplets in disper- the output is :


An excellent introduction to business soids (7,M) were discussed. From cor-
games was given for the nonspecialist relations of the maximum stable droplet M(no + 6x cos a t ) =(Pa + 1/413116x2) +
(4L), and a good discussion of opera- size, the drop size distribution may be P16x cos wl + ‘/*PI1 ( s x y cos w t
tions research for executives appeared estimated. The evaporation from drops
where
(6L). The mathematics of linear pro- containing dissolved solids ( 3 M ) was
graming and game theory were covered treated using some statistical concepts, Po = M(1)
(ZL, 7L). The size and frequency of gas bubbles

Statistics
in fluidized b-ds affect the density
fluctuations of the bed (2M). Bounce
phenomena of particles wirh randomly
(a1 = g) n = xo

distributed angles of reflection were de-


The growing importance of statistics tailed ( 9 M ) . Various stochastic models
to chemical engineers may be seen in associated with dynamic programing The coefficient of the fundamental fre-
the increasing number of special con- formulation of catalyst replacement were quency in the output response is pro-
ferences and lecture courses, as well as discussed (LIB>101M, 7 7 M ) . portional to the slope of the response
the increasing number of statistical ses- In a very good report, Petersen (22G) at x = X O . By looking for the funda-
sions of the professional societies. l n - described a procedure and a computer mental frequency one can tell whether
cluded in these are the Gordon Research program to test statistically various pos- the process is at the optimum. For ex-
Conference ; Purdue University‘s sympo- sible reaction mechanisms. The pro- ample, if p l is positive, the frequency
sium on engineering applications of gram then generates automatically and is in phase with the forcing function.
probability, November 1960; the Con- tests more complicated reaction mech- If 81is negative, the fundamental fre-
ference on the iVew Chemical Engineer- anisms if required. quency is 180’ out of phase xvith the
ing, sponsored by Midwest Research In- The method of least squares was used forcing function. When the process is
stitute and Chemzcal Engfneeizng, Novem- by TVhitaker and Pigford (3SG) to fit at optimum conditions, the fundamental
ber 1960, Kansas City, M o . ; the ninth the data by Gram orthogonal polyno- frequency does not appear in the out-
Tappi-Canadian Pulp and Paper Associ- mials. The least square curve was put, since p l = 0. The authors, after
ation statistical course in August 1960, then differentiated to give an expression considering other. models, proposed via
Brevard, N. C . ; the special A.1.Ch.E. for the derivative of the data for five a hardware block diagram a scheme for
lecture series on response surface meth- evenly spaced points. The standard carrying out this optimum searching
odology and similar courses offered by error of the derivatives was found, and continuously.
the ACS and American Society for Qual- a comparison was made with the more Another worthwhile study (20AY) by
ity Control; and recent ACS and A.1.- complicated Douglass-Avakian expres- Jenkins and Chanmugan discussed auto-
Ch.E. meetings. sion. correlation and the design of exper-
Engineering Science. T h e principal .4 stochastic model for emulsion poly- iments. Considerable increase in ef-
item of interest this year in this area merization was developed (61M). A ficiency is claimed if a systematic de-
is the number of studies that report first-order diffusion model of monomer sign of experiments is employed in-
results using statistical concepts in diffusing from the ambient liquor into stead of randomizing the order in which
planning the experiment, analyzing the blobs of monomer-polymer mixture experiments are performed.
results, or other statistical concepts was proposed. In addition, radicals from The Box-Tt‘ilson technique has been
such as imposing white noise on the the ambient liquor diffuse into the blobs implemented by “ridge analysis” for
process and measuring the response. at random time and alternately trigger multivariable systems (76i\‘). Ridge
Several studies ( 7 M , 4 M , 72M, and inhibit polymerization. The sto- analysis consists of examining the yields
73M) employed dimensional analysis chastic element in the process is the ran- a t various fixed radii from the center of
reasoning to develop fiinctional groups dom polymerization function. Based the design.

332 INDUSTRIAL AND ENGINEERING CHEMISTRY


an m dChemical Engineering Fundamentals Review
-4 quadratic likelihood function was tions, and to assist in the design of a in performance it is important to detect)
set u p by Box (3N) to study a response new plant. For the numerical example, type I and type I1 errors, and standard
surface. H e discussed the adequacy of cost, yield, and production responses deviation.
the model in terms of the residual vector were given. An unusual method in process simula-
and then sought explanations for the For the practical problems of operat- tion optimization was given (27N).
residual. Box pointed out that linear ing a pulp mill, Sheldon (30N) wrote T h e simulated noise input into the proc-
least square estimates are useful over about the analysis of variance, multiple ess is developed by a random number
limited ranges even for nonlinear func- regression, and response surface experi- generator. T h e technique was used to
tions. Mention was made of the Prince- ments. H e stressed the need for max- test the applicability of Optimizing Con-
ton IBM-704 share program that uses imum amount of information with a troller (OPCON).
linear approximations. Designs for min- minimum of tests. T h e improvements Two articles on customer acceptability
imizing variance error and bias error in a chemical process by response sur- of product were published. A designed
were discussed. face methods were described by Tidwell experiment was conducted o n gas
T h e contributions of Box and his ( 3 3 N ) . By using the log of mole ratios scrubber conditions to produce a house-
associates were summarized (79N) on of the reactants in his first designed ex- hold product with odor acceptability
a level most chemical engineers would periment, a model with a high degree ( 2 8 N ) ,and a method of testing designed
find acceptable. T h e summary con- or interaction was obtained. By re- experiments for customer preference was
tains a number of tables of data and defining the variables, the final model discussed (37N).
designs which are good companions to became simpler. Other designed experiments included
the text. I t was pointed out by Hoerl that statis- a factorial design on polyurethane
A number of popular and expository tical testing may give results not pre- coatings (74N) ; a central composite
articles on Box’s contributions have ap- dicted from theory ( 7 7 N ) . H e set u p design for predicting chemical com-
peared. While the popularization of five basic steps for carrying out the statis- position of the precipitation of calcium
concepts has the advantage of spreading tical analysis of a production problem. hydrogen orthophosphate (26N); and
the word, it has the disadvantage of gloss- These are: definition of objectives, a factorial design for determining heat
ing over difficulties and problems. In- collection of operating data over a transfer coefficient for concurrent flow
cluded in this category are two articles period consistent with reliability of data, in gas absorbers (72N).
(78,V, 27N). Grohskopf (75N) cited statistical analysis of data, determination Articles were published by Connor
the two important contributions of Box: of operating conditions consistent with for the serious student (SN,91\7), and
surface fitting and central composite de- goals, and application of results to proc- a collection of Youden’s articles has
sign. The contributions of Youden on ex- ess and then evaluation. Hoerl showed been published as a booklet (22s).
perimental design were also discussed. how inaccuracies in data with high The use of half-normal plots in inter-
Some problems to be attacked in the degree of variability can be handled, preting two level factorial experiments
future by statistics are definition of chem- provided a large amount of data is was discussed by Daniel (70144. The
ical reactions, estimation of reaction analyzed. H e gave a n example of a analysis of factorial experiments without
rate in systems with concurrent re- catalyst regeneration and replacement replication was described by several
actions, reduction of physical facts to cycle. Chang and others ( 7 N ) described methods (ZN), and the analysis of
mathematical statements, computer response surface experimentation to Latin squares with certain types of row-
simulation of reactor systems to evaluate develop optimum conditions and the column interactions may be handled
various design schemes, and design of possible reaction mechanism for the by special techniques (27N).
systems that will produce desirable synthesis of 2,5-dimethylpiperazinea I n a contintation of earlier work
products and suppress undesirable ones. I n a n interesting study, Carr and Dykstra (73N) recommended that cer-
Bennett ( 7 N ) reviewed the EVOP ap- others ( 5 N ) found that a statistical pro- tain runs of a central composite, second-
proach. gram is particularly useful when the order, response surface design be re-
As a result of increased interest and process is transferred from exploratory peated to provide a more general es-
experience in running designed experi- research to process development. They timate of the experimental error, as
ments, there were a number of articles stated that statistical programs should well as more reliable estimates of the
citing practical experience. Lind and be planned for experiments in small effects. Daniel pointed out that after
others (23.47) discussed a case history of groups to answer specific questions studying the effect of many factors the
a process optimization through use quickly and yet be useful for further experimenter is likely to gain some in-
of a designed experiment in a fermenta- studies. Screening experiments using sight into the problem and is able to
tion process. A “pulse” testing method highly fractionated factorials with “fold decide which factors are important
was used, whereby during alternate over” designs were recommended. After ( 7 7 N ) . This knowledge permits more
weeks the plant was run in normal man- screening for the key variables, more efficient planning, and fractional rep-
ner and then a t designed conditions. tests should be run to firm u p the results. licates may be constructed to take
Barnard’s sequential “P-test was used Finally, more elaborate designs are advantage of this knowledge.
in analyzing and plotting data. Better needed to evaluate nonlinear response A simple graphical technique to aid
yields and lower costs resulted. surfaces. in comparisons between laboratories
Three statistical techniques were em- T h e design of experiments, analysis of was presented by Youden (,75A7).
ployed ( 6 N ) to evaluate a petrochemical variance, and sequentional testing to A multiple comparison rank sum test
process. These were: analyses of plant determine best fermentation yields in a for the simultaneous comparison of all
records to obtain a yield equation, pilot plant were investigated by Schultz pairs of treatments in a one-way classi-
EVOP to improve yields, time-series and others (29N). I n a lucid exposition, fication with equal numbers of observa-
analysis to study process dynamics. they described a case history. They tion was presented ( 3 2 N ) .
T h e kinetics of the catalytic isomeriza- pointed out that sequential analysis A series of three articles ( Z S N ) de-
tion of n-pentane were investigated (5G) evaluates data as they are determined scribed linear contrasts in a set of “k”
using the Box-Hunter rotatable designs. and permits flexibility in choosing future means. Orthogonal contrasts, the
Designed experiments using EVOP were course of project. T o use sequential Scheffe method, the methods of Duncan
devised ( 3 4 N ) to evaluate product qual- analysis and to set u p the decision re- and Turkey, and the method of Student-
ity. to find optimum operating condi- quires determination of A (the difference Newman-Keuls were discussed. Lieblein

VOL. 53, NO. 4 0 APRIL 1961 333


an r dChemical Engineering Fundamentals Review
described a procedure for handling the positively correlated. Taking advan- (11A) Wilde, D. J., Acrivos, A., Cheni.
general analysis of variance which is tages of this, a study (34) showed that Eng. Sci. 12, 175 (1960).
(12A) Wolfe, P., The Rand Corp. Rept.
applicable to a large computer (22;c’). the sentencing of the sample depends on P-2063, August 1960.
Correlation. T h e compressibility ex- the number of defectives in a random
pression of COz and argon mixtures sample of fixed size, drawn from the par-
Dynamic Programing
was curve fitted by least squares (IP), and ticular batch: and upon the number of
a correlation technique was employed defectives found in batches before and (IB) Aris, R., Chem. Eng. Sci. 12, 56 (1960).
(2B) Ibid.. p. 243.
to develop a short term prediction for a after. (3B) Ibid.;13, 1 8 (1960).
long term biochemical oxygen demand T’ariations of flow analysis (44) is a (4B) Ark, R., Bellman, R . , ICaIaba, R.,
test ( 4 P ) . A parametric method for technique of evaluating the transfer of Chem. Eng. Progr. Symposium Ser. 56, NO.
determining the 50th and 90th percentiles 71 > 9
.-5 (\ -i.9- m .
variations in stock when the product from I _
- / -

of octane number requirements for new (5B) Ark, R., Rudd, D. F . , Amundson,
several machines a t one processing stage N. R., Chem. Ena. Sci. 12, 88 (1960).
model automobiles was presented by is fed randomly to several machines of (6B).Howard, R.-.4.: “Dynamic Prograni-
Brinegar and Miller (3P). The method the succeeding stage. This report de- ming and Markov Processes.” Tech-
was shown to be more efficient than co- scribed procedures, based on modifica- nology Press of M.I.T.. Cambridge,
Mas;.; 1960.
ordinating the Research Council non- tions of range methods, for analysis (7B) Kalman, R. E.. Lapidus, L., Shapiro,
parametric method. of variance. The sufficient statistics E.. Chem. E n p . Propr. 56, 55 (February
Y I

The programming for electronic com- and interval estimates for the parameters 1960).
puters of Fisher’s exact method of com- of two parameter exponential distribu- (8B) Merriam, C. W., Inform. and Control
3, 32 (1960).
paring two percentiles was described tions were given for the case of censored (9B) Roberts. S. M., Chem. Fng. Progr.
( 6 P ) . A detailed study was made ( 2 P ) of data (SQ). .Symposium Ser. 5 6 , No. 31, 1 0 3 (1960).
the effect of routine application of re- Probability. Using probability theory
jection criteria to replicate determination and the theory of errors, Zemany and System Stability
of a single value. A special log normal others (3R)showed how precision in x-ray
distribution function, called the “nearly (1C) Kalman, R. E., Bertram, J. E., J .
emission spectrography can be predicted Basic Eng. 1, 371, 394 (1960).
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for describing oil mixtures and polymers significant. T h e Society for Industrial Rational M p c h . and Anal. 5 , 194 (1960).
(5P). and Applied Mathematics is now pub-
Quality Control. T h e uses of control lishing a translation of the Russian jour- Linear System Analysis
charts in operating plants \\’ere discussed nal Theory of Probability and I t s Application. (1D) Acrivos, A , , Chem. Eng. Sci. 12, 279
by Aldredge (7Q) and Beazley (ZQ). One of the best studies on the applica- (1 960).
T h e application of statistics for estimat- tion of probability to an engineering (2D) Choletle, A., Blanchet, J., Cloutier,
ing plant costs was the subject of another problem appeared (7R). From probabi- L., Can. J . Cizem. Eng. 38, 1 (1960).
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may be estimated within closer toler- evaluated in terms of the statistical ge- (4D) Gutoff, E. B., .4.I.Ch.E. Journal 6,
ance if a standard deviation is assigned ometry of an ideal two-dimensional filter 347 (1960).
to each part of the project, rather than network. Miller (2R) treated as a (5D) Homan, C. J . , Tierney, J. W.,
G e m . Eng. Sci. 12, I 5 3 (1960).
using a n over-all standard deviation. Markov chain the process of interplant (6D) Kalman, R. E., J . Basic E,nc. 1,
A sampling procedure was developed storage in continuous manufacturing. ‘ 35 (1960).
for estimating the magnitude of basic Books. A4 large number of books (77)) Masubuchi, M., Zbid., 1, 31 (1960).
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(704). Jackson 19Q) extended his relating to various aspects of statistics ‘ 269, 274 (1960).
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methods for quality control in two related ( 7s-225’). ‘-4,’ 197 (1960).
variables to the case of several related (10D) Solodovnikov, V. V., “Introduction
variables. Another report (.5Q) con- to the Statistical Dynamics of Auto-
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tions, New York, 1959.
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( 2 4 Boyd, K. T., Computer J . 3 , 45 (1960).
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334 INDUSTRIAL AND ENGINEERING CHEMISTRY


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336 INDUSTRIAL AND ENGINEERING CHEMISTRY

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